JPH09208593A - Phosphate triester and cosmetic and external preparation containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphate triester containing specific ester residues, excellent in skin affinity, touch and safety to skins, and useful as a wax base material for cosmetics, external preparations. SOLUTION: This phosphate triester comprises a chemical structure of the formula [R<1> is a 25-50C (branched) alkyl or alkenyl, especially a 28-40C branched alkyl, e.g. 2-dodecylhexadecyl (Ry), 2-hyxadecylicosyl (Rz); R<2> is a 6-50C (branched or cyclic) alkyl, a linear alkenyl, an aryl, especially a 28-40C branched alkyl, e.g. Rx, Ry, Rz; R<3> is a 1-6C (branched or cyclic) alkyl or of alkenyl, an aryl, especially a 1-4C alkyl]. The phosphate triester is obtained e.g. by successively adding and reacting approximately 1 mole of a compound of the formula: R<1> -OH, approximately 1 mole of a compound of the formula: R<2> -OH and approximately 1 mole of a compound of the formula: R<3> -OH to 1 mole of an oxyhalogenated phosphorus.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic composition and an external preparation which are excellent in skin affinity and feeling of use and have low skin irritation.

[0002]

2. Description of the Related Art Waxes are extremely important as a cosmetic base, and their characteristics are as follows:
Not only basic performances such as imparting lubricity to the skin, barrier ability due to formation of hydrophobic film, and ability to suppress percutaneous water loss, but recently 1) skin affinity, 2) feel on skin, 3) In terms of skin safety and the like, excellent performance is being demanded.

In order to meet such demands, many wax bases have been developed and applied. For example, synthetic esters such as myristyl myristate aim at skin affinity due to the polarity of the ester bond. However, these conventional wax bases cannot be said to have sufficient skin compatibility.

[0004]

As described above, none of the conventional wax bases satisfy 1) high skin affinity, 2) good feeling in use, and 3) skin safety. Therefore, it has been desired to develop a wax having all of these properties.

Under the circumstances, the inventors of the present invention have conducted extensive studies, and as a result, phosphoric triester having a specific ester residue represented by the general formula (1) described below has high polarity and excellent skin affinity. And it is also excellent in safety, it was found that the cosmetics and external preparations containing this as a wax base have good familiarity with the skin, excellent feeling in use, and excellent safety, Was completed.

[0006]

That is, the present invention provides the following general formula (1):

[0007]

Embedded image

[In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 25 to 50 carbon atoms, and R ² represents a linear, branched or cyclic alkyl group or linear chain having 6 to 50 carbon atoms. It represents an alkenyl group or an aryl group, and R ³ represents a linear, branched or cyclic alkyl group, alkenyl group or aryl group having 1 to 6 carbon atoms. ] The phosphoric acid triester represented by the following and cosmetics and external preparations containing the same are provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), the linear alkyl group having 25 to 50 carbon atoms represented by R ¹ is, for example, n.
-Pentaicosyl group, n-hexaicosyl group, n-heptaeicosyl group, n-octaeicosyl group and the like, and examples of branched alkyl include 2-decylpentadecyl group, 2-decylhexadecyl group, 2-decyloctadecyl group. , 2-dodecylhexadecyl group, 2-dodecylheptadecyl group, 2-dodecyloctadecyl group, 2-tetradecyldodecyl group, 2-tetradecylhexadecyl group, 2-tetradecyloctadecyl group, 2-hexadecylicosyl group Etc. As the alkenyl group,
Examples thereof include a 17-hexacosenyl group and a 21-tricontenyl group. Of these R ¹ , a branched alkyl group having 28 to 40 carbon atoms is preferable from the viewpoint of retaining the properties as a wax at room temperature.

In the general formula (1), the number of carbon atoms represented by R ² is 6
As the linear or branched alkyl group of ˜50, the above R ¹
In addition to those exemplified above, n-hexyl group, n-octyl group, n-decyl group, n-octadecyl group, n-icosyl group, 2-ethylhexyl group, 2-methyldodecyl group, 2
-Hexyldecyl group and the like, as the cyclic alkyl group, for example, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group and the like, and as the linear alkenyl group, for example, an undecenyl group, a hexadecenyl group, octadecenyl group. Group, hexadecadienyl group, octadecadienyl group, eicosadienyl group and the like, and the aryl group includes phenyl group, naphthyl group and the like, but is not necessarily limited thereto. Among such R ² , a linear or branched alkyl group or linear alkenyl group having 12 to 50 carbon atoms, particularly 25 to 50 carbon atoms is preferable from the viewpoint of reducing skin irritation, and further,
2 carbon atoms from the point of maintaining the properties as a wax at room temperature
8-40 branched alkyl groups are preferred.

In the general formula (1), the number of carbon atoms represented by R ³ is 1
As the straight-chain alkyl group of ~ 6, a methyl group, an ethyl group,
n-propyl group, n-butyl group, n-pentyl group and n
Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. The alkenyl group includes, for example, an allyl group and a methallyl group, and the aryl group includes, but is not limited to, a phenyl group. Of such R ³ , a linear or branched alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of skin compatibility and a good feeling in use, and a linear alkyl group having 1 to 4 carbon atoms, particularly low viscosity. To ethyl group is preferred.

Further, in the phosphoric acid triester (1), R ¹ and / or R ² is a branched alkyl group having 28 to 40 carbon atoms and R ³ is R ³ from the viewpoint of properties as a wax and retention of skin affinity. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a linear or branched alkyl group in which R ¹ and R ² are the branched alkyl groups is particularly preferable. As R ¹ and R ² , 2-
Dodecylhexadecyl group, 2-tetradecyloctadecyl group, and 2-hexadecylicosyl group are particularly preferable.

The phosphoric acid triester (1) can be prepared by a known method, for example, by directly adding an alcohol corresponding to R ¹ , R ² and R ³ to phosphorus oxyhalide such as phosphorus oxychloride in the presence of a base or a catalyst. Can be synthesized by sequentially reacting with.

That is, when a phosphoric acid triester having different R ¹ , R ² and R ³ is intended, R ¹ -O
Three kinds of alcohols of H, R ² —OH and R ³ —OH are sequentially added and reacted in about 1-fold moles with respect to phosphorus oxyhalide.
When a phosphoric acid triester in which R ¹ and R ² are the same or R ² and R ³ are the same, one of the two alcohols is used in an amount about 1 mole per mol of the phosphorus oxyhalide (or After about 2 times mol) and reacted, one remaining alcohol is added and reacted about 2 times mol (or about 1 mol).

As R ¹ -OH and R ² -OH, those having an alkyl group having a branched chain at the β-position of the -OH group and having a total carbon number of 28 to 40 are preferable, and so-called Guerbet type alcohols are particularly preferable. Preferably, for example, the following general formula (2)

[0016]

Embedded image

[In the formula, n represents a number of 12 to 20. ] What is represented by these is preferable.

The solvent used in this reaction is not particularly limited as long as it is inert to the reaction and is capable of dissolving phosphorus oxyhalide. For example, an ether solvent such as tetrahydrofuran (THF) and dioxane, Examples thereof include aliphatic hydrocarbons such as hexane, heptane and octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. These solvents can be used alone or in combination of two or more. The amount of solvent used is not particularly limited,
Generally, the phosphorus oxyhalide concentration is 60% by weight or less,
The amount is preferably 30% by weight or less.

As the base which can be used in this reaction,
Examples thereof include organic tertiary amines such as triethylamine, tributylamine and pyridine, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. These bases can be used alone or in combination of two or more.

The amount of the phosphoric acid triester (1) to be incorporated into the cosmetic or external preparation of the present invention is not particularly limited, but in the case of an emulsified cosmetic or external preparation, for example, 0.001 of the total composition is used.
1 to 90% by weight, particularly 1 to 50% by weight is preferable.

The forms of the cosmetics and external preparations of the present invention are not particularly limited, and they may be either water-in-oil type or oil-in-water type emulsion type and oil type.

The types of the cosmetics and external preparations of the present invention are not particularly limited, and examples thereof include packs, foundations, lipsticks, skin cleansers, shampoos, rinses, hair conditioners, hair restorers, hair restorers, ointments and the like. Such cosmetics and external preparations include, in addition to phosphate triester (1), oils, water, surfactants, humectants, UV protectors, chelating agents that are generally used as cosmetic ingredients and external preparation components. Various components such as a pH adjuster, an antiseptic, a thickener, a dye, a fragrance, and a medicinal component can be appropriately added. The medicinal component is not particularly limited, and examples thereof include analgesic and anti-inflammatory agents, antipruritic agents, bactericidal and antiseptic agents, astringent agents, skin ointments, hormone agents, vitamins and the like.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 Di (2-hexadecylicosanyl) ethyl phosphate [Compound (a)] 7.67 g of phosphorus oxychloride in a 500 ml four-necked flask.
(0.05 mol), while stirring with 100 ml of THF, 48.7 g (0.10 mol) of 2-hexadecylicosanyl alcohol (Calcol 360GH, manufactured by Kao),
Triethylamine 10.1 g (0.10 mol), THF
200 ml of the mixed solution was added dropwise while cooling so that the reaction temperature was 30 ° C or lower. After completion of dropping, the mixture was aged at 30 ° C. for 3 hours. Then, the formed triethylamine hydrochloride was removed by filtration, 500 ml of ethanol was added, and the temperature was raised to 30 ° C.
For 24 hours. After aging, THF and excess ethanol were distilled off, hexane extraction was performed, and the extract was washed with water. Hexane was distilled off from the extract, and the obtained crude product was purified by flash column chromatography to obtain the target compound (a) 35.0.
g (white solid; purity 9 from ¹ H-NMR, ³¹ P-NMR 9
8% or more) was obtained.

IR [ν (cm ^-1 )]: 2932, 2860,
1467, 1278, 1029 ¹ H-NMR [CDCl ₃ , δ (ppm)]: 0.89 (t, 12H), 1.2-1.4 (br, 1
31H), 1.64 (m, 2H), 3.94 (dd, 4H), 4.12 (dg, 2H)

Example 2 Di (2-tetradecylhexadecyl) ethyl phosphate [compound (b)] 15.3 g of phosphorus oxychloride in a 500 ml four-necked flask.
(0.10 mol) and THF (100 ml) were added to the mixture while stirring, and 93.4 g (0.10 mol.
20 mol), triethylamine 20.2 g (0.20 mo
l), a mixed solution of 200 ml of THF was added dropwise while cooling so that the reaction temperature was 30 ° C or lower. After completion of dropping, 30
Aged at ℃ for 3 hours. Then, the produced triethylamine hydrochloride was removed by filtration, 500 ml of ethanol was added, and the mixture was aged at 30 ° C. for 24 hours. After aging, THF and excess ethanol were distilled off, hexane extraction was performed, and the extract was washed with water.
Hexane was distilled off from the extract, and the resulting crude product was purified by flash column chromatography to obtain 70.0 g of the target compound (b) (white solid; ¹ H-NMR, ³¹ P-N).
Purity of 98% or more) was obtained from MR.

IR [ν (cm ^-1 )]: 2932, 2860,
1467, 1275, 1022 ¹ H-NMR [CDCl ₃ , δ (ppm)]: 0.90 (t, 12 H), 1.2-1.4 (br, 1
15H), 1.64 (m, 2H), 3.95 (dd, 4H), 4.12 (dg, 2H)

Example 3 Phosphoric acid (2-hexadecylicosanyl) dodecylethyl [compound (c)] 15.3 g of phosphorus oxychloride in a 500 ml four-necked flask.
(0.10 mol) and 100 ml of THF were added, and while stirring, 48.7 g (0.10 mol) of Calcol 360GH (manufactured by Kao).
10 mol), triethylamine 10.1 g (0.10 mo
l), a mixed solution of 100 ml of THF was added dropwise while cooling so that the reaction temperature was 30 ° C or lower. After completion of dropping, 30
Aged at ℃ for 3 hours, followed by dodecyl alcohol 18.6
g (0.10 mol), triethylamine 10.1 g
A mixed solution of (0.10 mol) and 100 ml of THF was added dropwise while cooling so that the reaction temperature was 30 ° C or lower. After completion of dropping, the mixture was aged at 30 ° C. for 6 hours. Then, the produced triethylamine hydrochloride was removed by filtration, 500 ml of ethanol was added, and the mixture was aged at 30 ° C. for 24 hours. After aging, THF and excess ethanol were distilled off, hexane extraction was performed, and the extract was washed with water. Hexane was distilled off from the extract, and the resulting crude product was purified by flash column chromatography to obtain 62.0 g of the target compound (c) (white solid; ¹ H-NM
The purity was 98% or more from R, ³¹ P-NMR).

IR [ν (cm ^-1 )]: 2932, 2860,
1467, 1281, 1035 ¹ H-NMR [CDCl ₃ , δ (ppm)]: 0.88 (t, 9H), 1.2-1.4 (br, 85)
H), 1.6-1.9 (br, 3H), 3.92 (dd, 2H), 4.03 (dt, 2H), 4.12 (d
g, 2H)

Example 4 Phosphoric acid (2-hexadecylicosanyl) hexylethyl compound (d)! Into a 500 ml four-necked flask, 15.3 g of phosphorus oxychloride.
(0.10 mol) and 100 ml of THF were added, and while stirring, 48.7 g (0.10 mol) of Calcol 360GH (manufactured by Kao).
10 mol), triethylamine 10.1 g (0.10 mo
l), a mixed solution of 100 ml of THF was added dropwise while cooling so that the reaction temperature was 30 ° C or lower. After completion of dropping, 30
Aged at ℃ for 3 hours, followed by hexyl alcohol 10.2
g (0.10 mol), triethylamine 10.1 g
A mixed solution of (0.10 mol) and 100 ml of THF was added dropwise while cooling so that the reaction temperature was 30 ° C or lower. After completion of dropping, the mixture was aged at 30 ° C. for 6 hours. Then, the produced triethylamine hydrochloride was removed by filtration, 500 ml of ethanol was added, and the mixture was aged at 30 ° C. for 24 hours. After aging, THF and excess ethanol were distilled off, hexane extraction was performed, and the extract was washed with water. Hexane was distilled off, and the obtained crude product was purified by flash column chromatography, and 58.0 g of the desired compound (d) (white solid; ¹ H-NMR, ³¹ P-
A purity of 98% or more was obtained from NMR.

IR [ν (cm ^-1 )]: 2932, 2860,
1467, 1280, 1033 ¹ H-NMR [CDCl ₃ , δ (ppm)]: 0.89 (t, 9H), 1.2-1.4 (br, 77)
H), 1.6-1.9 (br, 3H), 3.91 (dd, 2H), 4.02 (dt, 2H), 4.11 (d
g, 2H)

Example 5 Cream Oil phase component: (wt%) Octyldodecyl myristate 5.0 Cetanol 2.0 POE (20) Sorbitan monostearate 1.5 Sorbitan monostearate 0.5 Compound (a) 2. 0 Butylparaben 0.1 Aqueous phase component: Glycerin 3.0 Methylparaben 0.2 Perfume 0.1 Purified water Balance 100.0 According to the above formulation, the oil phase components are mixed and heated to dissolve 80
C. Similarly, the water phase component was heated and mixed at 80 ° C., and this was added to the oil phase portion and emulsified by an emulsifier. The emulsion was gradually cooled to obtain a cream.

Example 6 Lipstick Base: (wt%) Octyldodecyl myristate 30.0 Castor oil 20.0 Batyl alcohol 25.0 Lanolin 5.0 Compound (b) 6.0 Compound (c) 6.0 Tocopherol 0.2 Propylparaben 0.2 Colorant: Titanium oxide 2.5 Organic dye 5.0 Perfume 0.1 100.0 According to the above prescription, the base was heated and melted and uniformly mixed.
The coloring material was added thereto, kneaded with a roll mill, and uniformly dispersed. It was redissolved, added perfume, degassed, poured into molds, quenched and solidified. The stick was removed from the mold, filled in a container, the appearance of the stick was adjusted, the surface was made uniform by passing through a flame, and a lipstick was obtained.

Example 7 Hair Tonic (% by Weight) Compound (d) 2.0 Menthol 0.2 Antibacterial Agent (Piroctone Auramine) 0.1 Methyl Nicotinate 0.1 Ethanol 45.0 Purified Water Balance 100.0 The above ingredients were dissolved by heating at 70 ° C. and cooled to obtain a hair tonic.

Example 8 Hair rinse (% by weight) Distearyldimethylammonium chloride 2.0 Polyoxyethylene cetyl ether 2.0 2-Heptyl undecanol 1.0 Compound (a) 3.0 Glycerin 2.0 Methylparaben 0. 1 Ethylparaben 0.1 Perfume 0.1 Purified water Balance 100.0 To purified water heated to 70 ° C., methylparaben and perfume were added and dissolved. The remaining components heated and mixed at 70 ° C. were added to this and emulsified. The hair was rinsed slowly.

Example 9 Medicinal Cream (% by Weight) (1) Dexamethasone 0.025 (2) Propylene Glycol 8.0 (3) Glycerin 5.0 (4) Liquid Paraffin 1.0 (5) Compound (d) 3 0.0 (6) Fatty acid alkanolamide 1.8 (7) Sorbitan monooleate 1.0 (8) Glycerin monofatty acid ester 1.5 (9) Preservative proper amount (10) Clay mineral (bentonite) 6.0 (11 ) Purified water Add (1), (4), (8) and (9) to the balance (5),
It is heated to 70 ° C., dissolved and mixed, and this is referred to as composition (A). (6) and (7) are added to a part of (11) and dissolved, and (2) and (3) are further added and mixed to obtain a composition (B). While maintaining the temperature at 70 ° C. and stirring the composition (B), the composition (A) was gradually added, preliminarily emulsified, and then emulsified with a homomixer. This was added to a mixture of (11) in which (10) had been added and dispersed in advance with stirring and cooled to obtain a cream.

Each of the cosmetics and external preparations obtained in Examples 5 to 9 has an excellent feel, a good affinity with skin and hair, excellent safety, and is extremely stable. It was

Example 10 Shampoo (% by weight) Lauryl ether sulfate sodium salt (EO = 3) 15.0 Lauric acid amidopropyl betaine 3.0 Decanoic acid monoglyceride 2.0 Compound (c) 2.0 Water balance 100.0 A shampoo having the above formulation was manufactured by a conventional method. The obtained shampoo was excellent in detergency and low irritation, and had a very high conditioning effect.

Example 11 Rinse in shampoo (% by weight) Polyoxyethylene (20) lauryl ether 10.0 Lauric acid amidopropyl betaine 5.0 Trimethylstearyl ammonium chloride 2.0 Silicone emulsion (BY22-029, Toray Dow Corning Incorporated) 3.0) Ethylene glycol distearate 1.0 The above compound (d) 2.0 Water balance 100.0 A rinse-in shampoo having the above formulation was produced by a conventional method. The rinse-in shampoo obtained was excellent in detergency and foamability and had a high rinse effect.

Example 12 Body shampoo (% by weight) Polyoxyethylene (20) lauryl ether 15.0 Lauroyl diethanolamide 3.0 Decanoic acid monoglyceride 2.0 Sodium laurate 2.0 Sodium myristate 1.5 Compound (c ) 2.0 water balance 100.0 A body shampoo having the above formulation was produced by a conventional method. The obtained body shampoo was excellent in detergency, foamability and rinsability, and had a high skin moisturizing effect.

Example 13 Cleansing Agent (Gel) (% by Weight) (1) Polyoxyethylene (20) Octyldodecyl Ether 15.0 (2) Glycerin 10.0 (3) Sorbitol 10.0 (4) Tri-2 -Ethylhexanoic acid glyceride 15.0 (5) Liquid paraffin (K-230) 5.0 (6) Compound (a) 10.0 (7) Water balance 100.0 According to the above formulation, (1) to (6) Is heated to 70 to 80 ° C to dissolve and mix, cooled to 50 ° C, and then stirred (7).
Was prepared by adding. The cleansing agent obtained was excellent in cleanability against makeup stains, and had a moisturized and moistened skin after rinsing.

Example 14 Facial cleanser (wt%) Emanone 1112 (manufactured by Kao Corporation) 10.0 Potassium laurate 5.0 Potassium myristate 3.0 Potassium palmitate 1.0 Stearic acid 1.0 Glycerin 15.0 Sorbitol 5.0 1,3-Butylene glycol 5.0 Lauric acid diethanolamide 2.0 Compound (a) 1.0 Compound (d) 1.0 Water balance 100.0 The face wash of the said prescription was manufactured by the conventional method. The obtained facial cleanser was excellent in detergency, had an extremely high skin care effect on the skin, and had almost no feeling of tightness.

[0043]

The compound (1) has a very high skin affinity, is highly polar, and has excellent safety and stability. Therefore, the cosmetics and external preparations of the present invention containing the compound (1) have excellent skin compatibility, good feel and high safety.

Claims (5)

[Claims] 1. The following general formula (1): [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 25 to 50 carbon atoms, and R ² has 6 to 50 carbon atoms.
Represents a linear, branched or cyclic alkyl group, a linear alkenyl group or an aryl group, wherein R ³ has 1 to 6 carbon atoms.
Represents a linear, branched or cyclic alkyl group, alkenyl group or aryl group. ] The phosphoric acid triester represented by these. 2. In the general formula (1), R ¹ and / or R ² is a branched alkyl group having 28 to 40 carbon atoms, and R ³
Is an alkyl group having 1 to 4 carbon atoms, and the phosphoric acid triester according to claim 1. 3. In the general formula (1), R ¹ and / or R ² is a group selected from a 2-dodecylhexadecyl group, a 2-tetradecyloctadecyl group and a 2-hexadecylicosyl group. Or the phosphoric acid triester according to 2. 4. A cosmetic containing the phosphoric acid triester according to claim 1. 5. An external preparation containing the phosphate triester according to any one of claims 1 to 3.