JPH0138764B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cosmetic containing an alkyl phosphate polyvalent metal salt and a cosmetic powder. Therefore, the purpose of the present invention is to achieve excellent properties of polyvalent metal alkyl phosphates that are not found in conventional cosmetic bases, such as smoothness, spreadability, and ease of spreading on the skin. The purpose of the present invention is to provide a cosmetic with an excellent feeling of use, which takes advantage of the moisturizing feeling, appropriate adhesion, and covering properties that appear on the skin. There are various types of cosmetics containing powder, such as makeup cosmetics such as foundation, white powder, blusher, eye shadow, and eyebrow makeup, and body cosmetics such as body powder and baby powder. These chemical agents include inorganic extender pigments such as talc, kaolin, sericite, and mica; inorganic coloring agents such as titanium oxide, zinc oxide, ultramarine blue, chromium oxide, and iron oxide; and organic coloring agents such as organic tar pigments and lakes. Composite pigments such as titanium mica and iron oxide coated mica; and coated powders obtained by treating the surface of these powders for cosmetics with known coating agents such as silicone, higher fatty acids, higher alcohols, esters, and waxes. It is formulated with cosmetic powder as the main ingredient. The performance of these powders almost determines the performance of cosmetics, but the above powders alone cannot provide the smoothness, spreadability, moisturizing feeling, and appropriate adhesion required for excellent cosmetics. However, in order to improve these properties, metal soaps are currently blended into cosmetics containing powder. Metallic soaps are said to be able to impart a moisturizing feel, smoothness, spreadability, adhesion, and covering properties to cosmetics, but in reality, the metal soaps used as raw materials for cosmetics are Cosmetics cannot be given satisfactory performance in terms of smoothness and spreadability. Therefore, in powder pressed cosmetics, in order to improve the press moldability of the product,
Binding oils such as hydrocarbons, esters, waxes, and silicones are added, but in this case, the added binding oils tend to negate the lubricity and spreadability of the metal soap, and the performance of the product is almost limited. The current situation is that they are not being utilized. In addition, spherical polymers such as nylon powder styrene copolymer are used as raw materials for cosmetics as substances that impart lubricity and spreadability, but these have a strong bulky feel and poor adhesion. However, they have the disadvantage that they cannot impart softness and moisturizing feel to cosmetics, worsen the adhesion of cosmetics to the skin, and reduce press moldability. Under these circumstances, the present inventors conducted intensive research in order to provide cosmetics with excellent usability without the above-mentioned drawbacks, and as a result, they found that alkyl phosphate polyvalent metal salts are excellent as bases for cosmetics. When blended into cosmetics, it has excellent smoothness and spreadability, and when spread on the skin, it gradually becomes moisturizing, has appropriate adhesion, and has excellent covering properties. We have discovered that it is possible to obtain a sticky cosmetic, and in the case of a pressed powder cosmetic, it is possible to obtain a cosmetic that does not deteriorate its excellent feel even when a binding oil is added to improve the binding strength. , completed the invention. That is, the present invention provides a cosmetic containing a polyvalent metal salt of mono- or di-alkyl phosphate (hereinafter referred to as a polyvalent metal salt of alkyl phosphate) and a cosmetic powder. In the present invention, known polyvalent metal salts and novel polyvalent metal salts produced by the present inventors are used as the alkyl phosphate polyvalent metal salts. These alkyl phosphate metal salts have the general formula () or (), (In the formula, R ₁ , R ₂ and R ₃ are saturated or unsaturated straight chain or branched hydrocarbon groups having 1 to 45 carbon atoms, X ₁ ,
X ₂ and X ₃ represent hydrogen, an alkali metal, or an amine. (n represents an integer corresponding to the valence of Y and M) It can be produced by reacting with a metal salt represented by: For example, Japanese Patent Publication No. 42-12646 or Japanese Patent Publication No. 53-
() or () in which X ₁ to _{X 3} are represented by an alkali metal or an amine by the method described in No. 84919
By reacting a compound of formula () with a compound of formula (), an alkyl phosphoric acid polyvalent metal salt represented by the following general formula () or () can be obtained. (In the formula, l represents the valence of M, and R ₁ , R ₂ , R ₃ and M are the same as above.) Furthermore, by the method discovered by the present inventor, in the formula () , when a monoalkali metal salt of monoalkyl phosphoric acid in which X ₁ is an alkali metal and X ₂ is hydrogen is reacted with a compound of formula (),
A novel alkyl phosphate polyvalent metal salt represented by the following general formula () can be obtained. (In the formula, R ₁ is the same as above. M' represents an alkaline earth metal or a divalent transition metal) All of these polyvalent metal salts of alkyl phosphates represented by () to () can be used in the present invention. However, whereas the compounds of formulas () and () are in powder form, the new compound () has a needle-like, plate-like, or scaly crystal form, and has particularly excellent properties as a lubricant. It is particularly suitable because it has the following. As mentioned above, the alkyl phosphate polyvalent metal salts () and () are known compounds, but their only known use is to add them to resins as antistatic agents, etc. It has not been previously known that the above effects can be achieved by adding it to cosmetics. The hydrocarbon groups represented by R ₁ to _{R 3} in the formulas () and () have 1 to 45 carbon atoms, but preferably have 8 or more carbon atoms. When the number of carbon atoms is less than 8, the alkyl phosphate polyvalent metal salt exhibits tackiness, and lubricity and spreadability may decrease. Such hydrocarbon groups include, for example, octyl, nonyl, decyl, dodecyl, undecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl. , nonacosyl, triacontyl, hentriacontyl, dotriacontyl, octenyl, nonenyl, decenyl, dodecenyl, undecenyl, tridecenyl,
Tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, niicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacenyl, octacosenyl, nonacosenyl, triacontenyl,
Hentriacontenyl, dotriacontenyl, octadienyl, nonadienyl, decadienyl, dodecadienyl, undecadienyl, tridecadienyl, tetradecadienyl, pentadecadienyl, hexadecadienyl, heptadecadienyl,
Octadecadienyl, nonadecadienyl, eicosadienyl, heneicosadienyl, docosadienyl, tricosadienyl, tetracosadienyl,
Pentacosadienyl, hexacosadienyl, heptacosadienyl, octacosadienyl, nonacosadienyl, triacontadienyl, hentriacontadienyl, dotriacontadienyl, 2-hexyldecyl, 2-octylundecyl, Examples include 2-decyltetradecyl, 2-undecylhexadecyl, 2-tetradecyloctadecyl, and the like. Examples of the salts represented by X ₁ to _{X 3} in formulas () and () include alkali metals such as potassium and sodium; amines such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, morpholine, and arginine. It will be done. In addition, M in the metal salt represented by the formula () is a metal other than an alkali metal, such as alkaline earth metals such as Mg, Ca, Sr, and Ba; Zn, Cu, Ni, Co, Fe,
Divalent transition metals such as Mn, Cd, Pb, Cr, Ti; Al
Among others, Ca, Mg, Ba, Zn,
Particularly preferred are Fe, Ni, and Al. In addition, examples of X include halogens, inorganic anions such as SO ₄ , NO ₃ , CO ₃ , PO ₄ , and OH; anions of organic carboxylic acids such as acetic acid, propionic acid, and citric acid;
Among these, halogen, SO ₄ , PO ₄ , NO ₃ and CO ₃ are particularly preferred. The metal salt represented by the formula () is preferably water-soluble, and among these, CaCl ₂ ,
_MgCl2 , _FeCl2 , _ZnCl2 , _ZnSO4 , _MgSO4 ,
FeSO ₄ , Ni(NO ₂ ) ₂ , etc. are suitable. In the present invention, any known cosmetic powder, which is another essential component of cosmetics, can be used, such as inorganic pigments such as talc, sericite, mica, and kaolin; titanium oxide,
Inorganic colorants such as zinc oxide, ultramarine blue, chromium oxide, and iron oxide; Organic colorants such as organic tar pigments and lakes; Composite pigments such as titanium mica and iron oxide coated mica; and the surface of the above cosmetic powders. Examples include coating agent-treated powders treated with known coating agents such as silicone, higher fatty acids, higher alcohols, esters, and waxes. These may be used alone or in combination of two or more. Among these cosmetic powders, talc, sericite, mica,
Inorganic powders such as kaolin, titanium oxide, titanium mica, and iron oxide coated mica are preferred. In preparing the cosmetics of the present invention, in addition to the essential ingredients of the alkyl phosphate polyvalent metal salt and the powder for cosmetics, various conventionally used oils, surfactants, wetting agents, and preservatives are required. Optional ingredients such as antioxidants, fragrances, etc. can be added as appropriate. Oil agents include liquid paraffin, petrolatum, paraffin wax, squalane, ceresin wax, beeswax, carnauba wax, candelilla wax, hydrogenated castor oil, olive oil, lanolin alcohol, lanolin fatty acid, higher alcohol, fatty acid, and synthetic esters of higher alcohol and fatty acid. Oil, silicone, etc.; surfactants include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid Wetting agents include sorbitol, glycerin, propylene glycol, 1,3 butylene glycol, lactic acid, sodium lactate, polyethylene glycol, etc. Preservatives include paraoxybenzoic acid alkyl ester, sodium benzoate, potassium sorbate, etc. , phenoxyethanol, etc.; Examples of the antioxidant include tocopherol, cezamol, cezamorin, lecithin, etc. The amount of alkyl phosphate polyvalent metal salt in the cosmetic composition of the present invention is generally 0.1 to 99% by weight of the total composition.
(hereinafter simply expressed in %) is preferable. Particularly in the case of pressed powder cosmetics, it is preferably 0.1 to 30%; if it is less than this, the effect of the polyvalent metal salt will not be achieved, and if it is more than this, the surface of the press-molded cosmetic will be covered with a cosmetic puff. After several times of rubbing, the surface may become rough. Further, it is preferable that the cosmetic powder is blended in an amount of 70 to 99.9% of the total composition. The cosmetic of the present invention can be prepared by mixing the essential ingredients polyvalent metal salt of alkyl phosphate, cosmetic powder, and optional ingredients in a Henschel mixer, Nauta mixer, ribbon blender, mortar, etc. Prepared by molding into shape. The cosmetics of the present invention can be in the form of make-up cosmetics such as foundation, blusher, eyeshadow, eyebrow, etc.; body cosmetics such as body powder, baby powder, etc. The cosmetic composition of the present invention obtained as described above has not been found in conventional cosmetic compositions. It has extremely excellent smoothness and spreadability, and when spread on the skin, it has unique properties such as a moisturizing feeling, appropriate adhesion, and covering properties. Next, reference examples for producing polyvalent metal alkyl phosphate salts and examples of the present invention will be described. Reference example 1 Monolauryl phosphate calcium salt [compound of formula ()]: Pour 500 ml of acetone into a 3-volume beaker and add 40 ml of acetone.
While stirring at ℃, add 100 g (0.376 mol) of monolauryl phosphate (acid value 211.0, molecular weight 266).
After adding, after stirring for about 30 minutes, 10%
40-50 g of NaOH solution (NaOH: 0.376 mol)
The mixture was added dropwise over 30 minutes at 40°C to 50°C, followed by stirring and reaction at 40 to 50°C over 1 hour. After cooling to 30°C, the reaction mixture was filtered and dried at 60°C for 10 hours. Pour 500ml of water into a 3-volume beaker, add the above reaction mixture, stir at 60-70℃ for 30 minutes,
After dissolving, 184.7 g of 15% CaCl ₂ 2H ₂ O solution
(0.188 mol as CaCl ₂ ) was added, and salt exchange was performed at 60 to 70°C for 1 hour. After salt exchange, 500
After washing twice with ml of water and 500ml of acetone,
It was dried at 60°C for 30 hours. 80 g of monolauryl phosphate calcium salt was obtained as a white powder. Elemental analysis (as C ₂₄ H ₅₂ O ₈ P ₂ Ca): Ca P C H Cl Calculated value (%) 7.0 10.9 50.5 9.1 0.0 Analysis value (%) 7.0 11.0 50.3 9.0 0.0 Infrared absorption spectrum (KBr method): Wave number ( cm ^-1 ) Strength Attribution 2950 M ν _as CH 2920 S ν _as CH ₂ 2850 M ν _s CH ₂ 1470 W CH ₂ scissors 1170 M νC−O 1100 M 1075 S νC−O 940 M 930 M 840 W Reference example 2 Monolauryl phosphate calcium salt [compound of formula ()]: Pour 500 ml of acetone into a 2-volume beaker and add 40 ml of acetone.
50 g (0.188 mol) of monolauryl phosphate (oxidation: 211.0, molecular weight: 266) was added while stirring at °C. After addition and stirring for approximately 30 minutes, 10% NaOH
150.4g of liquid (NaOH: 0.376mol) at 40-50℃
The mixture was added dropwise over a period of 1 minute, and then stirred and reacted at 40 to 50°C for 1 hour. After cooling to 30°C, the reaction mixture was filtered and dried at 60°C for 10 hours. Pour 500ml of water into a 2-volume beaker, add the above reaction mixture, stir at 60-70℃ for 30 minutes, and then dissolve.
15% CaCl ₂ 2H ₂ O184.7 (as CaCl ₂
0.188 mol) and salt exchange was performed at 60 to 70°C for 1 hour. After completing the salt exchange, strain and add 500ml of water.
After washing twice with water and 500ml of acetone, store at 60℃ for 30 minutes.
Dry for an hour. 57 g of monolauryl phosphate calcium salt was obtained as a white powder. Phosphorus content
9.0%, potassium content 11.0%. Reference example 3 Dicetyl phosphate calcium salt (compound of formula ()): Pour 500 ml of ethanol into a 3-volume beaker,
100 g (0.183 mol) of dicetyl phosphate (acid value: 103.0, molecular weight: 546) was added while stirring at 60 to 70°C. After addition, after stirring for about 30 minutes, 10%
73.3g of NaOH solution (NaOH: 0.183mol) at 60℃ for 30 minutes
The mixture was added dropwise over a period of minutes, and then stirred at 60 to 65° C. for 30 minutes to react. After cooling to 30°C, the reaction mixture was filtered and dried at 60°C for 10 hours. 3
Pour 500 ml of water into a volume beaker, add the above reaction mixture, stir at 70-75°C for 30 minutes, dissolve, and then add 179.6 g of 15% CaCl ₂ 2H ₂ O (CaCl ₂ :
0.183 mol) and salt exchange was performed at 70 to 75°C for 1 hour. After completing the salt exchange, strain and add 500ml of water.
After washing twice with water and 500ml of acetone, store at 60℃ for 30 minutes.
Dry for an hour. 100 g of dicetyl phosphate calcium salt was obtained as a white powder. Phosphorus content
5.3%, calcium content 3.3%. Example 1 Regarding Reference Examples 1 to 3 or the alkyl phosphate polyvalent metal salt obtained in the same manner as these, a sensory evaluation of the feeling in use and a coefficient of friction resistance as a smoothness index were investigated. Note that metal soap and nylon powder were used as comparison products. The results are shown in Table-1. [Sensory evaluation] A sensory evaluation was conducted by a panel of 10 experts regarding the feeling of use of the powder itself. [Friction resistance coefficient] It was investigated using a surface tester HEIDON-14 manufactured by Shinto Kagaku Co., Ltd. 〔result〕

【table】

【table】

[Manufacturing method]

After mixing ~ with a Henschel mixer, was added and mixed again, followed by press molding.

[Manufacturing method]

After mixing with a Henschel mixer, was added, mixed again, and press-molded. As shown in Figure 1, the product of the present invention is a foundation that spreads better, has a smoother feel, is moisturized, and has appropriate transparency and coverage compared to comparative products. It became clear. Example 4 (Ishadou) [Composition] Titanium mica 90.7 (%) Monolauryl zinc phosphate 5.0 Squalane 4.0 Fragrance 0.3 Total 100.0 After mixing with a Henschel mixer, was added and the mixture was press-molded again. As a result, an eye shadow that was extremely slippery, spreadable, moist, and had good adhesion was obtained. Example 5 (Hoho Red) [Prescription] Talc 50.0 (%) Mica 36.7 Magnesium dilauryl phosphate salt produced by the manufacturing method of Reference Example 3 5.0 Red No. 226 3.0 Squalane 5.0 Flavor 0.3 Total 100.0 After mixing ~ in an automatic mortar, The mixture was added, mixed again, and press-molded. As a result, it is very slippery,
A hot red blush that spreads well, is moisturizing, and has appropriate coverage and adhesion was obtained.

[Brief explanation of drawings]

FIG. 1 is a drawing showing the sensory evaluation results of the powder foundation in Example 3.

Claims (1)

[Scope of Claims] 1. A cosmetic comprising a mono- or di-alkyl phosphoric acid polyvalent metal salt and a cosmetic powder. 2 The mono- or di-alkyl phosphoric acid polyvalent metal salt has the general formula () or (), (In the formula, R ₁ , R ₂ and R ₃ are saturated or unsaturated straight chain or branched hydrocarbon groups having 1 to 45 carbon atoms, X ₁ ,
X ₂ and X ₃ represent hydrogen, alkali metal or amine), MmYn () (where M is a polyvalent metal, Y is an organic or inorganic anion, m and 2. The cosmetic according to claim 1, which is obtained by reacting with a metal salt represented by (n represents an integer corresponding to the valence of Y and M).