Polyglycerol ethers and their use in cosmetics and in pharmacy

Mixture of compounds of general formula: ##STR1## in which R denotes a saturated C.sub.10 -C.sub.12 hydrocarbon radical, or mixture of such radicals, and n has a mean statistical value from 2 to 15, and preferably from 3 to 12. These products are very well tolerated by the skin and the mucosa, and are advantageously used in cosmetic or pharmaceutical compositions.

The invention relates to new nonionic surfactants, to the compositions 
containing them and to their use in cosmetics and in pharmacy. 
These new surfactants are of the polyglycerol alkyl ether type. They show 
excellent biological tolerability; they can thus be used in compositions 
for treating the skin and the scalp. 
The Applicant has already described, in U.S. Pat. No. 3,666,671, 
polyglycerol alkyl ethers and alkylaryl ethers of formula: 
EQU RO--C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.n H 
in which n denotes a numher less than or equal to 10 and R denotes a linear 
or branched alkyl or alkenyl radical containing from 8 to 22 carbon atoms 
or alternatively a radical having from 8 to 30 carbon atoms and derived 
from lanolin alcohols, chiefly consisting of sterols (cholesterol, 
lanosterol) and, in smaller proportions, monohydric alcohols or 
1,2-alkanediols which may be normal, iso- or anteiso-. 
These are surfactants which have, depending on the number of carbon atoms 
in the radical R, wetting, foaming, detergent or emulsifying properties. 
The subject of the present invention is new polyglycerol ethers which are 
mainly non-foaming or weakly foaming surfactants which can be used as 
emulsifiers, as dispersants, as carriers or excipients or as additives in 
cosmetic and pharmaceutical compositions. Compared with the previous 
compounds mentioned above, these compounds show a substantial improvement 
as regards their properties in solution, in particular their emulsifying 
properties and their biological properties. 
They can be represented by the following general formula (I): 
##STR2## 
in which R denotes a saturated C.sub.10 to C.sub.12 hydrocarbon radical, 
or mixture of such radicals, and n denotes a mean statistical value from 2 
to 15; R preferably denotes a decyl radical and n preferably denotes a 
mean statistical value from 3 to 12 and more especially from 3 to 8. The 
structure of the products of the invention is characterized by a 
substantial lipophilic block which contains at least 24 carbon atoms, 
combined with a portion which is more or less hydrophilic, depending on 
the number of units derived from glycerol. Despite the size of the 
lipophilic block, the products possess relatively low melting points, 
thereby avoiding the phenomena of crystallization in the compositions 
containing them. 
These products show good emulsifying, dispersant or solubilizing 
properties, as well as good compatibility with the skin and the ocular 
mucosa. They are well tolerated in solution or in aqueous, oily or 
oleo-aqueous dispersion, and they also bring about a reduction in the 
attacking properties of other ionic or nonionic surfactants. 
In effect, the compounds of formula (I), and more especially those for 
which n denotes 3 to 8, can be readily combined with surfactants such as 
foaming agents, in proportions from 5 to 50% by weight, and preferably 
from 10 to 30% by weight, of the weight of the foaming surfactants and, 
under these conditions, possess the advantage of reducing the attacking 
properties of the compositions containing them, in particular towards the 
ocular mucosa. 
The subject of the invention is consequently also a non-attacking cosmetic 
composition for the skin and the ocular mucosa, containing one or more 
foaming surfactants and 5 to 50% by weight, relative to the weight of the 
foaming surfactants, of a compound of formula (I) in which n denotes a 
mean statistical value from 3 to 8. 
The subject of the invention is also a process for reducing the attacking 
properties of foaming surfactants towards the skin or the ocular mucosa, 
characterized in that from 5 to 50% by weight, and preferably from 10 to 
30% by weight, relative to the weight of the foaming surfactants, of a 
compound of formula (I) in which n denotes a mean statistical value from 3 
to 8 is added to the foaming surfactants. 
As a result of their high chemical stability and their nonionic nature 
which enables them to be combined readily with the different constituents 
customarily used in cosmetics, the compounds of formula (I) represent very 
advantageous products for the preparation of compositions for treating the 
skin, the scalp and the hair. 
The products of formula (I) are obtained by two-stage reactions of an 
alcohol or a mixture of alcohols of formula (II): 
##STR3## 
where R has the same meaning as above, with: 
(i) an epihalohydrin as described in French Pat. No. 1,477,048 or in U.S. 
Pat. No. 3,666,671, or alternatively with 
(ii) t-butyl glycidyl ether as described in French Pat. No. 2,027,585 or in 
U.S. Pat. No. 3,840,606. 
When 1 mole of alcohol of formula (II) is reacted with n moles of glycerol 
epihalohydrin (n having the same meaning as above), the polyhalogenated 
intermediate compounds of formula: 
##STR4## 
are obtained in which X denotes a halogen such as chlorine or bromine, and 
preferably chlorine. 
During the polyaddition reaction of the epihalohydrin with the alcohol of 
formula (II), a mixture is formed of compounds all of which correspond to 
the general formula (III), but for which the number of moles of 
epihalohydrin bound can be greater than, equal to or less than the mean 
statistical value corresponding to the number of moles of epihalohydrin 
used for 1 mole of alcohol of formula (II). As a result, the formula (III) 
represents a mixture of compounds for which the set of values n is 
statistically distributed about a mean value corresponding to the number 
of moles of epihalohydrin used for 1 mole of hydroxyl compound. 
The polyaddition reaction of epihalohydrin is performed in the presence of 
a Lewis acid catalyst such as boron trifluoride, stannic chloride or 
antimony pentachloride, at a temperature of between 25.degree. and 
120.degree. C., and preferably between 60.degree. and 100.degree. C. 
The mixture of intermediate compounds of formula (III) is then 
"hydroxylated", that is to say the halogen atom X is replaced by an OH 
group, by reaction with an alkali metal salt of a carboxylic acid, and 
advantageously an alkali metal acetate, in stoichiometric proportions or 
in slight excess with respect to the halogenated compound. This reaction 
is carried out in the presence of a solvent chosen from glycols or ethers 
thereof, such as ethylene glycol, diethylene glycol or dipropylene glycol, 
at a temperature of between 150.degree. and 200.degree. C. 
When the alcohol of formula (II) is reacted with t-butyl glycidyl ether, 
the intermediate poly-t-butyloxy compounds of formula (IV): 
##STR5## 
where T denotes a t-butyl radical, are obtained. 
The reaction of the mixture of alcohols of formula (II) with t-butyl 
glycidyl ether is performed in the presence of a basic or acid catalyst. 
As basic catalysts, catalysts chosen from the group consisting of alkali 
metals, alkali metal hydroxides, alkali metal alcoholates and tertiary 
amines may be used. When an alkali metal catalyst is used, the reaction is 
performed at a temperature of 80.degree. to 180.degree. C. 
As an acid catalyst, a catalyst chosen from the group consisting of Lewis 
acids, such as: 
EQU BF.sub.3, SnCl.sub.4, SbCl.sub.5, 
may be used, at a temperature below 120.degree. C. 
The intermediate poly-t-butyloxy compounds of formula (IV) are then 
hydrolysed in the presence of water and a strong acid which is used as 
catalyst. Among acids, methanesulphonic acid, p-toluenesulphonic acid or 
sulphoacetic acid may be mentioned in particular. The hydrolysis reaction 
is performed at a temperature of 50.degree. to 120.degree. C., and 
preferably from 90.degree. to 100.degree. C. 
The hydroxylation of the intermediate compounds of formula (III), or the 
hydrolysis of the intermediate compounds of formula (IV), leads to a 
mixture of compounds of formula (I), containing a number of units derived 
from glycerol which is less than, equal to or greater than the value of n, 
which represents a mean statistical value. 
The products which form the subject of the invention consist of mixtures of 
polyglycerol ethers (I) as obtained after the hydroxylation or hydrolysis 
reactions, without separation of the different homologues, this separation 
always being tedious and expensive. 
The products of the invention generally take the form of thick liquids or 
of pastes which are soluble in oils for values of n equal to or less than 
approximately 7 and dispersible in water for values of n equal to or 
greater than approximately 5. The compounds for which n is between 5 and 7 
can be both soluble in oils and dispersible in water. 
The subject of the invention is also compositions, and especially cosmetic 
and pharmaceutical compositions, containing the mixtures of compounds of 
formula (I). These compositions can be aqueous compositions or oily 
compositions in the form of liquids, gels or waxes, or alternatively 
oleo-aqueous compositions in the form of water-in-oil or oil-in-water 
emulsion, or alternatively aqueous alcoholic solutions. The compositions 
can, in addition, take the form of aerosols. 
The aqueous or oily compositions, in liquid or gel form, are, for example, 
shampoos, make-up removal lotions for the eyes or the face, foaming oils 
for the hair or the skin, products for the bath or shower and, generally, 
toilet products. 
The compositions in wax form are sticks for application to the lips, 
designed either to colour them or to prevent chapping, or make-up products 
for the eyes, or make-up or make-up foundations for the face. 
When the compositions according to the invention take the form of a 
water-in-oil or oil-in-water emulsion, the emulsifying agent can consist 
exclusively of the compound or compounds (I) according to the invention. 
The compounds of formula (I) can also be combined with any other 
traditional emulsifier such as, for example, polyoxyethylenated fatty 
acids or fatty alcohols, polyglycerol alkyl ethers, polyoxyethylenated 
sorbitan esters, or amine or polyvalent metal salts of fatty acids. 
The fatty substances forming the fatty phase of the emulsions are oils or 
waxes. Among oils, there may be mentioned mineral oils such as liquid 
paraffin; animal oils such as whale oil, seal oil, halibut-liver oil, cod 
oil, tuna oil, tallow oil and mink oil; and vegetable oils such as almond 
oil, groundnut oil, wheatgerm oil, corn oil, olive oil, jojoba oil, sesame 
oil and sunflower oil. 
Among waxes, there may be mentioned sipol wax, lanolin wax, beeswax, 
candelilla wax, microcrystalline wax, carnauba wax, spermaceti, cocoa 
butter, shea butter, silicone waxes and hydrogenated oils which are solid 
at 25.degree. C. 
The oils or waxes can also be chosen from the esters formed by saturated or 
unsaturated C.sub.12 to C.sub.22 fatty acids with lower alcohols or 
polyols such as isopropanol, glycol or glycerol, or with saturated or 
unsaturated linear or branched C.sub.8 to C.sub.22 fatty alcohols, V or 
with C.sub.10 -C.sub.22 1,2-alkanediols. 
As fatty substances, vaseline, paraffin, lanolin, hydrogenated lanolin, 
acetylated lanolin and silicone oils may also be mentioned. 
When the compositions of the invention take the form of a solution or 
aqueous dispersion, or an emulsion, or the form of an oily composition, to 
constitute washing products or products for skin care and hair care, the 
compounds of formula (I) can be used alone or with other surfactants. The 
compounds of formula (I) can be used as emulsifiers, cleaning agents, 
dispersants, carriers or excipients, or superfatting agents, and they also 
possess the advantage of reducing the toxicity of the surfactants with 
which they are combined, in particular towards the mucosa. In this case, 
from 5 to 50% by weight of compounds of formula I, relative to the total 
weight of the surfactants, is preferably used. 
The compositions according to the invention can also be dispersions of 
lipids in water, and can take the form of dispersions of lamellar phases 
or vesicular dispersions. In these compositions, the compounds of formula 
(I) can be combined with neutral lipids such as cholesterol, or with 
charged lipids such as cholesterol sulphate, cholesterol phosphate, 
ditetradecyl phosphate or dihexadecyl phosphate, in acid form or in the 
form of sodium or potassium salt. 
The compounds according to the invention can contain amounts of products of 
formula (I) between 0.1 and 80% by weight, and more generally from 0.5 to 
25% by weight. 
In the compositions according to the invention, the products or mixtures of 
compounds (I) can be combined with other surfactants, with ionic or 
nonionic lipids, with ionic or nonionic natural or synthetic polymers, 
with oils or waxes, with proteins hydrolysed to a greater or lesser 
extent, with thickeners, with pearlescent agents, with emollients, with 
colourings, with reducing or oxidizing agents, with preservatives, with 
perfumes, with inorganic or organic acids or bases, with pigments, with 
solvents, with propellants or with pharmaceutical or parapharmaceutical 
active products. 
The subject of the invention is also a process for treating the skin, the 
scalp or the hair with a composition containing a mixture of compounds of 
formula (I).

Other subjects of the invention will emerge on reading the examples. 
EXAMPLE 1 
Preparation of a mixture of compounds of general formula (I) in which: 
R denotes a decyl radical and 
n the mean statistical value 3. 
To 354 g (1 mole) of 2-decyltetradecanol, sold under the name "Isofol 24" 
by Condea, 1.6 ml of BF.sub.3 etherate is added, followed, at 
50.degree./55.degree. C. in the course of 1 hour 40 minutes, by 277.5 g (3 
moles) of epichlorohydrin. 
The mixture is then left for approximately 15 minutes with stirring at the 
same temperature. 
A brown viscous liquid is thereby obtained. 
630 g of dipropylene glycol (DPG), 297 g (3.03 mole of potassium acetate 
and 1.3 g of sodium hypophosphite are added to 631.5 g of polychlorinated 
derivatives (3 equivalents of chlorine) thereby obtained. The reaction 
mixture is then heated to 180.degree. C. for 5 hours. 
The extent of reaction, determined by assaying the unreacted potassium 
acetate or the amount of inorganic chlorine formed, is greater than 96%. 
The inorganic salts are separated by filtration and rinsed with 100 ml of 
DPG. The solvent is removed by heating under reduced pressure. The residue 
is then taken up with 600 ml of absolute ethanol in the presence of sodium 
methylate (30 meq). 
After 24 hours at room temperature, the precipitated mineral salts are 
filtered off and the solvents evaporated off under reduced pressure. 
A viscous, amber coloured liquid product, which is insoluble in water and 
soluble in liquid paraffin, is thereby obtained. 
The cloud point, measured at 5% in an aqueous solution containing 25% of 
diethylene glycol butyl ether (DGB) is 70.degree. C. 
EXAMPLE 2 
Preparation of a mixture of compounds of general formula (I) in which: 
R denotes a decyl radical and 
n the mean statistical value 5. 
To 70.8 g (0.2 mole) of 2-decyltetradecanol, 0.4 ml of BF.sub.3 etherate is 
added, followed, at 50.degree./55.degree. C. in the course of 1 hour 15 
minutes, by 92.5 g (1 mole) of epichlorohydrin. 
After 30 minutes stirring at 50.degree. C., it is verified by assay that 
all the epoxide has reacted. 
The mixture of polychlorinated derivatives thereby obtained is taken up in 
163 g of diethylene glycol (DEG). 84.5 g of sodium acetate (1.03 mole) are 
then added, and the mixture is then heated to 180.degree.-185.degree. C. 
under an atmosphere of nitrogen for 4 hours. The inorganic salts are 
filtered off and the DEG distilled off under reduced pressure. The 
residual mass is taken up with 140 g of absolute ethanol in the presence 
of sodium methylate (7 meq). 
After the mixture has been left standing overnight at room temperature, a 
slight precipitate is separated by filtration and the solvents are 
distilled off under reduced pressure. 
A brown product, which takes the form of a soft paste which is soluble in 
liquid paraffin, is thereby obtained. 
The cloud point, at 5% in an aqueous solution containing 25% of DGB, is 
90.degree. C. 
EXAMPLE 3 
Preparation of a mixture of compounds of general formula (I) in which: 
R denotes a decyl radical and 
n the mean statistical value 8. 
To 265.5 g (0.75 mole) of 2-decyltetradecanol, 2 ml of BF.sub.3 etherate 
are added, followed, in the course of 2 hours 20 minutes at 55.degree. C., 
by 555 g (6 moles) of epichlorohydrin. 
When all the epoxide has reacted, the reaction mass is taken up with 820 g 
of DEG. 497 g (6.06 mole) of sodium acetate and 1.6 g of sodium 
hypophosphite are added, and the mixture is then heated under an 
atmosphere of nitrogen to 180.degree. C. for 5 hours. The inorganic salts 
are then filtered off, and then rinsed with DEG. The solvent is driven off 
under reduced pressure. 
The residue, taken up in 700 g of absolute ethanol in the presence of 6.3 g 
of a methanolic solution of sodium methylate (36 meq), is left overnight 
at room temperature. 
After the precipitate has been filtered off and the solvents have been 
distilled off, a soft, amber coloured paste, which is dispersible in 
water, is obtained. 
The cloud point in DGB is above 100.degree. C. 
EXAMPLE 4 
Preparation of a mixture of compounds of general formula (I) in which: 
R denotes a decyl radical and 
n the mean statistical value 12. 
To 17.7 g of 2-decyltetradecanol (0.05 mole), 0.25 ml of SnCl.sub.4 are 
added followed, dropwise at 60.degree. C. in the course of 2 hours 10 
minutes, by 55.5 g of epichlorohydrin (0.6 mole). 
After the mixture is cooled, a very pale coloured viscous liquid is 
obtained. 
The mixture of polychlorinated derivatives is washed at 95.degree. C. with 
75 g of a 20% strength aqueous solution of Na.sub.2 CO.sub.3. 
After decantation and drying, 61 g of the residue thereby obtained (0.5 
equivalents of chlorine) are taken up with 60 g of DEG. 41 g of sodium 
acetate (0.5 mole) and 0.12 g of sodium hypophosphite are added and the 
mixture is heated under an atmosphere of nitrogen to 180.degree. C. for 4 
hours 30 minutes. 
The extent of reaction is then 98%. 
After the inorganic solvents have been filtered off and the solvents 
distilled off under reduced pressure, and ethanolysis, as in the above 
examples, a brown paste is obtained which is almost soluble in water, with 
thickening. 
APPLICATION EXAMPLES 
Example A1 
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Oxidation dyeing composition for the hair 
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Mixture of compounds prepared according to 
10 g 
Example 1 
Mixture of compounds prepared according to 
5 g 
Example 3 
Coconut fatty acid diethanolamides 
13 g 
Ethyl alcohol 5 g 
Propylene glycol 12 g 
Ethylenediaminetetraacetic acid 
0.2 g 
2-Butoxyethanol 6 g 
20% Strength ammonia solution 
10 g 
Resorcinol 0.6 g 
m-Aminophenol 0.22 g 
p-Aminophenol 0.23 g 
Ammonium thiolactate 0.80 g 
Water q.s. 100 g 
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This composition is mixed at the time of use with an equal volume of 6% 
strength hydrogen peroxide. A transparent gel is obtained which is applied 
on grey hair for 30 minutes. 
After rinsing and washing, the hair is dyed an iridescent blonde. The hair 
is shiny and has body. 
Example A2 
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Composition for bleaching the hair 
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Mixture of compounds prepared according to 
12 g 
Example 1 
Mixture of compounds prepared according to 
6 g 
Example 3 
Coconut fatty acid diethanolamides 
11 g 
Ethyl alcohol 4.5 g 
Propylene glycol 12.5 g 
2-Butoxyethanol 6 g 
Ethylenediaminetetraacetic acid 
0.2 g 
20% Strength ammonia solution 
12 g 
Water q.s. 100 g 
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This composition is mixed with an equal volume of 6% strength hydrogen 
peroxide to form a gel, and is applied on chestnut coloured hair for 40 
minutes. 
After rinsing and shampooing, the hair is bleached blonde. The hair is 
lively, shiny and has body. 
Example B1 
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Demulcent cream for the face: Water-in-oil 
emulsion 
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Mixture of compounds of Example 1 
11 g 
Paraffin oil 10.7 g 
Volatile silicone oil 10.7 g 
Modified hectorite sold under the name 
5 g 
MYGLYOL GEL by DYNAMIT NOBEL 
Magnesium sulphate 2 g 
Glycerin 3 g 
Water q.s. 100 g 
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Example B2 
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Skin cream: Oil-in-water emulsion 
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Mixture of compounds of Example 3 
10 g 
Paraffin oil 40 g 
Water q.s. 100 g 
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Example C 
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Oil for the body, to be rinsed 
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Mixture of compounds of Example 2 
15 g 
Coconut fatty acid diethanolamides 
8.75 g 
Polyethoxylated C.sub.12 -C.sub.14 alcohols containing 
8.75 g 
2.2 ethoxy units 
Cationic surfactant of formula: 
2.5 g 
##STR6## 
R = mixture of unsaturated C.sub.16 -C.sub.18 radicals, 
sold under the name EMPIGEN FKH by MARCHON 
Liquid paraffin 25 g 
Antioxidants 0.1 g 
Propyl p-hydroxybenzoate 0.2 g 
Rapeseed oil q.s. 100 g 
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This oil is used for washing the skin. 
After rinsing, the skin is smooth. 
Example D 
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Shampoo 
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Mixture of compounds of Example 2 
3 g 
Polyglycerol alkyl ethers (containing 10 to 
10 g 
12 carbon atoms in the alkyl portion and 4 
units derived from glycerol) 
Copolymer of dimethyldiallylammonium chloride 
7.5 g 
and acrylamide, sold containing 8% AS (active 
substance) by 
MERCK under the name MERQUAT 550 
Perfume, colouring, preservative q.s. 
Water q.s. 100 g 
The pH is adjusted to 7. 
______________________________________ 
When applied on soiled hair, this composition develops a gentle and creamy 
foam which is easily rinsed. The wet hair is soft and easy to disentangle. 
The dry hair is shiny and soft. 
Example E 
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Body milk 
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Polyoxyethylene/polydodecyl glycol copolymer 
2.5 g 
sold under the name "ELFACOS ST9" by AKZO 
Mixture of compounds of Example 1 
2.5 g 
Hectorite modified with dimethyldistearyl- 
1.0 g 
ammonium chloride, sold under the name 
"BENTONE 38" by NL INDUSTRIES 
Volatile silicone 8.0 g 
Cetyl/stearyl ethylhexanoate having 
6.0 g 
low freezing point (of the palmiped 
feather grease type), sold under the name 
"PUR-CELLIN OIL" 
Sunflower oil 6.0 g 
Preservatives 0.35 g 
Glycerin 5.0 g 
Demineralized water q.s. 100 g 
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Example F 
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Night care cream for dry skin 
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Polyoxyethylene/polydodecyl glycol copolymer 
2.5 g 
sold under the name "ELFACOS ST9" by AKZO 
Mixture of compounds of Example 1 
2.5 g 
Dodecanediol/polyethylene glycol (45) 
0.8 g 
ether sold under the name "ELFACOS C 26" 
by AKZO 
Hectorite modified with dimethyldistearyl- 
1.0 g 
ammonium chloride, sold under the name 
"BENTONE 38" by NL INDUSTRIES 
White vaseline 6.0 g 
Grape pip oil 6.0 g 
Vitamin F 2.0 g 
Light liquid paraffin 6.0 g 
Preservatives 0.2 g 
Glycerin 5.0 g 
Demineralized water q.s. 100 g 
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Example G 
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Washing oil 
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Mixture of compounds of Example 2 
3.0 g 
Mixture of monoisopropanolamine lauryl 
30 g 
ether sulphate and coconut diethanolamides, 
sold under the name "TEXAPON WW99" by 
HENKEL 
Liquid paraffin 25 g 
Colouring, perfume, preservative q.s. 
Rapeseed oil q.s. 100 g 
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Example H 
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Fluid milk for the face 
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Mixture of compounds of Example 3 
3.1 g 
Cholesterol 1.65 g 
Dicetyl phosphate (acid) 0.25 g 
Water q.s. 100 g 
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