DE2113453A1 - Method and means of caring for oily skin - Google Patents

Description

Colgate-Palniolive Company (prio 6.4.70 - US 26 063

New York, N.Y., V.St.A. -7950) 21

⁷ Ö. MAR. 1971

Method and means of caring for oily skin

The invention relates to a method and means for delaying or preventing the skin from becoming greasy Set) uma "bsommungen.

Those lying under the skin near the hair follicles Sebum glands secrete a sebum-like or fatty substance known as sebum. In particular, sebum is secreted of the sebum glands of the face relatively quickly, which affects the appearance of the person. When the sebum glands secrete the correctly dosed amount of sebum, the skin appears fresh and supple and has a healthy one Shine. If too little sebum escapes, the skin becomes dry and prone to brittleness and wrinkling. If too much When sebum is secreted, the skin becomes unattractive and greasy. It also has too strong a The layer of fat on the skin has a detrimental effect on cosmetics and make-up preparations, which are often theirs Change color or tint by using cosmetic ingredients, especially dyes and pigments, dissolve or "wet" ground.

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The present invention is now intended to propose means which allow unimpeded sebum secretion allow, but at the same time the greasy appearance of the normally caused by the sebum leakage Counteract the skin. In particular, methods and means for the care of the human skin, especially the Facial skin, proposed, with which the oiliness of the skin in a simple manner by inexpensive and stable agents can be corrected without inhibiting sebum secretion.

The invention is therefore a method for Delaying the skin becoming greasy by using a fat-free aqueous or alcoholic or aqueous-alcoholic suspension of pyrogenic colloidal Applying silica to the skin. The silica suspension is preferably used as an aqueous-alcoholic Suspension used containing additives like thickeners, skin desquamation agents, bactericides and the like can contain and in which practically all of the fumed colloidal silica in the form of Particles are present whose smallest unit is spherical and whose diameter is in the range of 2 to 20 millimicrons lies. Furthermore, the invention has thickened suspensions of fumed colloidal silica for use the use in the method described above is the subject.

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The pyrogenic colloidal silica used in the method according to the invention and the agents according to the invention is a very special type of adsorption powder. Due to the production method according to the vapor phase process, at which silicon tetrachloride is hydrolyzed at 1100 C, The silica is obtained in very small, uniformly sized particles. The smallest particle unit is spherical and smaller than the particles of ordinary carbon black. In solvents, however, the particles sometimes tend to chain one another; this concatenation or clumping plays a role in the thickening Effect that has been observed in some liquid products. By applying shear forces or by others mechanical or physical effects, however, the smallest particle size of the silica can be achieved. This is between 2 and 20 millimicrons in diameter for the X-beads. The diameters are in this size range nearly all particles, i.e. usually at least $ 90, generally in excess of $ 95, and preferably of over $ 99.5 of the particles. For a given average size the particle sizes of most particles generally vary by no more than 6 millimicrons on the average size. It is true that fumed silicas with various other particle sizes can also be used produce, for example, those with diameters averaging 50 millimicrons, but such

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larger particles are considered unsuitable for the adsorption purposes of the present invention.

Process for the production of pyrogenic silicic acids of the Types used in the compositions of the invention can be found in U.S. Patents 2,886,414 and 3,391,997 will. The products suitable for the present invention are commercially available under the name "Cab-O-Sil" from from Cabot Corporation, Boston, Mass., V.St.A. For example, "Cab-O-Sil M-5" has an average Particle diameter of about 11 millimicrons, while "Cab-O-Sil H-5" has a smaller average particle diameter of about 7 millimicrons. The surfaces of the fumed colloidal silicas are extraordinary great; this property in combination with the small and uniform particle size and shape apparently contributes contributes considerably to the special adsorbing, covering and smoothing effects of these silicas. the Surface areas are between about 50 and 450 m / g and usually between about 200 and 400 m / g. The described Silicas are relatively light, i.e. they have densities which are significantly lower than the densities of Are water and oils including sebum. Their densities are typically between about 0.032 and 0.040 g / cm ^. The chain structures mentioned above, which are temporary Form between the particles also seem

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considerably to the "special properties of the pyrogenic Silicas contribute. The most important of these properties for the present invention are the high adsorption capacity for various liquids, such as sebum, moisture and sweat, and the ability to hold these liquids in place without them becoming deleteriously visible.

Because the fumed silica has such a small particle size and have a spherical particle shape, they apply well to the skin, show the desired Lubricant effect and prevent scratching or irritation of the skin. The adsorption capacity of silica for Sebum and sweat, the outflow of which from the skin pores is not inhibited, can go up to $ 100 to $ 200 and often even more than the weight of the fumed silica itself. In some cases adsorption of $ 50 viewed as easily achievable, so the amount of Fumed silica can be calculated without risk on this basis. Instead of the above especially said fumed silicas can contain other products of the same particle shape and size and the same other 'properties are used. So the pyrogenic silicas used according to the invention can, for example, partially by the under the

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Name "Quso" silica from the Philadelphia Quartz Company traded colloidal silicas provided they are the same Have particle sizes, particle size distributions and other properties.

The medium in which the fumed colloidal silica is suspended can be aqueous or alcoholic or be watery-alcoholic. The medium serves to disperse the silica and in a simple manner to be able to distribute evenly on the skin. The medium can be in solid or liquid form, however, liquid suspensions of the silicas are generally preferred. Ground the solid products liquid when rubbed into the skin and thus ensure an even distribution of the silica particles over the surface of the skin. The solid products preferably consist of gels, pastes or the like, in which contain a substantial proportion of solvent to facilitate use.

The water used preferably has only a low content of hardness components and dissolved solids, preferably less than 150 ppm of such substances. Deionized or distilled water can be used

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will. Lower monohydric alcohols are preferably used as alcohols, but a lower one can also be used Part of the alcohol component should consist of di- or polyhydric alcohols ". The latter, however, should only a small proportion of the total amount of alcohol in the. Products. Suitable monohydric alcohols are for example ethanol, isopropanol, n-butanol, isobutanol and tert-butanol. In most cases it will be ethanol or isopropanol is used, with ethanol being preferred. However, preparations are also suitable, which mixtures of ethanol with other monohydric alcohols or water. In some cases, very small amounts, usually less than $ 5> in higher alcohols with up to to 12 carbon atoms in the molecule can be used. The dihydric alcohols, which are in small amounts and usually not more than 10 $ of the total amount of alcohol can also be used, are preferably those with 2 to 4 carbon atoms in the molecule, of which ethylene glycol and propylene glycol are preferred. A preferred polyhydric alcohol is glycerin, but can also various other alkane triols of up to 6 carbon atoms can be used in the molecule. In addition to the alcohols derived from hydrocarbons, those with internal oxygen atoms, such as polyoxyethylene glycols, triols and polyols are used in small amounts, as are the lower polyalkylene diols

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and polyols, such as polyethylene glycols. These alcohols preferably contain 2 Ms 4 Kb hl ens to ff atoms in the repeating molecular groups and a total of at most 20 carbon atoms in the molecule j usually if they contain 3 Ms 10 hydroxyl groups in the molecule.

Suitable aqueous-alcoholic suspension media normally contain "based on the total product 15 Ms 85 $ Alcohol and 20 Ms 70 $ water. The ratio of Alcohol to water is usually between about 1: 3 and 3: 1, with ratios in the range of 1: 2 Ms 2: 1 to be favoured. In most cases there is the presence of alcohol in the products according to the invention expedient, but under certain circumstances der.Alkohol can be omitted and the product only on based on water. Alcohol is an important component of the products according to the invention, since it does the job of the water, the fumed colloidal silica to form an even layer over the To distribute skin, supports and the quick and pleasant evaporation of the solvent from the skin promotes, so that the skin has the desired dry state again soon after use. The alcohol promotes the contact of the sebum by wetting the sebum on the skin surface and in the pollicle canals

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the silicic acid and the flow of sebum through e ducts, thereby avoiding blockages of the ducts. In the specified amounts, the alcohol / contributes to keeping the pyrogenic colloidal silica in dispersion and serves as a solubilizer for various additives that may be contained in the product, such as skin desquamation agents, bactericides and non-greasy perfumes. Preferably at least 5 $> ethanol is used

The fumed colloidal silicas and other inorganic thickeners, such as colloidal silicates, have the property of increasing the apparent viscosity of their suspensions, presumably due to the Formation of polymeric chains, however, it has been found advantageous in addition to the inorganic silica add an organic thickener in order to obtain more homogeneous suspensions of the silica. Such organic thickeners or gums stabilize when used in very small amounts the suspensions, allow a more even application of the silica and prevent one after application The silica becomes chalky or dusty and accidentally detached from the skin. This is especially important shortly after application, if the previously washed skin has not yet released enough oil,

109852/1838 ORIGINAL INSPECTED

to hold the silica particles in place. To the preferential The gums or hydrocolloids used include carboxymethyl celluloses, hydroxyalkyl celluloses, carboxypolymethylenes and the various natural gums. However, various other thickeners can also be used, such as polyvinylpyrrolidone, various acrylates, vegetable proteins, starch derivatives, gelatins, polyacrylates and Dextrins, can be used. Suitable natural gums include karaya, tragacanth, acacia gum, algine, Agar-agar, pectin,! Carrageenan, guar gum, carubin gum, Irish moss extracts and various derivatives thereof.

Celluloses include the various ethers and esters, such as methyl cellulose, methyl ethyl cellulose, sodium carboxymethyl cellulose, sodium carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ^1- n-propyl-cellulose, hydroxyethyl-n-butyl cellulo se, hydroxyethyl-n-hexyl-cellulo se and hydroxyethyl-henzylcellulose. Z _n the starches include hydroxyethyl starch, alkali starch phosphates, carboxymethyl starch and similar compounds. When using alcohol, care must be taken that the gums or other organic thickeners used are compatible with the alcohol.

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(one of the most interesting synthetic thickeners include polyvinyl alcohol, polyvinyl pyrrolidone, vinyl pyrrolidone copolymers and compounds known as carboxyviTiyl polymers can be designated, such as "Carbopol 934". The various synthetic and natural organic gums and thickeners are detailed in "The Chemistry and Manufacture of Cosmetics ", Volume 11, 2nd Edition, by Maison G. DeNavarre (D. Van Nostrand. Co., Inc., 1962), pp. 109-154 described.

Inorganic thickeners, which are used in small quantities as a supplement to the organic thickeners in The agents according to the invention which can be used are the various silicates, such as water-containing ones Aluminum silicates, zeolites, magnesium aluminum silicates, lithium silicates, zirconium silicates, calcium silicates and Magnesium silicates, which are obtained chemically or found in nature. These fabrics, for which bentonite and veegum are representative have a similar thickening effect when finely ground like the pyrogenic colloidal silicas used according to the invention. A list of the various hydrous Silicates and inorganic silicates, which act as thickeners, are described in "The Chemistry and Manufacture of Cosmetics ", Vol. II, pages 49-59.

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ORIGINAL INSPECTED

• - 12 -

As a skin desquamation agent, which in the invention Products used to remove dead skin cells or other unwanted solids from the skin, the chemicals known for this purpose can be used. The most suitable of these substances apparently sulfur, but other compounds such as resorcinol, salicylic acid and the like are also suitable. In addition to their ability to remove dead skin particles, these substances also have a certain drying effect on the skin and thus have an effect on the skin becoming greasy opposite.

Furthermore, various bactericides suitable for cosmetics can also be used in the skin treatment according to the invention can also be used. Suitable bactericides are, for example, hexachlorophene, halosalicylanilides and trichlorocarbanilide and quaternary ammonium salts such as benzalkonium halides, cetyltrimethylammonium bromide and dimethyldibenzylammonium chloride, as well as various other phenol derivatives, halogenated phenol derivatives or sulfur-containing ones Phenol derivatives, amides and anilides. Preferably, compounds with some substantivity become skin used so that their antibacterial effects even after Removal of the remaining silica preparation is still ongoing. The use of bactericides and pungicides in low levels Quantities helps keep the suspensions during the

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Storage "stay pure and" its beneficial when in use Have an effect on the skin.

In addition to the so-called active components, the agents according to the invention can also contain various additives included for other purposes. For example, a suitable perfume can be used in the agents according to the invention can be added provided it is not greasy. It is of course also important that perfumes are only used in small amounts Amounts are used so that they are not adsorbed by the fumed silica and hence the sebum adsorption affect. Non-greasy perfume components are that Known to those skilled in the art. There are those substances, which are not, for example, for higher fatty acid triglycerides and higher Fatty alkanes typically have a fatty or oily character. Additives that can be used include also coloring additives, such as the dyes and pigments customary in cosmetics.

For the agents and methods according to the invention, only non-fatty components are used, since the presence fatty ingredients, such as fats, higher fatty acids, tallow, petrolatum, higher fatty acid amides, and alkylolamides Glycerides that prevent sebum from being adsorbed by the fumed colloidal silica. Although between sebum and common fatty oils there are differences, it is

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-H-

Obviously, the agents according to the invention are not May be fatty in order to prevent the silica from preferring components of the agent itself instead of Adsorbed sebum.

The agents according to the invention preferably have a weakly acidic pH, which is close to the pH of the skin is approximated. In some cases a pH value down to 3 is still suitable and in special cases it is even pH values up to 9 are acceptable, especially if the skin is more acidic than usual. In general is the pH of the agents according to the invention but between 3 and 7 and preferably between 4 and

In the agents according to the invention, the pyrogenic is colloidal Silica only in small amounts and the solvent as the predominant component. Pie colloidal Silica can be used in amounts up to $ 25 and in some Cases can also be used in even larger quantities, but in general it makes only 1.5 to 10 $ des liquid or solid product. When used less than $ 1.5, the adsorbent capacity of the agent will decrease diminished and when used less than $ 0.5 v / ground the adsorptive properties are generally so strong reduces the fact that too large a quantity of the product has to be used for the desired effect. Ss can

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the amount of collidal fumed silica through Application of larger or smaller amounts of the suspensions according to the invention can be varied, but is no longer available For the reasons mentioned above, the lowest limit for the silica content of the product is $ 0.5 and preferably $ 1.5 · The silica used can Contain very small amounts of other substances such as water, inorganic salts and metal oxides, but will generally used acidic acids with a degree of purity of at least $ 95 and in particular $ 98 or above. These can only be used to calculate the quantities to be used Silicas can therefore be regarded as pure.

Water, which is in both the liquid and the solid products is an important component (in the latter case, the means are usually a gel or a paste), is available in amounts of $ 5 to $ 98, preferably $ 20 "to $ 70, and especially $ 30 to $ 60 des Entire product used. Alcohol, usually ethanol, is based on the agents according to the invention Total product in amounts from 0 to 90 $, preferably up to 75 $ and in particular 30 to 60 $. That The ratio of water to alcohol has already been discussed above.

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The skin desquamation agent, which can optionally be contained in the products according to the invention, is generally used in amounts of 0 Ms 2 $, preferably 0.2 to 0.25 ° and in particular 0.5 to 2 $ of the total product. Bactericides and fungicides are added in amounts from $ 0 to $ 2, and usually from $ 0.1 to $ 1 of the total product. Perfume and coloring additives can be added in the amounts necessary to achieve the desired smell or appearance, but the non-greasy perfume is normally used in amounts from 0 to 2 $. When using skin smoothing agents,

Humectants and excipients become these generally used in M, narrow from $ 0.5 to $ 5. Agents for modifying the pH, such as boric acid, monosodium phosphate, Gluconates or other suitable pH modifiers, are added in small amounts, e.g. from $ 0.1 to $ 2.

In addition to the pyrogenic colloidal silica, no other thickener needs to be used, however, it is generally advantageous to add an organic thickener or gelling agent in order to to improve the suspension of the silica in the solvent or dispersant and the binding and Suspensibility as well as the distributability of the

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To promote dispersion during storage or during use. The proportion of thickener, preferably organic thickener, is generally from 0 to 10 $, preferably from 0.2 to 5 $ and in particular from 1 to 3 $ of the product. In addition to the organic gum or thickener, inorganic thickeners, such as clays or silicates, can also be added. Such clays, which include bentonite and silicates, are generally added in amounts from 0 to A $> and preferably from 0.2 to 3 $. In particular, when using such thickeners, an addition of 1 to 2 $ is preferred.

The adsorbents according to the invention can on can be made in different ways. For example, when using a thickening agent, this can be used Mix in the solvent, then the remaining components and finally the fumed colloidal silica admit. The batch can then be stirred using conventional mixing, shearing or dispersing equipment, homogenized or reduced in particle size. If some of the components are sparingly soluble, you can Dissolve this in the beginning in alcohol or water and then add the remaining components to the solution described above Meddle wisely. The sequence of steps in the production of the gowns according to the invention is not viewed as critical. However, the silica is preferably used in the

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Solvent dispersed before using concentrated liquid components other than water and lower Comes into contact with alcohol.

During use, the agent is applied to the skin surface applied so that there is a substantially uniform

- 5 forms a layer of silica, which is about 5 x 10 to

—2 2

Contains 1 χ 10 g of silica per cm of skin area. Larger amounts can usually be applied at bedtime so that the fumed colloidal silica can work overnight, promoting the flow of sebum through the sebum ducts to the face while preventing the skin from becoming excessively greasy. Smaller amounts are used for daily use, v / ie 5 x 10 ^J to 2 χ 10 ^J g

ρ
Silicic acid per cm of skin surface, suitable to achieve the desired effect of sebum adsorption and promotion of sebum flow without adversely affecting the user's appearance. Of course, once the adsorbent becomes saturated with sebum, it is convenient to wash it off before applying new agent. If the correct amount of silica is used to adsorb the secreted sebum, the powder can in most cases be left on the skin for longer than 4 hours and often up to hours without it becoming excessively greasy.

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After applying an even layer of fumed colloidal silica on the skin you can normal make-up preparations, preferably in an amount that does not interfere with sebum adsorption, are used on top will.

The invention is illustrated in more detail by the following examples, but is not restricted to the same. Unless otherwise noted, all quantities are based on weight.

example 1

A liquid suspension of fumed colloidal silica of the following composition was prepared:

Parts by weight

Fumed colloidal silica

(Cab-O-Sil 1.1-5) 2.5

Sodium carbonyl methylcellulose 1.5

Glycerin 1.0

Water, deionized 55.0

Ethanol, denatured (SD 40) 40.0

To produce the product, the fumed colloidal silica dispersed in water was mixed with an alcohol-glycerin mixture, in which the sodium carboxymethyl cellulose was dispersed, mixed in. The mixed operations

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were kept at room temperature in a stainless steel container Stahl carried out, which was equipped with an adjustable propeller stirrer. After going together the liquids were stirred for another 15 minutes "bis the liquid thickens to a lotion-like consistency was.

The pyrogenic remained in the bottled product colloidal silica in dispersion during storage. Small amounts, which are on the ground or on the surface of the product had settled could be redispersed simply by shaking or stirring.

The product was in layer thicknesses of 0.002 to 0.08 g / cm applied to the faces of three male and three female test subjects, each one normally had skin labeled as oily. Before use, it was found that the test subjects' skin was

ρ borrowed at least 0.7 mg lipoids per cm per hour.

Each test person applied as much of the described suspension of fumed colloidal silica as they were for held required. The men used less product than the women and the women wore it afterwards nor her usual make-up in the usual way. The average application quantities of the product were

between 0.002 and 0.03 g / cm for men and between

Women between 0.02 and 0.08 g / cm.

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After an exposure time of 6 hours, the skin of the test subjects was examined for its oiliness. It was found that neither the men's nor the women's skin had become too greasy after this time. The women's makeup was not affected in color.

The adsorbent could be washed off the skin with warm water at 49 ^° C. without the use of soaps or detergents. During the washing process, sebum and fatty components were removed from the skin along with the fumed colloidal silica, and the skin was left clean. The same agent could then be reapplied to continue adsorbing sebum.

In the same way, an agent similar to the above, but containing 8 $ fumed colloidal silica, 3 $ sodium carboxymethyl cellulose , 2 $ glycerin, Vfa non-greasy perfume, 40 $ ethanol and 46 $ deionized water, was made about the same by the test subjects Amount of total product used as the daily product above. This agent was left on for about 8 to hours overnight, continuously adsorbing sebum and preventing the skin from becoming excessively greasy.

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In another group of test persons, the daily product was “in three male and three female adults applied to half of the forehead skin in such an amount that about 0.05 to 2.0 mg / cm of pyrogenic colloidal Silica in a smooth, uninterrupted layer on the skin. The amount applied was intentional kept so small that it was not noticeably noticeable. The other half of the forehead skin was left untreated calmly. At intervals of 4 to 8 hours after application Imprints of the remedies were taken from the forehead using an absorbent pad for three seconds each long pressed against each half of the forehead. The flaps were left to dry over trays to avoid volatility Allow sweat components to evaporate. The lobules were then examined. In every pail it was against the with the pyrogenic colloidal silica treated forehead area pressed lobes significantly less greasy than the against the untreated forehead area pressed. Similar results were obtained with products according to the invention, in which small amounts of lactericides, fungiids, dyes, Pigments, inorganic thickeners and skin desquamation agents were incorporated.

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Example 2

A liquid sebum adsorption preparation was made with the following composition:

Parts by weight

Fumed colloidal silica

(Cab-O-Sil M-5) 2.0

Veegum HV (thickener,

Manufacturer R.T. Vanderbilt Co.) 0.5

Hydroxypropyl cellulose (EZLusel NAP, Manufacturer Hercules Powder Corp.) 1.0 Chelating agent (Chel DTPA,

Manufacturer Geigy Corp.) 0.025

Hexachlorophene 0.10

Blue Dye "F.D. & C. Blue Dye

No.1 ", 17Sige aqueous solution 0 * 07

Yellow Dye "F.D. & C-. Yellow Dye

No.5 ", 0.5% aqueous solution 0.12

Yfasser, deionized 48.7

Ethanol, 95 # (SD. 40) 47.5

To produce the product, the hydroxypropyl cellulose was sieved into a solution of the hexachlorophene in the alcohol, which took about 60 minutes, the pyrogenic colloidal silica was vigorously stirred with about 30% of the water and the homogeneous mixture of silica and water was added to the mixture of Hydroxypropyl cellulose, hexachlorophene and alcohol are added. The remainder of the water was heated to about 80 C and the chelating agent and Veegun HV were added to make the Veegum

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could hydrate, whereupon the mixture was cooled to ^{25 0 G.} The previously prepared mixture of the other components was then stirred into the mixture of water, chelating agent and Veegum and then the dye solutions were added, stirring until a homogeneous product was obtained.

The obtained cosmetic preparation was made in the same manner as the product prepared in Example 1 tested. In comparison with other allegedly useful sebum adsorbents, the properties described in Example 1 test procedure described shows superior sebum adsorption established. The product was stable, pleasant to use, antibacterial and effective Adsorbents for fatty substances on the skin, such as sebum.

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2113453 Parts by weight Example 3 2.0 A product of the following composition was produced 1.0 posed: 48.0 0.1 Fumed colloidal silica
(average particle diameter
knife about 11 millimicrons) 0.2 Hydroxypropyl cellulose 0.5 Ethanol Hexachlo rophen Resorcinol Veegum HY

Blue Dye "P.D. & C. Blue Dye

No.1 »0.0008

Yellow Dye "F.D. & C. Yellow

Dye No.5 »0.0006

Water 48.2

The product was prepared in the same way as in Example 2, with the resorcinol with the hexachlorophene was added to alcohol. The product obtained in this way did not have the chelating properties that the Product according to Example 2 had been obtained by the chelating agent Chel DTPA, but when applied to the in Example 1 has an equally good sebum adsorption.

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Claims (4)

Claims 1. Skin care products for delaying the greasiness of the facial skin, characterized in that it in the form of a liquid or solid, non-fatty, aqueous and / or alcoholic suspension between 0.5 and 10 $ of the total product amount of fat-absorbing pyrogenic colloidal Silica with spherical primary particles and an essentially between 2 and 20 millimicrons contains lying particle diameter. 2. Composition according to claim 1, characterized in that it is 5 to 98 $ water, 0 to 90, preferably 5 to 90 $ Ethanol and 0 to 10, preferably 0.2 to 5 $ organic thickener contains. 3 · Means according to claim 1 and 2, characterized in that that it is in liquid form and 1.5 to 10 $ fumed colloidal silica, 15 to 85 $ alcohol and contains $ 20 to $ 70 water. 4. Composition according to claims 1 to J>, characterized in that it contains 0 to 2, preferably 0.1 to 1.5 $ non-greasy perfume, 0.2 to 3 $ skin desquamation agent and 109852/1838 O, 1 to 2 $ bactericid as well as a vegetable gura, one lower hydroxyalkyl cellulose, a lower carboxyalkyl cellulose or a lower carboxypolyalkylene than contains organic thickener. coll: re 09852/1838