DE1492101A1 - Cosmetic preparation - Google Patents

Description

Dr. Walter Beil Alfred Hoeppener Ή · Dec, 1965

Dr HansJcaa in Wolff Dr. Hans Chr. Beil

KechUacwälte Frankfurt a. M. -Highly

Adl

Our number 12-49

Ohae. Pfizer & Co., Inc., New York, NY, V ₈ St.A.

Cosmetic preparation

The present invention relates to a cosmetic preparation which can be applied to the skin or to the hair, especially on a smudge-proof, non-staining liquid make-up.

There are already dry and liquid make-up preparations, e.g. Face powder, compact powder and creams are known that are applied to the skin. All of these preparations rub sifcoh but proportionally easily off and stain clothing so that it is difficult to apply it to the neck. “The usual hitherto known cosmetic preparations smear under the action of moisture and are for example stained and unsightly from sweat or rain.

A completely new group of water-based make-up preparations has now been found which has the disadvantages described above do not exhibit. The new cosmetic preparations are water-resistant, rub-proof, smudge-proof and earth-proof not stained. As a result, they can also be applied to the neck, right up to the edge of the clothing, without the

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There is a risk of soiling the blouse or clothing. The new cosmetic preparations according to the invention can also be applied to the legs. After application, they dry quickly to a natural-looking I ¹ IIm, which makes the skin appear dull and which is nonetheless permeable to sweat and fat. Despite their water resistance, the preparations according to the present invention can be easily removed from the skin with cream or with soap and water.

The cosmetic preparations that have these essential advantages consist of aqueous dispersions of water-insoluble addition polymers, which are considered a polyhydric alcohol Contain humectants, a finely divided inert pigment and finely divided inorganic silicate.

All non-toxic, water-insoluble addition polymers in aqueous dispersion are suitable. For example, polyvinyl acetate, polyvinyl butyral, vinyl chloride-vinyl acetate copolymers, vinylpyrrolidone-vinyl acetate copolymers and polyacrylic esters result in excellent non-adhesive flexible films _o The person skilled in the relevant field of work will select further polymers and copolymers based on his experience for the given individual case. Polyacrylic esters, especially copolymers of ethyl acrylate and methyl methacrylate, are particularly suitable because of their excellent film-forming properties. These plastics are commercially available as aqueous emulsions and generally contain one or more anionic and / or nonionic surfactants in low concentrations. The commercially available synthetic resins of the type mentioned are generally produced by copolymerization of about 30-40 percent by weight of methyl methacrylate with about 60-70 percent by weight of ethyl acrylate; if necessary, the mixed polymer can also contain a small amount of an α-, ß-unsaturated carboxylic acid, for example acrylic acid, methacrylic acid or itaconic acid. It is of course not necessary to use the commercially available copolymers for the cosmetic preparations of the present invention; watery

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Rather, dispersions of suitable addition polymers can also - using well-known polymerization methods, in particular by emulsion polymerization, - are specially prepared for the given Pail. The procedures for As already mentioned, the preparation of such polymer dispersions is known and detailed in the relevant literature described.

The proportion of water-insoluble addition polymers in the cosmetic Preparations according to the present invention can be of different sizes. Purely one has most of the application purposes Amount of about 3-7 weight percent in the unit volume (e.g. g / 100 ml) has been found to be suitable; at this amount results in sioh an optimal combination of durability and natural appearance; however, it is also possible for special purposes lent drugs with a salary less than $ 3 or more than $ 7 To produce addition polymer dispersion.

The humectant can be any polyhydric alcohol, for example a glycol such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, or polyethylene glycol, which are sold under various trade names; if necessary, other polyols such as sorbitol οΔ. Glycerin is used. A humectant used with particular advantage ± propylene glycol. The humidifying agent can be used in amounts of about 2.5 percent by weight / unit volume or more - possibly also less.

Inert pigments of inorganic or organic origin in the form of fine powders can be used as inert pigments. It has to be Naturally, they are pharmaceutically acceptable products, i.e. the products must not be unpleasant or harmful Show properties in normal use. Suitable Pigments are the various red, yellow and black iron oxides, titanium dioxide, pharmaceutical and cosmetic colors, Eye shadow colors like Prussian blue, ultramarine blue, iron blue,

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chrome green etc. To achieve optimal opacity, the total pigment content should be at least about 5 percent by weight / volume unit be; it is possible in the given pail to adjust the pigment content to be increased up to 20 percent by weight or more without disadvantages having to be accepted. The preparations can be made in a variety of hues to match or match exactly the hue of the skin lighten or darken as desired.

The cosmetic preparation according to the present invention can also use an inorganic silicate as a dispersing and smoothing agent contain. Various magnesium silicates, magnesium aluminum silioates and colloidal silica are suitable for this purpose. The silicates or the colloidal ones are used Silica in amounts of at least 0.5 weight percent / volume unit j the proportion can in the given case be increased to about 5 percent by weight / unit volume or more without disadvantage.

The make-up preparation according to the invention is adjusted to be neutral, for example to a pH value between 6.5 and 8, preferably 7.5 ».

The pharmaceutically acceptable surface-active agents used in the make-up preparations can be non-ionic or, preferably, anionic in nature. Suitable surface-active agents are, for example _, diethanolamine alkanoic acid esters, sorbitan monoalkanoic acid esters and polyoxyethylene sorbitan monoalkanoarboxylic acid esters, such as ötearates, palmitates, oleates and laurates, and also polyoxyethylene alkyl ethers, including stearyl ethers, oleyl cetyl ethers, including stearyl ethers, oleyl cetyl ethers. Emulsion stabilizers such as glyceryl monostearate and stearyl monoglyceridyl citrate are also preferably added. It is preferred to use 3 percent by weight, optionally up to about 6 percent by weight or more, of the surface-active agents in the preparation.

Preferably used together with the surfactants

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oily smoothing agents used in the amounts specified above, which have a wholesome and plasticizing effect and for one Ensure a natural appearance of the make-up · Suitable smoothing agents are, for example, certain «esters, including vegetable ones Oils such as safflower oil and other glyoerides, as well as alkyl myristates, for example isopropyl and isocetyl myristates. Another Class of suitable smooth == medium includes mineral or hydrocarbon oils Finally, it is also possible to use lanolin · -and

such as lanolin derivatives, silicone oils and higher alkenols / cetyl and Use stearyl alcohols as smoothing agents · The smoothing agent should be in an amount of about 1 percent by weight / unit volume or more (up to about 3 weight percent) can be used. If necessary, this amount can be increased without any disadvantage

No surfactant is used (except for traces left by the manufacturing process in the water-insoluble addition polymer are contained,), a water-soluble resin is preferably used in the preparation to disperse the pigments to facilitate · In this case, any non-toxic water-soluble addition polymers can be used, for example the salts of various polyelectrolytes such as polyacrylic and polymethaoryl acids · The quantities for these products should be between about 2 and 4 weight percent / volume unit The amount of finely divided inorganic SUioate is when using these agents to at least about 2 percent by weight / Volume unit set. Eventually the humectant becomes in this particular embodiment of the cosmetic preparation according to the invention to at least about 5 percent by weight, preferably about 5 to 10 percent by weight, adjusted to the oily Smoothing agent is then omitted.

As is common practice for liquid and creamy cosmetics the cosmetic preparations according to the invention also cons agents added, agents that can be used for this purpose are, for example, formaldehyde, alkyl parahydroxybenzoates, orthophenylphenol, Sorbic acid and its salts, tetrachlorosalioyl anilide, p-chlorophenyl glycerol ether and the like. The preservation

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tion agents are used in amounts of about 0.1 to 0.8 percent by weight - whereby the amount depends on the means used «- added

The cosmetic preparations according to the invention can be mixed with perfume, antiseptic agents, agents to reduce bleeding of the skin, Sunscreens or other agents suitable for a specific purpose are added. So you can the invention add hexachlorophene, resorcinol, allantoin and sulfur preparations to cosmetic preparations · Some of these Means have a weak medicinal effect, so that eioh the product is suitable for users with acne skin or otherwise blemished skin.

The various components of the preparation are simply listed below Stir mixed so that there is a uniform dispersion in liquid or creamy form. If you bring the so produced If you apply a cosmetic preparation to the skin, you will get a smudge-proof, non-blotchy one after rubbing it in Coating which, on the other hand, can easily be removed again with cleansing cream or soap and water.

In the examples below are various preparations described in accordance with the present invention.

example 1

A. oily phase:

Palmitic acid 1.5 g

Stearic acid 1.5 g

Grlyceryl monostearate 1.5 g

"Marcol 90" (a) 1.0 g

"Viscolan" (b) 1.2 g

Ortho-phenylphenol 0.2 g

(a) A low viscosity white oil available from Company Esso is distributed

(b) Weiohmacheröl, which is sold by the American Cholesterol Co.,

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B. Aqueous phase:

Propylene glycol 5.0 g

Triethanolamine 1.3 g

"Veegum" (c) 15.0 g

Anti-ionized water 58.9 g

(c) 59 * aqueous dispersion of magnesium aluminum silicate, sold as a commercial product by R. T. Vanderbilt Co.

C. Pigments: 5.0 g

Composition of the pigments (micropulverized twice): Talcum HO (d) 12 - 18.596

Titanium Dioxide (s) 49-82 $

Red Oxide A-6205 (e) 1,3 -'8,53 *

Yellow ocher 0-1624 (β) 3.2 - 32? Ί

Cosmetic black A-8214 (β) 0.14-25 * cosmetic umber 1985 (β) 0.04 - 19 *

D & C Red Wr. 30 K-7156 (e) 0.1-1.19 *

(d) Available from Whittaker, Clark & Daniels Co.

(e) Available from Konstamm Co.

D. Aqueous emulsion, water-insoluble addition polymer 7.5 g

The aqueous phase (B) is heated to 70 ° C., after which the pigments (C) are dispersed therein with stirring. Then one adds the aqueous Pofymeremulsion (D) added and the mixture heated back to 7O ⁰ C. Next, the oily phase (A) is heated to 70 ⁰ C and slowly added with stirring to the aqueous phase. The mixture is then cooled with stirring, 0.3 g of perfume - as soon as the temperature has reached 45 ° C. - and 0.1 g of formaldehyde - as soon as the temperature has reached 30 ^° C. - is added. The cosmetic preparation produced in this way can then be packaged.

Preparation of the aqueous polymer emulsion (D):

The emulsion of the water-insoluble addition polymer for the

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The preparation described above is produced in a two-stage procedure (emulsion polymerization) as follows ι ',. '- ■ §

First stage

Ethyl acrylate 69.3 g

Methyl methaorylate 40.8 g

Methacrylic acid 1.68 g

Deionized water 207 g

Triton X-200 (f) 13 _t 2 g

Ferrosulfate solution (g) 2.2 g

Ammonium perulfate 1.1 g

Sodium metabisulfite 1.1 g

t-butyl hydroperoxide 6 drops

(f) Alkaryl ether dee PolyäthoxyäthanolB (28 ^ ig), to refer from Rohm & Haas Oo

(g) solution of 0.3 g perrosulfate heptahydrate ⁱⁿ 200 ml deionized water.

The first six ingredients are homogenized with stirring, by blown with nitrogen and heated in a flask equipped with a reflux condenser at 20 · C ^0. Half of the remaining three constituents are added at the beginning of the reaction in the order given with an interval of one minute each time. After a reaction time of 42 minutes, the other half of the three constituents mentioned is added and after one hour the heat supply is increased so that the temperature rises from 24 ° 0 to 45 ⁰ O within 10 minutes. The heat supply is then interrupted! due to the exothermic nature of the reaction, the temperature increases a total reaction time of 95 minutes within 8 minutes to 84 ⁰ O. NaOH, the reaction mixture is cooled and the constituents of the second reaction step.

Second step

Ethyl acrylate 69.2 g

Methyl acrylate 40.7 g

Methacrylic acid 1.67 g

De ^ oned water, 47.5 g

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friton 1-200 (f)

yerro sulfate solution (g) Ammonium sulfate Iatriuametabieulfite i-butylhydrop β roxy d

13.2 g

2.2 g

0.55 g in 2.75 ml of water 0.55 g in 2.75 ml of water 3 drops

The first seohs Best _a ndteile are mixed together and then slowly poured into the cooled Reaktionsmisohung the first Stuf ·; Thereafter, sets the three initiators · The Misohung is then heated to a temperature of 45 ⁰ O; the danaoh Putting · exothermic reaction causes the temperature drops further to 79 ⁰ O increase. After 2.5 hours (55 minutes of the second stage) the reflux condenser is removed and non-reacted BS monomer is distilled off by heating the mixture for about 30 minutes.

After cooling, the reaction mixture with ammonia is up to adjusted to a pH of 7.6 and filtered through a gauze. The Piltrat (45 # pesticide content) is used as an ingredient (D) used in the cosmetic preparation,

Example 2

Using the method described in Example 1, another five cosmetic preparations are produced, the Components were changed in the following manner · The components not shown were changed in the same Amount as indicated in Example 1 used

A. "Marcol 90"

B. Propylene Glyeol "Veegum" Deionized water

0 pigment

D. Aqueous · Polymer Emulsion

ι 1 G G G 1 2 G 1 2 G i 2 G 5 G G 4th , 5 G 4th G 3 G 16 G 19th G 17th G 18th G 54.4 52 G 49, ^ l-g 45, ' I- g VJl .7 , 9 G 10 G 15th G 11 8th G 10 G 9 G

1
3 g

2.5 g 20 g 34.4 g 20 g

12.4 g

\ There were also nooh other preparations in which instead of "maro oil" equal amounts of isopropyl myristate or

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Safflower oil were used. In a series of other preparations, "Marcol ^{11" was} replaced by the product "Silieonöl DO 200" from the company .i) öw-Qorning.

Example 3

There were other cosmetic products as in Example 1 and but an equal amount of "Polyco 2719" was used instead of the aqueous emulsion polymer (D). The latter mentioned aqueous emulsion is made by Bordon Chemioal Co sold and has a total solids content of 46-47 ^, The resin consists of a mixed polymer of etfa 63i * ethyl aorylate and 379 & methyl methaorylate in addition to a small amount of itaoonic acid

consists. The emulsifier content makes $ £ from} the emulsifier consists of "Triton X-200" and "Tri = t ± onsulfat ^w _#

In two further series of preparations according to the invention, instead of of propylene glycol corresponding amounts of glycerine or sorbitol are used.

Example 4

Propylene glycol 5 »0 g

"Oarbowax 400" (h) 5.0 g

"Veegum" (c) 20.0 g

Pigments (i) 7.5 g

"Cab-o-sil" M-5 (j) 1.0 g of ethyl parahydroxybenzoate (k) ^v 0.25 g

Perfume 0.2 g

Deionized water 43.0 g

"Oalgon" (1) 3.0 g

"Carboset 511" (m) 5.0 g

Aqueous emulsion, with water-insoluble addition polymers (p.) 10.0 g

(h) polyethylene glycol from Carbide &Carbon;

(i) as indicated in Example 1;

(3) Colloidal silica, preparation from Godfrey L. Parbot Go .;

(k) preservatives j

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(1) Sodium hexamethaphosphate with sodium carbonates, product from Calgon Co.j

(») Fibrous solution of a film-forming aoryl polymer with a Official solids content of 45 ^ and a pH of 7.8 * 8.2, Product of B. F. Ooodrich Chemical Co. |

(n) as in example 1.

The preservative and the perfume are dissolved in the propylene glycol, then Carbowax and Veegiun ^II dispersion are added with stirring, and finally the pigments and the silica. Calgon is first dissolved in a little warm water and then added; the polymer solution and the aqueous solution of the emulsion polymer are first diluted with water and then added. Finally, the mixture is mixed with the remaining amount of water and stirred until a homogeneous preparation is obtained.

Example 5

In the manner described in Example 4, five further cosmetic preparations are produced, with some components in other amounts as indicated below were used. The ingredients not listed were in the same amount as indicated in Example 4 used.

Propylene glycol oil "Veegum" pigments Deionized water Aoryl polymer solution

Aqueous emulsion «· polymer

Example 6

The cosmetic preparations produced according to Example 4 and Example 5 were modified by replacing the aqueous Emulsion polymers an appropriate amount of a "Borden Polyoo 2719 "acrylic resin copolymers used.

In two further series of preparations, instead of Propy

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I. G 7th 2 G 8th 2 G 6th G 35 G 30th G 40 G 9 G 9 G to G 18th , 5 G 24 G 12th G 7th G 6th G 7, 5 G 14th G 13th , 5 G 15th

£ G 10 G 9 G 20th G 25th G θ G 8th , 5 G 36 G 30th G 5.5 G 6th G 11 G 12th

lenglyool corresponding amounts of glycerine or sorbitol used

EXAMPLE 7

In each of the cosmetic preparations produced according to Examples 1-6, 1 g of hesoroin was incorporated and the perfume was omitted; In this way, mildly acting preparations were obtained which eiAh suitable for the treatment of acne.

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Claims (1)

H92101 13 Claims 1 · Koemetleoh.ee preparation which is applied to the skin or hair can be identified by the fact that it consists of a neutral. lon "" permanent aqueous dispersion, which is a nioht ~ toxic water-insoluble addition polymer, a polyhydric alcohol as a humectant, about 5-20 percent by weight / Unit volume of a pharmaceutically acceptable finely divided inert pigment and at least about 0.5 weight percent / volume unit of a finely divided inorganic silioate contains » 2 Eosmetisohes preparation according to claim 1, daduroh characterized, that its pH is between 6.5 and 8 3 · Koametisohei preparation naoh Anepruoh 1 or 2, characterized by the fact that the addition polymer is a polyacrylic acid ester · 4 Cosmetic preparation according to one of the preceding claims, This is marked as 3-7 percent by weight / volume unit of the non-toxic water-insoluble addition polymer, about 2.5-5% owioht per cent / volume unit of the water-insoluble addition polymer Intermediate polyhydric alcohol, at least about 3 Contains percent by weight / tolumene unit of a pharmaceutically acceptable surface-active agent and at least 1 percent by weight / unit volume of an oily smoothing agent « 5. Cosmetic preparation according to one of the preceding claims, daduroh characterized that the water-insoluble addition polymer a misoh polymer of ethyl aorylate and methyl methaorylate is. 6 · cosmetic preparation NaOH to claim 4 or 5, characterized daduroh _t that is used as a surface active agent such anionisoher Nature · 9098 U / 1007 H92101 7. Cosmetic preparation according to claims 4-6, characterized in that «· ' shows that the smoothing agent is a mineral oil or «In Seter 8. Cosmetic preparation naoh claim 1-7, daduroh characterized, that the aqueous dispersion is about 3-7 percent by weight / volume * unit of non-toxic water-insoluble addition polymer, about 2-4 weight percent / unit volume of a non-toxic water-soluble addition polymers, at least about 5% percent / volume unit of as humidifying agent; serving polyhydric alcohols, about 5-20 percent / volume unit the pharmaceutically acceptable finely divided inert pigment and at least about 2 percent by weight / volume of the finely divided divided inorganic silicate tea. for Chas. Pfizer dt ^ü o., Ine, New York, NY, V.3t.A. 809814 / t087 BATH