JP3447804B2 - Benzal malonate derivative having organosilicon group, method for producing the same, ultraviolet absorber and cosmetic containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel organosilicon group having an excellent ultraviolet absorbing action, good photostability and excellent solubility in silicone oil, which is useful as a raw material for cosmetics. The present invention relates to a salmalonate derivative, a method for producing the same, an ultraviolet absorber and a cosmetic containing the same.

[0002]

2. Description of the Related Art In recent years, the influence of ultraviolet rays on the skin has been feared due to the strengthening of ultraviolet rays by the destruction of the ozone layer and the development of dermatology.

UV rays are long-wavelength UV rays (UV-A) of 400 to 320 nm depending on the action wavelength in dermatology.
20-290nm medium wavelength ultraviolet (UV-B) and 290
It can be divided into short wavelength ultraviolet rays (UV-C) of nm or less. Of these, UV-A and UV except UV-C, which is absorbed in the ozone layer and hardly reaches the ground
-B is known to cause various skin disorders. For example, when the skin is exposed to UV-A, the skin is immediately blackened (immediate blackening effect), and its energy reaches the dermis, thereby changing the elastic fibers in the blood vessel wall and connective tissue. On the other hand, excessive exposure to UV-B causes erythema and blisters, promotes melanin formation, and causes disorders such as pigmentation. Further, excessive exposure to both UV-A and UV-B is considered to promote aging of the skin, causing spots, wrinkles, freckles, and the like, and causing long-term skin cancer.

Further, it is known that ultraviolet rays cause damage to hair such as fading, change in texture, decrease in water absorption, loss of elasticity and change in keratin structure.

As the influence of ultraviolet rays on human skin and hair is clarified, a compound (ultraviolet absorber) that absorbs UV-A and UV-B is developed to prevent it. It has become to. For example,
As a UV-A absorber, one containing a derivative such as benzophenone or benzoylmethane is known.
As the -B absorbent, cinnamic acid, benzophenone, 4-
Those containing derivatives such as aminobenzoic acid and salicylic acid are known.

However, these are (a) UV-A and U
Absorb V-B as much as possible, (b) stable to light and heat, (c) toxicity to skin, irritation,
Other properties such as no harmful effects, (d) sustained effect, and (e) excellent compatibility with cosmetic bases, which are required as UV absorbers for protecting skin and hair There is nothing to be satisfied. Among these properties, conventional ultraviolet absorbers are particularly insufficient in stability against light (ultraviolet rays) and are known to undergo decomposition or reaction by ultraviolet rays [eg, Int. J. Cosm
etic Science. 10 , 53 (1988)]. Degradation of such an ultraviolet absorber not only leads to a reduction in the duration of the effect, but the effect of the degradation product itself or the product of the reaction between the degradation product and the compound on the skin cannot be ignored [Fragrance Journal, 84 , 32 (198
7)].

Further, cosmetics containing an ultraviolet absorber are
Due to its high frequency of use in hot summers, there is an increasing need to prevent runoff due to sweat and sebum and increase sustainability. Therefore, in recent years, various silicone oil bases have been used to improve the water resistance (water repellency) of cosmetics. However, conventional ultraviolet absorbers have extremely low solubility in silicone oil bases.

Therefore, in order to improve the compatibility with a silicone oil base or the water resistance of the ultraviolet absorbent itself, an attempt to bond an ultraviolet absorbing group to a silicone or an organic silicon group has been disclosed in Japanese Patent Publication No. 63-16416. Kaihei 1-
299210, JP-A-2-167291, JP-A-2-217622, JP-A-2-270816, JP-A-2-270817, and JP-A-3-28.
No. 7588, No. 3-287589, No. 4-182421, No. 4-368392, No. 5-43585, No. 5-590.
No. 69, JP-A-5-178865, and the like.

However, these proposed UV absorbers are required to be used in the UV absorbers (a) to (a).
None of the conditions (e) are satisfied, and there is a drawback that stability to light (ultraviolet rays) is insufficient. Further, a silicone (polysiloxane) having a benzalmalonate functional group has been proposed in JP-A-2-270816 and JP-A-6-500125. However, these silicones are unstable due to decomposition of siloxane bonds under acidic conditions, and there is a problem that they are a major limitation when compounded in cosmetics and the like.

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned conditions (a) to (e) required for an ultraviolet absorber, especially the solubility in a silicone oil base which has hitherto been insufficient. The object of the present invention is to provide a novel substance having excellent light stability and excellent light stability and compounding stability in cosmetics.

[0011]

Means for Solving the Problems The present inventor has made extensive studies in view of such circumstances, and as a result, the novel benzalmalonate derivative having an organosilicon group represented by the following general formula (1) has excellent ultraviolet absorption. It has an action and excellent photostability, and also has good solubility in silicone oil and excellent compatibility with other cosmetic bases, and can be suitably used in cosmetics, etc. The present invention has been completed by finding that the ultraviolet absorber and the cosmetics have an excellent ultraviolet protection action having a long duration.

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

[0013]

[Chemical 4]

[In the formula, R ¹ and R ² represent hydrocarbon groups which may be the same or different, R ³ represents an alkyl group which may be the same or different, and R ⁴ , R ⁵ and R ⁶ represent The same or different alkyl groups having 1 to 8 carbon atoms or phenyl groups are shown, A is an alkylene group, and n is 0.
The present invention provides a benzalmalonate derivative represented by the formula [2], a method for producing the same, an ultraviolet absorber and a cosmetic containing the same.

The benzalmalonate derivative of the present invention is represented by the above general formula (1), and the hydrocarbon group represented by R ¹ and R ² in the formula has 1 to 20 carbon atoms.
Preferred are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group,
n-heptyl group, n-octyl group, n-decyl group, n-
Linear alkyl groups such as dodecyl group, n-tetradecyl group, n-hexadecyl group and n-octadecyl group; isopropyl group, isobutyl group, t-butyl group, 2,2-dimethylpropyl group, 2-methylbutyl group, 2- Methylpentyl group, cyclohexylmethyl group, cyclohexylethyl group, 2-ethylhexyl group, 3,5,5-trimethylhexyl group, 2-propylheptyl group, 3,7-dimethyloctyl group, 2-hexylundecyl group, 5, 7,7
-Trimethyl-2- (1,3,3-trimethylbutyl)
Branched-chain alkyl group such as hexyl group; cyclic alkyl group such as cyclohexyl group; allyl group, 3-butenyl group, 1
Examples thereof include linear alkenyl groups such as 0-undecenyl group, branched chain alkenyl groups such as 1-methyl-2-propenyl group and 3-methyl-3-butenyl group; aralkyl groups such as benzyl group. Among these, a linear or branched alkyl group is preferable, and a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferable from the viewpoint of solubility in silicone oil. Although R ¹ and R ² may be the same or different, it is preferable that they are the same from the viewpoint of easy availability.

In the general formula (1), the alkyl group represented by R ³ may be linear or branched, but in order to enhance the characteristics of solubility in silicone oil, A straight-chain alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group; an isopropyl group, an isobutyl group, a t-butyl group, 2 , Branched-chain alkyl groups such as 2-dimethylpropyl group, 2-methylbutyl group, and 2-methylpentyl group can be exemplified, but a methyl group is particularly preferable because of easy availability.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ in the general formula (1) may be linear or branched, but is easily available. Therefore, straight-chain ones are preferable, and those having 1 to 6 carbon atoms are particularly preferable from the viewpoint of solubility in silicone oil.
Methyl group, ethyl group, n-propyl group, n-butyl group,
Examples of the n-hexyl group include R ⁴ , R ⁵ , and R ^6.
May be the same or different. Further, a phenyl group can also be mentioned as a preferable example.

The alkylene group represented by A in the general formula (1) may be a straight chain or branched chain alkylene group, but the reactivity, selectivity and yield in the hydrosilylation reaction in the production may be improved. It is preferable that the carbon atom bonded to Si from the surface is methylene (-CH _2- ). Further, from the viewpoint of solubility in silicone oil, those having 2 to 6 carbon atoms are particularly preferable.

[0019]

[Chemical 5]

N represents a number from 0 to 2, and there is no limitation on the substitution position on the aromatic ring, but the compound with n = 0 has 305
It is particularly preferable because it has a maximum absorption (λ _max ) at up to 320 nm and has a very strong ultraviolet absorption effect.
^{_{-CH = C (CO 2 R 1}} ) (CO 2 R 2) compounds substituted at the meta-position i.e. 3-position relative to the group has a strong UV absorption indicates a maximum absorption at 320~335nm, n = 2 At -CH = C (CO ₂ R ¹ ) (CO ₂
The compound substituted at the 3- and 5-positions with respect to the R ² ) group is 305-
It has a maximum absorption at 320 nm and has a strong ultraviolet absorption effect, and these compounds can be mentioned as preferable examples.

Benzalmalonate derivative of the present invention (1)
Can be produced, for example, according to the following reaction formula.

[0022]

[Chemical 6]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , A and n are the same as the above, A ¹ is an alkenyl group] That is, a 4-hydroxybenzaldehyde derivative (7) and an alkenyl halide (6) are combined with an alkali metal hydride or an alkali metal carbonate. After reacting in the presence of a base such as a salt or an alkaline earth metal carbonate to convert it to a compound (5), Kn is added in the presence of a malonate derivative (4) and a catalyst.
The objective benzalmalonate derivative (1) can be obtained by subjecting the compound (3) to oevenagel condensation and reacting it with the silanes (2) in the presence of a catalyst.

Examples of the catalyst for the condensation reaction of the compound (5) and the malonate derivative (4) include amines, acids, and carboxylates, which can be used in appropriate combination. Further, this condensation reaction is preferably performed while heating and removing water generated by the reaction to the outside of the reaction system. The malonate derivative used here is malonic acid and R ¹
OH and R ² OH (R ¹ and R ² are the same as above) can be obtained by subjecting an alcohol to an ordinary esterification reaction using an acid catalyst. Various malonate derivatives (4), and further benzalmalonate derivative (1) of the present invention
Can be obtained.

The alkenyl group represented by A ¹ in the compounds (6), (5) and (3) may be linear or branched, and the olefinic double bond may be a terminal. It may be internal or internal, but from the viewpoints of reactivity in hydroxylation reaction, selectivity and yield, those having an olefinic double bond at the terminal are preferable, and the silicone oil of the compound (1) is further preferable. 2 to 6 carbon atoms in terms of solubility in
Are particularly preferred, for example CH ₂ = CH-, CH ₂ = CHCH _2- ,
CH ₂ = CHCH ₂ CH _2- , CH ₂ = CHCH ₂ CH ₂ CH _2- , CH ₂ = CHCH ₂ CH ₂ CH ₂ CH
_2- straight chain alkenyl group such as;

[0026]

[Chemical 7]

Alkenyloxybenzalmalonate induction
The reaction between the body (3) and the silanes (2) is solvent-free or solvent-free.
In the presence of a catalyst. As a catalyst used here
Are those commonly used for hydrosilylation, such as
Free-radical initiators; ruthenium, rhodium, palladium
Complex compounds of metals such as aluminum, osmium, iridium and platinum
Those supported on silica gel or alumina
Which can be mentioned. Of these, chloroplatinic acid, Sp
eier reagent (chloroplatinic acid dissolved in isopropyl alcohol
Liquid), Organometallics,6, 191
The vinyl siloxane platinum catalyst described in (1987) is preferable.
Good The amount of catalyst used should be sufficient to accelerate the reaction.
There is no particular limitation as long as it is compound (3) 1 mol
Against 10 ^-6-10^-1A mol range is preferred. This reaction
The use of reaction solvent is not essential in
Alternatively, the reaction may be carried out in a suitable solvent. As a reaction solvent
Is not particularly limited as long as it does not inhibit the reaction
Is a charcoal such as pentane, hexane, cyclohexane, etc.
Hydrogenated solvent; Ben such as benzene, toluene, xylene
Zen-based solvent; diethyl ether, diisopropyl ether
Ether solvents such as methanol; ethanol, iso
Alcoholic solvents such as propyl alcohol and butanol
Are preferred.

This reaction proceeds at 0 to 200 ° C., but it is preferable to carry out at 40 to 150 ° C. in consideration of the reaction rate and coloring of the product. The reaction time is preferably about 0.5 to 24 hours.

The ultraviolet absorber of the present invention may be the benzalmalonate derivative (1) obtained as described above, which is used as it is. preferable. The carrier used here is not particularly limited as long as it is inactive with respect to the benzalmalonate derivative (1), and may be any form such as solid, liquid, emulsion and gel. Specifically, water, alcohol, fats and oils (hydrocarbon oils, fluorine-based oil agents, fatty acid esters, higher alcohols, silicone oils, etc.), fine powders such as starch and talc, low boiling point hydrocarbons used as aerosol propellants or A halogenated hydrocarbon etc. can be mentioned.

Further, the ultraviolet absorbent of the present invention may be blended with other ultraviolet absorbents. Other UV absorbers include p-methylbenzylidene-D, L-camphor or its sulfonic acid sodium salt, 2-phenylbenzimidazole-5-sulfonic acid sodium salt,
3,4-Dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, 4-phenylbenzophenone-2'-carboxylic acid isooctyl ester, 4
-Methoxycinnamic acid ester, 2-phenyl-5-methylbenzoxazole, 4-dimethylaminobenzoic acid ester, 4-methoxy-2'-carboxydibenzoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 1-
(3,4-dimethoxyphenyl) -4,4-dimethyl-
Examples thereof include 1,3-pentanedione, 2-hydroxy-4-methoxybenzophenone, dibenzylidene camphor and the like. Further, the ultraviolet absorbent of the present invention may be blended with other components, if necessary, such as preservatives, fragrances, colorants and surfactants.

Benzalmalonate derivative of the present invention (1)
Can be used not only for protecting the skin and hair from UV rays, but also as a UV protectant to be added to substances such as plastics that are affected by UV rays.

The cosmetic of the present invention can be obtained by blending the benzalmalonate derivative (1) with a known cosmetic base and various components. The dosage form of the cosmetic is not particularly limited, and may be a desired dosage form such as cream, lotion, solution, oil, spray, stick, emulsion, foundation, ointment, shampoo, and rinse.

Known cosmetic bases include hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, ozokerite and montan wax; plant or animal oils and fats such as olive, ground wax, carnauba wax, lanolin and whale wax. And waxes; fatty acids such as stearic acid, palmitic acid, oleic acid, glycerin monostearate ester, glycerin distearate ester, glycerin monooleate ester, isopropyl myristate ester, isopropyl stearate ester, butyl stearate ester and their esters. Silicones such as methylpolysiloxane, methylpolycyclosiloxane, methylphenylpolysiloxane, silicone polyether copolymer; perfluoropolyether, fluorine-modified Fluorine-based oils such as recone; ethanol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, alcohols such as hexyl dodecyl alcohol;
Examples thereof include polyhydric alcohols having a moisturizing action such as glycol, glycerin and sorbitol.

As the powder base, extenders such as mica, talc, sericite, kaolin, nylon powder, polymethylsilsesquioxane and barium sulfate; red 2
Organic pigments such as No. 02, 226, Yellow No. 4 and aluminum lake; UV scattering agents such as titanium oxide, zinc oxide, iron oxide and the like can be used. Among these, titanium oxide and zinc oxide include fine particle titanium oxide having a particle size of 100 nm or less, fine particle zinc oxide, and JP-A-1-17959.
The flaky zinc oxide described in the claims of JP-A No. 21 can be used. In addition, these extender pigments, organic pigments, and ultraviolet scattering agents can be prepared by known methods such as silicones such as methyl hydrogen polysiloxane, fluorine compounds such as perfluoroalkyl phosphates, metal soaps, N-acyl glutaric acid, silica, It is also possible to use those surface-treated with alumina, silica-alumina or the like.

Further, in the cosmetic of the present invention, the above-mentioned known ultraviolet absorber, W / O or O / W type emulsifier, polyether modified silicone for emulsifying various silicone oils, polyether / alkyl modified silicone, Glyceryl ether modified silicone, methylcellulose,
Thickeners such as ethyl cellulose, carboxymethyl cellulose, polyacrylic acid, tragacanth, agar and gelatin, flavors, preservatives, moisturizers, emulsion stabilizers, various medicinal ingredients, physiologically acceptable coloring agents and the like can also be added. .

The content ratio of the benzalmalonate derivative represented by the formula (1) in the cosmetic can be appropriately determined according to the kind of the cosmetic, but is generally 0.1 to 2.
0% by weight is preferred and 0.5-10% by weight is particularly preferred.

[0037]

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

Example 1 According to the method shown below, the following formula;

[0039]

[Chemical 8]

A compound (1a) represented by the following formula was prepared.
First, 3.65 g (12.0 mmol) of diethyl 4-allyloxybenzalmalonate was placed in a 100 ml two-necked flask, and this was dissolved in 10 ml of toluene. Next, 1.47 g (14.4 mmol) of diethylmethylsilane was added,
After raising the temperature in the flask to 50 ° C., 19.7 μl (6.0%) of a 2% isopropyl alcohol solution of chloroplatinic acid.
0 × 10 ⁻⁴ mmol) was added, and the mixture was stirred at 50 ° C. for 10 hours.
After cooling the reaction mixture, 50 ml of hexane and 0.12 of activated carbon.
After adding g and stirring at room temperature for 1 hour, activated carbon was filtered off and the solution was concentrated under reduced pressure to obtain a colorless transparent oily substance. This oily substance was purified by silica gel column chromatography using hexane + ethyl acetate (40: 1) as a developing solvent, to obtain 4.44 g of the target compound (1a) (yield 91%).
Was obtained as a colorless transparent oil.

IR (ν _neat , cm ^-1 ): 2955, 2880, 1730,
1630, 1605, 1515, 1470, 1430,1380, 1305, 1255, 121
0, 1175, 1060, 1015, 960, 890, 795

¹ H-NMR (CDCl ₃ , δppm): 0.04 (3H, s), 0.45-
0.65 (6H, m), 0.97 (6H, t, J = 8.8Hz), 1.35 (3H, t, J = 7.1Hz),
1.36 (3H, t, J = 7.1Hz), 1.70-1.95 (2H, m), 3.97 (2H, t, J =
6.8Hz), 4.36 (2H, q, J = 7.1Hz), 4.39 (2H, q, J = 7.1Hz), 6.9
0 (2H, d, J = 8.8Hz), 7.44 (2H, d, J = 8.8Hz), 7.70 (1H, s)

Example 2 By the method shown below, the following formula:

[0044]

[Chemical 9]

A compound (1b) represented by
The production method is di (2-ethylhexyl) 4-allyloxybenzalmalonate 1.42 g (3.00 mmol),
0.368 g (3.60 mmol) of diethylmethylsilane,
2% isopropyl alcohol solution of chloroplatinic acid 4.9μ
Example 1 was repeated except that 1 (1.50 × 10 ⁻⁴ mmol) and 5 ml of toluene were used. Thus, 1.34 g (yield 78%) of the target compound (1b) was obtained as a colorless transparent oily substance.

IR (ν _neat , cm ^-1 ): 2960, 2880, 1735,
1630, 1605, 1515, 1470, 1425,1385, 1305, 1260, 120
0, 1170, 1120, 1060, 1010, 960, 830, 790

¹ H-NMR (CDCl ₃ , δppm): 0.03 (3H, s), 0.40-
0.75 (6H, m), 0.75-1.10 (18H, m), 1.10-1.55 (16H, m), 1.5
5-1.95 (4H, m), 3.96 (2H, t, J = 6.8Hz), 4.15-4.20 (4H, m),
6.89 (2H, d, J = 8.8Hz), 7.43 (2H, d, J = 8.8Hz), 7.69 (1H, s)

Test Example 1 UV absorbers comprising the compounds (1a) and (1b) of the present invention obtained in Examples 1 and 2 and 2-hydroxy-4-methoxybenzophenone, which is a UV absorber currently widely used. Using (Comparative Example 1) and 2-ethylhexyl 4-methoxycinnamate (Comparative Example 2), the ultraviolet absorption effect (absorbance) was measured by the following method. The results are shown in Table 1.

(Measurement method) Each ultraviolet absorber was dissolved in ethanol (99.5% reagent special grade) to obtain 2.5 × 10 ^-5 mo.
Prepare a l / l concentration solution and put it in a quartz cell (1 x 1c
m) and put it in a self-recording spectrophotometer (Hitachi U-34
Absorbance was measured according to 10 type).

[0050]

[Table 1]

As is clear from Table 1, the ultraviolet absorber comprising the compound of the present invention showed the same or higher absorption effect as compared with Comparative Examples 1 and 2.

Test Example 2 An ultraviolet absorber consisting of the compounds (1a) and (1b) of the present invention obtained in Examples 1 and 2, 2-ethylhexyl 4-methoxycinnamate (Comparative Example 2) and the same as the one currently used. The stability to light was measured by the following method using 2-ethylhexyl 4-dimethylaminobenzoate (Comparative Example 3), which is a UV absorber currently used. The results are shown in Table 2.

(Measurement method) Each ultraviolet absorber was dissolved in ethanol (99.5% reagent grade) to give 1.0 × 10 ^-4 mo.
Prepare a l / l concentration solution and put it in a quartz cell (1 x 1c
m) and put it in a self-recording spectrophotometer (Hitachi U-34
Absorbance was measured according to 10 type). Next, a xenon light resistance tester (Heraeu) was added to each solution placed in the quartz cell.
s company; SUNTEST CPS type) was used for 2 hours or 6 hours to irradiate light having a wavelength and intensity similar to summer sunlight, and then the absorbance was measured again in the same manner as described above. From these absorbance values, determine the residual rate of ultraviolet absorption effect,
The light stability was evaluated. The residual rate is λ after light irradiation.
Despite obtained by dividing the value of the absorbance at _max the value of absorbance at lambda _max before light irradiation the percentage.

[0054]

[Table 2]

As is clear from Table 2, the ultraviolet absorbent of the present invention was used for 2 hours or 6 hours as compared with the ultraviolet absorbent of the comparative example.
Even after irradiation with light for a long time, a high UV absorption effect was maintained, and the decrease in the absorption effect with the passage of time was very small.

Test Example 3 An ultraviolet absorber comprising the compounds (1a) and (1b) of the present invention obtained in Examples 1 and 2 and dimethyl 4-methoxybenzalmalonate used as an ultraviolet absorber for polymers (comparative). The solubility of the silicone oil in Example 4) was evaluated.

(Evaluation Method) The solubility of each ultraviolet absorber when 5% by weight was added to octamethylcyclotetrasiloxane was observed. The results are shown in Table 3.

[0058]

[Table 3]

As is clear from Table 3, the compounds of the present invention were more excellent in solubility in silicone oil agents than the ultraviolet absorbers of Comparative Examples. Furthermore, the compounds (1a) and (1) of the present invention
b) was added to ethanol or stawalan, respectively.
It dissolved even when added by weight% and had excellent compatibility with the cosmetic base.

Example 3 A powder foundation having the following composition was produced by a conventional method.

[0061]

[Table 4] (Composition) (Blending ratio; wt%) Mica remaining amount Talc 20 Titanium oxide 10 Bengal 1 Iron oxide yellow 2 Black iron oxide 1 Liquid paraffin 10 Beeswax 2 Preservative Amount Amount of the present compound (1a) 5 Aroma chemical 100.0

Further, a powder foundation was prepared with the same composition except that the compound (1b) of the present invention was used instead of the compound (1a) of the present invention.

Example 4 A creamy foundation having the following composition was produced by a conventional method.

[0064]

[Table 5] (Composition) (Blending ratio;% by weight) Stearic acid 5 Lipophilic glyceryl monostearate 3 Cetostearyl alcohol 1 Propylene glycol monolaurate 3 Squalane 7 Olive oil 8 Purified water Residual amount of preservative Appropriate amount triethanolamine 1. 2 Solbit 3 Titanium oxide 10 Talc 5 Coloring pigment Appropriate amount Compound of the present invention (1a) 7 Perfume Appropriate amount 100.0

Furthermore, a creamy foundation was prepared with the same composition except that the compound (1b) of the present invention was used in place of the compound (1a) of the present invention.

Example 5 An oily foundation having the following composition was produced by a conventional method.

[0067]

[Table 6] (Composition) (Blending ratio; wt%) Inventive compound (1a) 5 Talc Remaining amount Kaolin 12 Titanium oxide 13 Bengala 1.5 Yellow iron oxide 20 Black iron oxide 0.5 Liquid paraffin 15 Isopropyl palmitate 10 Lanolin Alcohol 3 Microcrystalline Wax 7 Ozokerite 8 Preservative Suitable amount Perfume Suitable amount Total 100.0

Furthermore, an oily foundation was produced with the same composition except that the compound (1b) of the present invention was used instead of the compound (1a) of the present invention.

Example 6 An O / W type cream having the following composition was produced by a conventional method.

[0070]

[Table 7] (Composition) (Blending ratio; wt%) Beeswax 6 Cetyl alcohol 5 Hydrogenated lanolin 7 Squalane 33 Fatty acid glycerin 3.5 Lipophilic monoglyceryl monostearate polyoxy ethylene (EO 20) sorbitan 2 Monolaurate 2 Inventive compound (1a) 6 Fragrance Trace amount Preservative Suitable amount Antioxidant Suitable amount Purified water Residual amount 100.0

Further, O / is the same composition except that the compound (1b) of the present invention is used in place of the compound (1a) of the present invention.
A W cream was produced.

Example 7 An O / W type cream having the following composition was produced by a conventional method.

[0073]

[Table 8] (Composition) (Blending ratio; wt%) 5 Compound of the present invention (1a) 2-Ethylhexyl 4-methoxycinnamate 2 Silicone-treated titanium oxide 1 Lipophilic glycerin monooleate 2 Polyoxyethylene (EO 20) Sorbitan mono lauric acid ester 1 Squalane 10 Silicone treated talc 5 Glycerin 5 Preservative proper amount Fragrance proper amount Antioxidant proper amount Purified water Residual amount 100.0

Furthermore, O / is the same composition except that the compound (1b) of the present invention is used in place of the compound (1a) of the present invention.
A W cream was produced.

Example 8 A W / O type cream having the following composition was produced by a conventional method.

[0076]

Table 9 (Composition) (Blending ratio; wt%) Inventive compound (1a) 4 Silicone-treated flaky zinc oxide 2 4-Ethylhexyl 4-methoxycinnamate 4 Dimethylpolysiloxane methyl (polyoxyethylene) siloxane copolymer Combined 3 Methyl polysiloxane 10 Methyl polycyclopolysiloxane 10 Squalane 4 Magnesium sulphate 0.5 Glycerin 7 Perfume Trace amount Antiseptic proper amount Antioxidant proper amount Purified water Residual amount 100.0

Further, W / was prepared in the same composition except that the compound (1b) of the present invention was used in place of the compound (1a) of the present invention.
An O-type cream was produced.

Example 9 An O / W emulsion having the following composition was produced by a conventional method.

[0079]

[Table 10] (Composition) (Blending ratio; wt%) Inventive compound (1a) 4 Silicone-treated titanium oxide 1 4-Ethylhexyl 4-methoxycinnamate 4 Sorbitan sesquioleate 0.8 Polyoxyethylene (EO 20) Oleyl ether 1.2 Squalane 5 Vaseline 2 Beeswax 0.5 Silicone-treated talc 5 Propylene glycol 5 Ethanol 5 Carboxyvinyl polymer 10% aqueous solution 20 Potassium hydroxide 0.1 Purified water Residual amount 100.0

Further, O / is the same composition except that the compound (1b) of the present invention is used instead of the compound (1a) of the present invention.
A W-type emulsion was produced.

[0081]

INDUSTRIAL APPLICABILITY The benzalmalonate derivative (1) having an organosilicon group of the present invention has an excellent ultraviolet absorbing effect, is stable to light, and has a daily exposure to humans. Almost no decomposition by sunlight. For this reason,
There is almost no effect on the skin due to decomposition products. Moreover, there are no problems such as toxicity and irritation. Furthermore, it has excellent compatibility with other cosmetic bases, especially silicone oil. Therefore, both the ultraviolet absorber and the cosmetic containing the benzalmalonate derivative having an organosilicon group of the present invention can exhibit an excellent feeling of use and an excellent durability of the ultraviolet protection.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Genji Imokawa 1022-89 Himurocho, Utsunomiya City, Tochigi Prefecture (56) References JP-A-7-330679 (JP, A) JP-A-7-330693 (JP, A) ) JP-A-2-270816 (JP, A) JP-A-6-500125 (JP, A) J. Am. Chem. Soc. , 1992, Vol. 115, No. 16, P7103-7110 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07F 7/08 A61K 7/00 A61K 7/42 C09K 3/00 104 REGISTRY (STN) CA (STN)

Claims (5)

(57) [Claims] 1. The following general formula (1): [In the formula, R ¹ and R ² represent hydrocarbon groups which may be the same or different, R ³ represents an alkyl group which may be the same or different, and R ⁴ , R ⁵ and R ⁶ are the same or different. A C 1-8 alkyl group or a phenyl group which may be present, A represents an alkylene group, and n represents a number of 0-2]. 2. In the general formula (1), n is 0.
The benzalmalonate derivative described. 3. The following general formula (3): [In the formula, R ¹ and R ² represent hydrocarbon groups which may be the same or different, R ³ represents an alkyl group which may be the same or different, A ¹ represents an alkenyl group, and n is 0 to 0.
The number of 2 is shown] and an alkenyloxybenzalmalonate derivative represented by the following general formula (2) [Wherein R ⁴ , R ⁵ and R ⁶ are the same or different and each represents an alkyl group having 1 to 8 carbon atoms or a phenyl group] and are reacted in the presence of a catalyst. Item 2. A method for producing a benzalmalonate derivative according to Item 1. 4. An ultraviolet absorber containing the benzalmalonate derivative according to claim 1 or 2. 5. A cosmetic containing the benzalmalonate derivative according to claim 1 or 2.