JP2005206473A - External preparation for skin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an external preparation for skin having ultraviolet light absorption in a UV-A region, having excellent compatibility with an oil which is a base for the external preparation for skin, further preventing discoloring properties of 2-ethylhexyl p-methoxycinnamate and improving the persistence of ultraviolet protective effects by formulating a benzotriazole derivative having a specific structure in the external preparation for skin comprising the 2-ethylhexyl p-methoxycinnamate formulated therein. <P>SOLUTION: The external preparation for skin is obtained by formulating the benzotriazole derivative represented by general formula (I) (wherein, R' is a 1-6C straight-chain alkyl group; and R" is a 1-3C straight-chain alkyl group) in the external preparation for skin comprising the 2-ethylhexyl p-methoxycinnamate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an external preparation for skin containing an ultraviolet absorber. In more detail, by adding a benzotriazole derivative having a specific structure to a skin external preparation formulated with 2-ethylhexyl p-methoxycinnamate, the skin external preparation base has UV absorption in the UV-A region. It is related with the technique of the skin external preparation which was excellent in compatibility with the oil component which is, and also prevented the coloring property of 2-ethylhexyl p-methoxycinnamate, and improved the durability of the ultraviolet-ray protective effect.

  In cosmetics, an ultraviolet absorber is blended in order to increase the stability of the blended components against ultraviolet light or to protect human skin.

  On the other hand, the ultraviolet wavelength region is divided into a UV-A region (320 to 400 nm), a UV-B region (290 to 320 nm), and a UV-C region (up to 290 nm). Usually do not reach the ground. In addition, the UV-A region (320 to 400 nm) UV rays invade the skin black, but unlike the UV-B region (290 to 320 nm) UV rays, it is considered not to cause sunburn and promote skin aging. It was. However, in recent years, ultraviolet rays in the UV-B region stay relatively on the surface of the skin, whereas ultraviolet rays in the UV-A region reach the deep part of the skin, and induce skin cancer as well as skin aging. It has been found to be the cause.

  Cosmetic UV absorbers that have been used to date are classified according to the structure: (1) benzoic acid derivatives, (2) cinnamic acid derivatives, (3) benzophenone derivatives, (4) dibenzoylmethane derivatives, (5) Salicylic acid derivatives and the like. In recent years, the ultraviolet absorbers (2) and (4) are frequently used.

However, the ultraviolet absorbers listed above have their respective problems from a practical standpoint. For example, in the benzoic acid derivative of (1), for example, p-dimethylaminobenzoic acid-2-ethylhexyl is liquid and transparent, and has advantages that it is easy to handle, but there is a suspicion of safety including these derivatives. It has not been used in recent years. Further, the maximum absorption wavelength is in the vicinity of 290 nm, and the ultraviolet ray only in the UV-B region is absorbed.

  In the cinnamic acid derivative (2), there is p-methoxycinnamic acid-2-ethylhexyl ester as an ultraviolet absorber most frequently used in sun care cosmetics currently on the market. The maximum absorption wavelength is around 310 nm, and the absorption region does not reach the UV-A region. In addition, the color changes due to sunlight and there is a problem in the sustainability of the coloring property and the UV protection effect.

  In the benzophenone derivative of (3), for example, 2-hydroxy-4-methoxybenzophenone has absorption over the UV-A and UV-B regions and has relatively good solubility in a skin external preparation base, but has a maximum absorption wavelength. Slightly close to the UV-B region and the absorbance is not very large. In recent years, a basic skeleton structure (benzophenone) has been pointed out as an environmental hormone and its use has been avoided.

  Of the dibenzoylmethane derivatives of (4), 4-tert-butoxy-4-methoxydibenzoylmethane is often used as a skin external preparation. The maximum absorption is in the vicinity of 360 nm, the absorbance is large, and it is excellent as an ultraviolet absorber in the UV-A region. However, there is a problem in light stability, the compatibility with the oil for skin external preparation is poor, and only a small amount can be mixed.

In the salicylic acid derivative (5), octyl salicylate is used. It has a maximum absorption wavelength in the UV-B region, is oily, and is excellent in compatibility with paraffin oil or the like, but is not practically used because of its low absorbance.

  For this reason, 2-ethylhexyl p-methoxycinnamate (2) is used in the UV-B region, and 4-tert-butoxy-4-methoxydibenzoylmethane (4) is used in the UV-A region. Often done. In particular, in recent years, there has been an increasing demand for UV absorption in the UV-A region, but UV absorbers that are highly compatible with the oil of the skin external preparation base have not been commercialized.

  On the other hand, the benzotriazole derivative used in the present invention discloses the use of an ultraviolet absorber as a stabilizer for photographic film, lacquer, paint, etc., for example, in Patent Document 1. The production method is generally a method in which o-nitroaniline is converted to a diazonium salt with sodium nitrite or the like, coupled with phenol to synthesize a monoazo compound, and then reduced to benzotriazole. (See Patent Documents 2 to 7)

JP-A-3-223384 Japanese Patent Laid-Open No. 52-113973 Japanese Patent Laid-Open No. 52-113974 JP-A-2-134370 JP-A-4-59768 Japanese Patent Laid-Open No. 7-18246 JP 2003-26668 A

  Therefore, the problem to be solved by the present invention is excellent in compatibility with oils of various skin external preparation bases, has ultraviolet absorption in the UV-A region, and is excellent in light stability of the ultraviolet absorber itself, It is to provide a skin external preparation that can sustain UV absorption effect over a long period of time.

As a result of intensive studies from the above viewpoints, the present inventors have added a benzotriazole derivative having a specific structure to a skin external preparation containing 2-ethylhexyl p-methoxycinnamate, thereby forming a skin external preparation base. Discovered that it is extremely excellent in compatibility with various oils, and as a result, it was discovered that a skin external preparation having an excellent absorption effect in the UV-A region and a high durability of ultraviolet protection can be provided, and the present invention was completed. It came to do.

（式中、Ｒ’＝Ｃ１〜Ｃ６の直鎖のアルキル基、Ｒ”＝Ｃ１〜Ｃ３の直鎖のアルキル基である。） That is, this invention provides the skin external preparation which mix | blended the benzotriazole derivative shown with the following general formula (I) in the skin external preparation containing 2-ethylhexyl p-methoxycinnamate.
Formula (I)

(In the formula, R ′ = C1-C6 linear alkyl group, R ″ = C1-C3 linear alkyl group.)

  Moreover, this invention provides said skin external preparation characterized by the compounding mass ratio of a benzotriazole derivative and 2-ethylhexyl p-methoxycinnamate being 8: 2 to 2: 8.

  Further, in the present invention, the benzotriazole derivative is 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole, 2- (2-hydroxy-4-isobutoxyphenyl) -2H. -The above-mentioned skin external preparation characterized by being 1 type, or 2 or more types chosen from benzotriazole.

The ultraviolet absorber composition blended in the external preparation for skin of the present invention, that is, 2-ethylhexyl p-methoxycinnamate and the benzotriazole derivative have ultraviolet absorption in the UV-A region in the external preparation for skin, and the skin Excellent compatibility with various oils of external preparation bases. In particular, it is remarkably excellent in compatibility and stability with di-2-ethoxyethyl succinate which is important as an oil component.
Moreover, the coloring property of 2-ethylhexyl p-methoxycinnamate is prevented, and the durability of the UV protection effect is further improved.

  Hereinafter, the present invention will be described in detail.

第２工程

第３工程

第４工程

（式中、２，３−ＤＣＮは２，３−ジクロロ−１，４−ナフトキノンを表す。）
第５工程

（式中、Ｒ＝ＨもしくはＣＨ₃、Ｒ’＝Ｃ１〜Ｃ６の直鎖のアルキル基、Ｒ”＝Ｃ１〜Ｃ３の直鎖のアルキル基である。）

（Ｂ法）
第１工程

第２工程

第３工程

第４工程

第５工程

（式中、Ｒ’＝Ｃ１〜Ｃ６の直鎖のアルキル基、Ｒ”＝Ｃ１〜Ｃ３の直鎖のアルキル基である。なお、２，３−ＤＣＮは２，３−ジクロロ−１，４−ナフトキノンを表す。） 2-Ethylhexyl p-methoxycinnamate is a prominent UV absorber frequently used for external preparations for skin. The benzotriazole derivative represented by the above general formula (I) is a known compound and is synthesized as follows. That is, a method is generally used in which o-nitroaniline is converted to a diazonium salt with sodium nitrite or the like, coupled with phenol to synthesize a monoazo compound, and then reduced to benzotriazole.
(Method A)
First step

Second step

Third step

Fourth step

(In the formula, 2,3-DCN represents 2,3-dichloro-1,4-naphthoquinone.)
5th process

(In the formula, R = H or CH ₃ , R ′ = C1-C6 linear alkyl group, R ″ = C1-C3 linear alkyl group.)

(Method B)
First step

Second step

Third step

Fourth step

5th process

(In the formula, R ′ = C1-C6 linear alkyl group, R ″ = C1-C3 linear alkyl group. In addition, 2,3-DCN is 2,3-dichloro-1,4- Represents naphthoquinone.)

In the present invention, when the corresponding benzotriazole and alkyl halide are refluxed in a mixed solvent of methyl isobutyl ketone and dimethylformamide, the compound of the general formula (I) can be produced with a particularly high yield.
More specifically, 6- (2H-benzotriazol-2-yl) resorcinol is placed in a four-necked flask equipped with a thermometer and a reflux condenser, and methyl isobutyl ketone and dimethylformamide are added and stirred. To do. Sodium carbonate and 2-ethylhexyl bromide are added to this, and it heats to reflux temperature, stirring. After stirring for a predetermined time while maintaining the reflux temperature, methyl isobutyl ketone was recovered at normal pressure, and the remaining oil was washed with water to remove excess sodium carbonate and the produced inorganic substance, and liquid 2- [4- (2 -Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole is obtained in high yield.

In the external preparation for skin of the present invention, the blending amount of 2-ethylhexyl p-methoxycinnamate and the benzotriazole derivative represented by the general formula (I) is appropriately determined according to the target product. 2-Ethylhexyl p-methoxycinnamate is usually 0.01 to 20% by mass based on the total amount of the external preparation for skin. Moreover, the benzotriazole derivative shown with general formula (I) is 0.01-10 mass% normally with respect to the skin external preparation whole quantity.
The blending weight ratio of the benzotriazole derivative represented by the general formula (I) and 2-ethylhexyl p-methoxycinnamate is preferably 8: 2 to 2: 8. If the blending amount of the benzotriazole derivative deviates from this ratio, the excellent absorption effect in the UV-A region and the durability of UV protection may be difficult to be exhibited. In addition, if it is large, problems such as adhesion to clothes may easily occur.

  Among the benzotriazole derivatives of the above general formula (I), 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole, 2- (2-hydroxy-4-isobutoxy) Phenyl) -2H-benzotriazole is superior in terms of the most excellent absorption effect in the UV-A region and the durability of UV protection.

  In addition to the above essential components, the skin external preparation of the present invention is usually used in skin external preparations such as cosmetics and pharmaceuticals, such as whitening agents, moisturizers, antioxidants, oily components, other ultraviolet absorbers, Surfactants, thickeners, alcohols, powder components, colorants, aqueous components, water, various skin nutrients, and the like can be appropriately blended as necessary and can be produced by conventional methods. For example, the following are mentioned as a compounding component.

Avocado oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, evening primrose oil, castor oil, sunflower oil, tea seed oil, rice bran oil, jojoba oil, cacao butter, coconut oil, squalene, beef tallow, owl, beeswax, candelilla wax Oils such as carnauba wax, whale wax, lanolin, liquid paraffin, polyoxyethylene (8 mol) oleyl alcohol ether, glyceryl monooleate, cyclomethicone, dimethylpolysiloxane, diphenylpolysiloxane.
Higher alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cholesterol, phytosterol.
Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, linolenic acid.
Moisturizers such as polyethylene glycol, glycerin, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate and chitosan.
Thickeners such as methylcellulose, ethylcellulose, gum arabic, and polyvinyl alcohol.
Organic solvents such as ethanol and 1,3-butylene glycol.
Antioxidants such as butylhydroxytoluene, tocopherol and phytic acid.
Antibacterial preservatives such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid esters (such as ethylparaben and butylparaben), and hexachlorophene.
Amino acids and hydrochlorides such as glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, histidine.
Organic acids such as acyl sarcosine acid (eg, lauroyl sarcosine sodium), glutathione, citric acid, malic acid, tartaric acid, lactic acid.
Vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B such as vitamin B12, vitamin B15 and its derivatives, ascorbic acid, ascorbic acid phosphate ( Salt), vitamin C such as ascorbic acid dipalmitate, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin E nicotinate and other vitamin E, vitamin D, vitamin H, pantothenic acid, pantethine, etc. Vitamins.
Nicotinamide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucalyptol, thymol, inositol, saponins (psychosaponin, carrot saponin, loofah) Various drugs such as saponin, muclodisaponin, etc.), pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, cephalanthin, placenta extract.
Bark, Clara, Kouhone, Orange, Sage, Thyme, Yarrow, Zeni-Oyaku, Senkyu, Assembly, Spruce, Spruce, Birch, Horsetail, Loofah, Maronie, Yukinoshita, Arnica, Lily, Artemisia, Peonies, Aloe, Gardenia, Sahara Natural extract extracted with solvent, alcohol, polyhydric alcohol, water, aqueous alcohol.
Cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, and laurylamine oxide.
Metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate and gluconic acid.
Fragrance, scrub agent, purified water, etc.

  Particularly preferred bases for the external preparation for skin of the present invention are oils of liquid paraffin, squalane, cetyl isooctanoate, triglyceride isooctanoate, and di-2-ethylhexyl succinate. Especially this invention is preferably utilized for the skin external preparation which has di 2-ethylhexyl succinate as a main component base.

  The external preparation for skin of the present invention may be in any product form such as an ointment, cream, emulsion, lotion, pack or the like. It is particularly suitable as a sunscreen cosmetic. The dosage form is not particularly limited.

  The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples.

"Synthesis Example 1: Synthesis of 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole"
65.4 g (0.20 mol) of 6- (2H-benzotriazol-2-yl) resorcinol synthesized by a conventional method was placed in a 500 ml four-necked flask equipped with a thermometer and a reflux condenser, and 50 ml of methyl isobutyl ketone, 4.0 g of dimethylformamide was added and stirred. To this, 25.4 g (0.24 mol) of sodium carbonate and 77.2 g (0.40 mol) of 2-ethylhexyl bromide were added and heated to the reflux temperature with stirring. After stirring for 15 hours while maintaining the reflux temperature, methyl isobutyl ketone was recovered at normal pressure, and the remaining oil was washed with water to remove excess sodium carbonate and produced inorganic substances. This oil was distilled under reduced pressure to obtain 52.1 g of a yellow transparent fraction of 220 to 225 ° C./0.2 to 0.3 mmHg. This compound was liquid at normal temperature, and the yield was 76.7% and the HPLC purity was 99.0%.

"Synthesis Example 2: Synthesis of 2- (2-hydroxy-4-isobutoxyphenyl) -2H-benzotriazole"
The same procedure as in Synthesis Example 1 was carried out using the same molar amount of isobutyl bromide instead of 2-ethylhexyl bromide. A slightly yellowish white powdery crystal was obtained with a yield of 72.5%. m. p. They were 120.0 to 120.8 ° C., λmax = 345.6 nm, and ε = 21750.

Experimental Example 1 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole, which is a benzotriazole derivative synthesized in Synthesis Example 1, was dissolved in the following general-purpose oil for skin external use, and its solubility Was measured. As a comparative example, the solubility of 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789) having a maximum absorption region in the UV-A region was also measured.
Oil used Liquid paraffin: Kaneda Co., Ltd. High Coal K-230
Squalane: SQUATECH Corp. Super Squalane CIO: Nippon Seika Co., Ltd. Cetyl Isooctanoate IOTG: Nippon Seika Co., Ltd. Isooctanoic acid triglyceride [Method]
It melt | dissolved at 20 degreeC, it preserve | saved for 120 days in a cool dark place (5 degreeC), and the presence or absence of precipitation of the said added benzotriazole derivative, the odor after dissolution, and coloring were investigated. The results are shown in “Table 1”.
Table 1 Solubility of skin external preparation base in oil (Wt / Wt%)

  None of the compounds dissolved in the above dissolution amount was precipitated as crystals or oily components were separated. The dissolved colors were all slightly yellow and transparent and did not feel odor. Moreover, the amount of dissolution is not an upper limit. On the other hand, the solubility of 4-tert-butoxy-4-methoxydibenzoylmethane is particularly bad for liquid paraffin, and it has a solubility of about 5% to squalane and CIO. All of the benzotriazole derivatives synthesized this time showed excellent solubility.

Next, the above compound, p-methoxycinnamic acid-2-ethylhexyl ester and 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789) were each adjusted to 10 ppm with ethanol, and UV absorption was performed. The area was measured. Each maximum absorption wavelength λmax and maximum molar extinction coefficient ε are shown in “Table 2” below. The ultraviolet absorption spectrum is shown in FIGS.

  The compound of Synthesis Example 1 has λmax at a position close to parsol 1789 in the UV-A region, and the ε value is slightly inferior. Since it has a solubility of 2 to 4 times the various cosmetic bases than parsol 1789, it is possible to produce a skin external preparation with much higher ability to ultraviolet irradiation.

Experimental example 2
4-tert-butoxy-4-methoxydibenzoylmethane (trade name: parsol 1789), each compound of Synthesis Example 1 was dissolved in di-2-ethylhexyl succinate at a ratio of 20%, and 10 mL was placed in a petri dish and 150 watt xenon lamp. (Solar Ultraviolet Simulator Model 600 (manufactured by Solar Light)) was irradiated with ultraviolet rays, and after 60 minutes of irradiation, each ultraviolet absorber was diluted with ethanol so that its concentration became 10 ppm, and ultraviolet absorption spectra were measured before and after the irradiation.
The results are shown in FIGS. As can be seen from FIGS. 4 and 5, 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789) has no significant UV absorption effect before and after irradiation, whereas the synthesis example of FIG. It was found that the absorption spectrum of Compound 1 hardly changed before and after irradiation.

外観の変化 ◎ 変化なし
○ ごくわずかに着色が見られる
△ 着色が見られる Experimental example 3
Next, synthesis was performed with p-methoxycinnamic acid-2-ethylhexyl and 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789), the compound of Synthesis Example 1, and p-methoxycinnamic acid-2-ethylhexyl. Each equal mixture of the compound of Example 1 was examined for weight loss after heating at 200 ° C. for 1 hour and changes in appearance. The results are shown in “Table 3”.
Change in UV absorption after heating at 200 ° C for 1 hour

Appearance change ◎ No change
○ Slightly colored
△ Coloring is seen

"Examples 1-3"
Next, p-methoxycinnamic acid-2-ethylhexyl, 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789), the compound of Synthesis Example 1, and p-methoxycinnamic acid-2-ethylhexyl were synthesized. A combination of the compound of Example 1 and a combination of p-methoxycinnamic acid-2-ethylhexyl and 4-tert-butoxy-4-methoxydibenzoylmethane were each added to the skin external preparation of the following formulation, and ultraviolet rays SPF decay when irradiated with. The SPF was tested as follows. That is, the formulations shown in Table 4 were applied to Transpore ^TM tape (manufactured by 3M) (5 cm × 5 cm) at a rate of 2.0 mg / cm ² and dried for 15 minutes. A transpore ^TM tape of the same size was laminated to each sample to obtain each measurement sample. These measurement samples were each irradiated with ultraviolet rays at a distance of 10 mm with a 150 watt xenon lamp (Solar Ultraviole Simulator Model 600 (manufactured by Solar Light)), and the transmitted ultraviolet light of each applied formulation was a spectroradiometer USR-20B type The SPF value was calculated by multiplying by the relative effect coefficient of the action wavelength on the delayed erythema reaction of human skin, and measured twice (2 hours after the start of irradiation and 2 hours after the start of irradiation). , And compared SPF over time.

Attenuation of SPF by UV irradiation

  As can be seen from Table 4, the compound of Synthesis Example 1 is not only stable from the examples, but also when used in combination with 2-ethylhexyl p-methoxycinnamate from a comparison of the examples and the comparative examples. P-methoxycinnamate-2-ethylhexyl was found to suppress the SPF decay.

  Other examples of the present invention are shown below.

Example 4 Sunscreen
Blending amount (% by mass)
(1) Di-2-ethylhexyl succinate 14.0
(2) Isodecyl benzoate 1.0
(3) Dineeopentanoic acid tripropylene glycol 4.5
(4) 2-Ethylhexyl paramethoxycinnamate 7.0
(5) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 3.0
(6) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 1.0
(7) 2-ethylhexyl p-methoxycinnamate 0.5
(8) Polyoxyethylene 12-hydroxystearic acid condensate ester
0.5
(9) Polyglycerin 12-hydroxystearic acid condensate ester
1.5
(10) Zinc oxide 3.0
(11) Ion exchange water 52.3
(12) 1,3-butylene glycol 5.0
(13) Ethanol 8.0
(14) Methylparaben 0.1
(15) Sodium glutamate 0.8
(Production method)
A sunscreen was prepared by a conventional method. The sunscreen of this formulation was good in stability and feel in use, and the solubility of the UV absorber was also good.

Example 5 Cream
Blending amount (% by mass)
(1) Decamethylcyclopentasiloxane 20.0
(2) Ethanol 5.0
(3) Isostearyl alcohol 2.0
(4) Dipropylene glycol 3.0
(5) Isostearic acid 2.0
(6) Glyceryl tri-2-ethylhexanoate 5.0
(7) Cetyl 2-ethylhexanoate 2.0
(8) Dextrin fatty acid ester coated fine particle titanium oxide (40 nm) 2.0
(9) Sodium chloride 2.0
(10) Trisodium edetate appropriate amount (11) 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 2.0
(12) 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine 0.5
(13) 4-t-butyl-4′-methoxydibenzoylmethane 1.0
(14) 2-ethylhexyl p-methoxycinnamate 7.5
(15) Carboxymethylcellulose Na 0.5
(16) Ethyl cellulose 1.0
(17) Spherical acrylic resin powder 5.0
(18) Purified water Residue (19) Perfume appropriate amount (production method)
A cream was prepared by a conventional method. The cream of this formulation was good in both stability and use feeling, and the solubility of the UV absorber was also good.

Example 6 Cream
Blending amount (% by mass)
(1) Decamethylcyclopentasiloxane 20.0
(2) Trimethylsiloxysilicic acid 1.0
(3) Polyoxyethylene / methylpolysiloxane copolymer 2.0
(4) Dipropylene glycol 4.0
(5) Squalane 5.0
(6) Silicone-coated fine particle titanium oxide (20 nm) 10.0
(7) Talc (hydrophobized product) 6.0
(8) Paraben appropriate amount (9) Phenoxyethanol appropriate amount (10) Trisodium edetate 0.02
(11) 2- (2-hydroxy-4-isobutoxyphenyl) -2H-benzotriazole
1.0
(12) 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine 4.0
(13) 2-ethylhexyl p-methoxycinnamate 7.0
(14) Diparamethoxycinnamic acid mono-2-ethylhexanoic acid glyceryl
0.5
(15) Spherical polyethylene powder 5.0
(16) Dimethyl distearyl ammonium hectorite 1.0
(17) Purified water Residual (18) Perfume appropriate amount (production method)
A cream was prepared by a conventional method. The cream of this formulation was good in both stability and use feeling, and the solubility of the UV absorber was also good.

Example 7 Cream
Blending amount (% by mass)
(1) Dimethylpolysiloxane 5.0
(2) Decamethylcyclopentasiloxane 20.0
(3) Trimethylsiloxysilicic acid 3.0
(4) Polyoxyethylene / methylpolysiloxane copolymer 3.0
(5) Dipropylene glycol 3.0
(6) Cetyl 2-ethylhexanoate 1.0
(7) Silicone coated fine particle zinc oxide (60nm) 10.0
(8) Talc 1.0
(9) Silicone-coated fine particle titanium oxide (40 nm) 7.0
(10) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 0.5
(11) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 0.3
(12) 2-ethylhexyl p-methoxycinnamate 0.4
(13) Appropriate amount of paraben (14) Appropriate amount of phenoxyethanol (15) Trisodium edetate 0.2
(16) Dimethyl distearyl ammonium hectorite 1.0
(17) Polymethylmethacrylic acid copolymer spherical powder 3.0
(18) Purified water Residue (19) Perfume appropriate amount (production method)
A cream was prepared by a conventional method. The cream of this formulation was good in both stability and use feeling, and the solubility of the UV absorber was also good.

Example 8 Latex
Blending amount (% by mass)
(1) Dimethylpolysiloxane 5.0
(2) Decamethylcyclopentasiloxane 25.0
(3) Trimethylsiloxysilicic acid 5.0
(4) Polyoxyethylene / methylpolysiloxane copolymer 2.0
(5) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 4.0
(6) 2-Ethylhexyl p-methoxycinnamate 7.5
(7) Dipropylene glycol 5.0
(8) Fine zinc oxide (hydrophobized 60 nm) 15.0
(9) Paraben appropriate amount (10) phenoxyethanol appropriate amount (11) edetate trisodium appropriate amount (12) dimethyl distearyl ammonium hectorite 0.5
(13) Spherical polyalkyl acrylate powder 5.0
(14) Purified water residue (15) Perfume appropriate amount (production method)
An emulsion was prepared by a conventional method. The emulsion of this formulation was good in stability and feel in use, and the solubility of the UV absorber was also good.

Example 9 Latex
Blending amount (% by mass)
(1) Dipropylene glycol 5.0
(2) Stearic acid 1.0
(3) Palmitic acid 1.0
(4) Glyceryl tri-2-ethylhexanoate 3.0
(5) Cetyl 2-ethylhexanoate 2.0
(6) Polyoxyethylene glyceryl isostearate 1.0
(7) Glycerol monostearate 1.0
(8) Polystearic acid polyoxyethylene glycerol 1.0
(9) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 0.3
(10) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 0.3
(11) Fine particle titanium oxide (30nm) 2.0
(12) Sodium hexametaphosphate 0.1
(13) Phenoxyethanol appropriate amount (14) edetate trisodium appropriate amount (15) 4-t-butyl-4'-methoxydibenzoylmethane 1.0
(16) 2-ethylhexyl p-methoxycinnamate 7.0
(17) Bentonite 1.0
(18) Eicosene / vinylpyrrolidone copolymer 2.0
(19) Purified water Residue (20) Perfume appropriate amount (production method)
An emulsion was prepared by a conventional method. The emulsion of this formulation was good in stability and feel in use, and the solubility of the UV absorber was also good.

Example 10 Two-layer type cream
Blending amount (% by mass)
(1) Dimethylpolysiloxane 5.0
(2) Decamethylcyclopentasiloxane 25.0
(3) Trimethylsiloxysilicic acid 5.0
(4) 2- (2-hydroxy-4-isobutoxyphenyl) -2H-benzotriazole
0.2
(5) 2-ethylhexyl p-methoxycinnamate 0.1
(6) Polyoxyethylene / methylpolysiloxane copolymer 2.0
(7) Dipropylene glycol 5.0
(8) Dextrin palmitate coated fine particle zinc oxide (60nm) 15.0
(9) Dipotassium glycyrrhizinate 0.02
(10) Glutathione 1.0
(11) Thiotaurine 0.05
(12) Clara extract 1.0
(13) Paraben appropriate amount (14) Phenoxyethanol Appropriate amount (15) Trisodium edetate Appropriate amount (16) Dimethyl distearyl ammonium hectorite 0.5
(17) Spherical polyalkyl acrylate powder 5.0
(18) Butylethylpropanediol 0.5
(19) Purified water Residue (20) Perfume appropriate amount (production method)
A two-layer type cream was prepared by a conventional method. The two-layer type cream of this formulation was good in both stability and use feeling, and the solubility of the UV absorber was also good.

Example 11 Protector
Blending amount (% by mass)
(1) Dimethylpolysiloxane 3.0
(2) Methylphenylpolysiloxane 2.0
(3) Ethanol 5.0
(4) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 1.0
(5) 2-ethylhexyl p-methoxycinnamate 1.5
(6) Glycerin 4.0
(7) Dipropylene glycol 5.0
(8) 1,3-butylene glycol 2.0
(9) Di-2-ethylhexyl succinate 3.5
(10) Potassium hydroxide 0.1
(11) Sodium hexametaphosphate 0.1
(12) Thiotaurine 0.1
(13) Trisodium edetate 0.1
(14) 4-t-butyl-4'-methoxydibenzoylmethane 3.0
(15) Iron oxide 0.01
(16) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-2)
0.1
(17) Carboxyvinyl polymer 0.2
(18) Paraben appropriate amount (19) Purified water Residue (20) Fragrance Appropriate amount (production method)
A protector was prepared by a conventional method. The protector of this formulation was good in stability and feel in use, and the solubility of the UV absorber was also good.

Example 12 Hairdressing
Blending amount (% by mass)
(1) Microcrystalline wax 5.0
(2) Ceresin 10.0
(3) Sunflower oil 1.0
(4) Tetra-2-ethylhexanoic acid pentaerythritol residue (5) penta-octanoic acid diglycerol sorbitan 10.0
(6) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 0.1
(7) 2-ethylhexyl p-methoxycinnamate 0.1
(8) Lipophilic glyceryl monostearate 5.0
(9) Self-emulsifying glyceryl monostearate 5.0
(10) Silylated silica anhydride 5.0
(11) Mica titanium 11.0
(Production method)
A hair styling was prepared by a conventional method. The hair styling agent of this formulation was good in both stability and use feeling, and the solubility of the UV absorber was also good.

Example 13 Shampoo
Blending amount (% by mass)
(1) Dimethylpolysiloxane 1.5
(2) 2-ethylhexyl p-methoxycinnamate 0.2
(3) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 1.0
(4) Dipropylene glycol 3.0
(5) Ethylene glycol distearate 2.0
(6) Palm oil fatty acid monoethanolamide 2.0
(7) Lauroylmethyl taurine sodium 0.1
(8) Sodium polyoxyethylene lauryl ether sulfate 7.5
(9) Polyoxyethylene lauryl ether sulfate triethanolamine
3.5
(10) Palm oil fatty acid amidopropyl betaine 3.5
(11) Marcote 550 (Calgon) 7.5
(12) Citric acid 0.01
(13) L-glutamic acid 0.2
(14) Sodium chloride 1.0
(15) Sodium benzoate appropriate amount (16) Disodium edetate appropriate amount (17) Sodium hydroxide 0.01
(18) Purified water Residue (19) Perfume appropriate amount (production method)
A shampoo was prepared by a conventional method. The shampoo of this formulation was good in stability and feel in use, and the solubility of the UV absorber was also good.

Example 14 Rinse
Blending amount (% by mass)
(1) Polyoxyethylene / methylpolysiloxane copolymer 6.0
(2) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 0.2
(3) 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine 0.2
(4) 2-ethylhexyl p-methoxycinnamate 0.3
(5) Ethanol 10.0
(6) Octyldodecanol 0.15
(7) Glycerin 5.0
(8) 1,3-butylene glycol 2.0
(9) Squalane 0.1
(10) Pyroglutamate glyceryl oleate 0.05
(11) Stearyltrimethylammonium chloride (80%) 1.15
(12) Hydrolyzed keratin solution 0.1
(13) Paraoxybenzoic acid ester appropriate amount (14) Hydroxyethyl cellulose 1.0
(15) Purified water residue (16) Perfume appropriate amount (production method)
A rinse was prepared by a conventional method. The rinse of this formulation was good in both stability and use feeling, and the solubility of the UV absorber was also good.

  The external preparation for skin of the present invention absorbs the UV-A region by utilizing a benzotriazole compound having a specific structure as a coloring stabilizer of 2-ethylhexyl p-methoxycinnamate and an agent for imparting an ultraviolet persistence effect. It is an invention that solves the compatibility of 2-ethylhexyl p-methoxycinnamate, the most standard cosmetic UV absorber, with cosmetic bases, and its remarkable effect and utilization as a UV absorption-containing skin external preparation is Extremely expensive.

2 is an ultraviolet absorption spectrum of the compound obtained in Synthesis Example 1. It is an ultraviolet absorption spectrum of p-methoxycinnamic acid-2-ethylhexyl ester. It is an ultraviolet absorption spectrum of 4-tert-butoxy-4-methoxydibenzoylmethane. It is an ultraviolet absorption spectrum before and behind a time-dependent light stability test of 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789). It is an ultraviolet absorption spectrum before and after a time-dependent light stability test of the compound obtained in Synthesis Example 1.

Claims (3)

A skin external preparation containing 2-ethylhexyl p-methoxycinnamate, which contains a benzotriazole derivative represented by the following general formula (I).
Formula (I)

(In the formula, R ′ = C1-C6 linear alkyl group, R ″ = C1-C3 linear alkyl group.)   The external preparation for skin according to claim 1, wherein the blending mass ratio of the benzotriazole derivative and 2-ethylhexyl p-methoxycinnamate is 8: 2 to 2: 8. The benzotriazole derivative is selected from 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole and 2- (2-hydroxy-4-isobutoxyphenyl) -2H-benzotriazole. The skin external preparation according to claim 1 or 2, wherein the skin external preparation is one type or two or more types.

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