DE1241560B - Ointment base and skin protection and skin care products - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

A61k

German class: 30 h -9/04

3o I

Number: 1241 560

File number: W 31435IV a / 30 h

Filing date: January 9, 1962

Open date: June 1, 1967

The addition of small amounts, namely about 1 to 3 percent by weight, of organopolysuoxanes to aqueous and non-aqueous ointment bases to increase lubricity and hydrophilicity is known. The present invention, however, relates to ointment bases that contain at least 15 percent by weight Organopolysiloxane, based on the total weight of water and organopolysiloxane, contain.

The use of aqueous and non-aqueous emulsions of organopolysiloxane oils as an ointment base in medical and cosmetic preparations is also known. With the organopolysiloxane oils it is generally about dimethylpolysiloxanes of various chain lengths, in which a TeU of the methyl groups can be replaced by phenyl groups. These are diorganopolysiloxanes often end-blocked by trimethylsiloxy groups. Often compared to non-aqueous emulsions preferred aqueous emulsions are between those of the oil-in-water type and those of the water type to be distinguished in oil. Stable emulsions of the former type are relatively easy to prepare, since there are numerous dispersants that are suitable for this purpose. The particularly desirable Water-in-oil emulsions, especially those that contain more than 50% water, based on the total weight the emulsion, on the other hand, tend to show signs of segregation and lose their ointment-like consistency. With the ointment bases according to the invention and skin protection and skin care products on the basis of organopolysilanes emulsified with water, on the other hand, it is Water-in-oil emulsions that even without further dispersants with a water content of more than 50%, based on the total weight of the emulsion, are very stable.

The invention relates to ointment bases and skin protection and skin care products based on them of organopolysiloxanes emulsified with water and containing 50 to 85 percent by weight of water on the total weight of water and siloxane, characterized in that the organopolysiloxanes Si-bonded methyl groups, of which up to 80 mol percent can be replaced by phenyl groups, with an average of 1.9 to 2.5 S-bonded organic residues per Si atom, and each Molecule 5 to 40 percent by weight, based on the total molecule, Si-bonded polyoxyalkylene radicals via oxygen the formula

- (C _n H _2n O) ₁ -

Ointment base and skin protection
and skin care products

Applicant:
Wacker-Chemie G. mb H.,
Munich 22, Prinzregentenstr. 20th

Named as inventor:

Dr. Ewald Pirson,

Dr. Siegfried Nitzsche, Burghausen (Obb.)

(n = 2 and / or 3, χ = an integer and at least 5) with a molecular weight of 150 to 1000, with the valences of the polyoxyalkylene radicals not saturated by siloxane radicals through hydrogen atoms and the not saturated Si valences of the siloxanes through Oxygen atoms are saturated.
Preferably 10 to 25 percent by weight,

»5 based on the total molecule, present on polyoxyalkylene residues.

Of those known from the German Auslegeschrift 1108 917, as additives for water containing ointments recommended organosiloxymethylalkanes differ from the compounds used according to the invention in that they contain no tetra- or trioxymethylalkyl radicals and their polyoxyalkylene radicals are not end-blocked by alkoxy groups so that they are more easily accessible. aside from that are not in the German Auslegeschrift 1108 917

Water-in-oil emulsions are described which contain more than 3 percent by weight of organopolysilane compounds contain.

Of the Amer. Perfumer Aromatics, 68th year, No. 5, pp. 2293-2294, known, recommended for use in the cosmetic industry Organopolysiloxane-polyoxyalkylene compounds differ from those used according to the invention Compounds in that their polyoxyalkylene blocks are longer and not by trioxysiloxy, but are end-blocked by organopolysiloxane radicals or hydroxyl groups. Ointments containing water are in the last-mentioned reference, the hydrolytically very easily decomposing organosilicon compounds

describes, not mentioned.

Those in the organopolysiloxane used according to the invention - Polyoxyalkylene compounds available

709 588/312

3 4

which organopolysiloxanes are essentially composed of organopolysiloxane - polyoxyalkylene - compounds diorganosiloxane units, while so many of the type used according to the invention are mixed polymeric monoorganosiloxanes and triorganosiloxanes according to the aforementioned French patent units, possibly also SiO ₄ , ₂ units, written quite generally as emulsifying, dispersing and holding, recommended as the specified range for the 5 suspending agent. However, the ratio of the Si-bonded organic radicals to no emulsifying, dispersing or suspending agent has so far corresponded to the silicon atoms in the organopolysiloxane. or only of very few such agents from the Preferably, the organopolysiloxanes contain only a very large number of emulsifying, dispersing and diorganosiloxane units, linear and suspending agents have become known that they are or if end-blocked by triorganosiloxy groups. io that they are suitable as ointment bases. In particular

For the production of those used in accordance with the invention, there is currently no rule for a relationship

Compounds can be polyoxyethylene diols, polyoxy between the suitability of a substance as an emulsifier,

propylene diols or mixtures of these diols or dispersants and suspending agents and its suitability

the mixed condensates of polypropylene and poly as a non-aqueous phase of a water-in-oil emulsion

ethylene oxide can be used. These compounds 15 and so far none that have been usable as an ointment base

according to the general formula water-in-oil emulsion, containing an emulsifying,

HO (C _n H "O) zH dispersing and suspending agents suitable organic

* ^nx silicon compound known as a non-aqueous phase

where η and χ have the meaning given. been.

The ratio of organopolysiloxane to polyoxy- 20 The emulsification of those used according to the invention

alkylene is always to be chosen so that no more than organopolysiloxane-polyoxyalkylene compounds with

Part by weight of organopolysiloxane-polyoxyalkylene-water can be mixed with all common emulsifying agents

bonds are made in 50 parts by weight of 18 ⁰ C water apparatus. Such apparatus are

is soluble. z. B. Colloid Mills and the Mechanical High

The production of the as frequency mixers used according to the invention according to Prof. P. Willems (cf.

Organopolysiloxane - polyoxyalkylene - compounds DECHEMA - Monograph, Vol. XIX, pp. 72 to 79).

can be carried out by all processes suitable for this purpose. The emulsions according to the invention also show

and is not claimed here. with their water content of 50 or more than 50 weight

There are z. B. the following methods are available: percent the typical properties of water-in

a) Organopolysiloxanes of the general formula 3 <> Oil emulsions, such as greasy or oily texture,

stiff consistency and immiscibility with water.

-, ρ, The latter property is most important for skin ointments

• ο j α, _Λ ι * · * UU- »λ. ,, meaning because they have a great persistence and

where R is the methyl radical, with up to 80 molar _{adhesive strength on the} skin during washing,

percent of the methyl radicals replaced by phenyl radicals _The emulsions according to the invention are suitable

can be, a = l, 9 to 2.5, AeinSi-bound _{already without further addition as cosmetic} or

Alkoxyrest with preferably no more than _{protective ointments for the skin they ei themselves however}

8 carbon atoms or a halogen atom, especially _{from an ointment base and can as such with}

Chlorine is, y the desired content of po yoxides, _the usual additives for ointment bases, such as

aUcy residues are made with polyoxy- _{40 cosmetic and} medical active ingredients, fragrances

alkylene diols, optionally m the presence of _{material igmenten} p, u _{Fo st} open, z. B. zinc oxide, titanium

Condensation or transesterification catalysts, _diox y _d) silicon dioxide and other common ointments

implemented. Working methods according to _St J _{such as Vasel} [ _{ne> can be shifted} . _{To this}

or by analogy with the procedures as they are in the German _{way, one obtains particularly effective} medical ones

_{Patent specification} 1 012 602 or in the USA.

Scripture 2,441,066, applied _{tables and protective} ointments. The additives can be

It is preferable to mix in _{during or after the} emulsification

1 mol polyoxyalkylene diol, sometimes also as _{who (Jen Eg is irrelevant> whether these substances in water)}

"Polyalkylene glycol" denotes per mole of alkoxy in the organosilicon used _{according to the invention}

rest or halogen atom used. _{$ 0 connection or} i _n any of them are soluble.

b) Cyclic or non-cyclic - the latter

- Organopolysiloxanes of the general Example 1 are preferred
my formula

_RS -Q 200 g of dimethylpolysiloxane with 5 percent by weight

° - ^ - 55 terminal ethoxy groups are mixed with 40 g of poly-

oxyäthylenediol with a molecular weight of 400 so long

wherein R and α the importance _au f _e twa heated above 150 ⁰ C, until no more abhaben ethanol, are distilled in with polyoxyalkylenediols.

Presence of condensation or equilibrium 120 g of the oil obtained in this way are with 380 ecm

Bring catalysts, such as alkali hydroxides, e ₀ water mixed in a high-speed mixer,

strong inorganic and organic acids _D j _se i _ne stiff mass has arisen. You get one

and / or metal powders, e.g. B. Magnesium, copper emulsion of the water in oil type, which even after 6 months

fer, aluminum or zinc dust. naten storage no change in consistency

Processes of this type are e.g. B. in the German has.

Patents 1103 022 and French 65 Example2
U.S. Patent 1,284,858. Preferred

the method according to the last-mentioned 400 g of dimethylpolysiloxane with 6 percent by weight

Patent specification. terminal ethoxy groups with 120 g of poly

'5

oxy-1,2-propylenediol with a molecular weight of 600 implemented according to the procedure described in Example 1. 200 g of the oil thus obtained are emulsified with 800 ecm of water in a high-speed mixer and added during the emulsification with 20 g of salicylic acid methyl ester.

Example 3

400 g of diorganopolysiloxane, in which 60 mol percent of the organic radicals are phenyl groups and the rest Si-bonded organic radicals are methyl groups, corresponding to a phenyl: Si ratio of 0.6: 1.0, with 6 percent by weight of terminal ethoxy groups are according to the procedure described in Example 1 with 120 g of polyoxy-l, 2-propylenediol from Molecular weight 600 implemented. 52g of the oil obtained in this way are emulsified with 148 ecm of water, one Emulsion of the water in oil type is formed.

Example 4

170 g of the polyoxyethylene diorganopolysiloxane ester prepared according to Example 1 are mixed with 60 g Vaseline and heated to the melting point of the Vaseline. Then stir in a fast-moving one Mixing device through vigorously and lets 740 ecm of water run in with further stirring. It creates a permanent emulsion with an ointment-like consistency.

Example 5

850 g terminally blocked by trimethylsiloxy groups, dimethylpolysiloxane with average 34Dimethylsiloxaneinheiten per molecule and 150 g Polyoxyäthylendiol a molecular weight of 600 were heated together with 2.5 g of magnesium powder and 0.5 g of powdered potassium hydroxide under stirring within 1V ₂ hours at 25O ⁰ C. After allowing to cool, a little activated charcoal is added and the mixture is filtered. A clear, colorless oil is obtained.

50 g of the oil thus obtained are emulsified with 150 g of water, a stable emulsion being formed.

Example 6

400 g of dimethylpolysiloxane with 12 weight percent terminal ethoxy groups are heated under stirring with 76 g of polyethylene glycol of molecular weight 150 and 0.2 g of ferric chloride so long as at 140 to 150 ⁰ C, until no more ethanol distilled off more.

In the same way, 400 g of dimethylpolysiloxane with 5 percent by weight of terminal ethoxy groups are used reacted with 85 g of polyoxyethylene diol with a molecular weight of 1000.

In each case 120 g of the oils obtained in this way are mixed with ecm of water in a high-speed mixer stirred. In both cases it is an emulsion of the ίο type water in an oil and an ointment-like consistency obtain.

»5

Claims (1)

Claim: Ointment base and skin protection and skin care products based on water emulsified organopolysiloxanes containing 50 to 85 percent by weight of water, based on the Total weight of water and siloxane, characterized that the siloxanes are Si-bonded methyl groups, up to 80 mol percent of which have been replaced by phenyl groups can, with an average of 1.9 to 2.5 Si-bonded organic residues per Si atom, and per molecule 5 to 40 percent by weight, based on the total molecule, bound via oxygen Polyoxyalkylene radicals of the formula - (C _n H _2n O) * - («= 2 and / or 3, * = an integer and at least 5) with a molecular weight of 150 to 1000, with the valences of the polyoxyalkylene radicals not saturated by siloxane radicals by hydrogen atoms and the not, as described, saturated Si valences of the Siloxanes are saturated by oxygen atoms. Considered publications: German Auslegeschriften No. 1005 269, 1108 917; French Patent No. 1284 858; Coin 1, Büchi, Schultz, Galen. Practical Stuttgart (1959), p. 530; Amer. Perfumer Aromatics, 68, No. 5, pp. 19-21 (1956). 709 588/312 5.67 ® Bundesdruckerei Berlin