CH649707A5 - ANTI-TRANSPIRANT. - Google Patents

Description

The present invention relates to antiperspirants which contain as active substances aluminum chloride, aluminum chlorohydrate, at least one aluminum-zirconium-polychlorohydrate complex and optionally a buffer, for example glycine, and are suitable, for example, for preventing perspiration in humans.

Aluminum chlorohydrate (ACH) has been known for many years as an effective and safe antiperspirant. Nevertheless, improvements are still possible and the search for more effective antiperspirant materials continues. However, it has been known for some time that aluminum chloride and zirconium salts are exceptionally effective antiperspirants. However, since solutions of aluminum chloride hexahydrate and zirconium oxy- or hydroxychloride are very acidic, they cannot be used for a wide range of uses due to their strong skin irritation and the severe damage to textile materials. Various efforts have therefore been made to raise the pH to a range of 3-4 using less acidic aluminum salts and incorporation of organic nitrogen containing compounds.

US Pat. Nos. 2,814,584,2,814,585 and 2,854,382 show that when zirconium oxy- or hydroxychloride is buffered with ACH and glycon, the antiperspirant effect is greater than with an ACH system alone. Since then, the combination of aluminum chlorohydrate, zirconium hydroxychloride and glycine has been widely used as an extremely effective antiperspirant system.

US Pat. No. 3,792,068 proposes a process for producing an antiperspirant in which a solution which contains, for example, ACH, zirconyl hydroxy chloride and glycine is spray-dried. It is claimed that the combination obtained in this way has superior properties which cannot be achieved by separate drying and subsequent purely physical mixing of the individual components.

GB-PS 1 347 950 discloses the use of a combination of ACH and aluminum chloride as an effective antiperspirant material. This combination has proven particularly useful in aerosol packaging. However, as is the case with other antiperspirant agents of the prior art, this agent also leaves room for improvement.

Other antiperspirant systems containing aluminum and zirconium salts have also been reported, for example, in U.S. Patents 2,906,668, 3,979,510, 3,981,896, 417,79, 3,407,254, 3,970,748, and 4,202 879. In all of these prior publications, however, it was not clearly claimed that the antiperspirant activity of all these salts was superior to systems containing zirconium hydroxychloride, ACH and glycine.

Although aluminum chloride, aluminum chlorohydrate, zirconyl hydroxychloride and certain aluminum zirconium chlorohydrate complexes for individual use as antiperspirants and combinations of aluminum chloride and aluminum chlorohydrate on the one hand and aluminum chlorohydrate and zirconyl hydroxychloride on the other hand are already effective antiperspirants were surprisingly found that the combination of aluminum chloride, aluminum chlorohydrate, an aluminum-zirconium-polychlorohydrate complex explained in detail below shows a synergistic effect and has a higher antiperspirant activity at the same concentration of active substances than after the activity of the individual components or certain combinations of components known in the art could be expected. In combination with a buffer, for example glycine, these materials have a high antiperspirant effect and a low potential for skin irritation and / or damage to textile materials.

Accordingly, it is an object of the present invention to provide a highly effective antiperspirant which is suitable for sweating in humans by applying an effective amount of the agent

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to effectively prevent the areas of the skin that tend to sweat.

The invention relates to the antiperspirant defined in claim 1.

The percentage concentrations given below are by weight, based on the total weight of the composition, unless stated otherwise.

The aluminum chloride contained in the agent according to the invention can be hydrated in various stages. Aluminum chloride hexyhydrate (AlCl3 • 6H20) has, however, proven to be the most effective and is therefore preferred for the agent according to the invention.

The amount of aluminum chloride in the agent according to the invention can vary somewhat in the range of 0.5-6%, calculated as an anhydrous substance. This amount of hexahydrate is 0.9-11%, preferably 2-6%.

Aluminum chloride hexyhydrate is usually used in the form of a 50% aqueous solution, of which 1.8-22% is then used in the preparation of the agent according to the invention.

The proportion of aluminum chlorohydrate, sometimes also referred to as “aluminum chlorohydrate”, can also vary in the range according to the invention in the range from 1-15%, calculated as an anhydrous substance, and is preferably 2-10%. The aluminum chlorohydrate can also be used in the preparation of the agent in the form of a 50% aqueous solution, of which 2.6-38% is then used.

The ACH and aluminum chloride can be added in whole or in part in the form of a powder mixture, as described in British Pat. This mixture can be prepared by drying an aqueous solution of aluminum chloride hexahydrate and ACH in a conventional manner, for example by oven, vacuum oven, spray or freeze drying. In such mixtures, the molar ratio of aluminum to chloride is generally in the range from 0.78: 1 to 1.95: 1, preferably 1.2: 1 to 1.5: 1. With a molar ratio of less than 1, the addition can a larger amount of buffer, such as glycine, may be necessary to reduce potential skin irritation and damage to textile material.

In the aluminum-zirconium-polychlorohydrate complex of the formula I which is likewise present in the agent according to the invention, y usually stands for a value in the range from 5-29. From formula I it can be seen that the complex can contain glycon bound to it. The presence or absence of glycine bound in the complex determines the proportion of unbound glycine or other buffer which must be added to the agent according to the invention in order to bring its pH to 2.5-4.5, preferably 2.8-3 , 8, to increase. A number of aluminum-zirconium-polychlorohydrate complexes suitable for use in the agent according to the invention are known from the prior art, some of which are listed below, together with their molecular formula, for example: aluminum-zirconium tetrachlorohydrate (Al4Zr (OH ) 12Cl4); aluminum-zirconium-tetrachlorohydrate-glycine "wickenol" E-369 (Al4Zr (OH) 12Cl4 • NH2CH2COOH); aluminum zirconium trichlorohydrate (Al4Zr (OH) 13Cl3; aluminum zirconium trichlorohydrate glycine (Al4Zr (OH) 13Cl3 ■ NH2CH2COOH); aluminum zirconium pentachlorohydrate (AlioZr (OH) 29Cl5); aluminum zirconium pent Al10Zr (OH) 29Cl5 NH2CH2COOH); aluminum-zirconium-octachlorohydrate (Al6Zr (OH) 14Cl8); aluminum-zirconium-octachlorohydrate-glycine (Al6Zr (0H) 14ClB • NH2CH2COOH). The aluminum-zirconium-polychlorohydrate complex and A1C13 • 6H20 can be individually mixed in solution or powder or in numerous modifications.

The OTC group for antiperspirants of the American "Food and Drug Administration" has adopted certain names and specifications which are listed in Table A for numerous aluminum-zirconium polychlorohydrates which are suitable for use in the composition according to the invention.

Table A

Accepted

Mole ratio

Mole ratio

designation

Metal: halide

AI: Zr

Aluminum zircon

2.1 to, however

2.0 to, but not nium-trichloro-

not including including 6.0: 1

hydrated 1.5: 1

Aluminum zircon

1.5 to inclusive

2.0 to but not nium tetrachlor

0.9: 1

including 6.0: 1

hydrate

Aluminum zircon

2.1 to, however

6.0 up to and including nium pentachlor

not including 10.0: 1

hydrated 1.5: 1

Aluminum zircon

1.5 to inclusive

6.0 up to and including nium octachlor

0.9: 1

10.0: 1

hydrate

A number of aluminum-zirconium-polychlorohydrate complexes suitable for the agent according to the invention are commercially available and the Reheis Chemical Company sells a number of such products under the general trademark “Rezal”, some of which are listed in Table 1 with their specifications:

Table 1

1 «REZAL» 36G aluminum zirconium tetrachlorohydrex

Gly (sol.)

2 «REZAL» 36 aluminum zirconium trichlorohydrates

(PIv.)

3 «REZAL» 67 aluminum zirconium pentachlorohydrate

(Solution)

4 «REZAL» 67 aluminum zirconium pentachlorohydrate

(PIv.)

The particle size of the powdery products is such that at least 97% of the powder passes through a sieve with a mesh size of 45 μm.

1

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Approx. Molver

ratio AI: Zr

3.6: 1

3.6: 1

6.7: 1

6.7: 1

Approx. Molver

ratio metal: Cl

1.4: 1

1.6: 1

1.7: 1

1.7: 1

Solids content,

% By weight

-35

100

~ 40

100

Aluminum,

% By weight

5.0-5.7

16.3-17.7 7.6-8.4

19.0-21.0

Zirconium,

% By weight

4.4-5.7

13.8-

-15.2 3.7-4.3

9.2-10.8

Glycine,

% By weight 3.6-4.7

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(Continued) 12 3 4

Chlorine,

% By weight 5.9-6.7 16.0-19.0 6.5-7.2 16.2-18.0

Iron, at most,

ppm 50 100 50 100

Heavy metals, calculated as lead,

at most, ppm 10 20 10 20

Similar products are sold by Wickhen Products, Inc. and Comet Chemical Corp. expelled.

The amount of the respective aluminum-zirconium-polychlorohydrate complex can also vary somewhat in the range of 5-16%, calculated as an anhydrous substance, and is preferably 8-14%.

In the agent according to the invention, the aluminum-zirconium tetrachlorohydrate-glycine complex is preferred, the preferred proportion of which is 8-14%, calculated as an anhydrous substance. This complex is usually supplied in the form of a 35% aqueous solution and used in this form in a proportion of 18-60%.

Glycine as the preferred buffer is an important component of the agent according to the invention. It can be used as free glycine or as part of the aluminum-zirconium-polychlorohydrate complex or as a combination of these two forms. In general, the amount of glycine in any of the forms mentioned is a total of 0.5-5% by weight, preferably 1.5-3% by weight, based on the total weight of the composition.

In addition to glycine, the agent according to the invention can also contain other buffers or complexing agents, for example other amino acids or their salts, such as sodium glycinate, dihydroxy aluminum glycinate; Urea; Organic bases containing nitrogen; Metal hydroxides, carbonates and oxides, including alkali and alkaline earth metals such as Mg (OH) 2, Na2C03, Zn0 and the like. These buffers can be used alone or in a mixture with glycine in order to adjust the pH of the agent according to the invention to a range from 2.5-4.5, preferably 2.8-3.8. These complexing and buffering agents serve to reduce the potential skin irritation and damage to textile materials and also act as stabilizing agents for the antiperspirant system.

The agent according to the invention can be in various forms of use, for example in the form of an emulsion, clear aqueous / alcoholic or alcoholic liquid for application by roller. Aqueous solutions of aluminum chloride, ACH, aluminum-zirconium-polychlorohydrate complex and buffer, for example glycine, can be spray dried to a barely perceptible powder and this can be used as such or incorporated into bars, suspensions, powders or liquids for application by roller.

Although the agent according to the invention can exist in various application forms, it is very effective in a system with a relatively high water content. This can be a solution or emulsion in which the active components, i.e. aluminum chloride, ACH, aluminum-zirconium-polychlorohydrate complex and buffer, are contained in the aqueous phase. Such aqueous emulsion systems are preferred because they are organoleptically more elegant agents. Such emulsion systems are usually of the oil-in-water type, in which the active ingredients are contained in the continuous aqueous phase.

The water content of such preparations can vary somewhat and is usually 40-80% by weight, preferably 60-75% by weight, based on the total weight of the preparation.

Preparations of the agent according to the invention in the form of emulsions can contain further components which are generally contained in antiperspirants of a lotion or emulsion type for application by roller. Such other additives are plasticizers, surface-active agents, sequestering agents, fragrances, colorants and the like. Plasticizers suitable for the agent according to the invention are, for example, fatty acid esters, such as isopropyl myristate and palmitate; the esters of dicarboxylic acids, such as diisopropyl adipate and polyoxyalkylene glycol esters, such as polypropylene glycol 2000 monooleate; propylene-glycol diesters of short-chain fatty acids with 8-10 C atoms, such as «Neobee» -M20; polyoxypropylene fatty ethers such as Protectyl ”,“ Arlamol ”E,“ Witconol ”APS and APM and the like; propoxylated monohydric alcohol with a molecular weight of 180-930, such as "Fluid" AP; Fatty alcohol such as hexadecyl alcohol; Silicone oils such as dimethylpolysiloxane with a viscosity of 10-2000 mm2 / S; cyclomethi-cone, such as “Volatile Silicone 7207 and 7158” from the UCC; poly-oxyethylene / polyoxypropylene fat ether, such as "Protectyl" modified AWS, "Witconol" APES. The above-mentioned, non-polar liquids are equally suitable for use in the agent according to the invention alone or in a mixture with one another. In general, the above-mentioned plasticizers are organic oily liquids of a non-polar character and show a) a boiling point at normal atmospheric pressure of not less than 120 ° C., and b) specific weight of 0.7-1.6, preferably 0.7 -1.2.

The amount of plasticizer in the agent according to the invention can vary somewhat and is usually in the range from 1-30% by weight, preferably 2-15% by weight, based on the total weight of the agent.

A number of different surface-active agents and combinations thereof, which generally comprise non-ionic, cationic and amphoteric surface-active agents, are useful for the preparation of preparations of the agent according to the invention in the form of a lotion or emulsion. For example, the following are suitable:

I. Non-ionic surfactants:

1. Polyoxyethylene fatty ether, such as «Brij» 30, 35, 72.78 and the like.

2. Polyoxypropylene / polyoxyethylene fatty ether, such as "Protectyl" AWS, "Witconol" APEM and APES and the like.

3. Polyoxyethylene alkylphenyl ether, such as "Igepal" CO 530 and the like.

4. Polyoxyethylene sorbitan fatty acid esters such as "Tween" 20 and 80 and the like.

5. Sorbitan fatty acid esters such as "Span" 60 and 85 and the like.

6. Lanolin ether, such as "Laneto" 50, "Solulan" 98 and the like.

7. Fatty alcohols and polyoxyethylene fatty ethers, such as "Promulgen" G, "Polawax" and the like.

II. Cationic surfactants:

N- (Lauryl-colamino-formyl-methyl) pyridinium chloride «Emcol» E607L

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III. Amphoteric surfactants: coconut oil imidazoline "Monateric" CA-35%

IV. Auxiliary surfactants:

1. Glyceryl fatty acid ester, glyceryl monostearate.

2. Fatty acid amides, such as “Witcamide” 70 from Witco Chem. Co.

3. Fatty alcohols such as stearyl alcohol.

As with the plasticizers, the proportion of surfactants can vary somewhat and is usually in the range of 1-10% by weight, preferably 2-6% by weight, calculated as the anhydrous substance and based on the total weight of the agent.

As already mentioned, one of the popular anti-transpiration systems of the prior art is an aluminum-zirconium trichlorohydrate-glycine complex. Compared to this known popular system, the agent according to the invention has the following advantages:

1. Low cost of active substances. The popular system mentioned above is much more expensive than both

A1C13 • 6H20 as well as ACH.

2. Better emulsion stability and easier to produce. Unblended Al / Zr-polychlorohydrate-glycine systems are difficult to stabilize and to produce in emulsion form.

3. Low potential for staining on textiles. In general, unblended Al / Zr polychlorohydrate glycine salts are more staining than aluminum salts.

The following examples explain particular embodiments of the invention.

Example 1 Formula 1908

Components

% By weight

PPG-11 stearyl ether

2.25

Polyoxyethylene (2) stearyl ether

1.65

Polyoxyethylene (20) stearyl ether

0.60

Perfume

0.30

Disodium salt of ethylenediaminetetra-

acetic acid dihydrate

0.10

Deionized water

35.40

Aluminum chlorohydrate, 50% solution

18.00

Aluminum chloride hexahydrate, 50% solution

6.00

Amino acetic acid (glycine crystal USP)

0.50

Aluminum-zirconium-tetrachlorohydrex-glycine,

35% solution

35.00

Dye FD&C blue No. 1.0.1%

aqueous solution

0.20

100.00

Appearance: Smooth, milky lotion of light blue color pH: 3.3 + 0.3

Viscosity with spindle 15s No. 3 at 20 rpm:

Viscosity after standing overnight: 500-1500 mPa.s

Production method:

1, In a stainless steel kettle, the poly-oxypropylene fatty alcohol ether, polyoxyethylene (2) stearyl ether and polyoxyethylene (20) stearyl ether are combined

60 ° C melted and, just before process step 3, mixed together with the addition of the perfume.

2. In a separate stainless steel kettle the disodium salt of ethylenediaminetetraacetic acid is dissolved in water at 60 ° C.

3. In a mixer at low speeds, the oil phase is slowly stirred into the water phase, both phases being kept at 60 ° C., after which the stirring is continued at 60 ° C. for 15 minutes.

4. With further stirring at a low number of revolutions, a solution preheated to 45 ° C., containing the aluminum chlorohydrate, aluminum chloride hexahydrate, glycine and aluminum zirconium tetrachlorohydrex glycine is slowly added to the mixture at 60 ° C., and the stirring becomes continued until the batch has cooled to 50 ° C, after which mixing is continued for 15 min while maintaining the batch temperature of 45-50 ° C.

5. After the batch has cooled to 40 ° C., the dye solution is added and stirring and cooling are continued.

6. When the batch temperature has reached 27-30 ° C., the stirring is stopped and any water loss is replaced.

Example 2

The approach and production process of Example 1 are repeated with the exception that the PPG-15 stearyl ether “Arlamol” ESP is used instead of PPG-11 stearyl ether.

Example 3 Formula 1956

According to the procedure described in Example 1, the components listed below are processed in the stated proportions:

Components weight%

PPG-11 stearyl ether 2.25

Polyoxyethylene (2) stearyl ether 1.65

Polyoxyethylene (20) stearyl ether 0.60

Perfume _ 0.32 disodium salt of ethylenediaminetetra-

acetic acid dihydrate 0.10

Deionized water 35.13

Butylated hydroxytoluene 0.05

Aluminum chlorohydrate, 50% solution 18.00

Aluminum chloride hexahydrate, 50% solution 6.00

Amino acetic acid (glycine crystal USP) 0.50 aluminum-zirconium-tetrachlorohydrex-glycine,

35% solution 35.00

D&C red No. 19.0.1% aqueous solution 0.08

D&C yellow No. 10, 0.1% aqueous solution 0.32

100.00

A smooth, milky, pink lotion with a pH value of 3.3 ± 0.3 and a viscosity with spindle No. 3 at 20 rpm of 15 s is obtained, the viscosity of which is 500-1500 mPa.s after standing overnight is.

Example 4

The batch and production process according to Example 3 are repeated with the exception that the PPG-15 stearyl ether “Arlamol” ESP is used instead of PPG-11 stearyl ether.

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6

Example 5

According to the procedure described in Example 1, the components listed below are processed in the stated proportions:

Components weight%

PPG-11 stearyl ether 2.25

Polyoxyethylene (2) stearyl ether 1.65

Polyoxyethylene (20) stearyl ether 0.60

Perfume _ 0.30 disodium salt of ethylenediaminetetra-

acetic acid dihydrate 0.10

Deionized water 31.40

Aluminum chlorohydrate, 50% solution 12.00

Aluminum chloride hexahydrate, 50% solution 6.00

Amino acetic acid (glycine crystal USP) 0.50 aluminum-zirconium-tetrachlorohydrex-glycine,

35% solution 45.00

FD&C blue No. 1.0, 1% aqueous solution 0.20

100.00

A smooth, milky, light blue lotion with a pH of 3.3 + 0.3 and a viscosity with spindle no. 3 at 20 rpm of 15 s is obtained, the viscosity of which after being left to stand overnight is 500-1500 mPa.s is.

Example 6

The batch and production process according to Example 5 are repeated with the exception that the PPG-15 stearyl ether “Arlamol” ESP is used instead of PPG-11 stearyl ether.

Example 7 Formula 1979

According to the procedure described in Example 1, the components listed below are processed in the stated proportions:

Components weight%

PPG-11 stearyl ether 2.25

Polyoxyethylene (2) stearyl ether 1.65

Polyoxyethylene (20) stearyl ether - 0.60

Perfume 0.30 disodium salt of ethylenediaminetetra

acetic acid dihydrate 0.10

Deionized water 35.40

Aluminum chlorohydrate, 50% solution 15.50

Aluminum chloride hexahydrate, 50% solution 8.00

Amino acetic acid (glycine crystal USP) 1.00 aluminum zirconium tetrachlorohydrex glycine,

35% solution 35.00

FD&C blue No. 1.0.1% aqueous solution 0.20

100.00

A smooth, milky, light blue lotion with a pH value of 3.3 + 0.3 and a viscosity with spindle no. 3 at 20 rpm of 15 s is obtained, the viscosity of which is 500-2000 mPa.s after standing overnight is.

Example 8

The batch and production process according to Example 7 are repeated with the exception that the PPG-15 stearyl ether “Arlamol” ESP is used instead of PPG-11 stearyl ether.

Example 9 Formula 1991

According to the procedure described in Example 1, the components listed below are processed in the stated proportions:

Components weight%

PPG-11 stearyl ether 2.25

Polyoxyethylene (2) stearyl ether 1.65

Polyoxyethylene (20) stearyl ether 0.60

Perfume 0.30 disodium salt of ethylenediaminetetra-

acetic acid dihydrate 0.10

Deionized water 31.40

Aluminum chlorohydrate, 50% solution 10.00

Aluminum chloride hexahydrate, 50% solution 8.00

Amino acetic acid (glycine crystal USP) 0.50 aluminum-zirconium-tetrachlorohydrex-glycine,

35% solution 45.00

FD&C blue No. 1, 0.1% aqueous solution 0.20

100.00

A smooth, milky, light blue lotion with a pH of 3.3 + 0.3 and a viscosity with spindle no. 3 at 20 rpm of 15 s is obtained, the viscosity of which after being left to stand overnight is 500-1500 mPa.s is.

Example 10

The batch and production process according to Example 3 are repeated with the exception that the PPG-15 stearyl ether “Arlamol” ESP is used instead of PPG-11 stearyl ether.

Example 11 Formula 1955

According to the procedure described in Example 1, the components listed below are processed in the stated proportions:

Components weight%

PPG-11 stearyl ether 2.25

Polyoxyethylene (2) stearyl ether 1.65

Polyoxyethylene (20) stearyl ether 0.60

Perfume 0.30 disodium salt of ethylenediaminetetra-

acetic acid dihydrate 0.10

Deionized water 35.60

Aluminum chlorohydrate, 50% solution 18.00

Aluminum chloride hexahydrate, 50% solution 6.00

Amino acetic acid (glycine crystal USP) 0.50 aluminum-zirconium-tetrachlorohydrex-glycine,

35% solution 35.00

100.00

A smooth, milky white lotion with a pH value of 3.3 + 0.3 and a viscosity with spindle No. 3 at 20 rpm for 15 s was obtained, the viscosity of which was 500-1500 mPa.s after standing overnight.

Example 12

The batch and production process according to Example 11 are repeated with the exception that the PPG-15 stearyl ether “Arlamol” ESP is used instead of PPG-11 stearyl ether.

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For the following Examples 13-16, a primary emulsion A was prepared from the components listed below in the stated proportions by the procedure described in Example 1.

Components weight%

PPG-11 stearyl ether 5.56

Polyoxyethylene (2) stearyl ether 4.07

Polyoxyethylene (20) stearyl ether 1.48

Perfume _ 0.74 disodium salt of ethylenediaminetetra-

acetic acid dihydrate 0.25

FD&C blue No. 1, 0.1% aqueous solution 0.49

Deionized water 87.41

100.00

Example 13 Formula BA 1810-64 Powdered aluminum zirconium trichlorohydrate 31 was used. The number given here and in the following examples after “trichlorohydrate” denotes the molar ratio of Al: Zr of the respective compound. In the present example, “31” thus means a molar ratio of Al: Zr of 3: 1.

The formulation was prepared analogously to the procedure described in Example 1 from the components listed below in the stated proportions:

Components weight%

Al / Zr trichlorohydrate 31 PIv. 10.00

ACH 50% solution 18.00

A1C13 • 6H20, 50% solution 6.00

Glycine 1.50

Deionized water 24.00

Primary emulsion A ad 100.00

The preparation obtained had a pH of 3.4 + 0.3 and, after standing overnight, a viscosity of 500-1500 mPa.s.

Example 14 Formula BA 1810-65 Example 13 was repeated using powdered aluminum-zirconium trichlorohydrate 21, thus with a molar ratio of Al: Zr of 2: 1 and the following approach:

Components weight%

Al / Zr trichlorohydrate 21 PIv. 10.00

ACH 50% solution 18.00

AICI3 • 6H20, 50% solution 6.00

Glycine 1.50

Deionized water 24.00

Primary emulsion A ad 100.00

The preparation obtained had a pH of 3.5 + 0.3 and, after standing overnight, a viscosity of 500-1500 mPa.s.

Example 15 Formula BA 1810-56 Example 13 was repeated using powdered aluminum-zirconium-octachlorohydrex-glycine 81, thus with a molar ratio of Al: Zr of 8: 1 and the following approach:

Components weight%

Al / Zr octachlorohydrex glycine 81 PIv. 15.00

ACH 50% solution 10.00

AICI3 • 6H20, 50% solution 8.00

Glycine 0.50

Deionized water 26.00

Primary emulsion A ad 100.00

The preparation obtained had a pH of 3.2 ± 0.3 and, after standing overnight, a viscosity of 500-1500 mPa.s.

Example 16 Formula BA 1810-57 Example 13 was repeated using a solution of aluminum-zirconium pentachlorohydrate with a molar ratio of Al: Zr of 10: 1 and the following approach:

Components weight%

Al / Zr pentachlorohydrate, 30% solution 35.00

ACH 50% solution 10.00

A1C13-6H20, 50% solution 8.00

Glycine 2.00

Deionized water 4.50

Primary emulsion A ad 100.00

The preparation obtained had a pH of 3.4 + 0.3 and, after standing overnight, a viscosity of 450-1500 mPa.s.

A primary emulsion B was prepared for Examples 17 and 18 using the procedure described in Example 1 and using the components listed below in the proportions given:

Components weight%

PPG-11 stearyl ether 6.43

Polyoxyethylene (2) stearyl ether 4.71

Polyoxyethylene (20) stearyl ether 1.71

Perfume 0.86 disodium salt of ethylenediaminetetra-

acetic acid dihydrate 0.29

FD&C blue No. 1.0.1% aqueous solution 0.57

Deionized water 85.43

100.00

Example 17 Formula BQ 1856-83 In this example, sodium carbonate was used as a further additional buffer.

In the same way as in the examples above, a preparation was produced from the components listed below in the stated proportions:

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Components

% By weight

Al / Zr-tetrachlorohydrex-glycine, 35% solution 45.00

ACH 50% solution 10.00

A1C13 • 6H20, 50% solution 8.00

Glycine 1.20

Sodium carbonate monohydrate 0.50

Deionized water 0.30

Primary emulsion B ad 100.00

The preparation obtained had a pH of 3.4 + 0.3 and, after standing overnight, a viscosity of 500-1500 mPa.s.

Example 18 Formula BQ 1856-83 Example 17 was repeated using the following approach except that magnesium hydroxide was used as another additional buffer.

The preparation obtained had a pH of 3.4 ± 0.3 and, after standing overnight, a viscosity of 500-1500 mPa.s.

Example 19 Formula 1509-61 According to the procedure described above, a preparation was produced from the components listed below in the stated proportions:

10th

20th

25th

Components weight%

Al: Zr-tetrachlorohydrex-glycine, 35% solution 45.00

ACH 50% solution 10.00

AICI3-6H20, 50% solution 8.00

Glycine 0.50

Magnesium hydroxide 0.50

Deionized water 1.00

Primary emulsion B ad 100.00

Components

% By weight

PPG-11 stearyl ether

2.25

Polyoxyethylene (2) stearyl ether

1.65

Polyoxyethylene (20) stearyl ether

0.60

Perfume

0.30

Deionized water

41.20

Disodium salt of ethylenediaminetetra-

acetic acid dihydrate

0.10

"DC Antifoam" AF, 25%

0.10

Al / Zr-tetrachlorohydrex-glycine, 35% solution

35.00

ACH, 50% solution

15.00

A1C13-6H20, 50% solution

3.00

Glycine

0.60

FD&C blue No. 1.0, 1% aqueous solution

0.20

100.00

30th

35

40

A smooth, milky, light blue lotion with a pH of 3.4 + 0.3 and a viscosity with spindle No. 3 at 20 rpm of 15 s was obtained, the viscosity of which was 400-1200 mPa.s after standing overnight is.

To demonstrate that the combination of aluminum chloride, ACH, aluminum zirconium polychlorohydrate and glycine produces a synergistic effect, a number of formulations according to Table 2 were prepared analogously to the procedure described above, formula 1908 representing one embodiment of the invention and the rest Formulations for comparison purposes correspond to the prior art.

Table 2 formulations

Components by weight, based on the total weight of the commercially available emulsion

Formulation for application by

No. 1052 No. 1676 No. 1908 No. 1341 Roller Formula BR-4504

ACH, as an anhydrous substance

18.3

7.5

16.2

A1C13-6H20, anhydrous

substance

1.7

2.0

Al / Zr tetrachlorohydrate, water

Al / Zr trichlorohydrate free substance

anhydrous substance

18.6

9.3

19.7

Glycine

2.8

1.9

2.0

4.2

PPG-11 stearyl ether

3.0

2.0

2.25

3.5

Polyoxyethylene (2) stearyl ether

1.9

1.5

1.65

2.3

PEG-40 stearate, Gly-

Polyoxyethylene (20)

ceryl stearate, glycate

stearyl ether

1.1

0.6

0.6

1.2

rin, refined paraffin

Disodium salt of ethy-

Isopropyl palmitate,

lendiamine tetra vinegar

Mg / Al silicate and acid dihydrate

0

0.1

0.1

0.1

Fragrances

Perfume and dye, 1

Water ad 100% J

Total active substances

18.3

18.6

18.5

18.2

19.7 Total active substances

Glycine content

0

2.8

1.9

2.0

4.2 glycine content

9

649 707

It should be noted that all of these formulations, with the exception of the respective active substances, are similar and each contains the active substances in practically the same proportion in the order of 18% by weight, calculated as the anhydrous substance.

Each of these preparations was tested for the anti-transpiration effect. The general procedure used for this is described in the “Federai Register”, Vol. 43, No. 196 of October 10, 1978 under the title “Gravimetry Axillary Antiperspirant Test”. To assess the antiperspirant effectiveness of the respective antiperspirant emulsion, the tests were carried out in pairs, treated against treated.

The tests were carried out as follows:

A sample program provided by the statistical office is used, for example, for the assessment of a single preparation to be tested, half of a group of test persons uses the preparation to be tested in the left armpit and the other half in the right armpit, and the opposite armpit as a blind test. For the assessment of two different preparations to be tested, preparation A is used in half of the test group in the left armpit and preparation B in the right armpit and in the other half of the test group in reverse.

The test is carried out over a test period of 51 from Monday to Friday, with sweating under ambient conditions of 38 ± 2 ° C and 40 ± 2%. Moisture is stimulated.

Tagl:

Control measurement and subsequent application of the preparation to be tested.

The test persons wait for 30 minutes at room temperature of 18-27 ° C and then enter the test room. Then untared «Webril» test cushions, which are simply folded to a size of 10 x 5 cm, are placed in the armpits of the test persons, after which the test persons sit in the test room for a warm-up period of 40 minutes. After the warm-up period, the warm-up pads are removed and discarded.

Tared collecting cushions are then removed from plastic sets in paper bags, which the test subjects insert into the armpits according to the instructions of a technician and remain there for a period of 20 minutes. Thereafter, the test subjects are instructed to remove the pillows from the armpit, to seal them in plastic bags designated for this purpose, and to return them to the paper bags.

The test subjects then leave the test room, hand in the paper bags, wash their armpits with lukewarm water using gauze pads and dry them with a towel. After 1-3 minutes, the preparation to be tested is applied and the test persons are released. The plastic bags are then removed from the paper bags and weighed out by a technician. For further participation in the test, the test subjects must separate 200 mg of sweat per armpit.

Day 2:

Only use the preparation to be tested. After waiting for 30 minutes at room temperature, the test subjects wash their armpits with lukewarm water using a gauze cushion and dry them with the

Towel. After 1-3 minutes, the preparation to be tested is then applied and the test persons are released.

Day 3:

Use of the preparation to be tested and collection of the test samples.

After waiting for 30 minutes at room temperature, washing and drying the armpits as on day 2, the preparation to be tested is applied 5 minutes later. Then the test subjects wait for 1 h at room temperature, then enter the test room for a warm-up period of 40 min with untared test cushions inserted into the armpits. After the warm-up period, the warm-up pads are removed and discarded.

The test is then continued with tared test cushions delivered in plastic and paper bags for the same period of time and in the same way and assessed by weighing out as described under day 1.

Day 4:

Only use the preparation to be tested.

Same as described under day 2.

Day 5:

Use of the preparation to be tested and collection of the test samples.

Same as described under day 3.

The test results are summarized below:

I. Formula No. 1908 vs. Formula No. 1052

The data from this test, which was carried out by 47 female test persons, were submitted to the statistical office for evaluation.

In short, the evaluation showed that the antiperspirant according to the invention of formula No. 1908, intended for use with a roller, was significantly more effective than the comparative product of formula No. 1052, taking into account a significance limit of 0.01.

This conclusion is supported by the weight ratio of the amount of sweat from armpit A as determined from the final test on day 5 and rectified by means of the control measurement, to deqeni-gen from armpit B, which averaged 0.819, which is essentially equal to 1.0 differs.

From the above data it follows that the preparation according to the invention of the formula No. 1908 is about 18% more effective than the comparison product of the formula No.

1052.

II. Formula No. 1908 vs. Formula No. 1676

The test data obtained with 46 female test subjects were evaluated by the statistical office.

In short, the evaluation showed that the preparation according to the invention of the formula No. 1908 was significantly more effective than the comparison product of the formula No. 1676, taking into account a significance limit of 0.01.

This conclusion is supported by the weight ratio of the amount of sweat from armpit A to that from armpit B, which was determined from the final test on day 5 and rectified by means of the control measurement, which was 0.883 on average, which differs significantly from equality 1.0.

From the above data it follows that the preparation according to the invention of the formula No. 1908 is about 12% more effective than the comparison product of the formula No.

1676.

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649707

10th

III. Formula No. 1908 vs. Formula No. BR 4504

The data from this test, which was carried out by 48 female test persons, were submitted to the statistical office for evaluation.

In short, the evaluation showed that the preparation according to the invention of formula No. 1908, taking into account a significance limit of 0.01, was significantly more effective than the comparison product of formula No. BR 4504.

This conclusion is supported by the weight ratio of the amount of sweat from armpit A to that from armpit B, which was determined from the final test on day 5 and rectified by means of the control measurement, which was 0.881 on average, which differs significantly from equality 1.0.

From the above data it follows that the preparation according to the invention of formula No. 1908 is approximately 12% more effective than the comparison product of formula No. BR 4504.

IV.

The comparison product of formula No. 1341 according to Table 2, which contains a combination of ACH and A1C13 • 6H20 in a concentration of 18.2% by weight, calculated as anhydrous substance, as antiperspirant active substances, was found to be the same test and the same Evaluation, as described above, by an average of 9.6% less effective than the commercially available comparative product of the formula No. BR 4504, which according to Table 2 as an antiperspirant active ingredient 19.7% by weight Al / Zr trichlorohydrate, calculated as an anhydrous substance, contains. However, the latter comparison product also proved to be less effective than the preparation according to the invention of the formula No. 1908, since it is indicated in the preceding paragraph III that the preparation according to the invention of the formula No. 1908 is about 11% more effective than the comparison product of the formula No. BR 4505.

V.

With the same test and assessment as described above, it was found that the preparation according to the invention of formula No. 1991 according to Example 9 was 15% more effective than a commercially available suspension of formula No. BR 4751 to be applied by roller from the components listed below in the specified proportions.

Components weight%

Aluminum zirconium tetrachlorohydrate,

calculated as anhydrous substance 13.8

Glycine 2.0

"Benton" 38 3.25

Cyclomethicone and perfume, ad 100.00

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15

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30th

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40

45

50

55

60

65

S

Claims (7)

649 707 PATENT CLAIMS 1. antiperspirant, characterized in that it is buffered to a pH in the range of 2.5-4.5 and as active substances, based on the total weight of the agent and calculated as an anhydrous substance, 0.5-6% by weight aluminum chloride, 1-15% by weight .-% aluminum chlorohydrate and 5-16 wt .-% of at least one aluminum zirconium-polychlorohydrate complex of the formula AlxZr (OH) yClz • nCH2COOH • mH20 (I) NH2 wherein x is a number from 2-10, z a number from 3-8, m zero or a number from 1-12, n zero or a number from 1-3, y has the value (3x + 4) -z and the sum of y + z gives a number of 10-34. 2. Composition according to claim 1, characterized in that it contains glycine as a buffer. 3. Composition according to claim 2, characterized in that it contains the glycine in bound and / or unbound form in a proportion of a total of 0.5-5 wt .-%, based on the total weight of the agent. 4. Composition according to one of the preceding claims, characterized in that it contains the aluminum chloride in the form of the hexahydrate. 5. Composition according to one of the preceding claims, characterized in that the complex of formula I aluminum zirconium tetrachlorohydrate, aluminum zirconium tetrachlorohydrate glycine, aluminum zirconium tri chlorohydrate, aluminum zirconium trichlorohydrate glycine, aluminum-zirconium-pentachlorohydrate, aluminum-zirconium-tetrachlorohydrate-glycine, aluminum-zirconium-octachlorohydrate, aluminum-zirconium-octachlorohydrate-glycine, and that the agent contains one or more of these complexes in a mixture with one another. 6. Agent according to one of the preceding claims, characterized in that it is buffered to a pH in the range of 2.8-3.8, and that, based on the total weight of the agent and calculated as an anhydrous substance, 1, 5-3.3% by weight of the aluminum chloride, 2-10% by weight of the aluminum chlorohydrate and 8-14% by weight of at least one aluminum-zirconium-polychlorohydrate complex of the formula I, and also glycine in bound and / or unbound form in a proportion of 1.5-3 wt .-%, based on the total weight of the agent. 7. Composition according to one of the preceding claims, characterized in that it is in the form of an oil-in-water emulsion and at least for the most part contains the active substances and the glycine in the aqueous phase.