DE2238695A1 - ANTIPERSPIRANT IN AEROSOL FORM - Google Patents

Description

BLENDAX - ViERKE
R. Schneider & Co.
Patent department

65 M a i η ζ

Antiperspirant in aerosol form

The present invention relates to an aerosol can in the form of an aerosol spray composition Antiperspirant that is more stable than known products.

Antiperspirants, that is, means to inhibit perspiration, have long been known. The main active ingredients for such antiperspirants are astringents active substances that give irreversible precipitations in appropriate concentrations with proteins, used. Such substances are in particular metal compounds, tannins, for example tannin, formaldehyde and its polymerization and condensation products and organic acids and their salts and reaction products. A detailed summary of these substances and their mechanisms of action can be found in the work of H.P. Fiedler, "The Sweat" (1968, Editio Cantor KG, Aulendorf).

The various substances can be incorporated into solutions, creams, sticks, lotions or powders, if necessary to achieve a larger spectrum of activity, also in mixtures with one another. Has been particularly useful The incorporation of the antiperspirant substances into aerosol preparations has been shown, with the help of which a rapid and easy application of the active ingredients can be accomplished.

In the manufacture of aerosol spray compositions of the usual type, the antiperspirant ones. Substances as active Contain constituents, but have struggled

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results. When these active ingredients are inside the aerosol container, as with deodorants usual composition, in the form of an alcoholic solution, occurs after a short time Corrosion on the inner surface of the metal aerosol canister, which is primarily a The result is a change in the fragrance due to the decomposition of the perfume used and thus the uselessness of the Product.

Attempts have been made to avoid this unpleasant phenomenon by taking two measures. There is one possibility in it, the active, antiperspirant ingredients, especially aluminum or zinc compounds, in an organic aerosol propellant, optionally to suspend in the presence of a softening substance, a so-called emollient, that means making a dry spray. This form of application has the disadvantage that the product must be shaken well before use and, what is more consequential, through this Dry spray can very easily clog the dispensing valve.

Another possibility of the corrosion problems outlined in the presence of an alcoholic solution of the Avoid active ingredient is to use aerosol cans, in particular aluminum monobloc cans, their Inside is provided with a protective varnish. It has been shown, however, that even that is usually too Protective lacquers based on epoxy and / or phenolic resins used for this purpose to avoid corrosion damage not sufficient, as in aluminum aerosol cans with internal protective varnishes of this type were, also after a relatively short time, signs of corrosion in the presence of an alcoholic Solution of antiperspirant aluminum or zinc compounds occurred.

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It has now been found that over a long period of time stable antiperspirant agents in aerosol form can then be obtained if these agents are included in alcoholic solution and preferably alcohol-soluble as the active antiperspirant constituent Contains zinc or aluminum compounds, in an aerosol can, preferably an aluminum monobloc can, be bottled that have a protective coating on the inside Contains base of a vinyl chloride polymer. In addition to polyvinyl chloride, it is particularly suitable for this purpose a copolymer of a predominant proportion, preferably 80-99.5%, vinyl chloride and one lower proportion of a vinyl and / or (meth) acrylic ester, especially vinyl acetate.

To document the improved storage stability of the The following comparison tests were carried out for aerosol compositions according to the invention:

5o parts of an active ingredient solution of 5.o% by weight of an aluminum oxychloride-propylene glycol complex (sold under the trade name "Rehydrol A.S.C." by Reheis Co.),

o, l wt.% hexachlorophene,

1.5% by weight of hexadecyl alcohol,

1.5% by weight silicone oil,

4.2% by weight isopropyl myristate,

2, o wt.% Oleyl ether phosphate, acidic,

2.5% by weight perfume oil
lo, o wt.% Isopropyl alcohol, and
73.2% by weight of anhydrous ethyl alcohol were mixed with 50 parts of a propellant mixture of 60% by weight of dichlorotetrafluoroethane and 40% by weight of dichlorodifluoromethane

each filled in different aluminum monobloc cans. The aerosol can A did not contain an internal protective varnish Aerosol Can B was covered with a clear phenolic-epoxy resin varnish provided, the aerosol can C was equipped with a pigmented phenol-epoxy resin paint and the According to the invention, aerosol can D contained a copolymer of 9 8% vinyl chloride and 2% as an internal protective varnish

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Vinyl acetate. ψ

The aerosol antiperspirants were stored for 4 months at 45 C or room temperature. After a storage time of 4 months, the perfuming of the products was checked and, after removing the contents of the can, the cans were opened and examined for signs of corrosion.
The following results were obtained:

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Can Interior protective varnish Storage temperature Perfuming Appearance
the canned,
Inner surface A. none 45 ° C: completely the other way round
beat numerous
Corrosive
Points,. ·
black ver
coloring B. clear phenolic
Epoxy resin varnish Room temperature:
I. very strong
changes black ver
coloring the
Can C. more pigmented
Phenol epoxy
Resin varnish 45 ° C: very strong
changes numerous
Corrosion
Points D. pigmeriated
Lacquer based
of a copoly-
merisats from
9 8% vinyl chloro
rid and 2% Vi
nyl acetate Room temperature: greatly change
changes several
Corrosion
Points 45 ° C very strong
changes several
Corrosive
dots, bubbles
education Room temperature: greatly change
changes several
Corrosion
Points 45 ° C slightly ver
changes no changes
changes he
recognizable Room temperature: unchanged no changes
changes he
recognizable

As can be seen from these comparative tests, the Aerosol antiperspirants according to the invention which are coated on their inner surface with a vinyl chloride polymer Aerosol containers are housed, an increased stability compared to those products that are contained in aerosol cans are those with none or the usual interior protective coating are equipped.

Furthermore, an aerosol antiperspirant was used in aluminum monobloc cans that had the same protective coating on the inside as can D from the previous experiment (copolymer
at the; 98 & vinyl chloride and 2% vinyl acetate), was bottled, and from Γ> ο 'lV.ilcjη Dichlordi Γ. luorniothan and from 50 parts one

9/1159

BATH ORIGINAL

Active ingredient solution of the composition

7, ο% by weight "Rehydrol A.S.C." (Aluminum oxychloride propylene glycol complex),

3, ο wt.% Oleyl alcohol,

1.5% by weight of hexadecyl alcohol,

1.5% by weight silicone oil,

o.7% by weight perfume oil,
15.0% by weight isopropyl alcohol, and
71.3% by weight anhydrous ethyl alcohol

existed, stored for 9 months at 45 C or room temperature, whereby the following result was achieved:

Storage temperature Perfuming Appearance of the inside of the can
area 45 ° C: slightly changed
changes no changes he
recognizable Room temperature: unchanged no changes he
recognizable

As already indicated above, vinyl chloride polymers are in addition to homopolymers also copolymers of vinyl chloride can be used with one or more comonomers, but the vinyl chloride content is generally over 5o% should lie.

Suitable compounds that can be copolymerized with vinyl chloride are, in particular, vinyl esters such as vinyl acetate and vinyl propionate, Acrylic esters and methacrylic esters such as methyl, ethyl or. η-butyl (meth) acrylate, (meth) acrylonitrile, vinyl ether, Vinylidene chloride, maleic or fumaric acid esters, styrene and JL-methylstyrene.

Two aluminum monobloc cans coated with a pigmented lacquer based on a copolymer of 90% vinyl chloride and Lo% methyl acrylate were internally lacquered, were mixed with 3o parts of a propellant mixture of 6o parts of dichlorodifluoromethane and 4o parts dichlorotetrafluoroethane and 7o parts of an active ingredient solution

3 090Oi) / 1 159

3, ο% by weight of an aluminum hydroxide chloride-polyglycol ether complex, which is sold under the name "Glycoral",

o, l wt.% hexachlorophene,

3 _f o wt.% Oleyl alcohol,

1.5% by weight of hexadecyl alcohol,

1.5% by weight silicone oil,

0.6% by weight perfume oil,
15, ο wt.% Isopropyl alcohol, and
75.3% by weight anhydrous ethyl alcohol

filled and stored for 9 months at 45 C or room temperature, with the following result:

Storage temperature Perfuming Appearance of the inside of the can
area 45 ° C: slightly changed
changes isolated hints
of corrosion points Room temperature: unchanged no changes he
recognizable

The substances with an antiperspirant effect to be used in the context of the invention must, as already stated, be alcohol-soluble be. Aluminum and zinc compounds are ideal for this. Complexes are particularly suitable such salts with organic compounds containing hydroxyl groups, for example aluminum chlorohydroid complexes with polyhydric alcohols or polyglyccs, for example Polyethylene glycol, mono- or dihydroxycarboxylic acids, Aluminum chlorhydroxy alcoholate complexes, e.g. "an aluminum chlorhydroxyethylate complex, aluminum and zinc alcoholates, which can also be reacted with polyalcohols, an Alüminiumchlorhydroxyallantoinatkomplex or Aluminum dihydroxyallantoinate and aluminum acetylacetonate. Can be used particularly advantageously in the context of the present invention Invention is the under the name "Rehydrol A.S.C." of the Reheis & Co., Inc., sold aluminum hydroxychloride-propylene glycol complex and an aluminum hydroxychloride-polyglycol ether complex, as he did, for example, under the

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Trade name "Glycoral" from Waverly Chemical Co. is put on the market.

Also aluminum and / or zinc phenol sulfate, sulfo / ibenzoate, sulfoacetate or ethane disulphonate are suitable alcohol-soluble substances that inhibit perspiration. Of course In the context of the invention, mixtures of these or other known antiperspirant alcohol-soluble can also be used Astringents are used.

If desired, the antimicrobial agents known for this purpose, which inhibit or kill the sweat-decomposing bacteria, can be added to the preparations according to the invention in order to produce an additional deodorant effect. The substituted phenols may be mentioned in particular, for example the 2,2-dihydroxy-3,3 ', 5,5', 6,6'-hexachlorodiphenylmethane known under the common name hexachlorophene, and also 2,4-dichloro-3,5-m -xylenol, p-chloro-m-xylenol, 2,2'-thiobis (4,6-dichlorophenol) (bithionol), trichloroxixylenol, tetrabromo-o-cresol, 2-benzyl-4-chlorophenol and halogenated 2'-hydroxydiphenyl ethers, in particular 2,4,4 ^1- trichloro-2'-hydroxydiphenyl ether. Further substances suitable in this context are halogenated anilides, for example trichlorosalicylanilide, 3,5,4'-tribromosalicylanilide, 3,5,3 ', 4 ^1- tetrachlorosalicylanilide, 2-hydroxibenzoylanilide, 5-halo-3- (trifluoromethyl) salicylanilide , halogen-substituted diphenylureas or thioureas, for example 3,3,4'-trichlorocarbanilide, diguanides, in particular 2,6-bis (4-chlorophenylbiguanido) -hexane, 1- (3-chloroallyl) -3, known under the common name chlorhexidine, 5,7-triaza-l-azonium adamantane chloride or mixtures of these substances with one another or with other known bactericides. The proportion of bactericides in the aerosol compositions according to the invention is from about 0.05 to about 3% by weight.

The antiperspirants according to the invention in aerosol form usually contain a softening substance, a so-called emollient. As such substances are

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in particular fatty alcohols, for example cetyl alcohol, Lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, 2-octyldodecanol and its ethers and esters, the esters of higher fatty acids such as isopropyl myristate and ethyl palmitate and oil and fat-like nonionic surfactants, especially ethylene oxide adducts such as oxyethylated Lanolin or oxethylated fatty alcohols are used.

These substances with a softening effect are included in the inventive Preparations preferably contain in amounts of about 1 to about 10% by weight of the total composition.

The main quantitative components of the antiperspirant according to the invention are ethyl alcohol and / or isopropyl alcohol and the aerosol propellant, the latter can also be present as a mixture of different propellants. Examples of propellants that can be used are: dichlorodifluoromethane, monochlorotrifluoromethane, monochlorodifluoromethane, Monochlorodifluoroethane, dichlorotetrafluoroethane, Difluoroethane, octafluorocyclobutane, propane, butane, monofluorodichloroethane, trichlorotrifluoroethane, trichlorofluoromethane, Dichloromonofluoromethane and vinyl chloride. As already said, it can of course also be appropriate Propellant mixtures are used; the higher-boiling fluoromethane and ethane derivatives mentioned here by way of example can of course only be used in mixtures with low-boiling propellants. Particularly suitable propellants are dichlorodifluoromethane alone or in a mixture with dichlorotetrafluoroethane.

The use of anti-gelling agents has also proven useful proven; as such, for example, an acid oleyl ether phosphate, as it is available under the trade name "Crodafos N-Io sour "is sold in amounts from about 0.1 to about 5% by weight suitable.

Perfuming is a matter of course and indispensable and does not require any further explanation.

In the following a few more recipe examples for the according to the invention, in an aerosol container with a

- Lo -

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Protective layer made of a vinyl chloride polymer is provided, housed antiperspirants in aerosol form given:

Example 1 :

4o parts of an active ingredient solution

2.0% by weight "Rehydrol A.S.C." (Aluminum hydroxyl chloride-propylene glycol complex),

o, 17% by weight of hexachlorophene,

7.000% by weight isopropyl myristate,

1.74% by weight perfume oil,
12, oo wt.% Isopropyl alcohol, and
77.09% by weight anhydrous ethyl alcohol

were together with 60 parts of dichlorodifluoromethane in a Aluminum monobloc can filled with a pigmented inner protective varnish made of 98% vinyl chloride and 2% vinyl acetate was equipped.

Example 2:

7o parts of an active ingredient solution

2.5% by weight "Rehydrol A.S.C." (Aluminum chlorhydroxide-Pro - pylene glycol complex),

o, 12 wt.% hexachlorophene,

5.25% by weight isopropyl myristate,
2o, oo% by weight isopropyl alcohol, and
69.78% by weight anhydrous ethyl alcohol

were with 3o parts of a 60: 4o mixture of dichlorodifluoromethane and tetrafluorodichloroethane are filled into an aluminum aerosol can coated with polyvinyl chloride on the inside.

Example 3;

5o parts of an active ingredient solution
5, oo wt.% "Glycoral" (aluminum hydroxyl chloride-polyglycol-

ether complex),
o, 2o% by weight of tetrabromo-o-cresol,

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3.5o wt.% Ethyl palmitate,
l, 5o wt.% silicone oil,

l, 5o wt.% "Crodafos N-Io, acidic (acidic oleyl ether phosphate) ,

l, 3o% by weight perfume oil,
17, oo wt.% Isopropyl alcohol, and 7o, oo wt.% Anhydrous ethanol

were with 5o parts of a propellant mixture of 2o% propane / butane and 8o% dichlorodifluoromethane in an aluminum monobloc aerosol can filled, the inner surface of which is covered with a pigmented varnish made from a copolymer of 9 8% Vinyl chloride and 2% vinyl acetate was provided.

Example 4;

35 parts of an active ingredient solution of 5.5% by weight zinc phenolsulfonate,

o, 1% by weight of hexachlorophene,

0.1% by weight of bromochlorophene,

2, ο% by weight 2-octyldodecanol,

1.5% by weight silicone oil,

1.5% by weight oleyl alcohol,

1.3% by weight perfume oil, and
88, ο% by weight anhydrous ethyl alcohol

were placed in an aerosol can with 65 parts of dichlorodifluoromethane Filled from aluminum, the inside of which is covered with a coating based on a copolymer of 90% vinyl chloride and lo% methyl acrylate was provided.

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Claims (7)

BLENDAX - PLANTS
R. Schneider & Co,
Patent department 65_M a i η ζ Patent claims (I). Antiperspirant in aerosol form, containing, in addition to one or more propellants, an alcohol-soluble, antiperspirant substance, in particular an alcohol-soluble complex of a Aluminum or zinc salt in an alcoholic, essentially anhydrous solution in a common, Aerosol container preferably made of aluminum, characterized in that the inner surface this aerosol container with an optionally pigmented protective layer made of a vinyl chloride polymer is provided. 2. Antiperspirant agent according to claim 1, characterized in that that the vinyl chloride polymer is a copolymer of a predominant proportion of vinyl chloride and a small proportion of a (Feth) acrylic and / or vinyl ester. 3. Antiperspirant according to claim 2, characterized in that the vinyl chloride polymer is a copolymer of about Bo to about 99.5% vinyl chloride and about 0.5 to about 2o% vinyl acetate. 4. Antiperspirant according to one of the preceding Claims, characterized in that the alcohol-soluble, antiperspirant substance in one Amount of about 0.5 to about 12.5 percent by weight of the total composition is present. 5. antiperspirant according to one of the preceding claims, characterized in that the alcohol-soluble, Antiperspirant compound is a complex of aluminum hydroxyl chloride and a poly (alcohol) is. 3 0 08 0 9/11 59 * - BLENDAX - PLANTS
R. Schneider & Co,
Patent department M a i η ζ 6. antiperspirant according to claim 5, characterized in that that the aluminum hydroxyl chloride-polyalcohol complex is an aluminum hydroxyl chloride-propylene glycol complex. 7. Antiperspirant according to one of the preceding claims, characterized in that it is additionally contains one or more antimicrobial substances. 309809/1159 ORIGINAL INSPECXTED