JPH07330673A - Perfluoroalkyl group-bearing benzal malonate derivative, production thereof, and ultraviolet rays absorber and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To obtain the new derivative excellent in UV rays-absorbing ability and light stability and the affinity for fluorolubricants and resistance to water and oil, useful as, e.g. a raw material for cosmetics. CONSTITUTION:The benzal malonate derivative of formula I (Rf is a perfluoroalkyl or omega-H-perfluoroalkyl; R is H or a hydrocarbon; (p) is 0-3; (n) is 0-6), e.g. a compound of formula II. This compound of formula I is obtained by reaction between a malonate derivative of formula III and a benzaldehyde derivative of formula IV. The malonate derivative of formula III, in turn, is prepared by reaction between an alcohol of formula V and malonic acid. The other objective cosmetic, etc., containing this derivative have no problems concerning toxicity, irritancy, etc., presenting excellent use feeling and sustainable UV rays-screening effect.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is a novel substance useful as a raw material for cosmetics, which has an excellent ultraviolet absorbing action and good photostability, and has excellent affinity with a fluorinated oil agent and excellent water and oil resistance. The present invention relates to a benzalmalonate derivative having a novel perfluoroalkyl group, a method for producing the same, an intermediate for producing the same, an ultraviolet absorber containing the same, and a cosmetic.

[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, enhances 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 from 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. Along with this, an attempt to bond an ultraviolet absorbing group to a silicone or an organic silicon group for the purpose of improving the compatibility with a silicone oil base or increasing the water resistance of the ultraviolet absorber itself has been disclosed in JP-B-63-1641.
6, JP-A-1-299210, JP-A-2-
167291, JP-A-2-217622,
JP-A-2-270816, JP-A-2-27081
No. 7, JP-A-3-287588, JP-A-3-
287589, JP-A-4-182421,
JP-A-4-368392, JP-A-5-43585
JP-A-5-59069, JP-A-5-17
It is proposed in Japanese Patent Publication No. 8865.

However, although the silicone oil base and the ultraviolet absorber containing silicone are excellent in water resistance, they have a problem in that they have insufficient oil resistance (oil repellency) and insufficient sebum resistance. On the other hand, recently, as an oil agent that simultaneously satisfies water resistance and oil resistance, FOMBLIN
FSL-3, perfluoropolyether such as (manufactured by Montefloss) and Demnum S (manufactured by Daikin Industries, Ltd.)
No. 00 (manufactured by Asahi Glass Co., Ltd.) and JP-A-2-295912, JP-A-5-247214, and other fluorine-based oil agents such as fluorine-modified silicone have been found.

However, conventional ultraviolet absorbers have the drawbacks that they are difficult to dissolve in the above-mentioned fluorine-based oil agents and their oil resistance is insufficient. As an ultraviolet absorber that overcomes these drawbacks, the present applicant has proposed a cinnamic acid derivative having a perfluoroalkyl group in JP-A-5-246949. However, the cinnamic acid derivative has a drawback that it undergoes a photoisomerization reaction after absorption of ultraviolet rays and is transformed into a geometrical isomer having a low ultraviolet absorption ability [eg, Ph.
otochem. Phetobiol. , 36 , 395
(1982)].

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to satisfy the above-mentioned conditions (a) to (e) required for an ultraviolet absorber, particularly the affinity with a fluorine-based oil agent, which has hitherto been insufficient, and light. It is intended to provide a novel substance having excellent stability and to provide it as an ultraviolet absorber and a cosmetic.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted diligent research in view of such circumstances, and as a result, found that a novel benzalmalonate derivative having a perfluoroalkyl group represented by the following general formula (1) was obtained. It has excellent UV absorption and light stability, and also has good solubility in fluorinated oils, so it can be suitably used in cosmetics, and UV absorbers and cosmetics containing it have excellent UV protection. The present invention has been completed by finding that the effect is maintained for a long time and the water / oil resistance is excellent.

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

[0013]

[Chemical 6]

[In the formula, Rf represents a perfluoroalkyl group or an ω-H-perfluoroalkyl group, R represents a hydrogen atom or a hydrocarbon group which may be the same or different,
p represents a number of 0 to 3 and n represents a number of 0 to 6], a method for producing the benzalmalonate derivative, a UV absorber and a cosmetic containing the same. .

The benzalmalonate derivative of the present invention is represented by the above general formula (1). The perfluoroalkyl group or ω-H-perfluoroalkyl group represented by Rf in the formula is a straight chain. Although those having 1 to 20 carbon atoms are preferable, for example, trifluoromethyl group, pentafluoroethyl group,
n-heptafluoropropyl group, n-nanofluorobutyl group, n-undecafluoropentyl group, n-tridecafluorohexyl group, n-pentadecafluoroheptyl group, n-heptadecafluorooctyl group, n-nonadeca Fluorononyl group, n-heneicosafluorodecyl group, n-nonacosafluorotetradecyl group, n-pentacosafluorododecyl group, n-tritriacontafluorohexadecyl group, n-pentatriacontafluorooctadecyl group, 1 , 1-bis (trifluoromethyl) heptafluorobutyl group, 5-trifluoromethyldodecafluorohexyl group, 2H-tetrafluoroethyl group (H (CF ₂ ) _2- ), 4H-octafluorobutyl group (H (CF ₂ )
₄ -), 6H-dodecafluoro hexyl _{(H (CF 2) 6 -} ) and the like.

The hydrocarbon group represented by R in the general formula (1) may be linear or branched, and may be saturated or may have an unsaturated bond. However, from the aspect of affinity with the fluorinated oil agent, it has 1 to 10 carbon atoms.
Preferred are, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group,
n-hexyl group, n-heptyl group, n-octyl group, n
-Straight chain alkyl group such as decyl group; isopropyl group, isobutyl group, t-butyl group, 2,2-dimethylpropyl group, 2-methylbutyl group, cyclohexylmethyl group, 2
-Branched alkyl groups such as methylpentyl group, cyclohexylethyl group, 2-ethylhexyl group and 3,5,5-trimethylhexyl group; cyclic alkyl groups such as cyclohexyl group; allyl group, 3-butenyl group, 10-undecenyl group Linear alkenyl groups such as; alkenyl groups such as 1-methyl-2-propenyl group and 3-methyl-3-butenyl group; aralkyl groups such as benzyl group; aryl groups such as phenyl group. However, a straight-chain alkyl group or a branched-chain alkyl group is preferable, and a methyl group is particularly preferable because of easy availability.

Further, in the general formula (1), n represents a number of 0 to 6, but 1, 2 and 6 are preferable because of easy availability,
2 is particularly preferable from the viewpoint of stability and affinity with the fluorinated oil agent. p represents a number from 0 to 3, but 1 is preferable, and the substitution position of OR on the aromatic ring is not limited, but p =
1, the compound substituted in the para position, that is, the 4-position is 310 to 33.
It is preferable because it has a maximum absorption (λ _max ) at 0 nm and has an extremely strong ultraviolet absorbing action. Furthermore, with p = 2, 3
The compound substituted at the 4- and 4-positions has a maximum absorption at 325 to 345 nm and has a strong ultraviolet absorption effect.
The compounds substituted at the 4th, 4th and 5th positions show a maximum absorption at 310 to 330 nm and have a strong ultraviolet absorbing action, and these compounds can also be mentioned as preferable examples.

The benzalmalonate derivative of the present invention can be produced, for example, according to the following reaction formula.

[0019]

[Chemical 7]

[In the formula, Rf, R, p and n are the same as above]

That is, a perfluoroalkyl group or ω
Malonic acid is esterified with an alcohol (4) having a —H-perfluoroalkyl group to give a malonate derivative (2), which is reacted with a benzaldehyde derivative (3) to obtain the desired benzalmalonate derivative ( 1) can be obtained.

The malonate derivative represented by the above general formula (2) is a novel substance first synthesized by the present inventor. This compound (2) can be obtained, for example, by reacting an alcohol (4) having a perfluoroalkyl group or a ω-H-perfluoroalkyl group with malonic acid in the absence of solvent or in a solvent according to the above formula. The solvent used in this reaction is not particularly limited as long as it does not inhibit the reaction, and benzene, toluene, xylene, hexane and the like can be mentioned. In this reaction, it is preferable to use an acid catalyst, and as such an acid catalyst, those used in ordinary esterification, for example, mineral acids such as sulfuric acid and hydrochloric acid,
Examples thereof include organic acids such as p-toluenesulfonic acid and Lewis acids such as boron trifluoride. This reaction is preferably performed while heating and removing water generated by the reaction to the outside of the reaction system.

The desired benzalmalonate derivative can be obtained by Knoevenagel condensation of the malonate derivative (2) thus obtained and the benzaldehyde derivative (3) in the absence of a solvent or in the presence of a catalyst. it can. The solvent used in this reaction is not particularly limited as long as it does not inhibit the reaction, and benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, alcohols and the like can be mentioned. Examples of the catalyst include amines such as piperidine and pyridine, acids such as acetic acid, benzoic acid, zinc chloride and titanium tetrachloride, carboxylic acid salts such as sodium acetate and ammonium acetate, and acid anhydrides such as acetic anhydride. These can be used in appropriate combination. It is preferable to carry out this reaction while heating and removing water generated by the reaction out of the reaction system.

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 such as antiseptics, fragrances, colorants and surfactants, if necessary.

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 perfluoropolyethers, fluorine-based oils such as fluorine-modified silicones; hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, ozokerite and montan wax; olives and ground waxes. , Vegetable oils and waxes such as carnauba wax, lanolin and whale wax; Fatty acids such as acid esters and butyl stearates and their esters; methyl polysiloxane, methyl polycyclosiloxane, methylphenyl polysiloxane, silicone polyether Silicones such as polymers;
Examples thereof include alcohols such as ethanol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol and hexyldecyl alcohol; and 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.

[0032]

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 By the method shown below, the following formula:

[0034]

[Chemical 8]

A compound (2a) represented by the following formula was prepared.
First, in a 500 ml _two- necked flask, CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OH ₂
4.48 g (92.7 mmol) was added, and this was added to benzene 1
Dissolved in 50 ml. Next, 4.68 g of malonic acid (4
5.0 mmol) and 0.47 g (4.79 mmol) of sulfuric acid were added, and the water produced by Dean Stark was heated to reflux with stirring for 6 hours while azeotropically dehydrating. After cooling, the reaction mixture was diluted with 200 ml of ethyl acetate and neutralized with saturated aqueous sodium hydrogen carbonate solution,
The layer was further made basic, and the layer was separated, and then washed 4 times with water. After drying the organic layer over anhydrous sodium sulfate, the solvent and unreacted
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OH was distilled off under reduced pressure to obtain a cloudy liquid.
This liquid was purified by silica gel column chromatography using ethyl acetate as a developing solvent to obtain 24.28 g (yield 91%) of the target compound (2a) as a colorless transparent liquid.

IR (ν _neat , cm ^-1 ): 2985, 1750,
1465, 1415, 1350, 1220, 1130,
1080, 875, 740, 710

¹ H-NMR (CDCl ₃ , δppm): 2.30-2.7
0 (4H, m), 3.44 (2H, s), 4.46 (4
H, t, J = 6.5 Hz)

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

[0039]

[Chemical 9]

A compound (1a) represented by the following formula was prepared.
First, 1.36 g (10.0 mmol) of 4-methoxybenzaldehyde was placed in a 500 ml two-necked flask, and this was dissolved in 250 ml of benzene. Next, 5.96 g (10.0 mmol) of the compound (2a) produced in Example 1, 0.085 g (1.00 mmol) of piperidine and 0.036 g of acetic acid.
(0.60 mmol) was added, and Dean Stark (Dea
The water produced by n Stark) was heated to reflux with stirring for 24 hours while azeotropically dehydrating. After cooling, the reaction mixture was washed 3 times with water. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give white crystals. The crystals were recrystallized from ethanol to give the target compound (1a)
5.71 g (yield 80%) was obtained as white crystals.

Melting point: 62.5 ° C. IR (ν _KBr , cm ^-1 ): 1735, 1720, 1625, ¹
605, 1575, 1520, 1460, 1430, 1
400, 1340, 1305, 1260, 1205, 1
185, 1130, 1065, 1030, 880, 83
0,720,520

¹ H-NMR (CDCl ₃ , δppm): 2.35-2.6
5 (4H, m), 3.84 (3H, s), 4.54 (2
H, t, J = 6.4 Hz), 4.56 (2H, t, J =
6.6 Hz), 6.90 (2H, d, J = 8.8H
z), 7.41 (2H, d, J = 8.8Hz), 7.7
5 (1H, s)

Example 3 By the method shown below, the following formula;

[0044]

[Chemical 10]

A compound (2b) represented by
The manufacturing method is as follows: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OH 10.00 g (27.
5 mmol), 1.43 g (13.7 mmol) of malonic acid, 0.077 g (0.79 mmol) of sulfuric acid and 200 ml of benzene were used, and the same procedure as in Example 1 was carried out. In this way
9.45 g (yield 87%) of the target compound (2b) was obtained as a colorless transparent liquid.

IR (ν _neat , cm ^-1 ): 2990, 1745,
1470, 1345, 1240, 1200, 1085,
1010, 840, 810, 730, 700

¹ H-NMR (CDCl ₃ , δppm): 2.30-2.6
0 (4H, m), 3.43 (2H, s), 4.46 (4
H, t, J = 6.4 Hz)

Example 4 By the method shown below, the following formula;

[0049]

[Chemical 11]

A compound (1b) represented by
The manufacturing method is 4-methoxybenzaldehyde 0.682.
g (5.00 mmol), the compound prepared in Example 3 (2
b) 3.98 g (5.00 mmol), piperidine 0.04
3 g (0.50 mmol), 0.018 g acetic acid (0.30 mm
ol) and 200 ml of benzene were used. Thus, the target compound (1b) 3.5
2 g (yield 77%) was obtained as white crystals.

Melting point: 62.0 ° C. IR (ν _KBr , cm ^-1 ): 1735, 1722, 1625, ¹
605, 1575, 1520, 1460, 1340, 1
320, 1260, 1235, 1210, 1185, 1
140, 1070, 830, 720, 520

¹ H-NMR (CDCl ₃ , δppm): 2.35-2.6
5 (4H, m), 3.84 (3H, s), 4.54 (2
H, t, J = 6.4 Hz), 4.55 (2H, t, J =
6.7 Hz), 6.90 (2H, d, J = 8.9H)
z), 7.41 (2H, d, J = 8.9 Hz), 7.7
5 (1H, s)

Example 5 By the method shown below, the following formula;

[0054]

[Chemical 12]

A compound (2c) represented by the following formula was produced.
The manufacturing method is CF ₃ (CF ₂ ) ₂ C (CF ₃ ) ₂ (CH ₂ ) ₂ OH 21.85 g
(60.0 mmol), malonic acid 3.12 g (30.0 mmo
l), sulfuric acid 0.31 g (3.17 mmol) and benzene 1
Same as Example 1 except that 50 ml was used. Thus, the target compound (2c) (21.78 g (yield 91
%) As a colorless transparent liquid.

IR (ν _neat , cm ^-1 ): 3010, 1770,
1750, 1470, 1420, 1335, 1270,
1155, 1100, 1095, 1050, 965, 9
50, 825, 750, 735, 700

¹ H-NMR (CDCl ₃ , δppm): 2.55 (4H,
t, J = 7.7 Hz), 3.43 (2H, s), 4.4
4 (4H, t, J = 7.7Hz)

Example 6 By the method shown below, the following formula:

[0059]

[Chemical 13]

A compound (1c) represented by the following formula was produced.
The manufacturing method is 4-methoxybenzaldehyde 0.953.
g (7.00 mmol), the compound prepared in Example 5 (2
c) 5.57 g (7.00 mmol), piperidine 0.06
0 g (0.70 mmol), acetic acid 0.025 g (0.42 mm
ol) and 150 ml of benzene were used. Thus, the target compound (1c) 4.80
g (75% yield) was obtained as white crystals.

Melting point: 46.5 ° C. IR (ν _KBr , cm ⁻¹ ): 1740, 1725, 1620, ¹
600, 1575, 1520, 1470, 1435, 1
335, 1265, 1230, 1175, 1090, 1
060, 955, 830, 735, 520

¹ H-NMR (CDCl ₃ , δppm): 2.45-2.6
5 (4H, m), 3.85 (3H, s), 4.45-
4.60 (4H, m), 6.81 (2H, d, J = 8.
8Hz), 7.40 (2H, d, J = 8.8Hz),
7.77 (1H, s)

Example 7 By the method shown below, the following formula:

[0064]

[Chemical 14]

A compound (2d) represented by
First, 24.01 g of CF ₃ CH ₂ OH in a 500 ml _two- necked flask.
(240.0 mmol) was added and this was dissolved in 300 ml of benzene. Next, malonic acid 8.32 g (80.0
mmol) and 2.49 g (25.4 mmol) of sulfuric acid were added, and the mixture was heated under reflux with stirring for 80 hours. After cooling, the reaction mixture was diluted with 200 ml of ethyl acetate, neutralized with a saturated aqueous solution of sodium hydrogen carbonate, further basified, and the layers were separated. The organic layer washed with water 4 times was dried over anhydrous sodium sulfate,
The solvent and unreacted CF ₃ CH ₂ OH were distilled off under normal pressure to obtain a colorless transparent liquid. This liquid was purified by silica gel column chromatography using ethyl acetate as a developing solvent,
14.12 g (yield 66%) of the target compound (2d) was obtained as a colorless transparent liquid.

IR (ν _neat , cm ^-1 ): 2990, 1775,
1420, 1350, 1285, 1260, 1170,
1060, 980, 845

¹ H-NMR (CDCl ₃ , δppm): 3.62 (2H,
s), 4.55 (4H, q, J = 8.2Hz)

Example 8 By the method shown below, the following formula:

[0069]

[Chemical 15]

A compound (1d) represented by: was prepared.
The manufacturing method is 4-methoxybenzaldehyde 2.04 g.
(15.0 mmol), the compound (2d) prepared in Example 7.
4.83 g (18.0 mmol), piperidine 0.128 g
(1.50 mmol), acetic acid 0.054 g (0.90 mmol)
And 100 ml of benzene, and the same procedure as in Example 2 was carried out except that silica gel column chromatography using hexane-ethyl acetate (20: 1) as a developing solvent was used for purification. Thus, 2.17 g (yield 37%) of the target compound (1d) was obtained as white crystals.

Melting point: 64.5 ° C. IR (ν _KBr , cm ^-1 ): 1740, 1625, 1605, ¹
575, 1515, 1470, 1450, 1430, 1
410, 1380, 1310, 1290, 1270, 1
195, 1165, 1075, 1025, 980, 96
0,830,770,665,520

¹ H-NMR (CDCl ₃ , δppm): 3.86 (3H,
s), 4.62 (2H, q, J = 8.3Hz), 4.6
7 (2H, q, J = 8.3Hz), 6.92 (2H,
d, J = 8.8 Hz), 7.44 (2H, d, J = 8.
8Hz), 7.86 (1H, s)

Test Example 1 Compounds (1) of the present invention obtained in Examples 2, 4, 6 and 8
a) to (1d) UV absorber, and currently used UV absorbers 2-hydroxy-4-methoxybenzophenone (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.
Shown in.

(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).

[0075]

[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 Compounds (1a) of the present invention obtained in Examples 2, 4 and 6
An ultraviolet absorber composed of (1c), 2-ethylhexyl 4-methoxycinnamate (Comparative Example 2), and 2-ethylhexyl 4-dimethylaminobenzoate (Comparative Example 3), which is also an ultraviolet absorber which is also commonly used at present, are used. The light stability was measured by the following method. The results are shown in Table 2.

(Measurement method) Each ultraviolet absorber was dissolved in ethanol (99.5% reagent special grade) to obtain 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.

[0079]

[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 Compounds (1) of the present invention obtained in Examples 2, 4, 6 and 8
a) to (1d) UV absorber and 4-methoxycinnamic acid 2
The solubility of ethylhexyl (Comparative Example 2) and dimethyl 4-methoxybenzalmalonate (Comparative Example 4) used as a UV absorber for polymers in a fluorinated oil was evaluated. (Evaluation method) FOMB was used for each ultraviolet absorber.
The solubility of LIN HC-04 (perfluoropolyether, manufactured by Montefloss Co., Ltd.) and FSL-300 (fluorine-modified silicone, manufactured by Asahi Glass Co., Ltd.) at the time of heating was separately observed, and the solubility when heated was observed. The results are shown in Table 3.

[0082]

[Table 3]

As is clear from Table 3, the compound of the present invention had a good affinity for the fluorine-based oil agent and could be mixed, as compared with the ultraviolet absorbers of Comparative Examples.

Example 9 A powder foundation having the following composition was produced by a conventional method.

[0085]

[Table 4] (Composition) (Blending ratio; wt%) Mica remaining amount Talc 20 Titanium oxide 10 Zinc oxide 5 Fluorine-modified silicone (FLS-300 manufactured by Asahi Glass Co., Ltd.) 6 Inventive compound (1a) 3 Lanolin 5 Vaseline 2 Isopropyl myristate 1 Preservative Suitable amount Perfume Micrometer 100

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

Example 10 A powder foundation having the following composition was produced by a conventional method.

[0088]

[Table 5] (Composition) (Blending ratio; wt%) Mica remaining amount Talc 20 Titanium oxide 10 Bengala 1 Iron oxide yellow 2 Black iron oxide 1 Polyethylene powder 8 Perfluoropolyether (FOMBLIN HC-04 manufactured by Montefloss) 1 Inventive Compound (1a) 5 Squalane 7 Preservative Suitable amount Perfume Micrometer 100

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

Example 11 A cream foundation having the following composition was produced by a conventional method.

[0091]

[Table 6] (Composition) (Blending ratio; wt%) Stearic acid 5 Lipophilic glyceryl monostearate 3 Cetostearyl alcohol 1 Propylene glycol monolaurate 3 Squalane 7 Olive oil 8 Purified water Residual amount of preservatives 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

Furthermore, a creamy foundation was prepared with the same composition except that the compounds (1b) to (1d) of the present invention were used instead of the compound (1a) of the present invention.

Example 12 A cream foundation having the following composition was produced by a conventional method.

[0094]

[Table 7] (Composition) (Blending ratio; wt%) Dimethylpolysiloxane / polyoxyalkylene copolymer 2 Fluorine-modified silicone (Asahi Glass Co., Ltd., FSL-300) 10 Dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd.) "KF-96A", 6cs) 5 Aluminum stearate 0.2 1-Isostearoyl-3-myristoyl-glycerol 2 4-ethylhexyl 2-methoxycinnamate 2 Inventive compound (1a) 2 Fluorine compound-treated pigment (Per) Fluoroalkyl phosphate dioxyethyl amine salt treatment) Talc 5 Titanium oxide 9 Iron oxide (red, yellow, black) 1 Decamethylcyclopentasiloxane 15 Butyl paraoxybenzoate 0.1 Sodium benzoate 0.2 Magnesium sulfate 0.2 5 Glycerin 5.5 1,3-butylene glyco Le 2.5 Purified water Remaining fragrance Suitable amount 100

Furthermore, a creamy foundation was prepared with the same composition except that the compounds (1b) to (1d) of the present invention were used instead of the compound (1a) of the present invention.

Example 13 A cream having the following composition was produced by a conventional method.

[0097]

[Table 8] (Composition) (Blending ratio; wt%) Beeswax 6 Cetyl alcohol 5 Hydrogenated lanolin 7 Squalane 33 Fatty acid glycerin 3.5 New oil type glyceryl monostearate 2 Polyoxyethylene (EO20) sorbitan monolaurate 2 Invention Compound (1a) 6 Fragrance Trace amount Preservative Suitable amount Antioxidant Suitable amount Purified water Residual amount 100

Further, a cream was prepared with the same composition except that the compounds (1b) to (1d) of the present invention were used in place of the compound (1a) of the present invention.

Example 14 A cream having the following composition was produced by a conventional method.

[0100]

Table 9 (Composition) (Blending ratio; wt%) Inventive compound (1a) 4 Silicone-treated flaky zinc oxide 24 2-Ethylhexyldimethyl 4-methoxycinnamate 4 Polysiloxane / methyl (polyoxyethylene) siloxane copolymer Combined 3 Methyl polysiloxane 10 Methyl polycyclopolysiloxane 10 Squalane 4 Magnesium sulphate 0.5 Glycerin 7 Fragrance Trace amount Antiseptic proper amount Antioxidant proper amount Purified water Residual amount 100

Furthermore, a cream was prepared with the same composition except that the compounds (1b) to (1d) of the present invention were used in place of the compound (1a) of the present invention.

Example 15 A cream having the following composition was produced by a conventional method.

[0103]

Table 10 (Composition) (Blending ratio; wt%) Polyoxyethylene (EO50) hydrogenated castor oil 0.5 polyoxyethylene (EO20) sorbitan monolaurate 1 glycerin 6 1,3-butylene glycol 6 purified water residual amount Squalane 5 Jojoba oil 5 Octamethylcyclotetrasiloxane 18 Inventive compound (1a) 2 Fluorine modified silicone (X-22-819 manufactured by Shin-Etsu Chemical Co., Ltd.) 30 Zinc oxide 5.5 Titanium oxide 2 Sericite 5 Total 100

Further, a cream was prepared with the same composition except that the compounds (1b) to (1d) of the present invention were used instead of the compound (1a) of the present invention.

Example 16 An emulsion having the following composition was produced by a conventional method.

[0106]

Table 11 (Composition) (Blending ratio; wt%) Octamethylcyclotetrasiloxane 25 Fluorine modified silicone (FSL-300 manufactured by Asahi Glass Co., Ltd.) 15 Dimethylpolysiloxane polyoxyalkylene copolymer 1 Glycerin 2 Ethanol 12 Purification Remaining amount of water Compound of the present invention (1a) 2 Zinc oxide 5.5 Titanium oxide 2 Sericite 5 Perfume Micrometer 100

Further, an emulsion was prepared with the same composition except that the compounds (1b) to (1d) of the present invention were used in place of the compound (1a) of the present invention.

[0108]

INDUSTRIAL APPLICABILITY The benzalmalonate derivative having a perfluoroalkyl group of the present invention has an excellent ultraviolet absorbing effect, is stable to light, and has an amount of sunlight that humans are exposed to on a daily basis. Hardly decomposes depending on. Therefore, there is almost no influence on the skin by the decomposition products.
Moreover, there are no problems such as toxicity and irritation. Further, it is also excellent in affinity with other cosmetic bases, particularly fluorine-based oil agents.
Therefore, both the ultraviolet absorber and the cosmetic containing the benzalmalonate derivative having a perfluoroalkyl group of the present invention can exhibit an excellent feeling of use and an excellent durability of the ultraviolet protection action.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C07C 69/65 69/734 Z 9546-4H C09K 3/00 104 Z (72) Inventor Hiroko Shirokura Tochigi 3-2-5 Yamamoto, Utsunomiya City, Prefecture (72) Inventor Genji Imokawa 1022-89 Himurocho, Utsunomiya City, Tochigi Prefecture

Claims (7)

[Claims] 1. The following general formula (1): [In the formula, Rf represents a perfluoroalkyl group or a ω-H-perfluoroalkyl group, R represents a hydrogen atom or a hydrocarbon group which may be the same or different, p represents a number of 0 to 3, n represents a number of 0 to 6]. 2. The benzalmalonate derivative according to claim 1, wherein p is 1 in the general formula (1). 3. The following general formula (2): [In the formula, Rf represents a perfluoroalkyl group or an ω-H-perfluoroalkyl group, and n represents a number of 0 to 6]
A malonate derivative represented by the following general formula (3) A benzaldehyde derivative represented by the formula: wherein R represents a hydrogen atom or a hydrocarbon group which may be the same or different and p represents a number of 0 to 3 is reacted. Process for producing benzalmalonate derivative. 4. The following general formula (2): [In the formula, Rf represents a perfluoroalkyl group or an ω-H-perfluoroalkyl group, and n represents a number of 0 to 6]
A malonate derivative represented by. 5. Rf (CH ₂ ) _n OH (4) [wherein Rf represents a perfluoroalkyl group or an ω-H-perfluoroalkyl group, and n is the following general formula (4): Indicates a number from 0 to 6]
5. The method for producing a malonate derivative according to claim 4, wherein the alcohol represented by the formula and malonic acid are reacted. 6. An ultraviolet absorber containing the benzalmalonate derivative according to claim 1 or 2. 7. A cosmetic containing the benzalmalonate derivative according to claim 1 or 2.