JPH11116457A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic, excellent in UV-A absorptivity, excellently familiar with skin, capable of manifesting an excellent preservation stability by formulating a benzalhydantoin-based ultraviolet absorber having extremely small solubility. SOLUTION: This cosmetic is obtained by formulating the powder of a 5-(3,4- dialkoxybenzal)hydantoin of the formula (R<1> and R<2> are each a 1-3C alkyl) and/or the power obtained by carrying out a coating treatment of a power for cosmetics (e.g. a pigment) with the compound of the formula as an ultraviolet absorber. The compound of the formula can be obtained by condensing a 3,4-dialkoxybenzaldehyde with hydantoin using a basic catalyst. The powder formulated as an ultraviolet absorber preferably has an average particle diameter of 0.001-100 μm, and the mixing amount of the powder is preferably 0.01-10 wt.%. As a result, the cosmetic having no problem of crystal precipitation, etc., even if preserved for a long term, and excellent in functionality and form stability is expected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic having excellent ultraviolet absorbing ability, good adaptability to skin, and excellent storage stability.

[0002]

2. Description of the Related Art Ultraviolet rays are known to cause various changes on the skin. In dermatology, ultraviolet light is long-wave ultraviolet light (400-320 nm), medium-wave ultraviolet light (320-320 nm).
290 nm), short-wave ultraviolet light, UV-A,
They are called UV-B and UV-C. Of these, UV
-C is absorbed by the ozone layer and hardly reaches the ground.
In addition, it is known that when a certain amount or more of UV-B is irradiated on the skin, erythema, blisters, and pigmentation occur. On the other hand, it has been conventionally said that UV-A does not cause much change to the skin. However, recently, UV-A caused changes in elastic fibers in blood vessel walls and connective tissues from electron microscopy and histological evaluation,
It has been found to cause damage to sensitive skin. Also, it has been reported that UV-A promotes the action of UV-B [J. Invest. Derm.
59 (6), 416 (1973)], and it is important to shield UV-A.

[0003] A large number of ultraviolet absorbers have been developed for UV-B, such as a benzophenone ultraviolet absorber, a paraaminobenzoic acid ultraviolet absorber, a cinnamic acid ultraviolet absorber, and a salicylic acid ultraviolet absorber. Have been. But,
The history of research on UV-A is short, and as for substances that effectively absorb UV-A when applied to the skin, dibenzoylmethane derivatives, cinnamic acid derivatives, chalcone derivatives and benzalhydantoin derivatives are presently slightly. It is only known [West German Patent Publication Nos. 2728241 (1979) and 2728243 (1).
979), JP-A-51-61641, and JP-A-52-61641.
JP-A-46056, JP-A-57-59840, JP-A-57-59840
JP-197209, JP-A-60-109544, JP-A-63-101371, JP-A-63-10137
No. 2].

[0004] Dibenzoylmethane derivatives, cinnamic acid derivatives and chalcone derivatives, which are known as UV-A absorbers, have poor stability, especially coloring stability, when formulated, and are not safe. There's a problem. On the other hand, benzal hydantoin derivatives are disclosed in JP-A-63-101371.
JP-A-63-101372 and JP-A-63-101372, compounds represented by the following general formulas (2) and (3), all of which are resistant to discoloration and have excellent safety. It is.

[0005]

Embedded image

[0006]

Embedded image [In the formulas (2) and (3), X represents a hydrogen atom or -CH
₂ CHCO ₂ R, wherein R is an alkyl group having 3 to 18 carbon atoms, a cyclohexyl group or a trimethylcyclohexyl group.]

Conventionally, ultraviolet absorbers having high solubility have been desired for reasons such as stability of the dosage form when blended in cosmetics. The above general formulas (2) and (3)
The indicated benzal hydantoin derivative shows some solubility in animal and vegetable oils, fats and oils, organic solvents and the like. However, when this is blended in cosmetics, dissolution and precipitation are repeated due to temperature changes during storage, etc., and crystallization of the dimethoxybenzalhydantoin derivative proceeds. It has been found that the organoleptic properties (fitness and feel to the skin) of the cosmetic are significantly impaired, and that the ultraviolet absorbing effect is also reduced.

Japanese Patent Application Laid-Open No. 1-158090 discloses that p-dimethylbenzoate or p-methoxycinnamate is stabilized in a system in which 5- (3,4-dialkoxybenzal) hydantoin is dissolved in ethanol. It is disclosed that it has the effect of causing However, 5- (3,
No use in systems in which the 4-dialkoxybenzal) hydantoin is not dissolved is disclosed.

[0009] In recent years, there has been an increasing demand for safety for cosmetics, and there has been a concern that the ultraviolet absorbent dissolved in the cosmetics may be degraded due to decomposition or percutaneous absorption. The solubility of the UV absorber is rather a negative factor.

[0010]

SUMMARY OF THE INVENTION The present invention uses a benzalhydantoin-based ultraviolet absorber having extremely poor solubility, has excellent UV-A absorption ability, has good adaptability to skin, and has excellent storage stability. It aims to provide cosmetics.

[0011]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive research and have found that the following general formula (1)
A powder of 5- (3,4-dialkoxybenzal) hydantoin represented by the following formula or a powder obtained by coating the surface of a cosmetic powder with the dialkoxybenzalhydantoin is blended. The present invention has been found to meet the purpose well without the above-mentioned problems, and has completed the present invention.

[0012]

Embedded image (R ¹ and R ² each represent an alkyl group having 1 to 3 carbon atoms)

That is, 5- (3,4) in the general formula (1)
The UV-A absorption spectrum obtained by measuring (-dialkoxybenzal) hydantoin in a powder form has a large absorption characteristic in a long wavelength ultraviolet region (400 to 320 nm) as shown in FIG. Thus, unlike conventional UV absorbers, various animal and vegetable oils, fats and oils, organic solvents, surfactants, which are widely used cosmetic raw materials,
Almost insoluble in polyhydric alcohols, thickeners, water, etc., can be compounded as powder, and does not react with other base materials,
There is no decomposition or discoloration. From the viewpoint of safety, it hardly dissolves on the skin, so that there is no problem of percutaneous absorption or the like, which has been a concern in the past. This 5- (3,
Even when 4-dankoxy benzal) hydantoin is used as a powder in cosmetics such as foundations and emulsions, the UV-A absorption ability is not impaired, the composition is well adapted to the skin, and the form stability is good. It is.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The 5- (3,4-) represented by the above general formula (1) is used as an ultraviolet absorber in the present invention.
(Dialkoxybenzal) hydantoin can be prepared, for example, according to the method described in JP-A-63-101371.
It can be easily obtained by condensation of 4-dialkoxybenzaldehyde and hydantoin with a base catalyst.

[0015]

Embedded image (R ¹ and R ² each represent an alkyl group having 1 to 3 carbon atoms)

Most preferred for use in the present invention
(3,4-dialkoxybenzal) hydantoin is
In the general formula (1), R ¹ and R ² are both CH ₃ ;
5- (3,4-dimethoxybenzal) hydantoin.

The 5- (3,4-dialkoxybenzal) hydantoin according to the present invention is incorporated into cosmetics in the form of a powder. A powder obtained by subjecting the cosmetic powder to a coating treatment with the hydantoin compound in advance may be used. Or a mixture thereof may be used. 0.001 to 1 average particle size as powder
00 μm, preferably 0.01 to 10 μm. It is difficult to produce a powder having a particle size of less than 0.001 μm, and if the particle size exceeds 100 μm, the feeling of use of the cosmetic and the ultraviolet absorbing ability are reduced.

Such a fine powder can be prepared using, for example, a Henschel mixer (a power kneader manufactured by Dalton), a jet crusher (a jet micronizer manufactured by Dalton), or a ball mill.

The hydantoin compound powder, uncoated cosmetic powder, and the hydantoin compound powder coated with cosmetic powder may be included.

Coating the surface of the powder for cosmetics with the hydantoin compound and blending the same with the cosmetic can provide a cosmetic having better dispersibility and better form stability. The ultraviolet-absorbing powder produced by this coating method has excellent ultraviolet (UV-A) absorption ability and animal and vegetable oils, fats and oils, organic solvents, surfactants, polyhydric alcohols,
Cosmetics that are insoluble in thickeners, water, etc., are also excellent in storage stability and become unprecedented excellent ultraviolet absorbing powders.

The cosmetic powder coated with 5- (3,4-dialkoxybenzal) hydantoin includes nylon powder, polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene / acrylic powder. Organic resin powder such as acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, trimethylsilsesquioxane powder, talc, kaolin, mica, sericite, muscovite , Biotite, phlogopite, synthetic mica,
Rhodolite, Lithium mica, Titanium mica, Diatomaceous earth, Flastonite, Vermiculite, Fish scale foil, Magnesium carbonate, Calcium carbonate, Silicic anhydride, Aluminum silicate, Barium silicate, Calcium silicate, Magnesium silicate, Strontium silicate, Metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, calcium phosphate, hydrofluoric apatite, hydroxyapatite,
Ceramic powder, zinc myristate, calcium palmitate, aluminum stearate, boron nitride,
Titanium dioxide, zinc oxide, selenium oxide, cerium oxide,
Aluminum oxide, red iron oxide, bismuth oxyoxide, iron titanate, α-iron oxide, γ-iron oxide, yellow iron oxide, black iron oxide, carbon black, mango violet, baltic violet, chromium oxide, chromium hydroxide, cobalt titanate , Ultramarine, navy blue, mica coated with titanium oxide, bismuth oxychloride coated with titanium oxide, bismuth oxychloride, aluminum powder, copper powder, red No. 201, red 20
2, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203
No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505
No. Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202
No. 203, Green No. 3, Blue No. 1, chlorophyll, β-carotene and the like.

Among the above cosmetic powders, preferred are talc, sericite, mica, red iron oxide, titanium dioxide, zinc oxide, selenium oxide, nylon powder and the like.

The average particle size of these cosmetic powders is 0.001 to 100 μm, preferably 0.01 to 1 μm.
It is 0 μm.

The amount of 5- (3,4-dialkoxybenzal) hydantoin to be applied to the cosmetic powder in the present invention varies depending on the type, particle size, shape, etc. of the powder used, but is usually 0.1 to 0.1. 50% by weight. 0.1% by weight
If it is less than 50%, the effect of absorbing ultraviolet rays is not sufficient, while if it exceeds 50% by weight, the spread becomes poor and the feeling upon use is reduced.

Further, the 5- (3,4-dialkoxybenzal) hydantoin powder of the present invention (including a cosmetic powder coated with 5- (3,4-dialkoxybenzal) hydantoin) Depends on the dosage form.
Also, it depends on how much UV protection action is required and is not uniformly determined, but is usually 0.1.
01 to 10% by weight. If the amount is less than 0.01% by weight, a desired ultraviolet absorbing effect may not be obtained. If the amount is more than 10% by weight, a feeling in use may be reduced or precipitation may occur.

The external preparation for skin of the present invention includes other components usually used in cosmetics and the like, such as oils, antioxidants, surfactants, sequestering agents, fragrances, water, polyhydric alcohols, thickeners, Inorganic pigments, organic pigments, dyes, preservatives and the like can be appropriately compounded as needed. The dosage form of the external preparation for skin of the present invention is arbitrary, and may be any of powder, cream, paste, stick, spray, foundation and the like.

The 5- (3,4-dialkoxybenzal) hydantoin powder of the present invention (the powder for cosmetics is
4-dialkoxybenzal), including those coated with hydantoin) are inorganic pigments having UV-B shielding properties such as titanium dioxide, zinc oxide, zirconium oxide, oxidized oxide, as long as the objects and effects of the present invention are not impaired. It can be used in combination with selenium, cerium oxide, or the like.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail by reference examples and examples, but the present invention is not limited to these examples.

REFERENCE EXAMPLE 1 UV-A absorption spectrum 1.4 mg of powder of 5- (3,4-dimethoxybenzal) hydantoin (abbreviated as "compound A") was taken in 1 cm.
A visible light / ultraviolet absorption spectrum was measured by sandwiching the quartz plate between two x 3.5 cm quartz plates so as to be uniform, and as shown in FIG. 1, the absorption maximum was observed in the long wavelength ultraviolet region of 400 to 320 nm. UV-A, even in powder form
It has been found to act as an absorbent.

Reference Example 2: Solubility Experimental method: 0.2 g of Compound A was added to 20 g of a solvent, and the mixture was stirred with a magnetic stirrer at room temperature for 4 hours.
The solution was filtered through 5C filter paper, and the absorbance of the filtrate at 340 nm was measured to determine the solubility. The results are shown in Table 1. The solubility was calculated from the following equation. For comparison, dimethoxybenzylidene dioxoimidazolidine propionic acid 2
-Ethylhexyl (in the formula (2), X is H and R is 2-ethylhexyl; abbreviated as "compound B")
Are also shown.

[0031]

(Equation 1)

[0032]

[Table 1]

Example 1: Preparation of ultra-fine titanium dioxide treated with 5- (3,4-dimethoxybenzal) hydantoin Fine titanium dioxide 70 having an average particle diameter of 30 to 50 µm
30 parts by weight of 5- (3,4-dimethoxybenzal) hydantoin was added to the parts by weight, and the mixture was stirred and mixed with a Henschel mixer for 10 minutes to perform coating treatment.
Parts by weight were obtained.

Comparative Example 1 Preparation of Fine Particle Titanium Dioxide Treated with 2-Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate Fine Particle Titanium Dioxide 70 having an Average Particle Size of 30 to 50 μm
To 30 parts by weight of 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate was added to parts by weight,
The mixture was stirred and mixed for 10 minutes with a Henschel mixer to obtain 100 parts by weight of the desired powder.

Example 2: Preparation of fine particles of 5- (3,4-dimethoxybenzal) hydantoin 5- (3,4-dimethoxybenzal) hydantoin was pulverized in a jet stream to give an average particle diameter of about 10 to 50 µm.
m-microparticles 5- (3,4-dimethoxybenzal) hydantoin were obtained.

Comparative Example 2 Preparation of Fine Particles of 2-Ethylhexyl Dimethoxybenzylidenedioxoimidazolidinepropionate 2-Ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate was ground in a jet stream,
Fine particle dimethoxybenzylidene dioxoimidazolidine 2-ethylhexyl propionate having an average particle diameter of about 10 to 50 µm was obtained.

Storage stability test (1) A container was filled with the following O / W type liquid foundation of Example 3 or Comparative example 3, and a storage stability test (cycle test) was performed. The test conditions were as follows: 22 hours 40 degrees C. → Temperature decrease in 2 hours → 22 hours-5 ° C. → 2 hours. After storage for 3 months, sensory evaluation was performed.

<O / W Liquid Foundation> Example 3 Comparative Example 3 Powder Talc 33 3 Powder of Example 1 70 Powder of Comparative Example 1 7 Color Pigment 2 2 Aqueous Phase Bentonite 0.5 0. 5 monostearin polyoxyethylene sorbitan 1 1 triethanolamine 1 1 propylene glycol 10 10 water residue oil phase stearic acid 2 2 isohexadecyl alcohol 7 7 glyceryl monostearate 2 2 liquid lanolin 2 2 liquid paraffin 8 8 storage stability Test ^*) Sensory evaluation before ○ ○ Sensory evaluation after storage stability test ○ ×

Sensory evaluation: The composition was applied to the faces of 10 panelists and scored according to the following evaluation criteria. Good 5 Slightly good 4 Not good 3 Somewhat bad 2 Not good 1 1-2 points: ×, 3 points: △, 4-5 points: ○

As shown above, the product of Example 3 had a good sensory evaluation even after the storage stability test, but the product of Comparative Example 3 had a rough and poor sensory evaluation after the storage stability test. .

Storage stability test (2) A container was filled with the emulsion of the following Example 4 or Comparative Example 4, and the test was carried out in the same manner as described above.

<Emulsion> Example 4 Comparative Example 4 Aqueous Phase 1,3-butylene glycol 77 7 Titanium dioxide 55 5 Example 20 20 Comparative Example 20 2 Disodium edetate 0.05 0.05 Triethanolamine 1 1 Antioxidant proper amount proper amount perfume proper amount proper amount purified water residue residual oil phase oxybenzone 2 2 squalane 10 10 petrolatum 5 5 stearyl alcohol 3 3 stearic acid 3 3 glyceryl monostearate 3 3 ethyl polyacrylate 1 ⁾ Storage stability test ^* 1 ⁾ Sensory evaluation before ○ ○ Sensory evaluation after storage stability test ○ ×

As described above, the product of Example 4 had a good sensory evaluation even after the storage stability test, but the product of Comparative Example 4 had a rough and poor sensory evaluation after the storage stability test. .

Example 5: Sunscreen cosmetics (W / O cream) (1) Octamethylcyclotetrasiloxane 10.5% (2) Dimethylpolysiloxane (100 cs) 5.0 (3) Dimethylpolysiloxane (2.5 million) cs) 3.0 (4) Liquid paraffin 15.0 (5) Polyether modified silicone 6.0 (6) Powder of Example 1 4.0 (7) Purified water 48.1 (8) Sodium L-glutamate 3.0 (9) 1,3-butylene glycol 5.0 (10) Preservative 0.2 (11) Fragrance 0.2

Production method: (1) to (6) and (11) were mixed, dissolved by heating and maintained at 70 ° to obtain an oil phase. Separately, (7) to (10) were dissolved by heating and maintained at 70 ° C. to obtain an aqueous phase. The aqueous phase was added to the oil phase and sufficiently emulsified by an emulsifier. After the emulsification, the mixture was cooled with stirring, and when the temperature became 35 ° C. or less, the mixture was poured into a container and allowed to cool to be solidified.

Example 6: Powder foundation (1) Sericite 30.0% (2) Mica residue (3) Kaolin 5.0 (4) Bengala 2.5 (5) Yellow iron oxide 2.0 (6) Black Iron oxide 0.1 (7) Powder of Example 2 2.0 (8) Titanium oxide 10.0 (9) N-Lauroyl-L-lysine 8.0 (10) Squalane 2.0 (11) Preservative 0.1 (12) Suitable amount of fragrance

Production method: (1) to (9) were mixed and pulverized through a pulverizer. Transfer this to a high-speed blender, (10)-(12)
And mixed uniformly. This was treated with a pulverizer, and the particle size was adjusted through a sieve, and then compression-molded in a container such as a gold plate to obtain a desired powder foundation.

Example 7: Scarlet red (1) Powder of Example 1 12.0% (2) Talc residue (3) Sericite 10.0 (4) Iron oxide (red, black, yellow) 5.0 (5) Organic pigment (Red No. 202) 2.4 (6) Squalane 7.5 (7) Preservative 0.1 (8) Perfume

Manufacturing method: It was manufactured in the same manner as in Example 6.

Example 8: Powder Eye Shadow (1) Powder of Example 1 2.0% (2) Mica Titanium 30.0 (3) Sericite Remaining (4) Mica 10.0 (5) Color Pigment 15.0 (6) N-lauroyl-L-lysine 10.0 (7) Dimethylpolysiloxane 2.0 (8) Preservative 0.1 (9) Perfume

Manufacturing method: It was manufactured in the same manner as in Example 6.

Example 9: Dual-use powder foundation (1) Powder of Example 1 10.0% (2) Talc 4.8 (3) Titanium mica 5.0 (4) Mica remaining (5) Iron oxide ( (Red, yellow, black) 8.2 (6) Zinc oxide 4.5 (7) Barium sulfate 5.0 (8) Polyethylene powder 1.0 (9) Dimethylpolysiloxane 4.0 (10) Lanolin 5.0 (11) Vaseline 1.0 (12) Preservative 1.5 (13) Perfume

Manufacturing method: It was manufactured in the same manner as in Example 6.

[0054]

As described above, according to the present invention, 5-
Cosmetic products containing (3,4-dialkoxybenzal) hydantoin in the form of a powder can be treated with ultraviolet (UV-A)
It has absorptive capacity, has no problems such as crystal precipitation even when stored for a long period of time, and has excellent sensory and morphological stability.

[Brief description of the drawings]

FIG. 1 shows a UV-A absorption spectrum of 5- (3,4-dimethoxybenzal) hydantoin measured in powder form.

Claims (5)

[Claims] 1. 5- (3) represented by the following general formula (1)
A powder obtained by subjecting a powder of (4-dialkoxybenzal) hydantoin and / or a powder for cosmetics to a coating treatment with the 5- (3,4-dialkoxybenzal) hydantoin is blended as an ultraviolet absorber. Cosmetics characterized by doing. Embedded image (R ¹ and R ² each represent an alkyl group having 1 to 3 carbon atoms) 2. The cosmetic according to claim 1, wherein the average particle diameter of the powder blended as the ultraviolet absorbent is in the range of 0.001 to 100 μm. 3. The cosmetic according to claim 1, wherein the content of the powder is 0.01 to 10% by weight. 4. The cosmetic according to claim 1, wherein the cosmetic powder is a pigment. 5. The powder of 5- (3,4-dialkoxybenzal) hydantoin according to claim 1 and / or the powder for cosmetics is treated with said 5- (3,4-dialkoxybenzal) hydantoin. A cosmetic comprising a combination of a powder obtained by coating and at least one of titanium dioxide, zirconium oxide, zinc oxide, selenium oxide and cerium oxide.