JPH1087423A - Cosmetic for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a skin cosmetic containing a specific cationized UV absorbent as an active ingredient, excellent in adsorbability to skins, protecting skins from UV light, and excellent in effects for preventing the damages of the skins due to the UV light. SOLUTION: This skin cosmetic contains a compound of formula I (R<1> -R<3> are each an alkyl, or one or two of R<1> -R<3> are alkyl and the others are a hydroalkyl, benzyl; A is a residue obtained by removing a COOH or OH group relating to the bonding to a quaternary ammonium salt from an organic UV light absorbent having the COOH or OH group; X is Cl, F, Br, I, NO3 or 1/2 SO4 ). The compound of formula I is obtained e.g. by esterifying or etherizing the COOH or OH group of an organic UV light absorbent with a glycidyl ammonium salt of formula II or a compound of formula III (Y is Cl, F, etc.). The organic UV light absorbent having the COOH or OH group includes p- aminobenzoic acid and p-dimethylaminobenzoic acid. The compound of formula I is contained in an amount of 0.01-10wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic for skin, and more particularly, to a cationized ultraviolet absorber in which a quaternary ammonium salt is bonded to a carboxyl group or a hydroxyl group of an organic ultraviolet absorber having a carboxyl group or a hydroxyl group. The present invention relates to a cosmetic for skin which contains an agent and has an excellent effect of protecting skin from ultraviolet rays and preventing skin damage by ultraviolet rays.

[0002]

2. Description of the Related Art Conventionally, cosmetics include inorganic metal oxides having an ultraviolet scattering effect, such as zinc oxide and titanium oxide, for the purpose of protecting skin and skin from ultraviolet rays and preventing skin and skin damage due to ultraviolet rays. Or p-aminobenzoic acid,
Organic UV absorbers such as cinnamic acid and benzophenone have been widely used.

[0003] However, these inorganic metal oxides are insoluble in water and organic solvents, and when blended in cosmetics, it is necessary to use a dispersant or to shake them sufficiently before using them. There is a problem that it has no sorption property to the skin, is difficult to use for skin cosmetics that are washed away with water, and cannot provide a sufficient effect.

[0004] Organic UV absorbers are mostly oil-soluble, and when incorporated into aqueous skin cosmetics, they are dissolved in a large amount of polyhydric alcohol and then dissolved in the aqueous phase. It was necessary to add an emulsifier and the like (for example,
JP-A-6-336417, JP-A-6-34161
No. 9, etc.).

In view of the above, recently, ultraviolet absorbers having improved hydrophilicity by binding a functional group having a hydroxyl group to an organic ultraviolet absorber have been developed (for example, Japanese Patent Application Laid-Open No. 7-242693). However, even if such measures are taken, these organic UV absorbers do not sorb to the skin, so if they run down with sweat or swim in a sea bath or pool, they will be washed away and have a sufficient effect There was a problem that can not be raised.

[0006] Most sunscreen cosmetics containing an organic ultraviolet absorbent are commercially available as creamy or oily oily cosmetics. However, when sunscreen cosmetics are used for swimming in a pool using oily sunscreen cosmetics. Has a problem that an oil film floats on the water surface of the pool, and at present, some pools have banned the use of oil-based sunscreen cosmetics and sun oil.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems in the prior art, has excellent sorption to the skin, protects the skin from ultraviolet rays, and prevents damage to the skin due to ultraviolet rays. An object of the present invention is to provide a skin cosmetic having an excellent effect.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a quaternary ammonium salt is added to the carboxyl or hydroxyl group of an organic ultraviolet absorber having a carboxyl group or a hydroxyl group. Can increase the sorption property of the ultraviolet absorber to the skin, and further reduce the carbon chain length of all the functional groups directly connected to the nitrogen atom of the quaternary ammonium salt to 3 or less. As a result, the present inventors have found that the ultraviolet absorber can be made water-soluble and can be added to an aqueous skin cosmetic without using a dispersant or an emulsifier, thereby completing the present invention.

In the present invention, the cationized ultraviolet absorber contained in the skin cosmetic is an organic ultraviolet absorber having a carboxyl group or a hydroxyl group in which a quaternary ammonium salt is bonded to a carboxyl group or a hydroxyl group. The cationized ultraviolet absorber has the following general formula (I)

[0010]

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Wherein R ^{1 to} R ³ are an alkyl group having 1 to 20 carbon atoms or one or two of R ^{1 to} R ³ are an alkyl group having 1 to 20 carbon atoms, and And A is a residue obtained by removing a carboxyl group or a hydroxyl group hydrogen atom involved in binding to a quaternary ammonium salt from an organic ultraviolet absorber having a carboxyl group or a hydroxyl group. , X is C
1, F, Br, I, NO ₃ or 1 / 2SO ₄ ]
This cationized ultraviolet absorber is, for example, a carboxyl group or a hydroxyl group of an organic ultraviolet absorber represented by the following general formula (II)

[0012]

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Wherein R ^{1 to} R ³ are an alkyl group having 1 to 20 carbon atoms or one or two of R ^{1 to} R ³ are an alkyl group having 1 to 20 carbon atoms, and X is a hydroxyalkyl group or a benzyl group;
1, F, Br, I, NO ₃ or 1 / 2SO ₄ ]
Or a glycidyl ammonium salt represented by the following general formula (III):

[0014]

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[In the formula, R ^{1 to} R ³ are an alkyl group having 1 to 20 carbon atoms or one or two of R ^{1 to} R ³ are an alkyl group having 1 to 20 carbon atoms, and the rest is an alkyl group having 1 to 20 carbon atoms. X is a hydroxyalkyl group or a benzyl group;
l, F, Br, I, NO ₃ , 1 / 2SO ₄ , and Y represents a halogen atom such as Cl, F, Br, I, etc.] It is obtained by bonding or ether bonding.

As described above, since the quaternary ammonium salt is bonded to the organic ultraviolet absorber, the sorbability of the ultraviolet absorber to the skin is increased, and the ultraviolet absorber is provided with rinsing resistance to water. In addition, the ultraviolet absorbing action of the ultraviolet absorbing agent is more efficiently exhibited, and the action of preventing skin damage due to ultraviolet rays is improved.

[0017]

Further, when the carbon chain length of all the functional groups directly connected to the nitrogen atom of the quaternary ammonium salt bonded to the organic ultraviolet absorber is set to 3 or less, the ultraviolet absorber may be water-soluble. This makes it possible to easily incorporate an ultraviolet absorber into a water-based skin cosmetic without using a dispersant, an emulsifier, or the like.

As described above, in order to reduce the carbon chain length of all the functional groups directly connected to the nitrogen atom of the quaternary ammonium salt to 3 or less, the general formulas (I), (II) and (III) )), Wherein R ^{1 to} R ³ are an alkyl group having 1 to ³ carbon atoms, or one or two of R ^{1 to} R ³ are an alkyl group having 1 to 3 carbon atoms, and What is necessary is just to use 1-3 hydroxyalkyl groups.

Examples of the organic ultraviolet absorber having a carboxyl group or a hydroxyl group include benzoic acid ultraviolet rays such as p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-hydroxybenzoic acid and p-methoxybenzoic acid. Absorbents, cinnamic acid-based ultraviolet absorbers such as p-methoxycinnamic acid and 4-hydroxy-3-methoxycinnamic acid (ferulic acid), benzophenone-based ultraviolet absorbers such as oxybenzone and dihydroxydimethoxybenzophenone, and urocanic acid And urocanic acid-based ultraviolet absorbers. Some of these ultraviolet absorbers have both a carboxyl group and a hydroxyl group. In the present invention, those having both such a carboxyl group and a hydroxyl group can of course be used. In the above, having a carboxyl group or a hydroxyl group means not only having either a carboxyl group or a hydroxyl group but also having both a carboxyl group and a hydroxyl group.

The glycidyl ammonium salt represented by the above general formula (II) includes, for example, glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, glycidyl triethanol ammonium chloride, glycidyl tripropyl ammonium chloride, glycidyl trimethyl ammonium bromide, glycidyl lauryl. Dimethyl ammonium chloride, glycidyl myristyl dimethyl ammonium chloride, glycidyl cetyl dimethyl ammonium chloride, glycidyl stearyl dimethyl ammonium chloride, glycidyl coconut oil alkyl dimethyl ammonium chloride, glycidyl lauryl dimethyl ammonium bromide, glycidyl dilauryl methyl ammonium chloride, Triglycidyl lauryl dibenzyl ammonium chloride, glycidyl capryl dimethyl ammonium chloride, glycidyl cetyl diethanol ammonium chloride, and glycidyl dilauryl ethanol ammonium chloride is used.

Examples of the 3-halogen-2-hydroxypropylammonium salt represented by the general formula (III) include, for example, 3-chloro-2-hydroxypropyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltriethylammonium Chloride, 3-chloro-2-hydroxypropyltriethanolammonium chloride, 3-chloro-2-hydroxypropyltripropylammonium chloride, 3-chloro-2-
Hydroxypropyltrimethylammonium bromide, 3-bromo-2-hydroxypropyltrimethylammonium chloride, 3-bromo-2-hydroxypropyltrimethylammonium bromide, lauryl (3-chloro-2-hydroxypropyl) dimethylammonium chloride, myristyl (3-chloro -2-hydroxypropyl) dimethylammonium chloride,
Cetyl (3-chloro-2-hydroxypropyl) dimethyl ammonium chloride, stearyl (3-chloro-
2-hydroxypropyl) dimethylammonium chloride, coconut oil alkyl (3-chloro-2-hydroxypropyl) dimethylammonium chloride, caprylic (3-chloro-2-hydroxypropyl) dimethylammonium chloride, lauryl (3-chloro-2-hydroxy) Propyl) dimethylammonium bromide, lauryl (3-chloro-2-hydroxypropyl) dibenzylammonium chloride, lauryl (3-chloro-
2-hydroxypropyl) diethanolammonium chloride, dilauryl (3-chloro-2-hydroxypropyl) methylammonium chloride, capryl (3
-Chloro-2-hydroxypropyl) dimethylammonium chloride, cetyl (3-chloro-2-hydroxypropyl) diethanolammonium chloride and the like are used.

The reaction between an organic ultraviolet absorber having a carboxyl group or a hydroxyl group and a quaternary ammonium salt is carried out, for example, when the quaternary ammonium salt is a glycidyl ammonium salt represented by the general formula (II). Dissolving the glycidyl ammonium salt in a solvent such as N, N-dimethylformamide, adding the ultraviolet absorber to the solution,
This is performed by heating and mixing for 2 to 20 hours. If the reaction temperature is too low, the reaction does not proceed sufficiently, and if it is too high, the glycidyl ammonium salt is easily decomposed, so that the reaction temperature is preferably from 40 to 70 ° C, particularly preferably from 55 to 65 ° C.

The reaction between an organic ultraviolet absorber having a carboxyl group or a hydroxyl group and a 3-halogen-2-hydroxypropylammonium salt represented by the general formula (III) is usually carried out by hydroxylating the ultraviolet absorber. After converting to an alkaline salt with an aqueous alkali hydroxide solution such as an aqueous sodium solution or aqueous potassium hydroxide solution,
This is done by adding and mixing 2-hydroxypropyl ammonium salt. The reaction temperature and the reaction time are preferably 40 to 70 ° C, particularly preferably 55 to 65 ° C for 2 to 20 hours, as in the case of the glycidyl ammonium salt represented by the general formula (II).

In addition, for an organic ultraviolet absorber having both a carboxyl group and a hydroxyl group, the above-mentioned general formula (II)
The glycidyl ammonium salt represented by the general formula (III) and the 3-halogen-2-hydroxypropyl ammonium salt represented by the general formula (III) react preferentially with the hydroxyl group when reacted on the basic side, When a quaternary ammonium salt is ester-bonded to a carboxyl group with respect to an ultraviolet absorber having both hydroxyl groups, it is preferable to employ a reaction method using a glycidyl ammonium salt represented by the above general formula (II). When a quaternary ammonium salt is ether-bonded to a hydroxyl group, it is preferable to employ a reaction method using a 3-halogen-2-hydroxypropyl ammonium salt represented by the above general formula (III).

After the reaction, for example, the reaction solution is acidified with hydrochloric acid or sulfuric acid, extracted with ethyl acetate to remove the unreacted ultraviolet absorber, and the aqueous layer is concentrated to dryness under reduced pressure to remove the ethanol-soluble portion. After extracting and concentrating to obtain crude crystals, the crystals can be recrystallized with ethanol or a mixed solvent containing ethanol to obtain a purified product.

Examples of skin cosmetics containing the cationized ultraviolet absorber represented by the above general formula (I) include various creams such as lotion, cleansing cream, vanishing cream, face wash cream, milky lotion, face wash,
Various skin cosmetics such as body shampoos, soaps, body lotions, skin lotions, facial lotions, makeup cosmetics and the like can be mentioned.

The cationized ultraviolet absorber represented by the general formula (I) may be contained in a conventional skin cosmetic, and the content in the skin cosmetic is 0.01% by weight. %, Especially 0.1% by weight or more, and preferably 10% by weight or less, particularly preferably 5% by weight or less. When the content of the cationized ultraviolet absorber represented by the general formula (I) in the cosmetic for skin is smaller than the above, the effect of preventing the skin from being damaged by ultraviolet rays cannot be sufficiently obtained. When the content of the cationized ultraviolet absorber represented by the formula (I) in the cosmetic for skin is higher than the above, the effect of the increase in the content is not increased and the production cost of the cosmetic for skin is not increased. May increase.

In addition, the above-mentioned skin cosmetics may have the general formula (I)
Examples of the components that can be contained in combination with the cationized ultraviolet absorber represented by the following include alkyl sulfates such as sodium lauryl sulfate and triethanolamine lauryl sulfate, and polyoxyethylene (2EO) triethanolamine lauryl sulfate ( EO is ethylene oxide, and the value before EO indicates the number of moles of ethylene oxide added), polyoxyethylene (3EO) alkyl (any of 11 to 15 carbon atoms or a mixture of two or more) sodium ether sulfate Polyoxyethylene alkyl ether sulfates, such as sodium laurylbenzenesulfonate, triethanolamine laurylbenzenesulfonate, etc., and polyoxyethylene (3EO) tridecyl ether sodium acetate, such as sodium polyoxyethylene (3EO). Shi polyoxyethylene alkyl ether acetates, coconut oil fatty acid sarcosine sodium, lauroyl sarcosine triethanolamine, lauroyl methyl -β
-Sodium alanine, sodium lauroyl-L-glutamate, triethanolamine lauroyl-L-glutamate, coconut oil fatty acid-sodium L-glutamate, coconut oil fatty acid-L-glutamate triethanolamine, coconut oil fatty acid sodium methyltaurine, lauroylmethyltaurine N-acyl amino acid salts such as sodium, sodium ether sulfate alkane sulfonate, hydrogenated coconut oil fatty acid sodium glycerin sulfate, disodium undecylenoylamidoethyl sulfosuccinate, sodium octylphenoxydiethoxyethyl sulfonate, disodium oleate amide sulfosuccinate Dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate, polyoxyethylene alkyl (C12-16) Telluric acid (2~12EO), polyoxyethylene oleyl ether sodium phosphate,
Sodium polyoxyethylene cetyl ether phosphate,
Disodium lauryl polyoxyethylene sulfosuccinate, sodium polyoxyethylene lauryl ether phosphate, sodium lauryl sulfoacetate, sodium tetradecene sulfonate, collagen, keratin, fibroin, casein, soybean, wheat, corn, potatoes,
Anionic surfactants such as acylated hydrolyzed proteins obtained by acylating a protein hydrolyzate derived from animals and plants or microorganisms such as yeast with a fatty acid having 8 to 20 carbon atoms or salts thereof such as sodium, potassium and triethanolamine; 2-alkyl-N-carboxylmethyl-N-hydroxyethylimidazolinium betaine, sodium undecylhydroxyethylimidazolinium betaine,
Undecyl-N-hydroxyethyl-N-carboxymethylimidazolinium betaine, stearyl dihydroxyethyl betaine, stearyl dimethylaminoacetic acid betaine, coconut oil alkyl betaine, coconut oil fatty acid amide propyl betaine, coconut oil alkyl-N-carboxyethyl-N- Hydroxyethylimidazolinium betaine sodium, coconut oil alkyl-N-carboxyethoxyethyl-N-carboxyethylimidazolinium disodium hydroxide, coconut oil alkyl-N-carboxymethoxyethyl-N-carboxymethylimidazolinium disodium lauryl Sulfuric acid, N-coconut fatty acid acyl-
Amphoteric surfactants such as L-arginine ethyl / DL-pyrrolidone carboxylic acid, polyoxyethylene alkyl (C12-14) ether (7EO), polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene olein Glyceryl acid, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene cetyl stearyl diether, polyoxyethylene sorbitol lanolin (40EO), polyoxyethylene nonyl phenyl ether, polyoxyethylene polyoxypropylene cetyl ether, poly Oxyethylene polyoxypropylene decyl tetradecyl ether, polyoxypropylene (40) butyl ether, polyoxyethylene lanolin, poly Carboxymethyl ethylene lanolin alcohol,
Nonionic surfactants such as polyoxypropylene stearyl ether, alkyl glycoside and alkyl polyglycoside, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, ceto stearyl trimethyl ammonium chloride, stearyl bis (diethylene glycol) hydroxyethyl ammonium chloride, behenyl trimethyl ammonium chloride , Distearyl dimethyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride, behenyl trimethyl ammonium bromide,
Cetyltrimethylammonium iodide, oleylbenzyldimethylammonium chloride, oleylbis [polyoxyethylene (15EO)] methylammonium chloride, tri [polyoxyethylene (5EO)] stearylammonium, alkyltrimethylammonium salt, polyoxypropylene methyldiethylammonium chloride , Mink oil chloride fatty acid amidopropyldimethylhydroxyethylammonium, alkylpyridinium salt, chloride-γ
Cationic surfactants such as gluconamidopropyldimethylhydroxyethylammonium, cationic polymers such as cationized cellulose, cationized hydroxyethylcellulose, poly (diallyldimethylammonium chloride), polyvinylpyrrolidone and polyethyleneimine; amphoteric polymers and anionic polymers Synthetic polymers such as isostearic acid diethanolamide, undecylenic acid monoethanolamide, oleic acid diethanolamide, bovine fatty acid monoethanolamide, hardened bovine fatty acid diethanolamide, stearic acid diethanolamide, stearic acid diethylaminoethylamide, stearic acid monoethanolamide, Myristic acid diethanolamide, coconut oil fatty acid ethanolamide, coconut oil fatty acid diethanolamide , Thickeners such as lauric acid isopropanolamide, lauric acid ethanolamide, lauric acid diethanolamide, lanolin fatty acid diethanolamide, waxes, paraffins, fatty acid esters, glycerides, oils and fats such as animal and vegetable oils, animal and plant extracts, collagen, keratin , Fibroin, sericin, casein, soybean, wheat, corn, potato, rice (rice bran), yeast, mushrooms and other proteolytic peptides derived from animals and plants and microorganisms, and ester derivatives and N-quaternary ammonium derivatives thereof, Polysaccharide or a derivative thereof, propylene glycol, 1,3
-Wetting agents such as butylene glycol, ethylene glycol, glycerin and polyethylene glycol, lower alcohols such as ethanol, methanol, propyl alcohol and isopropyl alcohol, cetyl alcohol;
Higher alcohols such as stearyl alcohol, oleyl alcohol and behenyl alcohol, L-aspartic acid, sodium L-aspartate, DL-alanine,
Amino acids such as L-arginine, glycine, L-glutamic acid, L-cysteine, L-threonine, linear or cyclic methylpolysiloxane, methylphenylpolysiloxane, dimethylpolysiloxane polyethylene glycol copolymer, amino-modified silicone oil, Examples include silicones such as quaternary ammonium-modified silicone oils and silicone-modified peptides.

[0029]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. Prior to the examples, a method for producing the cationized ultraviolet absorber used in the examples is shown as a reference example. In the following Examples and Reference Examples,% indicating the concentration is% by weight.

Reference Example 1 Dimethylformamide 35 was placed in a 100 ml round bottom flask.
and a 75% aqueous solution of glycidyltrimethylammonium chloride in dimethylformamide.
g (0.033 mol) was dissolved. Then, 6 g of 4-dimethylaminobenzoic acid was added therein as an ultraviolet absorber.
(0.036 mol) was added and mixed at 60 ° C. for 12 hours to react. After completion of the reaction, the reaction solution was concentrated under reduced pressure to distill off the solvent, and 20 ml of ion-exchanged water was added to dissolve the residue. Next, 10% hydrochloric acid was added to adjust the pH of the solution to 3
After removing the unreacted insoluble material by filtration, the filtrate was distilled off under reduced pressure to obtain a pale yellow oily substance. The oily substance was transferred to a separating funnel and washed twice with about 20 ml of diethyl ether to remove unreacted p-dimethylaminobenzoic acid. Then, the ether-insoluble residue was recrystallized from ethanol-diethyl ether, and the crystals were collected by filtration to obtain 3.5 g of white crystals. Raw material p-
The yield based on dimethylaminobenzoic acid was 33.7%.

The melting point of the crystal is 221 to 222 ° C., and the crystal is RP-18F manufactured by Merck.
_254S (trade name) A single spot was obtained by thin-layer chromatography using a thin-layer chromatography plate with a developing solvent of acetonitrile: water = 20: 1 (color developed under iodine vapor). It seems that it has become a product.

The crystals were identified by mass spectrometry, infrared absorption spectrum analysis, ¹ H nuclear magnetic resonance spectrum analysis, and ultraviolet absorption spectrum analysis.

The results of mass spectrometry showed that M ⁺ was 281.18, and that glycidyltrimethylammonium chloride was ester-bonded to the carboxyl group of p-dimethylaminobenzoic acid. 2-hydroxypropyl ester (C
₁₅ H ₂₅ O ₃ N ₂ ).

The measurement of the infrared absorption spectrum was carried out by the KBr tablet method.
Absorption attributed to quaternary amine or hydroxyl in the vicinity of 300 cm ^-1, absorption attributed to an ester bond near 1700 cm ^-1, attributed to the aromatic ring in the vicinity of further 1600 cm ^-1 and around 1500 cm ^-1 absorption Was observed.

The ¹ H nuclear magnetic resonance spectrum was measured in dimethyl sulfoxide-d _{6. From the} ¹ H nuclear magnetic resonance spectrum, a peak of 6 H, which is considered to be due to a dimethyl group, 9 peaks attributable to the N group, two H peaks attributable to two types of methylene groups, an H peak attributable to the methine group and the hydroxyl group, and an H peak at the aromatic ring. Could be confirmed.

Further, in the ultraviolet absorption spectrum measured with an aqueous solution having a concentration of 2.5 × 10 ⁻⁵ mol / l, λ _max was observed at 315 nm, and an absorption peak was also observed at 223 nm. It was confirmed that the absorption wavelength of a certain p-dimethylaminobenzoic acid was maintained.

From these results, the crystals were identified as 3-trimethylammonio-2-hydroxypropyl ester of p-dimethylaminobenzoic acid.

Reference Example 2 30 ml of dimethylformamide and 6 g of a 75% aqueous solution of glycidyltrimethylammonium chloride (0.
The reaction, purification and recrystallization were carried out in the same manner as in Reference Example 1 except that 5 g (0.028 mol) of p-methoxycinnamic acid was used as an ultraviolet absorber, and the yield was 32.3% in a yield of 42.3%.
9 g of white crystals were obtained. The melting point of this crystal is 167-16
At 8 ° C., a single spot was obtained by the same thin layer chromatography as in Reference Example 1.

The identification of the crystals was performed by mass spectrometry, infrared absorption spectroscopy, ¹ H nuclear magnetic resonance spectroscopy and ultraviolet absorption spectroscopy as in Reference Example 1.

The result of mass spectrometry was M ⁺ 294.16, and 3-trimethylammonio-2-hydroxy of p-methoxycinnamic acid in which a glycidyltrimethylammonium salt was ester-bonded to the carboxyl group of p-methoxycinnamic acid. Molecular weight of propyl ester (C ₁₆ H ₂₄ O ₄ N) 29
Matched to 4.

In the infrared absorption spectrum analysis, 3400
absorption attributed to quaternary amine or hydroxyl in the vicinity cm ^-1, absorption attributed to the ester in the vicinity of 1700 cm ^-1, 1600 cm ^-1 and around 1500
At around cm ^−1, an absorption attributed to an aromatic ring was observed.

In the ¹ H nuclear magnetic resonance spectrum analysis, 9 H peaks attributed to a trimethyl group, 3 H peaks attributed to a methoxy group, and 2 types of methylene groups , A peak attributable to H on the aromatic ring and a peak attributable to H on the aromatic ring were confirmed.

Further, in the ultraviolet absorption spectrum measured with an aqueous solution having a concentration of 2.3 × 10 ⁻⁵ mol / l, λ _max was observed at 308 nm. In addition, a shoulder peak at 296 nm and peaks at 208 nm and 224 nm were also observed. An absorption peak was observed, and it was confirmed that the material retained the absorption wavelength of p-methoxycinnamic acid as a raw material.

From these results, the crystals were identified as 3-trimethylammonio-2-hydroxypropyl ester of p-methoxycinnamic acid.

Reference Example 3 35 ml of dimethylformamide and 7.5 g of a 75% aqueous solution of glycidyltrimethylammonium chloride were used.
(0.037 mol), 6 g of 4-hydroxy-3-methoxycinnamic acid (ferulic acid) as an ultraviolet absorber (0.
The reaction, purification and recrystallization were carried out in the same manner as in Reference Example 1 except that the compound was used in the same manner as in Reference Example 1 to obtain 4.8 g of white powder crystals in a yield of 45%.

The melting point of the crystals was 98 to 100 ° C., and the result of mass spectrometry was M ⁺ 310.16. Glycidyltrimethylammonium chloride was bound to the carboxyl group or hydroxyl group of 4-hydroxy-3-methoxycinnamic acid. (C ₁₆ H ₂₄ O ₅ N).

As a result of the infrared absorption spectrum analysis, 3
The absorption around 300 cm ^-1 was broad and the presence of hydroxyl groups was observed, and the absorption around 1700 cm ^-1 was considered to be attributed to an ester bond, suggesting that the substance had an ester bond.

As a result of ¹ H nuclear magnetic resonance spectroscopy, there is one H peak at δ5.94, which is considered to be due to OH on the aromatic ring, and the quaternary ammonium compound is ester-bonded to the carboxylic acid. It was confirmed that.

Further, the concentration was 2.26 × 10 ⁻⁵ mol / l.
The ultraviolet absorption spectrum measured in an aqueous solution, lambda _max
Is observed at 325 nm, and 214 n
m, 234 nm and 302 nm (shoulder peak)
Absorption was observed, and it was confirmed that the material retained the absorption wavelength of the raw material 3-hydroxy-4-methoxycinnamic acid.

From these results, the crystals were identified as 3-trimethylammonio-2-hydroxypropyl ester of 4-hydroxy-3-methoxycinnamic acid.

Reference Example 4 6 g (0.03 mol) of 4-hydroxy-3-methoxycinnamic acid (ferulic acid) as an ultraviolet absorber was dissolved in 35 ml of 1.5 N aqueous potassium hydroxide solution and placed in a 100 ml round bottom flask. Then, 9.5 g (0.03 mol) of a 60% aqueous solution of 3-chloro-2-hydroxytrimethylammonium chloride was added thereto, and the mixture was continuously reacted at 70 ° C. for 12 hours. After completion of the reaction, 10% hydrochloric acid was added to the reaction solution under ice cooling to adjust the pH to 3 to 4, and unreacted insolubles were removed by filtration. The filtrate was distilled off under reduced pressure to obtain 6.2 g of pale yellow crude crystals. The crude crystals were washed with diethyl ether to remove unreacted 4-hydroxy-3-methoxycinnamic acid, dissolved in ethanol, and recrystallized twice from ethanol-diethyl ether to obtain 3.8 g of a white powder. Crystals were obtained. The yield was 37%.

The melting point of the crystals was 82 to 83 ° C., and the result of mass spectrometry was M ⁺ 310.17, indicating that the carboxyl group or hydroxyl group of 4-hydroxy-3-methoxycinnamic acid had
Chloro-2-hydroxy trimethylammonium salt matches the molecular weight 310 of the union _{(C 16 H 24 O 5 N} ).

The results of the infrared absorption spectrum analysis indicate that the absorption at 3341 cm ^-1 was sharper than that of Reference Example 3 and that the number of hydroxyl groups was reduced.
At around 20 cm ^−1, an absorption considered to be due to an ether bond was observed.

The results of ¹ H nuclear magnetic resonance spectroscopy analysis show that the peak observed in Reference Example 3, which is attributed to OH on the aromatic ring, disappeared, and the quaternary ammonium salt was ether-bonded to the hydroxyl group. It was confirmed that.

Further, the concentration was 4.63 × 10 ⁻⁵ mol / l.
The ultraviolet absorption spectrum measured in an aqueous solution, lambda _max
Is observed at 310 nm, and 213n
m, absorption at 228 nm and 284 nm was confirmed, and it was confirmed that the absorption wavelength of the raw material 4-hydroxy-3-methoxycinnamic acid was maintained.

From these results, this crystal was converted to 4- (3-
It was identified as (trimethyl-2-hydroxypropyloxy) -3-methoxycinnamic acid.

[Absorbance of cationized ultraviolet absorber] Table 1
The ultraviolet absorption wavelength and molecular extinction coefficient of a cationized ultraviolet absorber obtained as a reaction product in each reference example and a methanol solution of the ultraviolet absorber used as a raw material are shown.

[0058]

[Table 1]

As shown in Table 1, the absorption wavelengths of the cationized UV absorber obtained as the reaction product and the UV absorber used as the raw material did not change so much, and the molecular extinction coefficient was large in each of the reference examples. There is no significant fluctuation, and the carboxyl group or hydroxyl group of the organic UV absorber has the general formula (II)
A glycidyl ammonium salt represented by the general formula (II
Even when a quaternary ammonium salt such as a 3-halogen-2-hydroxypropylammonium salt represented by I) is ester- or ether-bonded, the ultraviolet absorption wavelength hardly changes, and the molecular extinction coefficient is greatly reduced. No, it was found that the ultraviolet absorbent used as a raw material retained the ultraviolet absorbing power.

[Solubility of cationized ultraviolet absorber] Table 2
Shows the solubility when the cationized ultraviolet absorber obtained as a reaction product in each Reference Example was dissolved in ion-exchanged water at 18 ° C. For comparison, the solubility of the ultraviolet absorber used as a raw material in each Reference Example when dissolved in ion-exchanged water at 18 ° C. is shown together with the substance name.

[0061]

[Table 2]

As shown in Table 2, the raw material UV absorber used in each Reference Example was such that 4-hydroxy-3-methoxycinnamic acid was slightly soluble and the others were hardly soluble.
The cationized UV absorber obtained in each Reference Example shows a solubility 100 times or more higher than that of the UV absorber used as a raw material, and it may be water-soluble by cationizing the UV absorber of each raw material. It was clear.

Example 1 and Comparative Example 1 Two types of body lotions having the compositions shown in Table 3 were prepared.
Treat the skin with each body lotion,
The sunburn preventing effect was evaluated.

In Example 1, 3-trimethylammonio-2-hydroxypropyl ester of p-dimethylaminobenzoic acid prepared in Reference Example 1 was used as a cationized ultraviolet absorber. The p-dimethylaminobenzoic acid used as a raw material in 1 is used as an ultraviolet absorber.

The amounts of each component, including Table 3, are based on parts by weight. If the amount is not a solid content, the solid content concentration is shown in parentheses after the component name. The reason why the amounts of the ultraviolet absorbers differ between the examples and the comparative examples is that they were blended to have the same molar concentration.

[0066]

[Table 3]

The body lotions of Example 1 and Comparative Example 1 were applied to 10 panelists (5 males and 5 females).
The right arm is the body lotion of Example 1, and the left arm is Comparative Example 1.
Apply 2ml of each body lotion, lightly rinse with water, expose both arms to sunlight for 3 hours on a sunny day in summer, examine the degree of erythema immediately after the exposure,
The degree of sunburn 24 hours after the exposure was examined. Table 4
The results are shown in the figure, where the numbers are the number of people.

[0068]

[Table 4]

As is evident from the results shown in Table 4, the skin treated with the body lotion of Example 1 containing the cationized ultraviolet absorber was more sun-treated than the skin treated with the body lotion of Comparative Example 1. The occurrence of erythema due to exposure to light was small, and the occurrence of sunburn was reduced 24 hours after the exposure. The body lotion of Example 1 was excellent in the effect of preventing skin damage due to ultraviolet rays. This is presumably because the cationized ultraviolet absorber contained in the body lotion of Example 1 had rinsing resistance, stayed on the skin, and efficiently exhibited its ultraviolet absorbing effect.

Example 2 and Comparative Example 2 Two types of body shampoos having the compositions shown in Table 5 were prepared.
The degree of sunburn of the skin washed with each body shampoo was evaluated.

In Example 2, the p-methoxycinnamic acid prepared in Reference Example 2 was used as a cationized ultraviolet absorber.
In Comparative Example 2, p-methoxycinnamic acid used as a raw material in Reference Example 2 was used as an ultraviolet absorber using trimethylammonio-2-hydroxypropyl ester.

[0072]

[Table 5]

The body shampoos of Example 2 and Comparative Example 2 were used by five panelists (two males and three females) five days before going to sea bathing. Were evaluated by themselves to see if they were effective or not. The washing method was such that the whole body was divided into right and left, one was washed with the body shampoo of Example 2, and the other was washed with the body shampoo of Comparative Example 2, but the evaluation was made by comparing the sunburn condition of both hands and feet. Table 6 shows the results. The amount of body shampoo used was 5 in both Example 2 and Comparative Example 2.
ml, and for cleaning, apply body shampoo to the cleaning sponge and use the cleaning sponge to
Body washing was performed.

[0074]

[Table 6]

As is clear from the results shown in Table 6, all the panelists found that the body shampoo of Example 2 containing the cationized ultraviolet absorber had a higher sunburn preventing effect than the body shampoo of Comparative Example 2. Answering, the effect of including the cationized UV absorber was apparent.

Example 3 and Comparative Example 3 Two types of lotions having the compositions shown in Table 7 were prepared, and the skin was treated with each of the lotions to evaluate the effect of preventing sunburn.

In Example 3, 3-trimethylammonio-2-hydroxypropyl ester of 4-hydroxy-3-methoxycinnamic acid produced in Reference Example 3 was used as a cationized ultraviolet absorber. In Comparative Example 3, The 4-hydroxy-3-methoxycinnamic acid used as the raw material is used as an ultraviolet absorber.

[0078]

[Table 7]

The lotion of Example 3 and Comparative Example 3 was
As in Example 1, 10 panelists (5 males, 5 females)
To the person), the right arm was applied with the lotion of Example 3 and the left arm was applied with 2 ml of the lotion of Comparative Example 3, and rinsed lightly with water. Exposed,
The degree of erythema immediately after the exposure was examined, and the degree of sunburn 24 hours after the exposure was examined. Table 8 shows the results, where the numerical values are the numbers of each person.

[0080]

[Table 8]

As is evident from the results shown in Table 8, the skin treated with the lotion of Example 3 containing the cationized ultraviolet absorber was more effective than the skin treated with the lotion of Comparative Example 3. Less erythema due to light exposure,
There was little sunburn 24 hours after the exposure, and the lotion of Example 3 was excellent in the effect of preventing skin damage by ultraviolet rays, and the effect of including the cationized ultraviolet absorber was clear.

Example 4 and Comparative Example 4 Two types of emulsions having the compositions shown in Table 9 were prepared, the skin was treated with each of the emulsions, and the effect of preventing sunburn on the beach was evaluated.

In Example 4, 4- (3-trimethyl-2) produced in Reference Example 4 was used as a cationized ultraviolet absorber.
-Hydroxypropyloxy) -3-methoxycinnamic acid is used, and in Comparative Example 4, 4-hydroxy-3-methoxycinnamic acid used as a raw material in Reference Example 4 is used as an ultraviolet absorber.

[0084]

[Table 9]

The emulsions of Example 4 and Comparative Example 4 were mixed with 10 panelists (5 males and 5 females) in the same manner as in Example 1.
2), the right arm was applied with the emulsion of Example 4 and the left arm was applied with 2 ml of the emulsion of Comparative Example 3, respectively, and both arms were exposed to sunlight on the seashore in summer for 3 hours. Was evaluated individually to determine whether the emulsion was effective or not. Table 10 shows the results.

[0086]

[Table 10]

As is evident from the results shown in Table 10, 9 out of 10 panelists found that the emulsion of Example 4 containing the cationized ultraviolet absorber had a better effect of preventing sunburn than the emulsion of Comparative Example 4. The answer was high, and the effect of including the cationized ultraviolet absorber was apparent.

[0088]

EFFECTS OF THE INVENTION The skin cosmetic composition of the present invention can be used as a water-insoluble or sparingly soluble organic ultraviolet absorbent, for example, of the general formula (II)
A glycidyl ammonium salt represented by the general formula (II
A cationized ultraviolet absorber which has been cationized by binding a quaternary ammonium salt such as a 3-halogen-2-hydroxypropylammonium salt represented by the formula (I), and is incorporated into the skin. Since it has excellent properties and has rinsing resistance, it has an excellent effect of protecting the skin from ultraviolet rays and preventing the skin from being damaged by ultraviolet rays. Further, when the carbon long chains of all the functional groups directly connected to the nitrogen atom of the quaternary ammonium salt to be bonded are 3 or less,
The ultraviolet absorber becomes water-soluble, and can be added to water-soluble skin cosmetics, which could not be added conventionally, without using a dispersant, an emulsifier or the like.

Claims (4)

[Claims] 1. A compound represented by the following general formula (I): [Wherein, R ^{1 to} R ³ represent an alkyl group having 1 to 20 carbon atoms or one or two of R ^{1 to} R ³ have 1 to 20 carbon atoms.
Wherein the remaining is a hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group, and A represents a carboxyl group or a carboxyl group involved in binding to a quaternary ammonium salt from an organic ultraviolet absorber having a carboxyl group or a hydroxyl group. X is Cl, F, Br,
I, NO ₃ or ＳＯSO ₄ ]. 2. R ^{1 to} R ³ are an alkyl group having 1 to ³ carbon atoms, or one or two of R ^{1 to} R ^{3 have 1 to 3} carbon atoms.
The skin cosmetic according to claim 1, wherein the alkyl group is 3 and the remainder is a hydroxyalkyl group having 1 to 3 carbon atoms. 3. An organic ultraviolet absorber having a carboxyl group or a hydroxyl group is a benzoic acid ultraviolet absorber such as p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-hydroxybenzoic acid, or p-methoxybenzoic acid. Cinnamate UV absorbers such as p-methoxycinnamic acid and 4-hydroxy-3-methoxycinnamate; benzophenone UV absorbers such as oxybenzone and dihydroxydimethoxybenzophenone; and urocanic acid UV absorbers such as urocanic acid. The skin cosmetic according to claim 1, wherein the cosmetic is at least one member selected from the group. 4. The skin cosmetic according to claim 1, wherein the content of the cationized ultraviolet absorber represented by the general formula (I) is from 0.01% by weight to 10% by weight.