JPS5939404B2 - Anti-sun cosmetic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds capable of absorbing ultraviolet radiation in a specific range, and is useful in antisun cosmetic compositions for protecting human skin from the harmful effects of actinic radiation as well as for use in antisolar cosmetic compositions for protecting human skin from the harmful effects of actinic radiation. It is suitable for use as a preservative for cosmetic preparations that are susceptible to deterioration or discoloration.

For example, sunburn or erythema is caused by overexposure of a person's skin to sunlight and is often
It is known that wavelengths of light in the range of 280-315 IJ microns, called the erythema zone, cause such sunburns.

Below this wavelength range the sun's rays do not pose any danger.

This is because sunlight below this range is filtered by ozone in the atmosphere.

However, the UV radiation that causes or causes the desired tanning is in the range of 315 to 400 millimicrons.

Therefore, if exposure to sunlight is desired, it is important to protect the skin with compositions containing substances that absorb erythematous ultraviolet radiation to avoid unwanted sunburn.

However, the composition is one that obtains the desired t-B tan through the passage of light at wavelengths within the range of 315 to 400 millimicrons, particularly around 340 millimicrons, which provides the best tanning of the skin without causing erythema. It is necessary to pass light rays with a wavelength of .

Therefore, the protectant must exhibit a high absorption capacity between 280 and 315 IJ microns and a weak absorption capacity above 315 IJ microns.

In addition to this critical absorption capacity, the protective agent must possess other properties, in particular it must exhibit good resistance to external elements.

That is, it should exhibit good photochemical stability, good thermal stability, and have sufficient affinity for the skin and sufficient chemical stability that it will not be removed or degraded by perspiration or at least by washing. I have to do it.

Furthermore, they are often included in various cosmetic preparations, in particular hair compositions such as hair dyes and lacquers, shampoos and tinted hair set lotions, and other cosmetic products such as nail enamel compositions and tinted creams. It is also known that dyes do not always have sufficient photostability.

These cosmetic compositions, which are often presented in the form of solutions, emulsions, gels, suspensions or dispersions, are packaged in transparent glass or transparent plastic containers and are thus exposed to light not only during use but also during storage. exposed.

Hair lacquers are often packaged in transparent evaporative containers, especially so that the consumer can see and select the desired color.

Many of the dye components of this cosmetic composition do not have sufficient stability against light rays, especially when using triphenylmethane derivatives such as crystal violet, methyl violet and methyl green, so such cosmetics are It is also known that compositions often degrade rapidly.

This drawback is also experienced with a number of other dyes, which, although stable under certain concentration conditions, exhibit significant photosensitivity when used at relatively low concentrations.

It has also been observed that cosmetic compositions that are essentially colorless, such as colorless nail enamel, change somewhat and become yellow after prolonged exposure.

It has therefore been found that such cosmetic compositions, colored or uncolored, can generally only be stored for a certain period of time, on the order of only a few weeks.

In order to overcome this drawback, it has been proposed to add compounds capable of filtering the light rays into this composition.

However, such compounds must not only exhibit good filterability but also have good stability and sufficient solubility in carriers commonly used in cosmetic compositions.

The present invention provides new compounds meeting different criteria which effectively overcome the above-mentioned drawbacks.

It is therefore an object of the present invention to provide cosmetic antibodies and antibodies of the formula (1) in which R represents hydrogen and aralkyl having 1 to 12 carbon atoms, Y is chlorine, methyl or hydrogen, and X is chloride, para-toluene. The object of the present invention is to provide a cosmetic composition containing at least one antisun agent of the following types: sulfonate, ethylene sulfonate, methanesulfonate, camphosulfonate and methyl sulfate.

The present invention also relates to cosmetic compositions that are applied topically to the skin to protect the skin from ultraviolet radiation that causes erythema or sunburn, while at the same time browning the skin.

This composition is commonly used as a lotion solution, as a cream, gel, foam or milky emulsion, or in cosmetic preparations of this type.

For example, it can be provided as an aerosol. The compositions therefore contain the usual cosmetic adjuvants, such as thickening agents, emollients, superfatting agents.
Softeners, wetting agents, surfactants, preservatives, antifoaming agents, fragrances,
and any other ingredients commonly used in cosmetic compositions.

When the composition of the invention is provided in the form of an aerosol, it is preferably placed under pressure in a conventional aerosol cylinder or container in the presence of a propellant gas, which is a halogenated hydrocarbon or a mixture thereof, such as trichlorofluoromethane and dichlorodifluoromethane. packaged in.

In the compositions of the present invention, the sun protection agents mentioned above are generally present in an amount of 0.5-10% by weight of the composition.

As the solvent or cosmetic vehicle, water, lower alkanols, lower polyols or aqueous solutions of lower alkanols can be used.

Lower alkanols or lower polyols include, for example, ethanol, isopropanol, glopylene glycol,
Chrycerol or sorbitote may be used.

Compositions of the invention are often colorless, but may also be colored.

Therefore, the present invention also provides 0.0 based on the total weight of the composition.
01 - one or more components sensitive to ultraviolet radiation generally present in very low concentrations of the order of 0.01%;
In particular, it is an object to provide cosmetic compositions containing one or more light-sensitive dyes.

Such a composition is used as a protectant against ultraviolet light by the formula (■
) in an amount of about 0.05-5% based on the total weight of the composition.

In addition to dyes and Formula I compounds, such compositions may also include one or more of the following cosmetic adjuvants: surfactants, swelling agents, thickening agents, softening agents, superfats. bleaching agents, bleaching agents, film-forming agents, cosmetic resins, wetting agents, foam-forming agents, preservatives, fragrances, or any other ingredient commonly used in cosmetic compositions.

Typical cosmetic compositions containing compounds of formula (I) as ultraviolet filtration agents are capillary compositions, in particular hair lacquers, plasticized hair setting lotions, treating or' untangling.
) hair lotions, shampoos, dye shampoos, hair dye solutions, nail enamels, skin creams and dye foundations.

The compositions are also typically packaged in clear glass or clear plastic containers, as described above, and may also be provided in aerosol form.

Furthermore, the present invention also provides a cosmetic composition susceptible to alteration or deterioration by radiation, comprising incorporating into the composition a compound of formula (■)0 in an amount of about 0.05-5% based on the weight of the composition. Regarding how to protect.

The invention also relates to compounds of the formula (1) which are themselves good filters of light and which can be considered derivatives of benzylidenecamphor of the formula (1) as described in French Patent No. 2004142.

The compounds of formula (I) exhibit very interesting solubility properties, in which the compounds of formula (I) have a significantly better solubility than benzylidene camphor in a variety of media or vehicles.

For example, it is known that the use of conventional cosmetic vehicles and known filtration agents is often limited due to insufficient solubility of the filtration agents.

However, a number of compounds of formula (1) are particularly effective because their solubility in water or water-alcoholic media is considerably better than that of commonly used filter agents.

To illustrate this point, the following table shows the solubility values in water, ethanol, and a 50:50 water-ethanol mixture for the following compounds: (4) 4-((2-oxo-3-bornylidene) Methylcuphenyltrimethylammonium methylsulfate (compound of formula ■), (B) 4-((2-oxo-3-bornylidene)methylcuphenyltrimethylammonium p-toluenesulfonate (compound of formula ■), (C) 4- ((2-oxo-3-bornylidene) methylcouphenyltrimethylammonium methanesulfonate (compound of formula ■), (D) 4-((2-oxo-3-bornylidene)methylcouphenyltrimethylammonium chloride (compound of formula ■)
), and (E) 1,7,7-drimethyl-3-benzyritine [2,2,1]bicyclo-2-heptanone (benzylidene camphor, compound of formula 1, usual anti-solar radiation).

It can therefore be seen that the compounds of the present invention generally have better solubility in water and 50-50 water-ethanol solutions than benzylidene camphor.

Furthermore, the solubility of the compounds of the invention is not accompanied by their low level of retention on the skin.

On the contrary, the compounds of the invention show a marked improvement in their affinity for the skin.

The very desirable light absorption properties of the compounds of formula (I) of the present invention indicate that the compounds of formula (I) =
．． It can be seen from the table below showing the % transmission data at 0.01 mm.

Furthermore, the compounds of formula (I) were found to have excellent thermal and photochemical stability.

For example, exposure to an ultraviolet sun lamp for 3 hours or to 60° C. for 1 week did not change the transmission curve.

Furthermore, the harmlessness of this compound was confirmed from the results of skin toxicity tests.

Compounds of formula (I) are prepared according to the method of Haller by reacting substituted or unsubstituted p-dimethylaminobenzaldehyde with camphor and sodium or a strong base such as sodium alcoholate, sodium amide or sodium natride. the sodium salt of camphor prepared by and an inert solvent such as benzene,
It can be prepared by condensation in toluene, ether, dimethylformamide and dimethoxyethane.

The product is then subjected to quaternization or salt formation.

Example 1 Preparation of 1,7,7-drimethyl-4-dimethylamino-3-benzylidene (2,2,1)bicyclo-2-heptanone, i.e., 4-dimethylaminobenzylidene camphor, having the formula ■ Synthesis Camphor 577.5P (3 , 8 mol) and 205f of sodium methylate are heated at reflux in anhydrous toluene for 30 minutes.

After cooling to room temperature, p-dimethylaminobenzaldehyde 566P is added in one portion.

The resulting mixture is then heated under reflux for 4 hours, after which it is cooled to room temperature.

The reaction mixture is extracted with water, the toluene layer is collected and evaporated to dryness to yield a solid yellow residue 1013P.

This residue is then recrystallized from absolute ethanol to produce 711g of bright yellow crystals with a melting point of 110°C.

Elemental analysis: The compound of formula (I) is obtained starting from the 4-dimethylaminobenzylidene camphor of formula (e) prepared in Example 1 and by subsequent quaternization or salt formation.

Typical quaternizing agents that can be used are: (a) alkyl sulfates, such as methyl sulfate or ethyl sulfate; (b) alkyl-substituted alkyl sulfonates, such as methyl methanesulfonate; and (C) Alkyl-substituted arylsulfonates, such as methyl-p-4 luenesulfone-tt, = hamethylbromobenzenesulfonate.

The anion X- of structural formula (I) can also be obtained by anion exchange, for example by passing a compound of formula (I) through an anion exchange resin containing anions other than X-.

The compositions of the present invention may include one or more of the formula (1) land-water soluble protectants, other filtration agents such as other water-soluble filtration agents or one or more sun protection agents, or fat-soluble It may also be included together with one or more sun protection agents.

When the composition of the invention is provided in the form of an emulsion, the presence of both water-soluble and fat-soluble antisun agents is very advantageous since protection is obtained simultaneously in both the aqueous and oily layers of the emulsion. It is.

Furthermore, it has been observed that the highly desirable affinity of the compositions of the present invention for the skin may be improved even when containing other water-soluble sun protection agents that have less affinity for the skin than the compositions of the present invention. Ta.

The following example shows the preparation and application of compounds with the following formula: Preparation Example 2 Preparation of 4-dimethylaminobenzylidene camphor (prepared in Example 1) 750P and methyl sulfate) 334P is slowly heated to reflux in ethyl acetate.

An exothermic precipitate suddenly forms and when it subsides, the reaction mixture is heated to reflux for 3 hours.

A pale yellow solid precipitates out, which is then filtered, washed with ethyl acetate, and recrystallized in a benzene-acetonitrile mixture to yield 866 g of a white product with a melting point of 210°C.

Preparation of 4-((2-oxo-3-bornylidene)methyl]phenyltrimethylammonium p-toluenesulfonate. 4-Dimethylaminobenzylidene camphor (prepared in Example 1) 283f and methyl p-)toluenesulfonate 1861 were dissolved in toluene by diluent. Heat under reflux for 8 hours while stirring vigorously.

The precipitated white solid was filtered and dried to give 417 g of product, which after recrystallization in ethanol had a melting point of 305°C.
A white crystal 362'iI' having the following properties is obtained.

4-((2-oxo-3-bornylidene)methyl]phenyltrimethylammonium methanesulfonate produced in Production Example 1 28.3f and methyl methanesulfone) 16.
5? The mixture was thoroughly stirred and heated under reflux in 501 rL of toluene for 10 hours.

The precipitate formed is filtered and washed with toluene and then crystallized in a mixture of benzene and acetonitrile to form white crystals 26.1' with a melting point of 265°C.

Example 5 A solution of 10 g of the antisolar agent prepared in Example 2 in 20 ml of water is applied to an anion exchange resin in the form of chloride ions.

The resin is then eluted with water and the resulting eluate is concentrated by drying under reduced pressure.

The solid residue obtained is crystallized in a mixture of ethanol and benzene to recover 6.41 g of white crystals with a melting point of 240°C.

Elemental Analysis'C20H28CINO Example 6 3-Methyl-4-4:(2-oxo-3-bornylidene)methyl]phenyltrimethylammonium methyl sulfate Step (a): Formula % Formula % Production of bicyclo-2-heptanone.

2.32 ml of sodium is shaken vigorously in 100 ml of boiling toluene.

The toluene was then decanted, and the sodium particles formed were recovered with 100 ml of anhydrous sulfuric ether.

The recovered sodium grains were then treated with camphor 15.2°C while shaking and maintaining the temperature at 25°C by cooling.
? Add.

When all the sodium has reacted (4 to 5 hours)
, cool the reaction mixture to 0°C.

4-dimethylamino-2-methylbenzaldehyde 16
．． 3f was then added and the resulting mixture was first brought to 0°C.
Shake for 3 hours and then for 30 minutes under reflux of ether.

The reaction mixture is then cooled, at which point 100 ml of water are added to it.

The ether layer was then separated and dried over sodium sulfate.
The ether is then evaporated.

The resulting oily residue was fractionated and placed under 1 mynHg for 2
Both fractions (23,1') distilled at 43°C are collected and purified by crystallization in sulfuric ether to give yellow crystals with a melting point of 115°C.

Preparation of 3-methyl-4-((2-oxo-3-bornylidene)methyl]-phenyltrimethino J ammonium methyl sulfate.

Compound 14.9P prepared in step Qa) and methyl sulfate 6,3P are slowly heated under reflux in ethyl acetate for 3 hours.

The white solid formed is filtered and washed with ethyl acetate to give 12 g of white crystals with a melting point of 245°C.

Example 7 3-chloro-4-((2-oxo-3-bornylidene)
Preparation of methyl]phenyltrimethylammonium methyl sulfate (a) Quadratic formula % Formula % Preparation of (22 1)-bicyclo-2-heptanone A mixture of 76 g of camphor and 19.El' of sodium amide in 150 ml of dry toluene is mixed with 3 Shake under reflux for an hour.

After cooling to room temperature, 92 g of O-chloro-p-dimethylaminobenzaldehyde are added.

The resulting mixture is heated under reflux for 5 hours. Thereafter, the mixture is cooled and 400 ml of fishing rod are added to the cooled mixture.

The toluene layer is then separated, dried and concentrated to dryness.

The resulting residue is crystallized in isopropanol to yield 82 g of yellow crystals with a melting point of 128°C.

Elemental analysis: Preparation of 3-chloro-4-((2-oxo-3-bornylidene)methylrhophenyltrimethylammonium methyl sulfate of C19H24NOCI).

Acetonitrile4. A mixture of 42 g of the product of step (a) and 15.29 g of methyl sulfate in OOrul is heated under reflux for 12 hours.

The precipitate formed is filtered and crystallized in a mixture of benzene and acetonitrile to form pale yellow platelets with a melting point of 210°C.

Example 8 Preparation of sulfonate 4-dimethylamino-benzylidene-camphor (Example 1
56.1' and methylcamphorsulfone) 4.9.2 P in 300 ml of ethyl acetate are heated under reflux for 15 hours with good stirring.

After cooling to room temperature, the precipitate is filtered and washed with ethyl acetate, then recrystallized in a toluene-acetonitrile mixture, yielding 73 g of snow-white crystals with a melting point of 265°C.

Example 9 4-[(2-oxo-3-bornylidene)methyl J-
Preparation of phenyldimethylethylammonium ethyl sulfate 4-dimethylamino-benzylidene-camphor (Example 1
14 g of ethyl acetate and 8 g of diethyl sulfate were heated under reflux for 6 hours with thorough stirring in 100 rrLl of ethyl acetate.

After cooling to room temperature, the precipitate is filtered and washed with acetic acid (ethyl acetate) to yield 9.92 deliquescent white crystals with a melting point of 126-127°C.

Example 10 Preparation of 1-toluenesulfonate 4-dimethylamino-benzylidene-camphor (Example 1
) 2.8P and lauryl tosylate 3.4
1 at a temperature of 130-140°C for 6.5 hours.

The entire reaction mixture is dissolved in a sufficient amount of Improper Tool and the Improper Tool is then evaporated to yield white crystals of the product of the above formula with a melting point of 135°C.

Compounds in which R represents a hydrogen atom are obtained by protonation of the tertiary amine corresponding to the compound of formula (I), for example by reaction with a strong acid.

Use Example 11 An anti-sun lotion is produced as follows: Lanolin
2.52 Butylhydroxyanisole 0.025P Butylhydroxytoluene 0.025S' Octyl gallate
0.01251 has 8-12 carbon atoms
40 Triglyceride flavoring of 11 fatty acids 1.25 1 4-((2-oxo-3-borylidene)methyl]-phenyltrimethylammonium methyl sulfate ethanol (96° titer), total amount required
100 1 Example 12 An anti-sun lotion is prepared as follows: Glycerin 5 Polyethylene glycol (0.51 molecule - 400) Ethoxylated lanolin 1 Perfume (
Soluble) 2 gu4-((2-
oxo-3-pol 2 gniritene) methyl]
- Phenyltrimethylammonium methyl sulfate ethyl alcohol (96° tie 50 getter) Water, required amount Total amount 1001 Example 13 An anti-sun aerosol formulation is prepared as follows: Anhydrous ethyl alcohol 30 gisopropyl myristate 201 ricin oil (
Ricin oil) 2?
U/Rin 5g fragrance
11 4-((2-oxo-3-bornylidene) 2 g Methyl]-phenyltrimethylammonium methyl sulfate dichlorodifluoromethane 40 g The above composition is packaged under pressure in a conventional aerosol container.

Example 14 An anti-sun aerosol foam composition is prepared as follows: Nidipol wax (5ipol 3.5
? wax) Vaseline oil 6 Gisopropyl myristate 3 G preservative [Nipa Esthe 0.3 Glu 825
21,1 (Mixture of methyl, ethyl, butyl, and benzyl esters of hydroxybenzoic acid) Glycerin 10 g Fragrance
0,3g 4,-((2-oxo-3-pol 2.5gnyritene)methylcouphenyltrimethylammonium methyl sulfate water, required amount total amount 100g'dichlorodifluoromethane 15g The above composition was placed in a normal aerosol container. packaged under pressure.

Example 15 An anti-sun cream is prepared as follows: Cetylstearyl alcohol 2 Guglycerol monostearate 4 Gucetyl alcohol
4 Glaceline oil
5 Gubutyl stearate
5 Propylene glycol
7 Silicone oil 0.
1251 Sold under the trade name rPOLYOXJ 3
0.3 1825 to ethylene oxide polymer preservative with molecular weight 100,000 to 1,000,000 sold in
21) Fragrance 0.41 4-((2-oxo-3-pol 4 gniritene) methylcouphenyltrimethylammonium methyl sulfate Water, required amount Total amount 100 1 Example 16 Rainbow ball wax for producing anti-sun emulsion as follows 5 Glaceline oil 6 Gisopropyl myristate 3 Glysilicone oil
1 Gusetyl alcohol
II? glycerin
201 Preservative [Nipaester 0.
3g 82521J Fragrance 0.31 4-((2-oxo-3-pol 3 gniritene) methylcuphenyltrimethylammonium methyl sulfate water, required amount Total amount 100'?Example 1
7. A colored hair set lotion is prepared as follows: Vinylpyrrolidone-Copolymer of Vinyl 2 Guacetate (70730) (molecular weight 40000) Dye-Blue Victoria 0.001P (D
ye-Blue Victoria)BSA,
CI44045 Ethyl alcohol 50 1 Triethanolamine, required pH 7 4-((2-oxo-3-pol 0.2 gniritene)methylcouphenyltrimethylammonium methyl sulfate Water, required amount Total amount 100 ral Example 18 Colored hair set lotion Dicrotonic acid-vinyl acetate 2 g (10
Copolymer (part weight 50,000) of (90) (viscosity 7-9 cps at 35°C in a 5% wt solution in tetrachloroethane) Dye-CI Basic Violet 0.0 IP (Ba5ic Violet) 43, Cl42
555 Ethyl alcohol 50 1 Triethanolamine, required amount pH 74-((2-oxo-
3-borni 0.21 lithine) methylcouphenyltrimethylammonium p-) luenesulfonate water, required amount Total amount 100 rrtl.

Example 19 An anti-sun emulsion with moderate protection is prepared as follows: Cetylstearyl alcohol 51 condensed with 25 mol of ethylene oxide Cetyl alcohol 1 g 2-octyldodecyl alcohol-15 L? "Code
(Mixture of methyl, ethyl, butyl and benzylic esters of p-hydroxybenzoic acid) Fragrance 0.51 Water, required amount Total amount 1001 Example 20 An anti-sun cream with a strong protective effect is prepared as follows: Hydrogenation Polyoxyethylated PA 5 Cetylstearyl alcohol condensed with 52 moles of game oil ethylene oxide Lanolin 3 Alcohol of granolin 1 Turnesol oil (Turnesol 5 S'o
il) Vaseline oil 10 gbenzylidene camphor-2,51 4-(:(2-oxo-3-pol 4 gnyritene) methylcouphenyltrimethylammonium methyl sulfate preservative "Nipaester 82521j appropriate amount propylene glycol 5 g fragrance
0.51 Water, required amount Total amount 1001 Each compound or mixture of compounds of formula (0) is present in each one of the cosmetic compositions of Examples 11 to 20, based on the weight of the composition.
Can be used in an amount of 10%.

Example 21 (1) Compounds of Examples 3.4 and 7 in ethanol (96°
titer) 1.5% solution, thickness 0.01mm
The transmittance take is as follows.

(2) The solubility of the compounds of Examples 3.4 and 6 is as follows.

Claims (1)

Claims: A compound of the following formula: wherein R is hydrogen and alkyl having 1-12 carbon atoms, Y is chlorine, methyl and hydrogen, and X is chloride, para-toluenesulfonate, ethyl 1. A cosmetic composition containing a solution of antisun agents (sulfonate, methanesulfonate, camphosulfonate and methylsulfate).