JPS6338970B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel emulsified cosmetic. Conventionally, emulsifiers used in preparing emulsified cosmetics have been combinations of higher fatty acid salts and nonionic surfactants. Emulsifiers using higher fatty acid salts have excellent emulsion stability, but
The pH increases due to higher fatty acid salts, and the cosmetic composition becomes alkaline. However, the surface of normal human skin is covered with a slightly acidic (PH4.5-6.5) film, and when alkaline substances come into contact with the skin, acidic substances are secreted from the body and the pH of the film is returned to normal, causing a weak acidity. It is designed to maintain acidity. Therefore, emulsified cosmetics such as creams and emulsions applied to the skin are preferably adjusted to be weakly acidic to neutral. For this reason, conventional methods for lowering the PH of emulsified cosmetics that use higher fatty acid salts as emulsifiers have been to use basic substances (sodium hydroxide, potassium hydroxide, trichloride, etc.) used to neutralize higher fatty acids. Methods used have been to drastically reduce the amount of ethanolamine, etc.) added, or to add an acidic PH buffer such as lactic acid-sodium lactate after preparing the emulsion system. However, these methods have the disadvantage that the emulsification state is poor, and moreover, the emulsification is destroyed over time, causing layer separation, resulting in a significant loss of appearance. In addition, higher alcohol sulfate ester salts are used instead of higher fatty acid salts, but although this emulsion system is stable in weakly acidic to neutral conditions, it is highly irritating to the skin and the higher alcohol sulfate ester salts over time. It has the disadvantage that it is gradually hydrolyzed and the emulsion system becomes unstable. Under such circumstances, the present inventor conducted intensive research to overcome the above-mentioned drawbacks, and found that a combination of a specific phosphoric acid ester partially or completely neutralized with a basic substance and a specific nonionic activator. The present invention was completed based on the discovery that the emulsifier is weakly acidic to neutral, has high stability on the skin, and is extremely stable over time. Therefore, the present invention provides the following components (a) to (d), (a) a phosphoric acid monoester represented by the general formula () and a phosphoric acid diester represented by the general formula () in a molar ratio: 0.1 to 5% by weight of a partially or completely neutralized product of a phosphoric acid ester having a ratio of 100:0 to 70:30 with a basic substance, (In the formula, R ₁ and R ₂ represent a branched saturated hydrocarbon group having 12 to 24 carbon atoms.) (b) Add a nonionic activator with an HLB of 6 or less to 0.1% of component (a).
(c) 1 to 60% by weight of an oily base; and (d) 25 to 95% by weight of water. In the ester residue constituting the phosphoric ester of the phosphoric ester neutralized product, which is a component of the emulsifier of the present invention, R ₁ and R ₂ need to have 12 to 24 carbon atoms, and the carbon number is 12 to 24. If the number is less than 24, the smell will be bad and the emulsifying property will be poor, while if it is more than 24, the emulsifying property will be poor and the emulsified state will worsen over time, which is not preferred. R ₁ and R ₂ are particularly preferably those having 12 to 18 carbon atoms. The number of branched chains and the number of branched carbon atoms in R ₁ and R ₂ are not particularly limited, but the following are preferred. (i) Methyl branched alkyl (In the formula, h is a number from 2 to 14, i is a number from 3 to 11, and h+i is preferably 9 to 21, particularly preferably 11 to 19) (ii) β-branched alkyl (In the formula, k is a number of 5 to 11, k is a number of 3 to 10, and k+l is preferably 8 to 20, particularly preferably 10 to 18) (iii) α-branched alkyl (In the formula, p is a number from 1 to 20, q is a number from 1 to 20, and p+q is preferably 9 to 21, particularly preferably 11 to 19) (iv) A hyperbranched alkyl group, e.g. Among these branched alkyl groups, (i) and (ii) are particularly preferred. Incidentally, the alcohol having the group represented by the formula () is commercially available as Fine Oxocol 1800 from Nissan Chemical Industries, Ltd. The mixing ratio of phosphoric acid monoester () and phosphoric acid diester () is 100:0 to 70:30, especially
A molar ratio of 100:0 to 80:20 is preferable; if the phosphoric acid monoester is less than 70 mol%, the emulsifying property is poor, the emulsified state deteriorates over time, the appearance deteriorates, and the consistency decreases. Significantly decreased. Basic substances for neutralizing phosphate esters include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; basic amino acids such as arginine, ornithine, lysine, and oxylysine;
Preferred are alkanolamines having a hydroxyalkyl group having 2 or 3 carbon atoms, such as triethanolamine, diethanolamine, and monoethanolamine. Neutralized phosphate esters can be prepared by neutralizing the phosphate ester with a basic substance in a separate system, or blended together in the system when used. Although it may be prepared, it is particularly preferable to prepare it in-system. Neutralization of the phosphoric acid ester with a basic substance does not necessarily have to be complete neutralization, but may be partial neutralization, or the basic substance may be present in excess of the neutralization amount. That is,
The amount of the basic substance is selected depending on the pH of the target emulsion, but in general, the amount of the basic substance is 0.2 to 1.8 mol, based on the phosphoric acid ester.
Particularly preferred is 0.4 to 1.0 mol. Further, it is preferable that the nonionic activator has an HLB of 6 or less, particularly 2 to 5. Examples of nonionic surfactants include polyoxyalkylene alkyl (or alkenyl) ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene Hydrogenated castor oil, polyoxyalkylene alkylamides (oxyalkylenes include oxyethylene and/or oxypropylene, preferably oxyethylene), glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, ethylene or Propylene glycol fatty acid esters and fatty acid alkanolamides (however, these alkyl, alkenyl and fatty acid residues preferably have 8 to 22 carbon atoms, particularly 14 to 18 carbon atoms). Among these, preferred are glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, diglycerin fatty acid ester, and ethylene or propylene glycol fatty acid ester, particularly glycerin monostearate and glycerin monoisostearate. , sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sucrose stearate, propylene glycol monostearate, ethylene glycol monostearate, diglycerin monostearate, diglycerin monoolein Preferred are acid esters, polyoxyethylene (1-3) monostearate, polyoxyethylene (2-10) hydrogenated mustard oil, and the like. Various methods can be adopted for the emulsification method using an emulsifier consisting of the neutralized phosphate ester of the present invention and a nonionic activator with an HLB of 6 or less. Alternatively, add and mix a phosphoric acid ester and a nonionic activator with an HLB of 6 or less, heat and melt (e.g. 70 to 80°C), stir to homogenize, and then add warm water or a heated basic substance aqueous solution while stirring. Emulsification gives good results. In this case, the phosphoric acid ester neutralized product is preferably added in an amount of 0.1 to 5% by weight (hereinafter simply expressed as %), particularly 0.3 to 3% by weight of the entire emulsion system. Further, it is particularly preferable that the phosphoric acid ester and the basic substance are added individually to the system and neutralized in the system. When the emulsifier of the present invention is used in the production of emulsified cosmetics, it is stable over a wide pH range, does not irritate the skin, and produces a weakly acidic to neutral emulsion that is most suitable for the skin, which cannot be obtained by using conventional higher fatty acid salts. You can get cosmetics. The emulsified cosmetic of the present invention contains (a) a neutralized phosphate ester, (b) a nonionic activator with an HLB of 6 or less, (c) an oily base, and (d) water as essential components, and further contains, if necessary, Known cosmetic ingredients, such as other types of surfactants, viscosity modifiers, medicinal agents, preservatives, humectants, colorants, fragrances, etc., can be blended. Examples of the oily base of component (c) include hydrocarbons such as liquid paraffin, paraffin wax, ceresin, and squalane; waxes such as beeswax, spermaceti, and carnauba wax; and natural oils such as olive oil, camellia oil, jojoba oil, and lanolin. Animal and vegetable oils and fats; examples include silicone oil, fatty acids, higher alcohols, and ester oils obtained by reacting these. In addition, as surfactants, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene hydrogenated castor oil alkyl sulfate, polyoxyethylene alkyl sulfate ester , alkyl phosphate ester, polyoxyethylene alkyl phosphate ester, fatty acid alkali metal salt, sorbitan fatty acid ester, glycerin fatty acid ester, etc., and viscosity modifiers include polyvinyl alcohol, carboxyvinyl polymer, carboxymethylcellulose, polyvinylpyrrolidone, hydroxyethylcellulose, Polymer compounds such as methylcellulose; natural gums such as gelatin and taracanth gum; alcohols such as ethanol and isopropanol; medicinal agents include bactericides, anti-inflammatory agents, and vitamins; humectants include propylene glycol, glycerin, ，
3-butylene glycol, sorbitol, lactic acid,
Examples of preservatives include sodium lactate and sodium pyrrolidonecarboxylate, and examples of preservatives include paraoxybenzoic acid ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and phenoxyethanol. A preferred composition of the emulsified cosmetic composition of the present invention is as follows.

[Table] The emulsified cosmetic composition of the present invention can be in various forms, such as vanishing cream, milky lotion, cold cream, cleansing cream, hair cream, foundation cream, hand cream, etc. It may be prepared in any emulsion type, water-in-oil type. Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. Example 1 An emulsion system having the formulation shown in Table 1 was prepared, and its emulsion state and emulsion stability were examined. The results are shown in Table 2.

[Table] Production method: Heat the oil phase to 70-80°C and melt it by stirring. Add the aqueous phase heated and dissolved at 70-80°C with stirring to emulsify, and immediately cool to room temperature.

[Table] Example 2 Moisture cream having the formulation shown in Table 3 was manufactured, and its emulsion stability and viscosity changes over time were investigated. The results are shown in Tables 4 and 5.

[Table] Production method: The oil phase was heated to 70-80°C and uniformly melted by stirring, and the aqueous phase heated and dissolved at 70-80°C with stirring was added to emulsify. After cooling this to 50°C, a fragrance was added, and the mixture was further cooled to room temperature while stirring to obtain a moisturizing cream.

【table】

【table】

[Table] As is clear from Tables 4 and 5, the molar ratio of phosphoric acid monoester and diester is from 100:0 to
Products A and B of the present invention having a ratio of 70:30 gave good results. Example 3 Nutritional cream (O/
W type) was manufactured and its emulsion state and emulsion stability were investigated. The results are shown in Table 7.

【table】

[Table] Dialkyl.
Manufacturing method: Same as the manufacturing method shown in Example 2. result:

[Table] As is clear from Table 7, products E and F of the present invention, in which the weight ratio of the lipophilic nonionic surfactant to the phosphate ester was in the range of 0.1 to 20, gave good results. Example 4 Nutrient emulsion (O/W) with the composition shown in Table 8
The emulsion state and emulsion stability were investigated. The results are shown in Table 9.

【table】

【table】 Manufacturing method: Same as the manufacturing method shown in Example 2. result:

[Table] As is clear from Table 9, the amount of phosphate ester
The products of the present invention in the range of 0.1 to 5% gave good results. Example 5 Nutritional cream (O/
W type) was manufactured and its emulsion state and emulsion stability were investigated. The results are shown in Table 11.

【table】

[Table] Manufacturing method: Heat the oil phase to 70-80°C and uniformly melt it by stirring. Add the aqueous phase heated and dissolved at 70-80°C with stirring and emulsify. After cooling to 50℃,
Add flavoring and cool to 30-35°C with stirring. Thereafter, this was further treated with a homogenizer to sufficiently emulsify and obtain a nutritional cream. result:

[Table] As is clear from Table 11, the product of the present invention had better emulsion stability against temperature changes than the comparative product. Example 6 Cold cream: Composition: (Oil phase) Liquid paraffin 25.0% Vaseline 18.0 Beeswax 2.0 Setanol 3.0 Isocetyl phosphate (same as phosphate ester *5 in Table 8)
1.0 Sorbitan monooleate (HLB 4.3) 2.0 Butylparaben 0.1 (aqueous phase) Propylene glycol 4.0 Sodium hydroxide 0.12 Methylparaben 0.1 Water Balance (fragrance) Small quantity manufacturing method: Same as the manufacturing method shown in Example 2. Example 7 Foundation cream composition: (Oil phase) Squalane 10.0% Isopropyl palmitate 3.0 Cetyl palmitate 3.0 Isostearyl phosphate (same as phosphate ester *1 in Table 3)
1.0 Glycerin monostearate (HLB3.5) 2.0 Butylparaben 0.1 (Aqueous phase) Propylene glycol 5.0% Potassium hydroxide 0.13 Montmorillonite 1.0 Titanium oxide 7.0 Talc 5.0 Iron oxide 3.0 Methylparaben 0.1 Water Balance (Fragrance) Small amount manufacturing method: Oil phase Dissolve by heating to 75-80℃ and stir to mix uniformly. On the other hand, the aqueous phase is heated and dissolved at 70-75℃,
After the powder is uniformly dispersed using a dispersion machine, an oil phase is added thereto and reacted and emulsified. After cooling to 50° C. with stirring, a fragrance was added, and after further cooling to 30 to 40° C., the mixture was treated with a homogenizer to thoroughly emulsify and obtain a foundation cream. Example 8 Moisture Cream A in Table 3 of Example 2
For this, the blending ratio (molar ratio) of basic substance (sodium hydroxide) to phosphoric acid ester is 0.05.
The emulsion state, emulsion stability, and changes in physical properties were investigated by changing the emulsion state from 2.0 to 2.0. The results are shown in Table 12. In the table, ◎ indicates very good, 〇 indicates good, and △ indicates slightly poor.

[Table] As is clear from Table 12, when the molar ratio of sodium hydroxide to phosphoric acid ester is in the range of 0.2 to 1.8, the resulting moisturizing cream is neutral or weakly acidic, especially 0.4 to 1.0. When it was within this range, there was little change in viscosity over time and the emulsion stability was good. Example 9 Moisture Cream A of Example 2, which is a product of the present invention, and Nutritional Emulsion I of Example 4, Moisture Cream O and P, which are comparative products shown in Table 13, and Nutritional Emulsion Q, which is a commercial product. For a total of 5 types of specimens, 10
A well-known expert panel conducted a sensory evaluation of its usability.
The results are shown in Table 14.

【table】

【table】 Manufacturing method: Same as the manufacturing method shown in Example 2.

【table】

[Table] As is clear from Table 14, both samples A and I, which are products of the present invention, gave good results with good adhesion to the skin and little stickiness. Example 10 An emulsion system having the formulation shown in Table 15 was prepared, and its emulsion state and emulsion stability were examined. Results first
Shown in Table 16.

【table】

[Table] *5: Same manufacturing method as in Table 8: Produced according to the method of Example 1. result:

[Table] As is clear from Table 16, the emulsification state of Invention Product Q and Comparative Product R immediately after preparation is good, but the cetyl phosphate (linear) used in Comparative Product R has a phase transition temperature of
Since Tc is high at 65°C or higher, crystals will precipitate over time at temperatures below Tc and the emulsion system will be destroyed. On the other hand, since the Tc of isocetyl phosphate (branched chain) used in Invention Product Q was 0°C or lower, no crystal precipitation was observed and the product was stable.

Claims (1)

[Scope of Claims] 1. The following components (a) to (d): (a) A phosphoric acid monoester represented by the general formula () and a phosphoric acid diester represented by the general formula () in a molar ratio: 0.1 to 5% by weight of a partially or completely neutralized product of a phosphoric acid ester having a ratio of 100:0 to 70:30 with a basic substance, (In the formula, R ₁ and R ₂ represent a branched saturated hydrocarbon group having 12 to 24 carbon atoms.) (b) Add a nonionic activator with an HLB of 6 or less to 0.1% of component (a).
20 times by weight, (c) 1 to 60% by weight of an oily base, and (d) 25 to 95% by weight of water. 2 Basic substance per mole of phosphoric acid ester
The emulsified cosmetic according to claim 1, which has a content of 0.2 to 1.8 mol.