DE3122283A1 - "METHOD FOR PRODUCING STABLE W / O EMULSIONS AND COSMETIC AGENT - Google Patents

Description

T .___.-_ _ dft ··. _{ι &} ^% μ K! κ ·> ■ ν · faientanwaiic unu IEDTKE - DOHLING "IVlNNE .." -. Representative fapi ^ EPA RUPE - Pellmann · „·: \ .- ö & ^

Dipl.-Ing. R. Kinne

Dipl.-Ing. R Group Dipl.-Ing. B. Pellmann

Bavariaring 4, Postfach 20 3122283 8000 Munich 2

Tel .: 089-539653 Telex: 5-24845 tipat cable: Germaniapatent Mund

June 4, 1981 DE 1282 / case 3902 DRST.U / DPICV / NG / 3-419

SOCIETE NATIONALE ELF AQUITAINE (PRODUCTION) COURBEVOIE / FRANCE

Process for the production of stable W / O emulsions and cosmetic agent

The invention relates to a method for producing stable W / O emulsions by means of emulsifying properties having, from a lipophilic and a hydrophilic portion existing compounds and a cosmetic product made according to this process.

Although a large number of surface-active substances suitable for producing emulsions is known, there is a need for an emulsifier that will certainly facilitate the manufacture of a W / O emulsion allowed to be sufficiently stable is, so that a segregation of the phases is avoided

XI / 13

Deutsche Bank (Munich) Account 51/61070 Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account 670-43-804

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will. Such an emulsifier is needed because it is desirable in certain instances is to use a W / O emulsion over a long period of time store or keep. As an example in the field In cosmetology it should be mentioned that creams, which consist of a dispersion of very fine water droplets in consist of a continuous, fatty phase, better properties in terms of moistening and protection of the skin. It often happens that

IQ the use of known emulsifying agents is associated with the risk of segregation. It is always difficult to find the right composition with regard to the emulsifying agent in new preparations consisting of such emulsions, and it is uncertain whether the properties will be retained over a long period of time. _;

Those currently proposed for such W / O emulsions Emulsifiers consist of an aliphatic chain linked to a hydrophilic part or fatty hydrocarbon chain. The aliphatic chain can be unsaturated and it can be free or carry ethoxylated, hydrophilic function. The hydrophilic part can be a carboxylate, Act glycerol ester, sorbitol ester, polyoxyethylene or phosphate group.

Compounds derived from oleic acid, ricinoleic acid or lanolin are also used as emulsifiers known that are used for cosmetic products. Due to their structure, these compounds can be in Dissolved oils and used to generate W / O emulsions. The necessary cohesion of the interfacial film between the oily and the aqueous phase is made by Van Der Waals forces or by

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Hydrogen bonds caused. However, these cohesive forces are weak, and it is difficult to maintain the stability of these emulsions. It is therefore difficult to be satisfactory To formulate W / O emulsions, especially in the case that a reduction in the proportion of the oily phase is sought.

It is the object of the invention to provide a method for producing W / O emulsions in which the above-mentioned disadvantages are eliminated and in which very stable emulsions can be obtained.

This object is achieved by the method characterized in claim 1.

When used in the field of cosmetology, the method according to the invention leads to cosmetic effects Means that because of a greater affinity of the new emulsifiers for the skin to become a better Lead protection of the epidermis.

It has been found that the introduction of the sulfinyl function, i.e. H. the group

- S- i

Il

* · Ο

in the molecule of a compound with a hydrophilic Function (where the compound can be a surface-active compound known per se) the effect aligns this compound to the formation of W / O emulsions and stabilizes the emulsions formed. It is possible that this influence of the sulfinyl func-

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tion is based on the strong polarization of this function, which is added to the classic intermediate bonds of the Van Der Waals type and the dipole bonds, which together stabilize the interfaces between the phases of the emulsion. Regardless of what the influence of the sulfinyl function is based on, the advantage is gained through the introduction of the groups

in compounds which contain a hydrophilic portion, is achieved by the known prior art has not been suggested in any way. 15th

The new emulsifiers used in the process according to the invention are characterized by that they consist of compounds with a hydrophilic portion, in which the ran the hydrophi len .Anteil

linked chain contains a sulfinyl group which is present in the lipophilic portion of the carbon molecule is bound.

These emulsifiers are

new chemical compounds represented by the general formula below

R ¹ - S - CH - (CH ₂ ) _n - A,

³⁰ SR ² .

1 2

where R is a hydrocarbon group and R is hydrogen or is a hydrocarbon substituent, η is an integer from 1 to 20 and A denotes the hydrophilic Share of the connection designated, shown

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can be.

In particular, R can be an alkyl, alkenyl, aryl, alkaryl, aralkyl or cycloalkyl group, the generally contains 1 to 20 carbon atoms.

ρ
R can be of the same type \ values from 4 to 18 are preferred.

2 '"1

R can be of the same type as R. For η be

Although the structure of the hydrophilic portion in the surface-active compounds is known, the meaning of the group A defined above will be explained with the aid of the most common examples. The group A can in particular a carboxyl group -COOH, a sulfonate group ~ ^S0 3 ~> ^one

Sulphate group -SO ₄ "or a phosphate group -PO ₄ ", whereby these groups can be free or in particular esterified with a polyol such as glycerol or sorbitol or a salt with an alkali or alkaline earth metal, an amine or a quaternary ammonium

; n as in imidazolinium · 'or another nitrogenous base. · May have formed. The group A can also consist of a polyoxyalkylene chain, in particular a polyoxyethylene chain (-CH-CH-O-) H or polyoxypropylene chain, in which m preferably varies from 2 to 20, consist. Other forms of the group A are, for example, amino acid groups such as

.Alkyl- "Η,» /

-HC. or —HC < ^ Alkyl.

COOH. ^X c00H

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The sulfinyl group must be sufficiently far from the hydrophilic portion A must be removed so that the emulsifier used in the process according to the invention good for the formation and stabilization of emulsions,

.5 in which the disperse phase is aqueous, is suitable. the Compounds that give the best results are those whose sulfinyl group is in a fatty one Phase is included, where they ensure a stabilization of the interface Can cause lamella of the surfactants. The values of η are therefore preferably above 4 and especially even over 6.

The application of the new, sulfoxidized Emulsifier does not differ from the way of application the known emulsifiers, which is why the method of application is not discussed in detail. as As an example, it should only be mentioned that good results can be obtained if the emulsifiers in in an amount from 0.01 x to 10% by weight, by weight based on the emulsion to be produced, the optimal proportion of the emulsifier in a Of the order of 1 to 3% by weight.

It may be necessary to adapt the emulsification system to the type of substances to be emulsified be that one or more emulsifying agents known per se are used. Because the stabilizing effect however, it is always very pronounced, it is of

30 Advantage if to stabilize the emulsion a

sulfoxidized compound according to the invention. Procedure is added. In this way, the new, claimed in the process according to the invention Emulsifiers in the form of a mixture of these emulsifiers

* "lubricant or in the form of a mixture with per se

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known emulsifiers are used, namely within the limits set by the rules for the compatibility of surfactants, the . consist in the fact that two surface-active substances with mutually opposite ionic Characters may not be mixed up.

The new emulsifiers "of the process according to the invention are not only suitable for the production of Emulsions in which one of the phases is aqueous, but also in the event that immiscible, non-aqueous products are to be emulsified, among others in the case of various insecticides or fungicides, for their production, for example, halobenzenes or other chlorinated, organic compounds (e.g. "Chlordan" or "DDT") with substances such as kerosene or xylene must be emulsified.

. The manufacture of organic sulfides and the manufacture of the corresponding sulfoxides are Although generally known, the use of known processes for the preparation of the in the invention Products used by the process

25 Examples 1 to 4 below are explained.

example 1

Production of Dodecylsulfinylundecanoic Acid '30

a) Chemical production of the sulphide

In a stirred, heated, and reflux condenser equipped reaction vessel were sequentially 300 ml of ethanol, 450 ml of water with a sodium

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hydroxide content of 120 g, 398 g (1.5 mol) of bromundecanoic acid and 303.6 g (1.5 mol) of lauryl mercaptan introduced. The temperature rose to about 80 ^° C. during the mixing. The reaction mixture was kept at this temperature with vigorous stirring in order, on the one hand, to prevent crystallization of the product formed and, on the other hand, to avoid overflowing of the reaction mixture due to the foam formation caused by the boiling.

After six hours of reaction, the mixture obtained was at 80 ° C with concentrated hydrochloric acid to acidified to achieve a pH of 2. Two layers occurred. The lower, aqueous layer was discarded and the top layer was poured into benzene. ? ■

The obtained product, crystallized at ambient temperature, was centrifuged, washed with benzene and dried at 50 ° C under a pressure of 133 Pa. In this way 434 g (70% of theoretical yield) of crystallized product having a melting point of 70 ⁰ C to 72 ° C.

25 Elemental analysis of the product

Found C 71.92% H 12.68% Calculated 71.50 % 11.92%

t ») Manufacture of sulfide on photochemical

ways

It became a 3 liter heated reaction vessel used, which was equipped with a medium pressure mercury vapor lamp of 125 W. The optical way

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this container was 7 cm. The stirring was through an external circulation or return loop is guaranteed.

Into this reaction vessel, 1288 g (7 mol) of undecylenic acid, 14.14 g (7 mol) of lauryl mercaptan, 5.4 g of benzophenone and 5.4 g of trimethyl phosphite were introduced. The reaction was carried out at 80 ° C. for 3 hours. When the reaction was complete, the reaction vessel was emptied into 4.5 liters of petroleum ether and the product was allowed to crystallize at ambient temperature. After centrifuging and washing the crystals with petroleum ether, 2361 g (87.5 % of the theoretical yield) of des

15 product received.

c) Conversion to the sulfoxide

A solution of 965 g (2.5 mol) of dodecylthioundecanoic acid in 3000 ml of acetone was heated under reflux of the acetone and with very vigorous stirring. 270 ml of 33% hydrogen peroxide (2.6 mol HpO_) were slowly introduced. The reaction was complete after 3 hours. After cooling, the crystals obtained were centrifuged, washed with acetone and ^{dried at 50 °} C. under a pressure of 133 Pa. The product obtained had a melting point of 95 ° to 96 ° C; its acidity was 99.6% of theory.

30 Elemental analysis of the product

Found C 68.85 % H 11.54 % S 11.50% Calculated 68.66% 11.44 % 11.94 %

3122283 Example 2 .... '
. -. ·
> · · *
.. - · »* · *
nc ·· "* * *
• * ¥ · ' - 13 - Methylthioundecanoic acid DE 1282 chemical ways

In a stirred, heated and equipped with a reflux condenser reaction vessel were a 1600 g (40 mol) of sodium hydroxide, 960 g (20 mol) of methyl mercaptan and 4500 ml of water and then a solution containing 5300 g (20 mol) of bromundecanoic acid in Containing 1200 ml of methanol was introduced. The resulting mixture was refluxed for 3 hours. Then 20 l of hexane were added. The temperature of the reaction mixture was held at 40 ° C. for 6 hours. 1900 ml of 13% hydrochloric acid was used to acidify until a pH value of 2 was achieved. The aqueous phase was removed by decantation and the organic phase was washed with water at 40 ° to 50 ° C. until the reaction was neutral. 13 liters of hexane were evaporated and the resulting solution was crystallized at about 5 ° C. After centrifugation and drying, 4450 g (95.5 % of the theoretical yield) of a crystallized product with a melting point of 45 ° C., the acidity of which was 100 % of theory, were obtained.

Elemental analysis of the product

Found C. 62 , 15 % H 10, 70 Calculated 62 .06 % 10, 54

Methylthioundecanoic acid by photochemical means .

It became a 3 liter heated reaction vessel applied that with a medium pressure mercury vapor lamp of 125 W. The optical way

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this reaction vessel was 7 cm. Agitation was provided by an external recirculation loop. Were in the reaction vessel 2245 g (12 moles) of undecylenic acid, 5.4 g of benzophenone and 5.4 g of trimethyl phosphite were introduced. The atmosphere was purged with nitrogen.

Had become liquid as the contents of the reaction vessel, the mixture was passed through the outer circulation loop passing in the circuit, and the temperature was regulated to a value of 55 ⁰ C. The mercury vapor lamp was switched on and methyl mercaptan was poured through a fritted glass plate at the bottom of the reaction vessel.

15 ters introduced.

After seven hours of reaction, the excess methyl mercaptan was removed by purging with nitrogen removed and the reaction vessel was removed

emptied into 3 l of hexane. The solution was ^{crystallized at 5 °} C., centrifuged and washed with cold hexane. After drying, 2637 g (93.7 % of the theoretical yield) of a crystallized product with a melting point of 44.5 ° C., the acidity of which was 99.6% of theory, were obtained.

Elemental analysis of the product

Found C 62.04 %. H 10.67% ³⁰ Calculated 62.06 % 10.34 %

Methylsulfinylundecanoic acid

A solution of 1000 g (4.31 mol) of methylthio- ^OJ decanoic acid in 2350 ml of acetone was with 449 ml

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33% hydrogen peroxide (4.3 mol ΗρΟ_) for 6 h refluxed.

After evaporation of the acetone and drying, 1070 g of crystallized product with a melting point of 85 to 87 ° C. were obtained, the acidity of which was 100 % of theory; fraud.

Elemental analysis of product 10 Found C 50.03 % H 9.35 % Calculated 50.08% 9.68 %

Example 3 15

Glycerol monomethylthioundecanoate

696 g. (3 mol) of methylthioundecanoic acid and 828 g (9 mol) of glycerin were added to a reflux condenser equipped reaction vessel heated to 180 ° C under a pressure of 2660 Pa. After 8 hours the remaining acidity 0.06 mol. When the reaction mixture was cooled to 60 ° C., it parted in two layers that were separated from each other

25 den.

The upper layer was dissolved in 1 liter of ether and washed with water. After the Ether and drying, 831 g (90.5% of the theoretical yield) of a pasty product were obtained.

The lower layer was returned to the next batch.

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A solution containing 770 g (2.5 mol) of glycerol monomethylthioundecanoate and.260 ml of 33% hydrogen superoxide in 1500 ml of acetone was refluxed for 4 hours.

After evaporation of the acetone and drying, 810 g of crystallized product were obtained.

Mp = 49 ° -52 ° C; Saponification Number = 184 C (96) = 55.89 (56.42) H (%) = 9.49 (9.33)

Example 4 Glycerol monododecyl thioundecanoate

A mixture of 965 g (2.5 mol) Dodecylthioundecansäure and 696 g (7.5 mol) of glycerol was heated under a pressure of 2660 Pa in a reaction vessel equipped with a reflux condenser at 195 C to 200 ⁰ C.

After seven hours of reaction, there was no longer any acid in the reaction medium. As the reaction mixture Was cooled to 75 C, it divided into two layers. The bottom layer was returned to the next batch. The top layer was in the form of a solid mass with a Melting point of 62 ° to 71 ° C, the saponification number was 128.

Glycerin monododecylsulfinylundecahoate 'A solution containing 874 g (2 mol) of glycerin monododec-

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Cylundecanoate and 200 ml of 33% hydrogen peroxide (2 mol H ₃ O ₂ ) in 1500 ml of acetone was refluxed for 6 hours.

The acetone was evaporated and the resulting crystallized product was dried. This gave 910 g of a product having a melting point of up to 100 ⁰ C.

Saponification number: 122 Elemental analysis of the product

Found C. 64, 87 % H 16 , 72 Calculated 65, 54 % 16 , 81 example 5

To 45 parts by weight of petroleum jelly with a temperature door of 20 ° C., 2 parts of an emulsifying agent explained below were added. After the addition 55 parts of distilled water was stirred with a rotary stirrer for 3 minutes. the obtained emulsion was placed in a 100 ml test tube poured into it, which was kept at 40 ° C in a drying cabinet. The behavior of the emulsion became daily observed.

'■ As an emulsifier, these were sold under Emulsifying agents known under the name NONlONIC 218 or the corresponding sulfoxidized compound used ·.

NONIONIG 218: t-Dodecylthiopolyethylene glycol 35 "C ₁₂ H ₂₅ -S

τ 18 - DE 1282

SULFOXIDE: t-Dodecylsulfinyl polyethylene glycol

The emulsion made with NONIONIC 218 remained stable for about 17 days while the emulsion produced with the corresponding sulfoxide did not detect any phase separation even after 40 days let.

Example 6

The foaming power of aqueous media each containing 0.1 % of the emulsifying agents indicated below was measured by the ROSS-MILES method, the results indicated below being obtained.

Foam height (mm)

at the beginning

Triethanolamine Lauryl Ether Sulphate ... 180

"+ Laurylamide (0.1-56) ²³ °

Triethanolamine methylsulfinylundecanoate 230

after 10 min

120 190 200

Accordingly, it can be found that the sulfoxidized compound of the present invention is more suitable is than the common lauryl ether sulfate and that it 'even leads to a somewhat more stable foam than Lauryl ether sulfate to which lauryl amide has been added.

Examples 7 and 8
Creams for cosmetic applications, in particular

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Night creams, performing emulsions were made from the usual remnants and, if necessary, with the addition of sulfoxidized compounds according to the invention prepared. Centrifugation, heating and and storage tests, the results of which are given in the table below.

Example 7 10

Components (Wt%) TA m preparation 6.80 6.80 1.40 1.40 Arlacel 481 (sorbitan sesquistearate) 0.08 0.08 vaseline 41 40 cholesterol 2.20 2.20 Marcol 82 (petroleum jelly) 10.50 10.50 Beeswax 1.60 1.60 Paraffin 50/52 0.47 0.47 Stearin (pressed three times) 0.15 0.15 Cetyl alcohol 1 Propyl p-hydroxybenzoate 34.70 3M0 Dodecylsulfinylundecanoic acid 0.30 0.50 water _— 0.10 Magnesium sulfate ■ 0.20 0.20 Triethanolamine 0.10 0 ^ Q Preserval LL (preservative) T 100 860 (perfume)

100.00 100.00 30

Example 8

Components

Vegetable wax vegetable fat isododecane
Isopropyl myristate

Imwitor 780 K (glycerol monoisostearate) Montane 73 (sorbitan sesquiisostearate) Simulsol 989 (hydrogenated and ethoxy-

lated castor oil) dodecylsulfinylundecanoic acid

Hostaphat KO 300 N (trioleyl phosphate) Bentone 27 (hectorite, dimethylbenzyl

stearylammonium)

Bentone 38 (hectorite, quaternary antonium-18) 20 preservatives.

water

Magnesium Sulphate Magnesium Hydroxide Glycerin
Preservatives

DE 1282 , 5 in ) (Wt%) 8th preparation 5 .ΠΑ , 5 10 8th VJl 5 , 2 2 10 , 2 1 5 ■ 0, 5 2 1 1 1 0 1, 5 2 2 O, 2 56, 1 2 1 O ₁ O, 1 56, 5 1 0, 6th - 100 5 O ₁ 00

co O

to cn

to

Tabel

Storage time
after
Manufacture Test procedure Preparation I. B. Preparation II B. 48 h Centrifugation (4000 rpm; 20 min)
Heating to 40 ⁰ C; 43 h
Heating to 50 C; 48 h A. Stable
Stable
Stable A. Stable
Stable
Stable 4 months Centrifugation (4000 rpm; 20 min)
Warming to 40 ° C; 48 h
Heating to 50 ° C; 48 h
Observations after storage Minor ent
mixture
Stable
Minor deviations
mixers Stable
Stable
Stable
Homogeneous Segregation
Stable
Stable Stable
Stable
Stable
Homogeneous 1 year Centrifugation (4000 rpm; 20 min)
Observations after storage Segregation
Stable
Minor ent
mixture
some droplets Segregation
Segregation
Segregation
some drip.
chen Stable
Homogeneous Segregation

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The superiority of the IB and HB creams over the IA and HA creams is obviously based on the Addition of dodecylsulfinylundecanoic acid, one of the compounds according to the invention.

Examples 9 and 10

In the above examples describing the manufacture of cosmetic creams, the Dodecylsulfinylundecanoic acid by methylsulfinylundecanoic acid (Example 9) or by glycerol monododecylsulfinylundecanoate (Example 10) replaced.

As in Example 5, it was found that the creams containing the sulfoxidized compounds, are stable over a much longer period of time than the creams that do not contain these compounds are.

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Example 11 Preparation of a cream

(Wt%)

Isododecane 12.00

Avocado oil 2.00

Corn oil ¹ > ⁰⁰

PPG 3 myristyl ether 2.00

Ethyl hexyl acetoxystearate 1 * 50

Sorbitan monooleate 0.50

Polyglycerol ether of dimerized soybean oil 1.00

Soy lecithin 0, U0

Dodecylsulfinylundecanoic acid 0; 90

Glycerol monododecyl sulfinyl undecanoate 1.00

Propyl p-hydroxybenzoate 0.10

10% sodium hydroxide 1.00

Glycerin 2.50

Magnesium sulfate 0.50

Methyl p-hydroxybenzoate 0.20

Distilled water . 73.10

This cream, the two according to the invention, sulfoxidized Contains compounds is stable over a very long period of time.

Incidentally, this preparation with a continuous oily phase is particularly noteworthy because it contains 75 % water.

Such a preparation with a continuous oily phase, which contains 75 % water, could not yet be obtained with the known emulsifiers and therefore makes the advantages of the invention

10

15th

25th 30th 35

- 24 - DE 1282 1 according to the method particularly clearly.

Claims (12)

Claims 1. Process for the production of stable W / O emulsions by means of emulsifying properties, Compounds consisting of a lipophilic and a hydrophilic component, characterized in that the lipophilic part of these compounds is a sulfinyl 20 function. 2. Procedure according to. Claim 1, characterized in that the emulsifying properties exhibiting, a Compound of the formula bearing a sulfinyl function CH OR ² corresponds to where R is a hydrocarbon group and ρ
R is hydrogen or a hydrocarbon substituent, η is 2 to 20 and preferably 4 to 18 and A is a hydrophilic group such as an acid group which may be esterified or converted to a salt, a polyoxyalkylene chain, a group with a XI / 13 Deutsche Bank (Munich) Account 51/61070 Dresdner Bank (Munich) Account 3939 844 Postal check (Munich) account 670-43-804 - 2 - DE 1282 Tetravalent nitrogen cation or an amino acid moiety is. 3. The method according to claim 2, characterized in that R is an alkyl, alkenyl, aryl, alkaryl, Is aralkyl or cycloalkyl group, preferably having 1 to 20 carbon atoms. 4. The method according to claim 2 or 3, characterized ρ
characterized in that R is a hydrocarbon group which is the same as or different from R. 5. The method according to any one of claims 2 to 4, characterized in that A is an acid group of the formula -COOH, -SO ₃ ", -SO ₄ " or PO ₄ , which is free or esterified or has formed a salt. 6. The method according to claim 5, characterized in that the acid group A with a polyol, in particular with glycerol or sorbitol, is esterified. 7. The method according to claim 5, characterized in that the acid group A is a salt with an alkaline one Base, an amine or a quaternary 25 has formed ammonium. 8. The method according to any one of claims 2 to 5, characterized in that A is a cationic, nitrogen-containing Group, especially a quaternary 30 ammonium or imidazolinium group. 9. The method according to any one of claims 2 to 5, characterized in that A is a polyoxyalkylene chain, in particular a preferably 2 to 20 sour polyoxyethylene or polyoxy containing atoms - 3 - DE 1282 propylene chain. 10. The method according to any one of claims 2 to 5, characterized in that A is an amino acid group, in particular an amino acid group of the type which may be substituted on the nitrogen atom is. 11. The method according to any one of claims 1 to 10, characterized in that as emulsifying properties Compound comprising dodecylsulfinylundecanoic acid, methylsulfinylundecanoic acid or glycerol monododecylsulfinylundecanoate is used. 12. Cosmetic agent, consisting of one stable W / O emulsion ,, characterized in that it contains a compound having emulsifying properties which, according to the method according to one of the Claims 1 to 10 has been used.