Oil-in-water emulsion and emulsifying or solubilizing agent composition useful therein

An emulsifying or solubilizing agent composition comprising 58 to 95% by weight of a polyoxyethylene (10 to 100) sorbitol branched saturated fatty acid (C.sub.11 to C.sub.21) ester having from 3 to 6 ester groups in the molecule, 0.5 to 2.5% by weight of an alkali metal salt of a linear or branched fatty acid (C.sub.11 to C.sub.21), 2.5 to 6.0% by weight of a linear or branched fatty acid (C.sub.11 to C.sub.23) and 2 to 35% by weight of a branched saturated fatty acid ester of polyethylene glycol having an average molecular weight of from 150 to 2000.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to an emulsifying or solubilizing composition 
which is capable of emulsifying or solubilizing liquid vegetable oils and 
highly polar synthetic ester oils which have heretofore been considered to 
be very difficult to emulsify or solubilize. The composition possesses 
excellent color and smell and excellent stability against 
photo-discoloration and decomposition. 
2. Description of the Prior Art 
As emulsifiers for cosmetics, there have heretofore been used non-ionic 
surface active agents such as polyoxyethylene sorbitan fatty acid esters, 
sorbitan fatty acid esters, glycerol fatty acid esters, polyethylene 
glycol fatty acid esters and polyoxyethylene alkyl ethers, and in 
addition, a great number of other non-ionic, anionic, cationic and 
amphoteric surface active agents. These emulsifiers, in general, have a 
good emulsifying power to mineral oils composed of hydrocarbons and the 
like and animal oils such as squalane and they provide stable emulsions of 
these oils. However, they scarcely emulsify liquid vegetable oils 
(hereinafter referred to as "vegetable oils") composed of triglycerides 
rich in alkyl groups having an unsaturated bond, such as camellia oil and 
olive oil, and esters (hereinafter referred to "synthetic esters") having 
at least one branched alkyl group, which are derived from branched or 
linear higher fatty acids and branched or linear higher alcohols, and 
stable emulsions of these oils cannot be obtained. 
We previously discovered an emulsifying or solubilizing agent composition 
having a high emulsifying or solubilizing property to vegetable oils and 
synthetic ester oils. That composition was formed by mixing in specific 
weight ratios, an alkali metal salt of a fatty acid, a fatty acid and a 
polyethylene glycol unsaturated fatty acid ester-type surface active agent 
into a polyoxyethylene sorbitol unsaturated fatty acid ester-type surface 
active agent, (see the specification of Japanese patent application No. 
91086/74, corresponding to U.S. Pat. No. 3,954,658). 
That composition is satisfactory in its emulsifying and solubilizing 
properties, but it is defective in that it becomes colored or generates 
unwanted odors under some storage conditions and it is readily discolored 
when it is exposed to sun-light. This defect is serious when the 
composition is used for emulsifying cosmetics and the like. 
SUMMARY OF THE INVENTION 
We have discovered an improved emulsifying or solubilizing composition 
which possesses excellent emulsifying and solubilizing properties and 
which possesses, surprisingly, reduced tendency toward coloration and 
generation of bad odors. 
More specifically, in accordance with the present invention, there is 
provided an emulsifying or solubilizing composition comprising 
I. from 58 to 95% by weight of a surface active agent of the 
polyoxyethylene sorbitol branched saturated fatty acid ester-type 
(hereinafter referred to as "component (I)") having the formula (A): 
##STR1## 
wherein the value of n.sub.1 + n.sub.2 + n.sub.3 + n.sub.4 + n.sub.5 + 
n.sub.6 is in the range of 10 to 100, and wherein from 3 to 6 of the total 
number of X's (i.e., 6) on the average of the mixture are branched 
saturated acyl (RCO-) groups having 11 to 21 carbon atoms (R is branched 
alkyl having 10 to 20 carbon atoms), the rest of the X's being hydrogen, 
Ii. from 0.5 to 2.5% by weight of an alkali metal salt of a linear or 
branched fatty acid having 11 to 21 carbon atoms (hereinafter referred to 
as "component (II)"), 
Iii. from 2.5 to 6.0% by weight of a linear or branched fatty acid having 
11 to 23 carbon atoms (hereinafter referred to as "component (III)"), and 
Iv. from 2 to 35% by weight of a branched saturated fatty acid ester of a 
polyethylene glycol having an average molecular weight of 150 to 2000 
wherein the branched saturated fatty acid moiety has from 11 to 21 carbon 
atoms (hereinafter referred to as "component (IV)"). 
When the above composition is used as an emulsifying or solubilizing agent, 
vegetable oils and highly polar oils synthesized as emollient oils, which 
have heretofore been considered difficult to emulsify, can easily be 
emulsified or solubilized, and ideal emulsions having a good color with a 
reduced odor can be obtained. 
As the vegetable oil to be emulsified or solubilized, there can be 
mentioned liquid vegetable oils composed of triglycerides rich in 
unsaturated alkyl groups, such as camellia oil, olive oil, safflower oil, 
rapeseed oil, palm oil and cotton seed oil, and as the synthetic ester 
oil, there can be mentioned esters having at least one branched alkyl 
group, which are derived from branched or linear higher fatty acids and 
branched or linear higher alcohols, such as 2-heptylundecyl isostearate, 
glycerol tri-2-ethylhexanoate, hexadecyl 2-ethyl-hexanoate, hexadecyl 
isostearate and hexadecyl isotridecanoate. These vegetable oils and 
synthetic ester oils are widely used in cosmetics. By using the 
composition of the present invention, it is possible for the first time to 
employ these oils, in the emulsified or solubilized state, in cosmetics. 
Namely, it is possible to incorporate these vegetable oils or synthetic 
ester oils into various cosmetic creams such as sun creams and hair creams 
and other cosmetics such as lotions. By incorporation of these oils, 
emulsified or solubilized by the composition of the present invention, it 
is possible to obtain milder cosmetics having a higher emollient effect 
than conventional cosmetics composed mainly of mineral oils. Of course, 
the composition of the present invention also has an excellent emulsifying 
power for mineral oils and animal oils, that can also be emulsified by 
conventional emulsifiers, as well as the above-mentioned vegetable oils 
and synthetic ester oils. 
The polyoxyethylene sorbitol branched saturated fatty acid ester (I) that 
is used in the present invention is, as is seen from the formula (A), an 
ester formed by esterifying an ethylene oxide adduct of sorbitol with a 
branched saturated fatty acid having 11 to 21 carbon atoms, such as 
isostearic acid or isotridecanoic acid. It is necessary that among the 
total of the 6 hydroxyl groups of sorbitol, from 3 to 6 of them, on the 
average, of the mixture should be esterified. More specifically, in the 
general formula (A), 3 to 6 of the 6 X's are acyl groups, the rest being 
hydrogen. (In the description given hereinafter, the number of such acyl 
groups will be called "the degree of esterification"). If the degree of 
esterification is lower than in the above range i.e. from 3 to 6, the 
emulsifying property is diminished and a good and stable emulsion cannot 
be obtained. 
As the fatty acid employed for the above esterification, there are 
preferably employed branched saturated fatty acids having 11 to 21 carbon 
atoms, such as isostearic acid, isotridecanoic acid and isoundecanoic 
acid. When a linear saturated fatty acid such as stearic acid or palmitic 
acid is used instead of the specified branched acids, the emulsifying 
property is diminished, and the resulting ester is solid at room 
temperature and hence, good results cannot be obtained. When a linear 
unsaturated fatty acid such as oleic acid or linoleic acid is used, a 
sufficient emulsifying or solubilizing property can be attained, but the 
resulting ester is inferior to an ester derived from a liquid branched 
saturated fatty acid, according to the invention, with respect to its 
chemical stability (the resistance to changes with the passage of time), 
smell, color and resistance to discoloration. 
The above ester is prepared by conventional procedures by adding sorbitol 
to a solvent such as xylene, adding ethylene oxide to sorbitol in the 
presence of a basic catalyst to effect the addition reaction, adding a 
branched saturated fatty acid in an amount of 3 to 6 moles per mole of the 
ethylene oxide adduct of sorbitol, heating the mixture at 180.degree. to 
240.degree. C. to effect the esterification reaction, and then 
decolorizing and purifying the resulting ester. 
It is necessary that the composition of the present invention comprises 58 
to 95% by weight of the component (I), 0.2 to 2.5% by weight of the 
component (II), 2.5 to 6.0% by weight of the component (III) and 2 to 35% 
by weight of the component (IV). If this requirement is not satisfied, the 
emulsifying property to vegetable oils and synthetic ester oils is 
diminished and the resulting emulsion is so poor in the stability that 
when it is allowed to stand, the emulsion is destroyed in a short time and 
phase separation takes place. 
In view of the properties of the oils which are to be emulsified or 
solubilized by the emulsifying or solubilizing composition of the present 
invention, the composition of the invention is utilized most effectively 
in the field of cosmetics. Of course, the composition of the present 
invention can also be used as an emulsifying or solubilizing agent in any 
fields where the foregoing oils are used, for example, in the fields of 
foods, fiber oiling agents, detergents, metal processing oils and the 
like. 
The features of the present invention will now be described in greater 
detail by reference to the following illustrative Examples: In the 
Examples all references to "%" are by weight unless otherwise indicated.

EXAMPLE 1 
Emulsifying agent compositions containing the ingredients indicated below 
were prepared and emulsifying tests were made on various oils by using 
these compositions. 
______________________________________ 
Composition (%) 
Ingredients Emulsifier (a) 
Emulsifier (b) 
______________________________________ 
Component (I)* 70 70 
Component (II) (sodium) 
isostearate) 1.2 1.2 
Component (III) (isoste- 
aric acid) 5.0 5.0 
Component (IV) (poly- 
ethylene glycol isoste- 
arate having an average 
molecular weight of 600) 
23.8 23.8 
______________________________________ 
*: In the component (I) of the emulsifier (a) the average total mole 
number of added ethylene oxide units was 30, and in the component (I) of 
the emulsifier (b) the total mole number of added ethylene oxide units wa 
60. Esterification was performed with isostearic acid. In each of the 
emulsifiers (a) and (b), 7 samples differing in the degree of 
esterification from 0 to 6 were tested. 
TEST METHOD 
A mixture of 20 parts (by weight; the same shall apply hereinafter) of an 
oil component, 5 parts of the emulsifying composition and 75 parts of 
deionized water were emulsified at a temperature of 70.degree. C., using 
an agitation vane rotating at 600 rpm, according to the phase inversion 
emulsification method. The emulsifiability and stability of the resulting 
emulsion were evaluated according to the following standards: 
(1) Emulsifiability: 
The state of the as-emulsified emulsion was observed with the naked eye and 
by a microscope and the emulsifiability was evaluated according to the 
following standards: 
A: bluish white emulsion of fine particles having an average particle size 
smaller than 1.mu. as measured under a microscope 
B: milky white emulsion of particles having an average particle size of 1 
to 5.mu. as measured under a microscope 
C: opaque emulsion of crude particles having an average particle size 
larger than 5.mu. as measured under a microscope 
(2) Stability: 
The emulsion formed was allowed to stand still at 25.degree. C. for 7 days, 
and the state of the emulsion was examined. The stability was evaluated 
according to the following standards: 
(-): homogeneous, no phase separation found 
(+): slight formation of an oil phase by coalescence or an aqueous phase by 
separation of water was observed 
(++): oil phase formed by coalescence or aqueous phase formed by separation 
of water was clearly observed 
(+++): both oil phase formed by coalescence and aqueous phase formed by 
separation of water were clearly observed 
The test results are shown in Table 1. 
Table 1 
__________________________________________________________________________ 
Emulsifying Degree of Estrification of Component (I) 
Agent Com- 
Oil Emul- (number of acyl groups in formula (A)) 
position sified 0 1 2 3 4 5 6 
__________________________________________________________________________ 
olive oil 
emulsifiabi- 
C B B A A A B 
lity 
stability 
(+++) 
(+++) 
(+++) 
(+) (-) 
(-) 
(++) 
(a) glycerol tri- 
emulsifiabi- 
C C B A A A B 
2-ethylhexa- 
lity 
noate stability 
(+++) 
(+++) 
(+++) 
(-) (-) 
(+) 
(++) 
hexadecyl-2- 
emulsifiabi- 
C C C B A A A 
ethylhexanoate 
lity 
stability 
(+++) 
(+++) 
(+++) 
(+) (-) 
(-) 
(-) 
olive oil 
emulsifiabi- 
C C B A A A B 
lity 
stability 
(+++) 
(+++) 
(+++) 
(++) 
(-) 
(-) 
(-) 
(b) glycerol tri- 
emulsifiabi- 
C B A A A A A 
2-ethylhexa- 
lity 
noate stability 
(+++) 
(+++) 
(++) (-) (-) 
(-) 
(-) 
hexadecyl-2- 
emulsifiabi- 
C C C B A A 
ethylhexanoate 
lity A 
stability 
(+++) 
(+++) 
(+++) 
(++) 
(-) 
(-) 
(-) 
__________________________________________________________________________ 
From the results shown in Table 1, it will be understood that the 
compositions of the present invention, in which the average degree of 
esterification (the number of acyl groups as X in the general formula (A)) 
in the component (I) is in the range of from 3 to 6, have an excellent 
emulsifying property and form emulsions, having good stability, whereas 
when a component (I) having a degree of esterification not higher than 2 
is employed, the emulsifying property is bad, and the stability of the 
resulting emulsion is low and phase separation takes place. 
EXAMPLE 2 (Emulsification Of Olive Oil) 
An emulsifying test for olive oil was carried out using various emulsifying 
compositions as listed in Table 2. In each run, an emulsion was prepared 
from 20 parts of olive oil, 5 parts of the emulsifier composition and 75 
parts of deionized water. The test and evaluation methods were the same as 
described in Example 1. The results obtained are shown in Table 2. 
Table 2 
__________________________________________________________________________ 
Type of Emulsifier Emulsifier 
Component I Composition 
Product.sup.1) of 
POE sorbitol branched 
n.sub.1 + n.sub.2 + n.sub.3 
Ratio (% by weight) 
Present fatty acid ester type 
+ n.sub.4 + n.sub.5 + 
(I) (II) (III) (IV) 
Invention n.sub.6 
10 73.5 1.0 4.8 20.7 
30 85.0 1.2 5.0 8.8 
40 90.0 0.8 4.4 4.8 
60 70.0 1.2 5.0 23.8 
Comparative 30 70.0 0 4.5 25.5 
Product (1).sup.2) 
" 30 69.8 0.3 0 29.9 
30 40.2 0.7 4.2 54.9 
60 70.0 0 3.8 26.2 
Comparative 
POE sorbitol linear 
30 64.5 1.0 3.5 31.0 
Product (2).sup.3) 
unsaturated fatty 
40 63.0 1.0 3.5 32.5 
acid ester type 
Comparative 
POE sorbitan ester/ 
POE sorbitan mono-oleate/sorbitan mono-oleate** 
Product (3) 
sorbitan ester type 
POE sorbitan trioleate 
Comparative 
POE fatty acid ester/ 
POE (8) stearate/glycerol monostearate 
Product (4) 
glycerin ester type 
POE (50) stearate/glycerol monostearate 
Comparative 
POE alkyl ether type 
POE (5) oleyl ether 
Product (5) POE (7) cetyl ether 
POE (9) oleyl ether 
Comparative 
polymer type polyoxyethylene-polyoxypropylene condensate 
Product (6) 
Comparative 
soap type sodium oleate 
Product (7) potassium oleate 
__________________________________________________________________________ 
Emulsifi- Stability 
Product.sup.1) 1) of ability (after stand- 
Present HLB Emulsion type 
(just after pre- 
ing at 25.degree. C 
Invention 
##STR2## (o/w or w/o) 
paration) for 7 
__________________________________________________________________________ 
days) 
7.8 o/w A (-) 
10.1 o/w A (-) 
11.7 o/w A (-) 
12.0 o/w AB (+++) 
Comparative 10.3 o/w C (+++) 
Product(1).sup.2) 
10.3 o/w C (++) 
10.1 o/w B (++) 
13.8 o/w C (+++) 
Comparative 10.4 o/w A (-) 
Product(2).sup.3) 
11.8 o/w A (-) 
Comparative 8.0 o/w C (+++) 
Product(3) 10.0 o/w C (+++) 
12.0 o/w C (+++) 
11.0 o/w B (+) 
Comparative 8.0 o/w C (-)* 
Product(4) 10.0 o/w C (-)* 
12.0 o/w C (-)* 
Comparative 8.8 o/w C (+++) 
Product(5) 10.7 o/w C (+++) 
12.1 o/w C (+++) 
Comparative -- o/w C (+++) 
Product(6) 
Comparative -- o/w B (+++) 
Product(7) -- o/w B (+++) 
__________________________________________________________________________ 
*Since the viscosity of the emulsion was extremely high, phase separation 
was not caused in spite of low emulsifiability. 
** POE(n); n denotes the mole number of added ethylene oxide units. 
Note.sup.1) The constituents of the product of the present invention were 
as follows: 
Average Degree Average Mole- 
n.sub.1 +n.sub.2 + n.sub.3 
of Esterifica- cular Weight 
+n.sub.4 +n.sub.5 +n.sub.6 
Component (I) 
tion of (I) 
Component (II) 
Component (IV) 
of PEG of (IV) 
__________________________________________________________________________ 
10 POE sorbitol 
3.0 sodium iso- 
isotridecanoic 
polyethylene 
150 
isotridecanoate tridecanoate 
acid glycol 
isotridecanoate 
30 POE sorbitol 
4.0 sodium iso- 
isostearic 
polyethylene 
450 
isostearate stearate acid glycol iso- 
stearate 
40 " 4.5 " " " 600 
60 " 5.5 sodium stea- 
" " 900 
rate 
80 " 6.0 sodium iso- 
" " 1200 
stearate 
100 " 6.0 " " " 1600 
__________________________________________________________________________ 
Note .sup.2) The constituents of the comparative product (1) were as 
follows: 
Average Degree Average Mole- 
n.sub.1 +n.sub.2 +n.sub.3 
of Esterifica- cular Weight 
+n.sub.4 +n.sub.5 +n.sub.6 
Component (I) 
tion of (I) 
Component (II) 
Component (III) 
Component (IV) 
of PEG of 
__________________________________________________________________________ 
(IV) 
30 POE sorbitol 
3.0 sodium iso- 
isostearic 
polyethylene 
450 
isostearate stearate acid glycol iso- 
stearate 
30 " 4.0 " " " 450 
30 " 4.0 " " " 450 
60 " 5.5 " " " 900 
__________________________________________________________________________ 
Note .sup.3) The constituents of the comparative product (2) were as 
follows: 
Average Degree Average Mole- 
n.sub. 1 +n.sub.2 +n.sub.3 
of Esterifica- cular Weight 
+n.sub.4 +n.sub.5 +n.sub.6 
Component (I) 
tion of (I) 
Component (II) 
Component (III) 
Component (IV) 
of PEG of 
__________________________________________________________________________ 
(IV) 
30 POE sorbitol 
4.5 sodium oleic acid 
polyethylene 
450 
oleate oleate glycol oleate 
40 " 4.5 " " " 600 
__________________________________________________________________________ 
The constituents of the product.sup.1) of the present invention, 
comparative product (1).sup.2) and comparative product (2).sup.3) in the 
following Tables 3 and 4 are the same as set forth above. 
EXAMPLE 3 (Emulsification of 2-Heptylundecyl Isostearate) 
A mixture of 20 parts of a synthetic ester oil obtained by esterification 
of 2-heptylundecanol with isostearic acid, 5 parts of an emulsifier 
composition and 75 parts of deionized water was emulsified and tested in 
the same manner as described in Example 2. The results obtained are shown 
in Table 3. 
Table 3 
__________________________________________________________________________ 
(Emulsification of 2-Heptylundecyl Isostearate) 
Type of Emulsifier 
Product .sup.1) of 
Component I Emulsifier Compositon 
Present POE sorbitol branched 
n.sub.1 + n.sub.2 + n.sub.3 
Ratio (% by weight) 
Invention 
fatty acid ester type 
+ n.sub.4 + n.sub.5 + n.sub.6 
(I) (II) (III) (IV) 
10 73.5 1.0 4.8 20.7 
30 85.0 1.2 5.0 8.8 
40 90.0 0.8 4.4 4.8 
60 70.0 1.2 5.0 23.8 
80 64.5 1.5 4.5 29.5 
100 63.0 1.0 4.5 31.5 
Comparative 
" 30 70.0 0 4.5 25.5 
Product (1).sup.2) 30 69.8 0.3 0 29.9 
30 40.2 0.7 4.2 54.9 
60 70.0 0 3.8 26.2 
Comparative 
POE sorbitol linear 
30 64.5 1.0 3.5 31.0 
Product (2).sup.3) 
unsaturated fatty acid 
40 63.0 1.0 3.5 32.5 
ester type 
Comparative 
POE sorbitan ester/ 
POE (20) sorbitan mono-oleate/sorbitan 
mono-oleate** 
Product (3) 
sorbitan ester type 
POE (20) sorbitan trioleate 
Comparative 
POE fatty acid ester/ 
POE (8) stearate/glycerol monostearate 
Product (4) 
glycerin ester type 
POE (50) stearate/glycerol monostearate 
Comparative 
POE alkyl ether type 
POE (5) oleyl ether 
Product (5) POE (7) cetyl ether 
POE (9) oleyl ether 
Comparative 
polymer type polyoxyethylene-polyoxypropylene condensate 
Product (6) 
Comparative 
soap type sodium oleate 
Product (7) potassium oleate 
__________________________________________________________________________ 
Emulsion Stability 
Product.sup.1) of Type Emulsifiability 
(after stand- 
Present HLB (o/w or (just after ing at 25.degree. C 
Invention 
##STR3## w/o) preparation) for 7 
__________________________________________________________________________ 
days) 
7.8 o/w B (+) 
10.1 o/w A (-) 
11.7 o/w A (-) 
12.0 o/w A (-) 
13.3 o/w A (-) 
14.3 o/w B (+++) 
Comparative 10.3 o/w C (+++ 
Product (1).sup.2) 
10.3 o/w B (+++) 
10.1 o/w B (+++) 
13.8 o/w C (+++) 
Comparative 10.4 o/w A (-) 
Product (2).sup.3) 
11.8 o/w A (- 
Comparative 8.0 o/w C (+++) 
Product (3) 10.0 o/w A (++) 
12.0 o/w C (+++) 
11.0 o/w B (+++) 
Comparative 8.0 o/w C (-)* 
Product (4) 10.0 o/w C (-)* 
12.0 o/w C (++) 
Comparative 8.8 o/w C (+++) 
Product (5) 10.7 o/w C (+++) 
12.1 o/w C (+++) 
Comparative -- o/w C (+++) 
Product (6) 
Comparative -- o/w C (+++) 
Product (7) -- o/w C (+++) 
__________________________________________________________________________ 
*Since the viscosity of the emulsion was extremely high, no phase 
separation was observed in spite of low emulsifiability. 
**POE(n): n indicates the mole number of added ethylene oxide. 
EXAMPLE 4 (Emulsification of Glycerol Tri-2-ethylhexanoate) 
A mixture of 20 parts of a synthetic ester oil (glycerol 
tri-2-ethylhexanoate), 5 parts of an emulsifier composition and 75 parts 
of deionized water were emulsified and tested in the same manner as 
described in Example 2. The results obtained are shown in Table 4. 
Table 2 
__________________________________________________________________________ 
(Emulsification of Glycerol Tri-2-ethylhexanoate) 
Type of Emulsifier 
Component I Emulsifier Compositon 
Product.sup.1) 
POE sorbitol branched 
n.sub.1 + n.sub.2 + n.sub.3 
Ratio (% by weight) 
Invention 
fatty acid ester type 
+ n.sub.4 + n.sub.5 + n.sub.6 
(I) (II) (III) (IV) 
10 7.35 1.0 4.8 2.7 
30 85.0 1.2 5.0 8.8 
40 90.0 0.8 4.4 4.8 
60 70.0 1.2 5.0 23.8 
80 64.5 1.5 4.5 2.5 
100 63.0 1.0 4.5 31.5 
Comparative 
" 30 70.0 0 4.5 25.5 
Product (1).sup.2) 30 69.8 0.3 0 2.9 
30 40.2 0.7 4.2 54.9 
60 70.0 0 3.8 26.2 
Comparative 
POE sorbitol linear 
30 64.5 1.0 3.5 31.0 
Product (2).sup.3) 
unsaturated fatty acid 
40 63.0 1.0 3.5 32.5 
ester type 
Comparative 
POE sorbitan ester/ 
POE(20) sorbitan mono-oleate/sorbitan 
mono-oleate** 
Product (3) 
sorbitan ester type 
POE(20) sorbitan troleate 
Comparative 
POE fatty acid ester/ 
POE(8) stearate/glycerol monostearate 
Product (4) 
glycerin ester type 
POE(50) stearate/glycerol monostearate 
Comparative 
POE alkyl ether type 
POE(5) oleyl ether 
Product (5) POE(7) cetyl ether 
POE(9) oleyl ether 
Comparative 
polymer type polyoxyethylene-polyoxypropylene condensate 
Product (6) 
Comparative 
soap type sodium oleate 
Product (7) potassium oleate 
__________________________________________________________________________ 
Emulsion Stability 
Product.sup.1) of Type Emulsifiability 
(after stand- 
Present HLB (o/w or (just after ing at 25.degree. C 
Invention 
##STR4## w/o) preparation for 7 
__________________________________________________________________________ 
days) 
7.8 o/w A (-) 
10.1 o/w A (-) 
11.7 o/w A (-) 
12.0 o/w A (-) 
13.3 o/w A (-) 
14.3 o/w A (-) 
Comparative 10.3 o/w C (+++) 
Product (1).sup.2) 
10.3 o/w B (+++) 
10.1 o/w A (+) 
13.8 o/w C (+++) 
Comparative 10.4 o/w A (-) 
Product (2).sup.3) 
11.8 o/w A (-) 
Comparative 8.0 o/w A (+) 
Product (3) 10.0 o/w C (++) 
12.0 o/w C (+++) 
11.0 o/w B (+++) 
Comparative 8.0 o/w C (-)* 
Product (4) 10.0 o/w C (-)* 
12.0 o/w C (+++) 
Comparative 8.8 o/w C (+++) 
Product (5) 10.7 o/w C (+++) 
12.1 o/w C (+++) 
Comparative -- o/w C (+++) 
Product (6) 
Comparative -- o/w B (+++) 
Product (7) -- o/w C (+++) 
__________________________________________________________________________ 
*Since the viscosity of the emulsion was extremely high, no phase 
separation was observed in spite of low emulsifiability. 
**POE(n): n indicates the mole number of added ethylene oxide. 
As will be apparent from the results shown in Tables 2 to 4, when known 
emulsifiers are used, vegetable oils or synthetic ester oils cannot be 
emulsified at all or they can be emulsified only insufficiently. In 
contrast, when the emulsifying composition of the present invention is 
used, such oils can easily be emulsified and good emulsions of excellent 
stability can be obtained. Even when the same components as used in the 
present invention are employed, if the weight ratio of the components is 
outside the ranges specified in the present invention, both the 
emulsifiability and the stability of the emulsions are diminished. 
EXAMPLE 5 (Resistance to Photo-Discoloration) 
The emulsifier agent compositions set forth in Table 5 were subjected to a 
photo-discoloration test. Each sample was exposed to artificial sunlight 
for 24 hours by using a sun-shine weather-meter, and the hue of each 
sample according to the Gardner color scale was measured before and after 
the exposure. The results are shown in Table 5. 
Table 5 
__________________________________________________________________________ 
n.sub.1 + Hue (Gardner 
Type of Emul- 
n.sub.2 +n.sub.3 + 
Composition (% by 
Color 
sifier n.sub.4 +n.sub.5 +n.sub.6 
weight) Scale) 
__________________________________________________________________________ 
before 
after 
(I) (II) 
(III) 
(IV) 
exposure 
exposure 
__________________________________________________________________________ 
Product.sup.1) of 
POE sorbitol iso- 
30 64.5 
1.2 3.5 30.8 
2 2 
Present stearate type 
40 63.0 
1.2 3.5 30.8 
3 3-4 
Invention 60 61.5 
1.2 3.5 30.8 
2 2 
Comparative 
POE sorbitol oleate 
30 64.5 
1.0 3.5 31.0 
2 4 
Product.sup.2) 
type 40 63.0 
1.0 3.5 31.0 
4 5-6 
60 61.5 
1.0 3.5 31.0 
3 4-5 
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.sup.1) The constituents of the product of the present invention were as 
follows: 
Average Degree Average 
n.sub.1 +n.sub.2 +n.sub.3 
Comp- of Esterifica- 
Comp- Comp- Comp- Molecular 
+n.sub.4 +n.sub.5 
onent tion of onent onent onent Weight of 
+n.sub.6 
(I) (I) (II) (III) (IV) PEG of (IV) 
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30 POE sorbitol 
4.5 sodium iso- 
isostearic 
polyethylene 
450 
isostearate stearate 
acid glycol iso- 
stearate 
40 ditto 4.5 ditto ditto ditto 600 
60 ditto 4.5 ditto ditto ditto 900 
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.sup.2) The constituents of the comparative product were as follows: 
Average Degree Average 
n.sub.1 +n.sub.2 +n.sub.3 
Comp- of Esterifica- 
Comp- Comp- Comp- Molecular 
+n.sub.4 +n.sub.5 
onent tion of onent onent onent Weight of 
+n.sub.6 
(I) (I) (II) (III) (IV) PEG of (IV) 
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30 POE sorbitol 
4.5 sodium oleic acid 
polyethylene 
450 
oleate oleate glycol oleate 
40 ditto 4.5 ditto ditto ditto 600 
60 ditto 4.5 ditto ditto ditto 900 
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As will be apparent from the results shown in Table 5, the polyoxyethylene 
sorbitol branched saturated fatty acid ester which is the main component 
(I) of the emulsifying composition of the present invention is superior to 
that of the polyoxyethylene sorbitol linear unsaturated fatty acid ester 
with respect to the resistance or stability to photo-discoloration. 
EXAMPLE 6 (Sensory Odor Test) 
A product (A) of the present invention and a comparative product (B), each 
having a composition as described below, were subjected to the sensory 
odor test by a panel of 30 persons according to the pair-comparison method 
of Scheffe. The results obtained are shown in Table 6. 
______________________________________ 
Composition (A) (present invention) : 
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(I) Polyoxyethylene (p = 30) sorbitol 
isostearate (average esterification 
degree = 4.5) 64.5% 
(II) Sodium isostearate 1.2% 
(III) Isostearic acid 3.5% 
(IV) Polyethylene glycol isostearate 
(average molecular weight of PEG 
being 450) 30.8% 
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Composition (B) (comparison) : 
______________________________________ 
(I) Polyoxyethylene (p = 30) sorbitol 
oleate (average esterification 
degree = 4.5) 60.5% 
(II) Sodium oleate 1.0% 
(III) Oleic acid 4.3% 
(IV) Polyethylene glycol oleate (average 
molecular weight of PEG being 458) 
34.2% 
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Table 6 
__________________________________________________________________________ 
B is bet- 
B is slight- 
no subst- 
A is sli- 
A is bet- 
ter than 
ly better 
antial 
ghtly ter 
A than difference 
better 
than 
Order 
(-2) A(-1) (0) than B(1) 
B(2) 
__________________________________________________________________________ 
A .fwdarw. B 
1 1 4 3 6 
B .fwdarw. A 
0 3 2 7 3 
Total 
1 4 6 10 9 
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When the above data were subjected to t inspection, the result of t 
(.alpha.) = 3.514 > t (n-1.0.01) = 2.756 (n = 30) was obtained. Thus, it 
was found that the odor of A was more pleasant than the odor of B with a 
significance level of 1%. 
Thus, it is apparent that with respect to the odor, a branched saturated 
fatty acid moiety is superior to a linear unsaturated fatty acid moiety 
for the fatty acid moiety of the polyoxyethylene sorbitol fatty acid which 
is the main component (I) of the composition of the present invention. 
EXAMPLE 7 (o/w Type Cream) 
An emulsifying composition comprising the following ingredients was 
prepared: 
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(I) Polyoxyethylene (p = 10) sorbitol 
isotridecanoate (average esterifi- 
cation degree = 3.0) 73.5% 
(II) Potassium isotridecanoate 
1.0% 
(III) Isotridecanoate acid 4.8% 
(IV) Polyethylene glycol isotridecanoate 
(average molecular weight of PEG 
20.7% 
equals 150) 
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The composition was a yellowish brown liquid having a specific gravity 
(d.sub.4.sup.20) of 0.981, a viscosity of 256 cps as measured at 
20.degree. C., a saponification value of 116.8 and an HLB value of 7.2. 
An o/w type cream having the following composition was prepared by using 
the thus prepared emulsifying composition: 
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(1) Olive oil 25 parts 
Bees wax 3 parts 
Hydrous lanolin 7 parts 
Paraffin wax 5 parts 
Emulsifying composition 
6 parts 
(2) Sorbitol 15 parts 
Water 39 parts 
(3) Perfume, antiseptic, etc. 
minor amounts 
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The ingredients of group (1) and of (2) were heated and melted at 
80.degree. C. separately, and the melts were mixed vigorously to effect 
emulsification. While the resulting emulsion was being cooled, the 
ingredients of group (3) were added thereto and dispersed therein. The 
resulting cream had a very good emulsion state. 
EXAMPLE 8 (Milky Lotion) 
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(I) Polyoxyethylene (p = 30) sorbitol 
isostearate (average esterification 
degree = 4.5) 64.5% 
(II) Sodium isostearate 1.2% 
(III) Isostearic acid 3.5% 
(IV) Polyethylene glycol isostearate 
(average molecular weight of PEG 
being 450) 30.8% 
______________________________________ 
The thus prepared emulsifying composition was a yellowish brown liquid 
having a specific gravity (d.sub.4.sup.20) of 1.012, a viscosity of 390 
cps as measured at 20.degree. C., a saponification value of 94.2 and an 
HLB value of 10.4. 
In the same manner as described in Example 7, a milky lotion comprising the 
following ingredients was prepared by using the thus obtained emulsifying 
composition: 
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(1) Olive oil 10 parts 
Hexadecyl 2-ethylhexanoate 
5 parts 
Cetyl alcohol 2 parts 
Bees wax 2 parts 
Emulsifying composition 
5 parts 
(2) Sorbitol 15 parts 
Water 61 parts 
(3) Perfume, antiseptic, etc. 
appropriate 
amounts 
______________________________________ 
The resulting milky lotion had a very good emulsion state, and the emulsion 
system was stable even after it had been allowed to stand for a long time.