GB2115817A

GB2115817A - Phosphate emulsifiers

Info

Publication number: GB2115817A
Application number: GB08233129A
Authority: GB
Inventors: Hisao Tsutsumi; Tomoko Inque; Atsuo Ishida
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1981-12-16
Filing date: 1982-11-19
Publication date: 1983-09-14
Also published as: IT1150599B; FR2517985A1; DE3246474A1; BE895356A; FR2517985B1; MY8700071A; GB2115817B; IT8249674A0

Abstract

An emulsifying composition comprises one or more phosphates represented by the general formula (I) and/or (II> <IMAGE> in which R may be the same or different and represent an alkyl or alkenyl group having 5-21 carbon atoms, or an alkyloxy or alkenyloxy group having 8-20 carbon atoms, X1 and X2 independently represent a pair ion selected from hydrogen, alkali metal, ammonium, alkylammonium and alkanolamine. The above emulsifying composition exhibits high safety against living body, and has good property in emulsification stability.

Description

SPECIFICATION Emulsifying composition i) Field of the Invention: This invention relates to an emulsifying composition and more particularly, to an emulsifying composition which comprises a specific phosphate or a salt thereof thereby ensuring good feeling to the touch and low irritativeness against living body and particularly skin with excellent emulsification stabilizing ability.

ii) Description of the Prior Art: In general, compounds used as an emulsifier can broadly be classified into two groups including a hydrophilic emulsifier group which shows high solubility in water or has a great HLB value and an oleophilic emulsifier group which shows high solubility in oil or has a small HLB value. The former has conventionally been used for stabilizing mainly O/W type emulsions and the latter used for W/O type emulsions. In this connection, however, oils to be emulsified greatly vary in property depending on the type of oil. Accordingly, there is little chance of using hydrophilic emulsifiers alone or oleophiiic emulsifiers alone and it is general to use a mixture of both the type emulsifiers to have a suitable level of HLB value.Especially when oils to be emulsified are in the form of a mixture, such a general way of the use is the common practice.

Conventionally employed hydrophilic emulsifiers are, for example, surface active agents which include anionic surface active agents such as alkali metal salts of fatty acids, alkylsulfates and the like, and ethylene oxide-added nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like. On the other hand, oleophilic emulsifiers include, for example, nonionic surface active agents such as sorbitan-fatty acid esters, glycerine-fatty acid esters and the like.

A method of preparing emulsifier compositions having different HLB values by mixing hydrophilic emulsifiers, which are obtained by combining fatty acid triethanolamine salts and ethylene oxide-added nonionic surface active agents, with oleophilic emulsifiers such as glycerine-fatty acid esters has been widely utilized for emulsification in order to obtain emulsion-type cosmetics such as creams, lotions and the like.

However, it has been suggested that ethylene oxide-added nonionic surface active agents contain formalin, dioxane and the like as impurities and these impurities have the alergic action on living body.

Further, it is known that anionic surface active agents are generally high in skin irritativeness and are thus not favorable as an emulsifier. Accordingly, in case that the anionic surface active agents are employed, alkali metal salts of fatty acids are used by virtue of giving relatively low skin irritativeness, this case however, accompanied by another disadvantage that the resulting emulsion is rendered alkaline.

That is, emulsion-type cosmetics using these known emulsifiers are not fully satisfactory in safety.

On the other hand, it has been known that there are present in living body a group of compound having surface activity and called phospholipids, which play an important role as main components of membranes of living body. Typical examples of the phospholipids include glycerophospholipids such as phosphatidyl choline (lecithin), phosphatidyl ethanolamine (cephalin), phosphatidyl serine and the like.

These phospholipids are components in vivo, and are thus surface active materials which are high in safety against living body. For instance, lecithin has been industrially utilized as an emulsifier. However, since these are of natural origin, they have various impurities and suffer deterioration in quality inherent of natural materials as time goes. Furthermore, the structure such as of a fatty acid composition cannot be arbitrarily changed, so that its HLB value cannot be changed freely. Moreover, in order to obtain emulsified cosmetics which ensure good feeling on use, it is known that relatively hydrophilic oils or polar oils are satisfactorily used as the oil phase. However, the emulsification of polar oils is comparatively difficult and sufficient emulsification stability cannot be obtained in case of using weak surface active materials such as lecithin.

SUMMARY OF THE INVENTION Accordingly, we have made an intensive study to develop an emulsifier or emulsifying composition which exhibits good emulsification stability and high safety against human body, as a result, found that the above object can be achieved by using, as an emulsifier, a phosphate represented by the general formula (I) and/or (II)

in which all the R may be the same or different and represent an alkyl or alkenyl group having 5-21 carbon atoms, or an alkyloxy or alkenyloxy group having 8-20 carbon atoms, X1 and X2 independently represent a counter ion selected from the group consisting of hydrogen, alkali metal, ammonium, alkylammonium which has an alkyl group containing 1-5 carbon atoms, and alkanolamine which has a hydroxyalkyl group containing 2 or 3 carbon atoms.

That is, the present invention provides an emulsifier or emulsifying composition which comprises one or more of the phosphates represented by the general formula (I) and/or (!I).

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1H-NMR spectrum chart of a compound (of the formula (I) in which R = CgH19) of the invention; Fig. 2 is a 13C-NMR spectrum chart of the same compound as indicated above; and Fig. 3 is an IR spectrum chart of the compound.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS The phosphates used in the present invention and represented by the formula (I) and/or (II) can be classified into the following two groups of the compounds: (1) Hydroxyalkyl or hydroxyalkenyl phosphates represented by the general formula (la) and/or (Ila);

in which R1, may be the same or different and represents an alkyl or alkenyl group having 5-21 carbon atoms, Hand X2 are the same as defined before.

(2) Alkyl or alkenyl glyceryl ether phosphates represented by the general formula (Ib) and/or (llb);

in which R2 may be the same or different and represents an alkyl or alkenyl group having 8-20 carbon atoms.

The preparation of the hydroxyalkyl or hydroxyalkenyl phosphates represented by the general formula (la) and/or (Ila) is not critical. For instance, they can be synthesized by reacting an alkylepoxy compound or alkenylepoxy compound with phosphoric acid according to the following formula to readily prepare a phosphate and then neutralizing the phosphate with a suitable alkali agent.

The salt may be formed by separately adding in a compounding vessel the phosphate and an alkali agent for neutralization or adjustment of the pH. In this connection, for preparing an emulsion, it is preferable to use a nascent emulsifying process in which the phosphate is added in the form of an acid and the emulsification is effected while being added an alkali agent.

Typical examples of the compound (a)-(f) thus obtained are shown along with their properties in Table 1 below.

TABLE 1

Sample a b c d e f White White White White White White Aoppearance Powder Powder Powder Powder Powder Powder Odor Little Little Littel Littel Little Little Solubility in Water (25 C) Good Good Good Good Good Good (70 C) " " " " " " pH (1%) 5.3 5.4 6.5 7.5 5.2 5.8 The method of preparing the alkyl or alkenyl glyceryl ether phosphate compounds of the general formula (Ib) and/or (llb) is not critical either and, for example, alkyl or alkenyl glycidyl ethers are reacted with phosphoric acid according to the following reaction formula:

The resulting alkyl or alkenyl glyceryl ether phosphates are, if necessary, neutralized with appropriate alkali agents. The salts may be formed by separately adding the phoshpates and an alkali agent in the compounding vessel for neutralization or adjustment of the pH. In a preferred aspect, a nascent emulsification method is used in which the phosphate is added in the form of an acid at the time when an emulsion is prepared, and the emulsification is effected while adding an alkali agent.

Typical phosphate compounds obtained by the above preparation method are indicated below along with their properties shown in Table 2.

TABLE 2

Sample g h i j k White White White White White Appearance Powder Powder Powder Powder Powder Odor Little Little Little Little Little Solubility in Water Insoluble (250C) Good (gel form) Good Insoluble Insoluble (709C) Good Good Good Good Good pH (1%) 5.3 6.5 7.6 6.4 5.8 The emulsifying composition comprising the phosphate compounds (I) and/or (II) of the invention is high in safety against skin and can be adjusted to a desired level of HLB using lipophilic emulsifiers in combination when occasion demands, so that oily components can be kept in the system in a wide range of amounts, coupled with another advantage that it can be widely used in either type of W/O or O/W.

The emulsifying composition of the invention has such a widely applicable stabilizing effect as mentioned above, so that it has wide utility not only in the fields of the medical, cosmetic and food industries, but also almost all the fields of the fiber, metal, agricultural and synthetic resin industries.

Above all, the composition can suitably used in the technical field of cosmetics and medicines which directly take part in skin. Then, an embodiment in the field of cosmetics is particularly described.

In the field of cosmetics and allied articles, safety against skin is first required and accordingly, suitable selection of the pair ion in the phosphate compound is necessary. That is, if the pair ions X, and X2 in the phosphate compound represented by the general formula (I) and/or (II) are both hydrogen, its aciditiy becomes too high, whereas if both are an alkali metar, the alkalinity becomes too high.

Accordingly, both the pair ions should not be hydrogen or an alkali metal. This control can be achieved by adjusting the pH in the range of 4-9, preferably 5-7.

The counter ion species should preferably be sodium, potassium, triethanolammonium, ammonium and hydrogen.

Above all, among various hydroxyalkyl or hydroxyalkenyl phosphate compounds represented by the formula (la) and/or (Ila), combinations of X, = H and X2 = K, X1 = H and X2 = Na, X, = H and X2 = triethanolamine, X, = X2 = triethanolamine, and X, = H and X2 = ammonium are preferably used.

Among the hydroxyalkyl or hydroxyalkenyl phosphate compounds represented by the general formula (la) and/or (ill), hydroxyalkyl phosphate salts are preferably used. Moreover, R, in the general formula (la) and/or (ill) has preferably 9-15 carbon atoms.

Further, among various alkyl or alkenyl glyceryl ether phosphate compounds represented by the general formula (Ib) and/or (lib), alkyl glyceryl ether phosphates are preferable.

The group R2 of the alkyl glyceryl ether phosphate compound should favorably be an alkyl group having 1 2-18 carbon atoms.

The phosphate compounds of the general formulas (I) and (II) may be used singly or in combination at arbitrary ratios depending on the type of an oil to be emulsified (and if mixed, the weight ratio of the general formula (1)/the general formula (II) is preferably 1 00/0--20/80). If necessary, the compound may be used by mixing with oleophilic emulsifiers at arbitrary ratios.

The lipophilic emulsifiers used are not critically limited but those containing ethylene oxide groups are preferable and include, for example, sorbitan-fatty acid esters, glycerine-fatty acid esters, sucrosefatty acid esters, propylene glycol-fatty acid esters and the like in the form of mono- or diesters whose fatty acid group has 10 to 20 carbon atoms. These esters are used singly or in combination.

Emulsified cosmetics using the emulsifier of the present invention can be prepared by compounding, according to the usual manner, the emulsifier and known cosmetic ingredients such as, for example, cosmetic oily substrates, surface active agents, viscosity modifiers, medical ingredients, preservatives and other wetting agents.

Examples of the cosmetic oily substrate include hydrocarbons such as liquid paraffin, paraffin wax, ceresine, squalane and the like; waxes such as bees wax, spermaceti, carnauba wax and the like; natural animal and plant oils and fats such as olive oil, tsubaki oil, jojoba oil, lanolin and the like; and silicone oils, fatty acids, higher alcohols and ester oils obtained by reaction of these acids and alcohols. As surface active agents there are mentioned polyoxyethylene alkyl ethers, polyoxyethylene-fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene hardened castor oils, alkylsulfates, polyoxyethylene alkylsulfates, alkylphosphates, polyoxyethylene alkylphosphates, alkali metal salts of fatty acids and the like. These agents can be added to an extent not impeding the effect of the present invention.Moreover, examples of the viscosity modifier include high molecular weight compounds such as polyvinyl alcohol, carboxyvinyl polymer, carboxymethy cellulose, polyvinylpyrrolidone, hydroxyethyl cellulose, methyl cellulose and the like; natural gum such as gelatin, tragacanth gum and the like; and alcohols such as ethanol, isopropanol and the like. The medical ingredients are bactericides, antiphlogistics, vitamins and the like and the wetting agents include propylene glycol, glycerine, 1,3-butylene glycol, sorbitol, lactic acid, sodium lactate, sodium pyrrolidonecarbonate and the like. The preservatives include, for example, paraoxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol and the like.

Preferred compositions of an emulsified cosmetic according to one embodiment of the present invention are as follows.

Compounding Preferable Amount (wt%) Compounding Amount (wt%) Cosmetic oil substrate 1-60 5-35 Emulsifier [general formula (I) 0.1-10 0.5 and/or (it)1 Viscosity modifier, etc. 0--10 0-5 Medical agent 0--10 Wetting agent 0--30 0-10 Preservative 0--1 0.02-1.0 Water 25-95 40-90 The emulsifier may be separately prepared or the starting materials for the emulsifier may be directly charged into the cosmetic compounding composition.

The emulsified cosmetic can be prepared in various forms including, for example, vanishing creams, lotions, cold creams, cleansing creams, hair creams, foundation creams, hand creams and the like. They can be in either of emulsification type, O/W or W/O.

The thus obtained emulsified cosmetics which are one of embodiments of the present invention exhibit excellent stability of emulsification and excellent skin-protecting effect and have excellent feeling to the touch.

The present invention is particularly described by way of Synthetic Examples and Examples.

Synthetic Example 1 Into a 2 litres round bottom flask equipped with a reflux condenser, thermometer, dropping funnel and agitator were charged 296 g (3 moles) of 99.5 wt% orthophosphoric acid and 500 ml of n-hexane.; Into the mixture was dropped 1 84 g of 1,2-epoxydodecane (oxirane value 304.5, 1.0 mole) in 1.5 hours while refluxing the n-hexane (65-700C). After completion of the dropping, the agitation was continued under heating conditions of 65-700C for further 5 hours. After completion of the reaction, 500 ml of diethyl ether and 500 ml of 1 N hydrochloric acid were added to the reaction mixture and mixed together.The thus obtained mixed solution was transferred to a separating funnel and shaked to extract unreacted phosphoric acid in the acidic aqueous phase of hydrochloric acid. The organic phase was separated and washed with 500 ml of 1/1 ON hydrochloric acid, after which the solvent was distilled off under reduced pressure to obtain a mixture of a phosphate and a nonionic substance. Then, the mixture was neutralized with an ethanol solution of potassium hydroxide to precipitate the phosphate cornponent as the potassium salt. After removal of the ethanol by distillation, the remaining white precipitate was reduced into pieces and washed several times with 500 ml of hot acetone to remove the nonionic substance therefrom.

Thereafter, the solid phase was removed by filtration and dried under reduced pressure to obtain the potassium salt of the phosphate. The potassium salt was dissolved in 1 liter of 6N hydrochloric acid and was thus made acidic. The resulting phosphate was extracted with 500 ml of diethyl ether and the organic phase was washed with 500 ml of 1/1 ON hydrochloric acid, after which the solvent was distilled off under reduced pressure to obtain 256 g of the purified phosphate. The acid value of the phosphate (mg of potassium hydroxide required for neutralization of 1 g of sample to the first equivalence point = AV1 = 1 75.2, mg of potassium hydroxide required for the second equivalence point = AV2 = 350.2) revealed that a monoester was obtained. The yield was found to be 80% (based on the glycidyl ether, with a water content of 12%).

The elementary analysis was effected as follows: the purified phosphate was again dissolved in an ethanol solution of potassium hydroxide to give a dipotassium salt and the salt was separated by filtration and dried under reduced pressure.

Elementary Analysis C12H2s 5PK2 Calculated: C 40.2, H 7.0, P 8.6, K 21.8 Found: C 4.06, H 6.8, P 8.8, K 21.0 HNMR [CDCI3, Internal Standard: tetramethylsilane (TMS)] Fig. 1 a 0.87 ppm (t, 3H, -CK3) a 1.26 ppm (broad s, 1 8H, (C!2)s) 3.37-4.13 ppm (broad, 3H,

13CNMR (CDCl3, Internal Standard TMS) Fig. 2

(ppm):: a 14.1, b 22.7, c 25.7, d 29.6, e 29.9, f 32.1, g 32.3, h 70.7-72.5 IR (film) Fig. 3 3400,2900, 2840, 1460, 1160, 1000 cm-l SYNTHETIC EXAMPLE 2 Into a 1 liter round bottom flask equipped with a reflux condenser, thermometer, dropping funnel and agitator were charged 277 g (2.8 moles) of 99% orthophosphoric acid and 250 ml of diethyl ether.

Into the mixture was dropped 231 g of lauryl glycidyl ether (oxirane value 225.8, 0.93 mole) in 1 hour while refluxing the diethyl ether (35-400C). After completion of the dropping, the agitation was continued under heating conditions of 35-400C for further 3 hours. After completion of the reaction, 500 ml of diethyl ether and 500 ml of 1 N hydrochloric acid were added to the reaction mixture and mixed together. The thus obtained mixed solution was transferred to a separating funnel and shaked to extract unreacted phosphoric acid in the acidic aqueous phase of hydrochloric acid. The organic phase was separated and washed with 500 ml of 1/1 ON hydrochloric acid, after which the solvent was distilled off under reduced pressure to obtain 410 g of a mixture of a phosphate and a nonionic substance.

Then, the mixture was neutralized with an ethanol solution of potassium hydroxide to precipitate the phosphate component as the potassium salt. After removal of the ethanol by distillation, the remaining white precipitate was reduced into pieces and washed several times with 500 ml of hot acetone to remove the nonionic substance therefrom. Thereafter, the solid was removed by filtration and dried under reduced pressure to obtain 328 g of the potassium salt of the phosphate.

The potassium salt was dissolved in 1 liter of 6N hydrochloric acid and was thus made acidic. The resulting phosphate was extracted with 500 ml of diethyl ether and the organic phase was washed with 500 ml of 1/1 ON hydrochloric acid, after which the solvent was distilled off under reduced pressure to obtain 275 g of the purified phosphate. The acid value of the phosphate (mg of potassium hydroxide required for neutralization of 1 g of sample to the first equivalence point = AV1 = 151.0, mg of potassium hydroxide required for the second equivalence point = AV2 = 302.6) revealed that a monophosphate was obtained. The yield was found to be 80% (based on the glycidyl ether, with a water content of 8%).

This compound was confirmed to be composed of a phosphorus compound alone when determined by a procedure comprising, after methyl esterification with diazomethane, trimethylsilylation with BSTFA (N,O-bis-trimethylsilyltrifluoroacetamide) and subjecting the resulting compound to the gas chromatography (flame photometer and hydrogen flame ionization detector).

Moreover, when the phosphate compound was trimethylsilylated with BSTFA and its Cl mass spectrum was observed, the molecular weight at the parent peak (m/e = 556) was coincident as the trimethylsilylated phosphate compound.

Elementary Analysis C15H21O@PK2 Calculated: C 43.2, H 7.5, P 7.4, K 18.8 Found: C43.5, H 7.9, P 7.1, K 18.0 'HNMR (CDCI3 Internal Standard: tetramethylsilane (TMS)) a 0.87 ppm (t, 3H,-CH3) a 1.27 ppm (broad s, 2OH, -(CH2)10) # 3.38-4.27 ppm (broad, 7H,

t3CNMR (CDCl3, Internal standard TMS) a bgd e d c f CH3CH2CH2CH2-(CH2)4-CH2CH2CH2CH2

(ppm):: a 14.1, b 22.7, c 26.2, d 29.5, e 29.8, f 29.8, g 32.0, h 66.6-71.0, i 72.0 IR (film) 3300, 2900, 2840, 1460, 1000 cm-1 EXAMPLE 1 An aqueous 10% solution of each of the compounds (a)-(f) of the present invention and comparative products was subjected to the close patch test for 24 hours in which three groups of guinea pigs, each group consisting of 6 guinea pigs, were used.After removal of the patch, the intensities of the skin reaction after 24 hours were evaluated in seven ranks including redness (+, +, ++), chemosis (i, +, ++) and negative (-). "-", "+", "+" and "++" were scored as 0, 0.5, 1.0 and 2.0, respectively, and the total score of the redness and chemosis was obtained and an average stimulative value which was an average value of 6 guinea pigs was calculated for comparing the skin stimulativeness. The results are shown in Table 3.

TABLE 3

@@@@@@@ Stimulative Other Skin Tested Compounds | Value | Reactions (a) 0.2 Same as water (b) 0.2 " Compounds of Invention (c) 0 " (d) 0.3 " (e) 0 " (f) 0 " Sodium laurylsulfate 3.2 Heavy falling-off wast Sodium dodecylben zenesulfonate 2.0 Moderate falling off Sodium α ;dodecene- waste Comparative Compounds Sulfonate 0.7 Slight falling off waste Sodium laurylpolyoxy ethylene sulfate 0.9 Slight gloss As will be apparent from the above results, the conventional anionic active agents used as the hydrophilic emulsifier exhibited a substantial degree of skin stimulativeness but the compounds of the invention exhibited little or no stimulativeness.

EXAMPLE 2 An O/W type emulsifier of the following composition was prepared to determine the pH and the stability by day of the emulsifier.

Test oil 25 wt% Test emulsifier 4 Water 71 The emulsification was effected by a phase inversion emulsification in which a test oil and a test emulsifier were mixed and heated to 700C, to which water of 700C was gradually added while agitating. As for some of the experiments, there was used, as indicated in the results of Table 4, a nascent emulsification method in which a non-neutralized test emulsifier and a test oil were mixed together, to which was added for emulsification an aqueous solution of an alkali agent to be a counter ion. The resulting emulsions were allowed to stand over 1 month at 200C and 40"C and their stability was evaluated according to the following judging standard.

(Standard of Stability) (-) No separation (+) Slight separation of oil component (++) Separation into two phases including cream phase and drainage phase (+++) Separation into three phase including cream phase, drainage phase and combined phase (++++) Disappearance of cream phase and separation into oil and water TABLE 4

Test Oil Octyldodecanol Olive Oil Stability Stability Test Emulsifier pH 20 C 40 C pH 20 C 40 C Mixture of compound (b) of Table 1 and monoglyceride stearate (mixing ratio 1/1)* 6.5 (-) (-) 6.6 (-) (-) Compounds of Mixture of compound (c) of Table 1 and compound Invention (f) of Table 1 (mixing ratio 1/1)* 6.6 (-) (-) 6.6 (-) (-) Mixture of compound (f) of Table 1 and monoglyceride stearats (mixing ratio 1/1)* 6.5 (-) (-) 6.6 (-) (-) Mixture of triethanolamine stearate and monoglyceride stearate (mixing ratio 1/1)* 8.4 (+) (++) 8.2 (-) (+) Mixture of polyoxyethylene (20) sorbltan Comparative monostearate and monoglyceride stearate Compounds (mixing ratio 1/1) 6.4 (+++) (+++) 6.3 (+++) (+++) Mixture of polyoxyethylene (20) oleyl ether and monoglycerlde stearate (mixing ratio 1/1) 6.0 (++) (+++) 6.0 (+++) (+++) Mixture of potasslum myristate and monoglyceride stearate (mixing ratio 1/1)* 8.4 (+) (+) 8.5 (++) (+++) Lecithin 6.7 (+++) (+++) 6.8 (+++) (+++) *Emulsified by a nascent emulsification.

The test results demonstrate that the phosphate salts to be compounds of the present invention have excellent stability of emulsification as a hydrophilic emulsifier, i.e. they emulsify polar and nonpolar oils with equal to or higher ability than alkali metal salts of fatty acid and ethylene oxide-added nonionic, surface active agent conventionally employed for the same purpose, and that the resulting emulsions can be made weakly acidic.

As will be apparently seen from Examples 1 and 2, the use of the phosphate compounds of the invention ensures ready preparation of emulsions of high safety.

EXAMPLE 3 Hand Cream (O/W type) 1. Non-neutralized product of 1.9 wt% compound (f) of Table 1 2. Monoglyceride stearate 2.0 3. Stearic acid 8.0 4. Stearyl alcohol 2.0 5. Squalane 3.0 6. Bees wax 0.5 7. Olive oil 5.0 8. Butyl paraoxybenzoate 0.1 9. Methyl paraoxybenzoate 0.1 1 0. Glycerine 4.0 11. Sodium hydroxide 0.1 12. Perfume suitable amount 13. Purified water balance 1-8 were heated to 700C and mixed together. Separately, a mixture of 9-11 1 and 13 was heated to 700C and was gradually added to the mixture of 1-8 for emulsification. Finally, 12 was added and mixed, followed by cooling and charging into a container.

EXAMPLE 4 Cold Cream (O/W type) 1. Non-neutralized product of 2.9 wt% compound (b) of Table 1 2. Sorbitan sesquioleate 2.0 3. Liquid paraffin 25.0 4. Octyldodecanol 10.0 5. Bees wax 2.0 6. Vaseline 6.0 7. Cetanol 2.0 8. Butyl paraoxybenzoate 0.1 9. Methyl paraoxybenzoate 0.1 EXAMPLE 4 - Continued Cold Cream (O/W type) 10. Glycerine 5.0 11. Propylene glycol 5.0 12. Perfume suitable amount 13. Purified water balance 1-8 were heated to 700C and mixed. Separately, a mixture of 9-11 1 and 13 was heated to 700C and gradually added to the mixture of 1-8 for emulsification. Finally, 12 was added to and mixed with the mixture, followed by cooling and charging into a container.

EXAMPLE 5 A 10% aqueous solution of each of the compounds g)-k) of the present invention and four comparative products were subjected to the close patch test using a total of three groups of guinea pigs, each consisting of 6 guinea pigs, for 24 hours. After removal of the patch, the intensity of the skin reaction after 24 hours was evaluated in seven steps including redness (+, +, ++), edema (+, +, and negative (-). "-", "+", "+" and "++" where scored as 0, 0.5, 1.0 and 2.0 respectively, and a total score of the redness and chemosis was determined, from which an average value of 6 guinea pigs was obtained as an average stimulative value for comparing intensities of the skin stimulativeness with one another. The results are shown in Table 5.

TABLE 5

Average Stimulative Sample Value | Other Skin Reaction g) 0.4 Same as water h) 0 Compound of the il 0.4 presentinvention i) 0.2 " k) 0 Sodium laurylsulfate | 3.2 Heavy falling-off waste Sodium dodecyl- Moderate falling-off benzenesunonate 2.0 waste Sodium alphadodecene Comparative product | sulfonate 0.7 Slight falling-off waste Sodium lauryl polyoxy ethylene sulfate 0.9 Slight gloss As will be apparent from the above results, the known anionic surface active agents which have been utilized as the hydrophilic emulsifier have a substantial degree of skin stimulativeness but the compounds of the present invention have a much reduced degree of stimulativeness.

EXAMPLE 6 An O/W type emulsion of the following composition was prepared to determine the pH and the day-by-day stability of the emulsion Test oil (olive oil) 25 wt% Test emulsifier 4 Water 71 The emulsion was made by a phase invention emulsification method in which the test oil and the test emulsifier were mixed together and heated to 700 C, to which was gradually added water of 700C under agitation. It will be noted that as described in the results of Table 6, in some of the experiments, a so-called nascent emulsification method was used in which non-neutralized test emulsifiers were mixed with test oils, to which was added an aqueous solution of an alkali agent to be a counter ion so that the neutralization was effected while emulsifying.The resulting emulsions were allowed to stand at 200C and 400C for 1 month and their stability was evaluated according to the following standard.

(Standard of Judging the Stability) (-) No separation (+) Slight separation of oil component (++) Separation into two phases of cream phase and drainage phase (+++) Separation into three phases including cream phase, drainage phase and combined phase.

(++++) Disappearance of cream phase and separation into two phases including oil phase and aqueous phase.

TABLE 6

Stat ability Test Emulsifier pH 200C 400C Mixture of compound (g) of Table 1 and monoglyceride stearate (mixing ratio 1/1)* 6.5 - - Compound of the present Mixture of compound (g) of Table 1 compound (d) of Table 1 Invention (mixing ratio 1/1) 6.4 - - Mixture of compound (h) of Table 1 and monoglyceride stearate (mixing ratio 1/1 )* 6.6 - - Mixture of triethanolamine stearate monoglyceride stearate (mixing ratio 1/1)* 8.2 - + Mixture of polyoxyethylene (20) sorbitan monostearate and monoglyceride stearate (mixing ratio 1/1) 6.3 l l l +++ Comparative Mixture of polyoxyethylene (20) oleyl ether and monoglyceride product stearate (mixing ratio 1/1) 6.0 Mixture of potassium myristate and monoglyceride stearate (mixing ratio 1/1)* 8.5 ++ +++ * Emulsification by the nascent emulsification method As the result of the test, it was found that the alkyl glyceryl ether phosphates to be the compounds of the invention had the excellent emulsifying ability as a hydrophilic emulsifier and that they had an emulsifying force equal to or higher than alkali metal salts of fatty acids and ethylene oxide-added nonionic active agents conventionally employed for the same purpose and served to render the emulsion weakly acidic.

As will be apparent from Examples 5 and 6, the use of the alkyl glyceryl ether phosphates which are the compounds of the present invention make it possible to readily manufacture emulsions of higher safety.

EXAMPLE 7 Hand Cream (O/W type) 1. Non-neutralized product of (g) 1.9 (%) compound in Table 1 2. Monoglyceride stearate 1.5 3. Stearic acid 8.0 4. Squalane 4.0 5. Stearyl alcohol 1.5 6. Butyl paraoxybenzoate 0.1 7. Methyl paraoxybenzoate 0.1 8. Dipropylene glycol 5.0 9. Sodium hydroxide 0.1 10. Perfume 0.1 11. Purified water balance 1-6 were heated to 700C and mixed together. Separately, a mixture of 7, 8, 9 and 11 was heated to 700C and was gradually added to the mixture of 1-6 for emulsification. Finally, 10 was added to the emulsion and well mixed, followed by cooling and charging into a container.

EXAMPLE 8 Cleansing Cream (O/W type) 1. Compound (h) in Table 1 2.8 (%) 2. Sorbitan sesquioleate 2.2 3. Liquid paraffin 25.0 4. Octyldodecyl myristate 1 5.0 5. Cetanol 2.0 6. Bees wax 1.0 7. Ceresine wax 1.5 8. Propyl paraoxybenzoate 0.2 9. Propylene glycol 5.0 10. 1,3-butanediol 5.0 11. Perfume 0.1 12. Purified water balance 1-8 were heated to 700C and mixed. Separately, a mixture of 9, 10 and 12 were heated to 700C and gradually added to the mixture of 1-8 for emulsification. Finally, 11 was added to and mixed with the mixture, followed by cooling and charging into a container.

Claims

CLAIM

1. An emulsifying composition comprising one or more of phosphates represented by the general formula (I) and/or (II)

in which R may be the same or different and represent an alkyl or alkenyl group having 5-21 carbon atoms, or an alkyloxy or alkenyloxy group having 8-20 carbon atoms, X1 and X2 independently represent a pair ion selected from the group consisting of hydrogen, alkali metal, ammonium, alkylammonium whose alkyl group has 1-5 carbon atoms, the alkanolamine which has a hydroxyalkyl group having 2 or 3 carbon atoms.