JPH05230081A - New phosphoric ester, ultraviolet absorber comprising the same as active ingredient and cosmetic containing the same absorber - Google Patents

Abstract

PURPOSE:To obtain the subject new compound having excellently ultraviolet protecting performance, useful as an active ingredient for ultraviolet absorber, showing neither oiliness nor greasiness in the case of addition to cosmetics such as milky lotion or cream, providing a cosmetic having a refreshing touch. CONSTITUTION:A phosphoric ester of formula I (R<1> is cinnamoyl or benzoyl; R<2> is 2-12C chainlike alkylene; M<1> and M<2> are H, alkali metal ion, etc.) such as a compound of formula II. The compound of formula I, for example, is obtained by reacting a carboxylic acid of formula R<3>COOH (R<3> is residue obtained by removing carbonyl from acyl of R<2>) with a dial of the formula HO-R<2>-OH in an inert solvent such as benzene in the presence of an acid catalyst such as p-toluenesulfonic acid to give a monoester compound of the formula R<1>-O-R<2>-OH and reacting this compound with phosphorus oxychloride in an inert solvent such as THF in the presence of a base such as triethylamine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphoric acid ester, an ultraviolet absorber containing the phosphoric ester as an active ingredient, and a cosmetic containing the ultraviolet absorber.

[0002]

2. Description of the Related Art In recent years, ultraviolet rays have attracted attention as one of the causes of skin diseases, and it is becoming clear that ultraviolet rays are deeply involved in skin diseases such as sunburn, aging, and skin cancer. Against this background, it is important to protect the skin from ultraviolet rays, and many cosmetics such as sunscreen preparations, skin care, foundations, etc. containing ultraviolet protective substances are on the market.

Ultraviolet rays are long wavelength ultraviolet rays (UV-A; 32).
0-400 nm), medium wavelength ultraviolet (UV-B; 290-3)
20 nm) and short-wavelength ultraviolet rays (UV-C; 290 nm or less). Among them, UV-A and UV-B reaching the surface of the earth have been shown to be harmful to the skin, and many of them are used to protect these ultraviolet rays. UV protection substances are being developed. For example, as UV-A protective substances, inorganic compounds such as titanium oxide, iron oxide and zinc oxide, and 4-t-butyl-
Oil-soluble organic compounds such as 4'-methoxydibenzoylmethane are known, and UV-A can be produced by methods such as fine particle formation, ultrafine particle formation, hydrophobic surface treatment, and compounding with other substances.
It has been devised to enhance the defense effect and to make it a material that can be used as a cosmetic material according to the purpose. Also UV-B
As protective substances, para-aminobenzoic acid, salicylic acid,
Methoxycinnamic acid, benzophenone and the like and their derivatives are known and used as cosmetic materials. The above-mentioned UV protective substance is an insoluble powder or an oil-soluble substance which is poorly soluble in water, so when it is applied to sunscreens and skin care products, it is blended in formulations such as emulsions, creams and oils for practical use. ing. However, it has been pointed out that such preparations have a drawback that they are greasy and sticky when applied to the skin, and a product having a non-greasy and refreshing feel is desired. Specifically, in addition to formulations such as emulsions, creams, oils, etc., a lotion or lotion, etc., containing an ultraviolet protective substance, is desired to have a formulation that is refreshing without stickiness and that keeps skin moist. As described above, most of the UV protective substances currently in practical use are insoluble powders and oil-soluble substances that are poorly soluble in water, so it was extremely difficult to compound them in lotions and lotions. ..

It is known that some extracts from animals and plants have an ultraviolet protection ability. For example, it is known that a water-soluble extract such as yarrow, aloe, biloba, burdock and salvia, and ferulic acid have a sun protection effect. Has been. However, extracts from these plants and animals are not always suitable as a cosmetic material in terms of insufficient sun protection, poor storage stability, problems such as coloring, supply amount and cost. Is hard to say.

[0005]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to show no greasiness and stickiness when compounded in preparations such as emulsions, creams, foundations, lotions, blushers and lipsticks, and to protect against UV rays. An object is to provide an ultraviolet absorber having excellent performance, and to provide a cosmetic containing the same.

[0006]

In view of such circumstances, the inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, the phosphoric acid ester having a specific acyl group has an excellent ultraviolet protection ability, and It has been found that emulsions and creams containing this have excellent stability and a refreshing feel,
The present invention has been completed.

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

[0008]

[Chemical 2]

[Wherein R ¹ is a cinnamoyl group which may have a substituent or a benzoyl group which may have a substituent, R ² is an oxygen atom inserted between carbon atoms A straight-chain or branched alkylene group having a total carbon number of 2 to 12 is shown, M ¹ and M ² : the same or different, a hydrogen atom, an alkali metal ion, an ammonium ion, and an alkanol ammonium ion having a total carbon number of 2 to 14 Which represents an alkylammonium ion having 1 to 14 carbon atoms in total].

The present invention also provides an ultraviolet absorber containing the phosphoric acid ester represented by the general formula (1) as an active ingredient, and a cosmetic containing the same.

In the general formula (1) representing the compound of the present invention, R ¹ represents a cinnamoyl group which may have a substituent or a benzoyl group which may have a substituent. Include an alkoxy group having 1 to 22 carbon atoms, a hydroxy group, an amino group, an alkylamino group, a dialkylamino group and the like. These may have 1 to 3 substituents on the benzene nucleus of the cinnamoyl or benzoyl group. Here, as the alkoxy group having 1 to 22 carbon atoms,
Methoxy group, ethoxy group, propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, sec-butyloxy group, isoamyloxy group, n-hexyloxy group, n-octyloxy group, 2
-Ethylhexyloxy group, dodecyloxy group, hexadecyloxy group and the like can be mentioned. The alkyl group of the alkylamino group and the dialkylamino group has 1 to 22 carbon atoms.
The alkyl group is preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t
ert-butyl group, sec-butyl group, isoamyl group,
Examples thereof include n-hexyl group, n-octyl group, 2-ethylhexyl group, dodecyl group and hexadecyl group. R ¹
Particularly preferred specific examples of p-methoxycinnamoyl group, o-methoxycinnamoyl group, p-ethoxycinnamoyl group, o-ethoxycinnamoyl group, o, p-
Dimethoxycinnamoyl group, 3-hydroxy-4-methoxycinnamoyl group, p- (N, N-dimethylamino)
Examples thereof include a benzoyl group, p- (N, N-diethylamino) benzoyl group, p-hydroxybenzoyl group, o-hydroxybenzoyl group, p-aminobenzoyl group and o-aminobenzoyl group.

R ² is ethylene, propylene, pentamethylene, hexamethylene, decamethylene,
Examples thereof include dodecamethylene, monooxapentamethylene, dioxaoctamethylene, trioxaundecamethylene and the like.

Particularly preferred specific examples of the compound (1) of the present invention include the following compounds (1a) to (1l).

[0014]

[Chemical 3]

[0015]

[Chemical 4]

The compound (1) of the present invention can be produced, for example, as follows.

[0017]

[Chemical 5]

[0018] wherein, R ³ represents a residue remaining after excluding the carbonyl group from an acyl group represented by R ^2, R ^1,
R ² , M ¹ and M ² have the same meanings as above]

That is, a carboxylic acid (2) or an acid halide thereof is reacted with a diol (3) to obtain a monoester body (4), which is then reacted with phosphorus oxychloride to form a monophosphate ester. Thus, the phosphoric acid ester (1) of the present invention can be obtained.

The reaction between the carboxylic acid (2) or its acid halide and the diol (3) is carried out by benzene, toluene,
It is preferable to use excess diols (3) in the presence of an acid catalyst such as paratoluenesulfonic acid in an inert solvent such as hexane. In addition, the obtained monoester body (4)
The reaction of phosphorus oxychloride with tetrahydrofuran (T
It is preferably carried out in an inert solvent such as HF) in the presence of a base such as triethylamine.

The compound (1) of the present invention thus obtained has an excellent ultraviolet absorbing action, particularly a UV-B absorbing action, and the ultraviolet absorbing agent of the present invention containing the compound (1) is the compound of the present invention ( One kind or two or more kinds of 1) may be used as they are, but a mixed form in addition to the carrier is preferable. The carrier may be any one that is inert to the compound (1) of the present invention, and may be a solid, liquid, emulsion, foam, gel or the like. Typical examples thereof include water, alcohols, oils and fats (for example, hydrocarbon oils, fatty acid esters, long-chain alcohols, silicone oils), fine powders such as starch or talc, and low boiling point hydrocarbons used as aerosol propellants. Or halogenated hydrocarbon etc. are mentioned. To the ultraviolet absorbent of the present invention, other components such as preservatives, fragrances, colorants, and surfactants may be added and compounded unless the ultraviolet absorbing effect of the compound (1) of the present invention is impaired. it can.

A cosmetic containing the compound (1) of the present invention (hereinafter referred to as "cosmetic of the present invention") is one of the compounds (1) of the present invention having an affinity for the cosmetic base or Two
It is prepared by appropriately selecting at least one kind and mixing this with a known cosmetic base by a conventional method to prepare a dosage form such as cream, solution, oil, spray, stick, emulsion, foundation, ointment and the like.

That is, the compound (1) of the present invention is used as a cosmetic group.
Depending on the agent, it can be used as an oil base
Cosmetic oil, oily cream or oily milk containing a large amount of oil
Liquid, a weak oily cream or oily emulsion containing a large amount of water,
Based on oils from basic cosmetics such as water-based lotions
Makeup such as foundation and lipstick
All forms with UV absorption, including cosmetics
Can be manufactured. Suitable base and
And solvents include solid or liquid paraffin and
Star oil, ceresin, ozokerite or montan filter
Hydrocarbons such as sea urchins; olives, earth wax, carnauba
Vegetable oil or animal oil such as carp, lanolin or whale wax
Fat and wax; further stearic acid, palmitic acid, olein
Acid, glycerin monostearate, glycerin
Distearate, glycerin monooleate
Stell, isopropyl myristate ester, isopro
Pill stearate or butyl stearate
Fatty acids such as ter and their esters; ethyl alcohol
, Isopropyl alcohol, cetyl alcohol,
Allyl alcohol, palmityl alcohol or hexyl
Alcohols such as dodecyl alcohol
It Also, such as glycol, glycerin or sorbitol
Use any polyhydric alcohol with moisturizing effect
You can

The compounding amount of the compound (1) of the present invention in the ultraviolet absorbent of the present invention and cosmetics is not particularly limited as it may vary depending on the use form, and an effective amount may be present, but generally in the entire composition. 0.1 to 20% by weight, preferably 0.5 to
It is preferable to add 10% by weight.

The ultraviolet absorbent and the cosmetic of the present invention may contain only the compound (1) of the present invention, but other UV-
More preferably, it is used as a usual sunscreen cosmetic in combination with a B absorber or a UV-A absorber.
Examples of such UV-B absorbers include p-methylbenzylidene-D, L-camphor or sulfonic acid sodium salt thereof; 2-phenylbenzimidazole-5-
Sulfonic acid sodium salt, 3,4-dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, 4-phenylbenzophenone-2'-carboxylic acid isooctyl ester, p-methoxycinnamic acid ester, 2
-Phenyl-5-methylbenzoxazole, p-dimethylaminobenzoic acid esters and the like can be mentioned. U
As the VA absorber, 4-methoxy-2'-carboxydibenzoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone or di Examples include benzylidene camphor.

In addition to the above components, various additives can be added to the cosmetics of the present invention. Suitable additives include, for example, W / O type and O / W type emulsifiers. As the emulsifier, a commercially available emulsifier can be used. Further, a thickening agent such as methyl cellulose, ethyl cellulose or carboxymethyl cellulose, polyacrylic acid, tragacanth, agar or gelatin can also be added as an additive. Furthermore, if necessary, a fragrance, a preservative, a moisturizer, an emulsion stabilizer, a medicinal component and / or a physiologically acceptable coloring agent may be added.

[0027]

EFFECTS OF THE INVENTION According to the present invention, a UV absorber having a large UV protection ability is obtained, and when it is blended in lotion, emulsion, cream, etc., it has a non-greasy, refreshing feel and protects against UV rays. A cosmetic excellent in action can be obtained.

[0028]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (Synthesis of Compound (1f)) (1) 30 g (0.17 mol) of p-methoxycinnamic acid, 60 g (0.97 mol) of ethylene glycol, 1.5 g of p-toluenesulfonic acid and 200 ml of benzene were added. The mixture was placed in a 500 ml four-necked flask and refluxed under nitrogen using a Dean Stark trap until water did not distill. After completion of the reaction, dilute with double amount of benzene, and then water, saturated sodium bicarbonate water,
The extract was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 35.8 g of p-methoxycinnamic acid 2-hydroxyethyl ester as white crystals. The purity was 97% by GLC analysis. At ^{_{200MH z 1 H-NMR, δ}} = 2.5 to hydroxyl, [delta] = 3.8 to methoxy, δ = 3.85,4.35
To methylene, δ = 6.3, 7.65 to olefin, δ =
Aromatic ring proton signals were observed at 6.9 and 7.45,
Formation of p-methoxycinnamic acid 2-hydroxyethyl ester was confirmed. (2) 16.6 g (0.108 mol) of phosphorus oxychloride was dissolved in 50 ml of THF, put in a 300 ml three-necked flask, and cooled to -60 ° C under nitrogen introduction. P-Methoxycinnamic acid 2-hydroxyethyl ester 2 obtained in (1)
0 g and 10.9 g of triethylamine were dissolved in 40 ml of THF and added dropwise. At this time, the reaction solution was kept at -30 ° C or lower. The stirring was continued for 3 hours as it was, then the temperature was raised to 0 ° C., and the stirring was further continued for 1 hour. Then add 9 ml of water,
Subsequently, 21.9 g of triethylamine was dissolved in 30 ml of THF and added dropwise. At this time, the temperature of the reaction solution was kept at 10 ° C. or lower. After completion of the dropping, the reaction solution was kept at 0 ° C. and stirred overnight. After that, the precipitated triethylamine hydrochloride was filtered off, the filtrate was concentrated, and the obtained residue was dissolved in ethyl acetate. This is washed with water, dilute hydrochloric acid and water, and the solvent is distilled off.
8.4 g of phosphoric acid monoester (1f) was obtained as yellowish white crystals. It was confirmed by 200 MH _Z ¹ H-NMR that the proton signal of the hydroxyl group disappeared and that the compound (1f) was produced due to the presence of the proton signal of the phosphate group. UV absorption maximum λ _{ma x} of the compound is 308nm
(MeOH).

Example 2 (Synthesis of compound (1j)) (1) 100 g of p-methoxycinnamic acid (0.561 mo)
l), triethylene glycol 500g (3.33mo
l), p-toluenesulfonic acid 4.1 g, toluene 40
Add 0 ml and 200 ml of hexane to a 2 l four-necked flask,
The mixture was refluxed with nitrogen using a Dean Stark trap until no water was distilled off. After completion of the reaction, the reaction mixture was diluted with 500 ml of toluene, washed with water, saturated aqueous sodium hydrogen carbonate, water and saturated saline, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 139 g of a triethylene glycol monoester of p-methoxycinnamic acid as a yellow oil. The purity was 95% or more by GLC analysis.
In 200MH _Z ¹ H-NMR, δ = 2.1 hydroxyl group, δ
= 3.8, methoxy group, δ = 3.5-4.5, methylene, δ = 6.35, 7.7, olefin, δ = 6.9,
A proton signal of the aromatic ring was observed at 7.5, and formation of a triethylene glycol monoester of p-methoxycinnamic acid was confirmed. (2) Add 25 g (0.163 mol) of phosphorus oxychloride to 50 m
Dissolve in 1 L THF, put in a 300 ml four-necked flask,
It was cooled to -60 ° C while introducing nitrogen. P obtained in (1)
-50 ml of 45.9 g of triethylene glycol monoester of methoxycinnamic acid and 16.5 g of triethylamine
Was dissolved in THF and added dropwise. At this time, the reaction solution is -3
The temperature was kept below 0 ° C. The stirring was continued for 3 hours, then the temperature was raised to 0 ° C., and the stirring was continued for 2 hours. Then 14 ml
Of water was added, and then 33 g of triethylamine was dissolved in 50 ml of THF and added dropwise. At this time, the temperature of the reaction solution was kept at 10 ° C. or lower. After completion of the dropping, the reaction solution was kept at 0 ° C. and stirred overnight. After that, the precipitated triethylamine hydrochloride was filtered off, the filtrate was concentrated, and the obtained residue was dissolved in ethyl acetate. This was washed with water, dilute hydrochloric acid and water, and the solvent was evaporated to obtain 60 g of compound (1j) as a yellowish white oil. It was confirmed by 200 MH _Z ¹ H-NMR that the proton signal of the hydroxyl group disappeared and that the compound (1j) was produced due to the presence of the proton signal of the phosphate group. The maximum UV absorption λ _max of this compound is 309 nm (M
OH).

Example 3 (Synthesis of Compound (1a)) (1) 70 g (0.393 mol) of p-methoxycinnamic acid,
266 g (2.25 mol) of 1,6-hexanediol,
p-toluenesulfonic acid 2.0 g, toluene 600 ml,
Hexane (300 ml) was placed in a 2 l four-necked flask, and the mixture was refluxed under nitrogen with a Dean Stark trap until no water was distilled off. After completion of the reaction, the mixture was diluted with a double amount of toluene, washed with water, saturated aqueous sodium hydrogen carbonate, water and saturated saline, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain 92.6 g of p-methoxycinnamic acid 6-hydroxyhexyl ester as white crystals. The purity was 95% or more by GLC analysis. 200MH _Z ¹ H-
By NMR, a hydroxyl group at δ = 1.7, a methoxy group at δ = 3.8, methylene at δ = 1.5-1.9 and 3.7, 4.2, and δ = 6.3, 7.7. Olefin, δ = 6.9,
A proton signal of an aromatic ring was observed at 7.5, and production of p-methoxycinnamic acid 6-hydroxyhexyl ester was confirmed. (2) 39.1 g (0.255 mol) of phosphorus oxychloride was dissolved in 100 ml of THF, placed in a 300 ml three-necked flask, and cooled to -60 ° C under nitrogen introduction. 61.4 g of p-methoxycinnamic acid 6-hydroxyhexyl ester and 25.8 g of triethylamine were dissolved in 100 ml of THF and added dropwise. At this time, the reaction solution was kept at -30 ° C or lower. The stirring was continued for 3 hours as it was, then the temperature was raised to 0 ° C., and the stirring was further continued for 1 hour. Then 21.2 ml of water was added, followed by 51.6 g of triethylamine in 30 ml of THF.
And was added dropwise. At this time, the temperature of the reaction solution is 10 ° C.
Kept below. After completion of the dropping, the reaction solution was kept at 0 ° C. and stirred overnight. After that, the precipitated triethylamine hydrochloride was filtered off, the filtrate was concentrated, and the obtained residue was dissolved in ethyl acetate. This is washed with water, dilute hydrochloric acid and water, and the solvent is distilled off.
7.2 g of compound (1a) was obtained as a pale yellow oil.
It was confirmed by 200 MH _Z ¹ H-NMR that the proton signal of the hydroxyl group disappeared and that the compound (1a) was produced due to the presence of the proton signal of the phosphate group. The maximum UV absorption λ _max of the compound is 308 nm (MeO
H).

Example 4 Using the compound (1f) of the present invention obtained in Example 1,
An emulsion having the following composition was prepared. Emulsion composition (% by weight) Squalane 5.0 Vaseline 2.0 Beeswax 0.5 Sorbitan sesquioleate 0.8 Polyoxyethylene (20 mol of ethylene oxide added) Oleyl ether 1.2 Butylparaben 0.1 Compound (1f) 3 0.0 Propylene glycol 5.0 Ethanol 5.0 Carboxyvinyl polymer (1% aqueous solution) 20.0 Potassium hydroxide 0.1 Methylparaben 0.2 Purified water Residual emulsion preparation method In purified water, the compound (1f) of the present invention and propylene were added. Glycol was added, ethanol was further added, and the mixture was heated and mixed at 70 ° C. to prepare solution A. Separately, squalane, petrolatum, beeswax, sorbitan sesquioleate, polyoxyethylene oleyl ether, butylparaben and methylparaben were mixed and maintained at 70 ° C. to prepare solution B. Then, the solution A was added to the solution B to carry out preliminary emulsification. An aqueous solution of carboxyvinyl polymer was added to the preliminary emulsion, and after uniform mixing, an aqueous solution of potassium hydroxide was added for neutralization. Then, it was uniformly emulsified with a homomixer and then cooled to 30 ° C. to prepare an emulsion. The obtained emulsion had a refreshing feel. Even after storage at 40 ° C. for 1 month, no change in appearance or feel such as separation or coloring was observed.

Example 5 Using the compound (1f) of the present invention obtained in Example 1, an O / W type cream having the following composition was prepared. O / W type cream composition (% by weight) Squalane 37.5 Reduced lanolin 8.0 Beeswax 6.0 Fatty acid glyceride 4.0 Cetanol 5.0 Methoxycinnamic acid octyl ester 2.0 Monostearic acid glyceride 2.0 Butylparaben 0 .1 Polyoxyethylene (20 mol of ethylene oxide added) Sorbitan monolauryl phosphate 2.0 Compound (1f) 3.0 Propylene glycol 5.0 Methylparaben 0.2 Purified water Residual O / W type cream preparation method Purified water, book Inventive compound (1f) and propylene glycol were mixed and maintained at 70 ° C. to prepare solution C. Separately, squalane, reduced lanolin, beeswax, fatty acid glyceride, cetanol, methoxycinnamic acid octyl ester, monostearic acid glyceride, butyl paraben,
Polyoxyethylene sorbitan monolaurate and methyl paraben were mixed and kept at 70 ° C. to prepare a liquid D. Solution D is added to solution C for pre-emulsification and homogenized with a homomixer, then cooled to room temperature and O / W
A mold cream was prepared. The resulting O / W cream is
It had a nice and refreshing feel. Even after storage at 40 ° C. for 1 month, no change in appearance or feel such as separation or coloring was observed.

Example 6 Using the compound (1f) of the present invention obtained in Example 1,
A W / O type cream having the following composition was prepared. W / O type cream composition (% by weight) α-monoisostearyl glyceryl ether 2.0 Squalane 1.0 Myristic acid octyldodecyl ester 5.0 Vaseline 6.0 Methoxycinnamic acid octyl ester 2.0 Butylparaben 0.1 Compound (1f) 3.0 86% glycerin 5.0 magnesium sulfate 1.0 methylparaben 0.2 purified water residual W / O type cream composition preparation method α-monoisostearyl glyceryl ether, squalane, myristic octyldodecyl ester, petrolatum, Methoxycinnamic acid octyl ester, butylparaben and methylparaben were mixed and kept at 70 ° C. to prepare solution E. Separately from this, glycerin, magnesium sulfate and purified water were mixed and kept at 70 ° C. to prepare solution F.
Solution F was added to solution E to emulsify, and the mixture was cooled to room temperature to prepare a W / O type cream. The obtained W / O type cream had a good spread and a refreshing feel. Even after storage at 40 ° C. for 1 month, no change in appearance or feel such as separation or coloring was observed.

Example 7 Using the compound (1f) of the present invention obtained in Example 1,
A milky liquid foundation having the following composition was prepared. Emulsion foundation composition (wt%) Stearic acid 2.4 Propylene glycol monostearate 2.0 Isostearyl alcohol 0.2 Liquid lanolin 2.0 Liquid paraffin 3.0 Myristic acid isopropyl ester 8.5 Methoxycinnamic acid octyl ester 2 0.0 Butylparaben 0.1 Titanium oxide 8.0 Talc 4.0 Compound (1f) 3.0 Sodium carboxymethylcellulose 0.2 Bentonite 0.5 Propylene glycol 4.0 Triethanolamine 1.0 Methylparaben 0.2 Purified water Preparation Method of Residual Milk Liquid Foundation To the purified water, the compound (1f) of the present invention and bentonite are added, to which sodium carboxymethyl cellulose previously dispersed in propylene glycol is added and dissolved. To this, triethanolamine and methylparaben were added and mixed to prepare a liquid G. Apart from this, stearic acid, propylene glycol monostearate, isostearyl alcohol, liquid lanolin, liquid paraffin,
Myristic acid isopropyl ester, p-methoxycinnamic acid ester and butylparaben are added and mixed, and the temperature is 80 ° C.
The solution H was prepared. Titanium oxide and talc were added to liquid G with stirring, passed through a colloid mill and kept at 75 ° C, to which liquid H heated to 80 ° C was added with stirring, mixed well, and cooled to room temperature. A milky liquid foundation was prepared. The obtained milky liquid foundation had a refreshing feel and good stability.

Example 8 A lotion having the following composition was prepared using the compound (1f) of the present invention obtained in Example 1. Toner lotion composition (% by weight) Glycerin 5.0 Propylene glycol 4.0 Oleyl alcohol 0.1 Polyoxyethylene (20 mol of ethylene oxide added) Sorbitan monolauric acid ester 1.5 Polyoxyethylene (20 mol of ethylene oxide added) Lauryl ether 0 .5 Compound (1f) 3.0 Ethanol 7.0 Methylparaben 0.2 Purified water Preparation method of residual cosmetic water Glycerin, propylene glycol and the compound (1f) of the present invention were mixed at room temperature and dissolved to prepare liquid I. Was prepared. Apart from this, ethanol, oleyl alcohol,
Liquid J was prepared by mixing polyoxyethylene sorbitan monolaurate, polyoxyethylene lauryl ether and methyl paraben at room temperature and dissolving them. J
The solution was added to solution I to solubilize it. The obtained lotion had a refreshing feel without stickiness. Even when stored at 40 ° C. for 1 month, no change in appearance or feel such as separation or coloring was observed.

Test Example A lotion containing the compound of the present invention and a water-soluble extract of aloe known as a water-soluble ultraviolet absorber was prepared, and its texture and stability were evaluated. The results are shown in Table 1.
The touch was evaluated by 10 panelists applying a lotion on their faces and the following criteria were used. ◯: Very refreshing. Δ: A little refreshing feeling is lacking. X: There is no feeling at all.

[0038]

[Table 1]

[Procedure amendment]

[Submission date] February 13, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The reaction between the carboxylic acid (2) and the diols (3) is carried out in an inert solvent such as benzene, toluene or hexane in the presence of an acid catalyst such as paratoluenesulfonic acid, and excess diols (3). Is preferably used. Also,
The reaction of the obtained monoester (4) with phosphorus oxychloride is preferably carried out in an inert solvent such as tetrahydrofuran (THF) in the presence of a base such as triethylamine.

Claims (4)

[Claims] 1. A compound represented by the general formula (1): [In the formula, R ¹ represents a cinnamoyl group which may have a substituent or a benzoyl group which may have a substituent, R ² : a total in which an oxygen atom may be inserted between carbon atoms. A straight-chain or branched-chain alkylene group having 2 to 12 carbon atoms is shown. M ¹ and M ² : the same or different, hydrogen atom, alkali metal ion, ammonium ion, alkanol ammonium ion having 2 to 14 carbon atoms, and total carbon Which represents an alkylammonium ion of the number 1 to 14]. 2. The phosphoric acid ester according to claim 1, wherein R ¹ in the general formula (1) is a p-alkoxycinnamoyl group. 3. An ultraviolet absorber containing the phosphoric acid ester according to claim 1 or 2 as an active ingredient. 4. A cosmetic containing the ultraviolet absorbent according to claim 3.