Patent Publication Number: US-4097403-A

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

Description:
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 &#34;vegetable oils&#34;) composed of triglycerides rich in alkyl groups having an unsaturated bond, such as camellia oil and olive oil, and esters (hereinafter referred to &#34;synthetic esters&#34;) 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 &#34;component (I)&#34;) having the formula (A): ##STR1## wherein the value of n 1  + n 2  + n 3  + n 4  + n 5  + n 6  is in the range of 10 to 100, and wherein from 3 to 6 of the total number of X&#39;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&#39;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 &#34;component (II)&#34;), 
     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 &#34;component (III)&#34;), 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 &#34;component (IV)&#34;). 
     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&#39;s are acyl groups, the rest being hydrogen. (In the description given hereinafter, the number of such acyl groups will be called &#34;the degree of esterification&#34;). 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° to 240° 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 &#34;%&#34; 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° 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 1μ as measured under a microscope 
     B: milky white emulsion of particles having an average particle size of 1 to 5μ as measured under a microscope 
     C: opaque emulsion of crude particles having an average particle size larger than 5μ as measured under a microscope 
     (2) Stability: 
     The emulsion formed was allowed to stand still at 25° 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)                                                        
         &#34;              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° 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       &#34;        4.5      &#34;        &#34;        &#34;        600                 
60       &#34;        5.5      sodium stea-                                   
                                    &#34;        &#34;        900                 
                           rate                                           
80       &#34;        6.0      sodium iso-                                    
                                    &#34;        &#34;        1200                
                           stearate                                       
100      &#34;        6.0      &#34;        &#34;        &#34;        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       &#34;        4.0      &#34;        &#34;        &#34;        450                 
30       &#34;        4.0      &#34;        &#34;        &#34;        450                 
60       &#34;        5.5      &#34;        &#34;        &#34;        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       &#34;        4.5      &#34;        &#34;        &#34;        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                                                               
         &#34;              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° 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                                                               
         &#34;              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° 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                        
__________________________________________________________________________
.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)                   
__________________________________________________________________________
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                           
__________________________________________________________________________
.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)                   
__________________________________________________________________________
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                           
__________________________________________________________________________
 
    
     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) :                                     
______________________________________                                    
(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%                                     
______________________________________                                    
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%                                     
______________________________________                                    
 
    
     
                                           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 → B                                                              
     1     1      4     3     6                                           
B → A                                                              
     0     3      2     7     3                                           
Total                                                                     
     1     4      6     10    9                                           
__________________________________________________________________________
 
    
     When the above data were subjected to t inspection, the result of t (α) = 3.514 &gt; 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: 
     
         ______________________________________                                    
(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)                                                       
______________________________________                                    
 
    
     The composition was a yellowish brown liquid having a specific gravity (d 4   20 ) of 0.981, a viscosity of 256 cps as measured at 20° 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: 
     
         ______________________________________                                    
(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                                
______________________________________                                    
 
    
     The ingredients of group (1) and of (2) were heated and melted at 80° 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) 
     
         ______________________________________                                    
(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 4   20 ) of 1.012, a viscosity of 390 cps as measured at 20° 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: 
     
         ______________________________________                                    
(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.