JP2011068566A - Sunscreen cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sunscreen cosmetic that is excellent in feeling at use and offers high SPF. <P>SOLUTION: The sunscreen cosmetic includes: (1) a benzotriazole derivative represented by formula (I) (wherein R' is 1-6C linear alkyl group; and R'' is 1-3C linear alkyl group); and (2) a spherical resin powder containing at least 35 mass% hydrophobized ultrafine particles of titanium oxide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sunscreen cosmetic. More specifically, the present invention relates to a sunscreen cosmetic having an excellent feeling of use and an ultraviolet absorption effect.

  The important ultraviolet absorption wavelength regions by sunscreen cosmetics are the UV-A region (320 to 400 nm) and the UV-B region (290 to 320 nm). UV rays in the UV-A region (320 to 400 nm) invade the skin black, but it is considered that sunburn occurs like the ultraviolet rays in the UV-B region (290 to 320 nm) and does not 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.

  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-butyl-4-methoxydibenzoylmethane (4) is used in the UV-A region. Often done. Particularly in recent years, there has been an increasing demand for ultraviolet absorption in the UV-A region.

  On the other hand, some ultraviolet absorbers have stickiness, and may be a major problem in blending into sunscreen cosmetics where the feeling of use is important. That is, when the blending amount of the ultraviolet absorber is increased in order to exhibit a high ultraviolet absorption effect, the feeling of use becomes extremely worse. Therefore, the desired ultraviolet absorber may not be blended in the desired blending amount.

In general, from the viewpoint of securing a wide absorption region, a plurality of ultraviolet absorbers are blended into a sunscreen cosmetic.
However, in sunscreen cosmetics containing an ultraviolet absorber, the feeling of use may be reduced. Since an excellent feeling of use becomes an important factor strongly demanded for cosmetics, blending a plurality of different ultraviolet absorbers is not usually performed even in order to secure a wide absorption region.

  On the other hand, a dibenzoylmethane derivative blended as a UV absorber in cosmetics has a reduced UV absorbing ability under UV irradiation due to light exposure. In order to ensure the light stability which suppresses this phenomenon, the technique which uses together a benzoylmethane derivative and (alpha) -cyano-beta, (beta) -diphenylacrylate which is another ultraviolet absorber (patent document 1) is developed.

  Further, in cosmetics using a UV absorber 1,3,5-triazine derivative and a dibenzoylmethane derivative in combination, if 4-tert-butyl-4'-methoxydibenzoylmethane is present, The 3,5-triazine derivative is chemically greatly deteriorated. Therefore, in order to ensure the photostability of the 1,3,5-triazine derivative and the dibenzoylmethane derivative, a technique using α-cyano-β, β-diphenyl acrylate has been developed (Patent Document 2).

  However, there is a problem in the technology for ensuring the light stability of the ultraviolet absorber itself by using a plurality of ultraviolet absorbers in combination. This is because UV absorbers have low compatibility with oils that are cosmetic bases and are hardly soluble. Therefore, it is necessary to add a large amount of specific oils with excellent compatibility in order to stably mix them with cosmetics. . And when such a specific oil content is blended in a large amount, it becomes a factor that causes a decrease in the stability of the cosmetic (particularly the emulsification stability of the water-in-oil emulsified cosmetic) and a feeling of use.

In addition, sunscreen cosmetics often contain fine particles of zinc oxide and / or titanium oxide as an ultraviolet scattering agent together with an ultraviolet absorber in order to increase the ultraviolet protection effect.
However, when the fine particle powder is blended, there is a problem that the ultraviolet absorbent absorbs clothes or becomes white after application.

  As described above, there are technical difficulties in blending sunscreen cosmetics with a plurality of different ultraviolet absorbers and powders of ultraviolet scattering agents. There are circumstances where the combined use is not easily performed.

（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。） The benzotriazole derivative represented by the following general formula (I) is described in detail in Patent Document 3 as an ultraviolet absorber for cosmetics in the UV-A region.






Formula (I)

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

  On the other hand, cosmetics containing titanium oxide resin powder containing titanium oxide powder in a resin are widely known as makeup cosmetics. In addition, regarding cosmetics imparted with ultraviolet shielding properties, the use of metal oxide particles contained in resin powder makes it possible to use the technical difficulties and organicities associated with the use of metal oxide fine particles as a raw material for cosmetics. Resin encapsulating metal oxides with an average particle diameter of 0.003 to 0.1 μm having an ultraviolet shielding ability in order to solve the problems caused by the use of only an ultraviolet absorber It is known to be composed of powder and to blend the resin powder into cosmetics (Patent Document 4). Furthermore, regarding a spherical resin powder suitable as a visible light transmissive raw material for cosmetics, a method for producing the same, and a cosmetic using the same, an organic ultraviolet absorber can be obtained by using metal compound particles contained in the resin powder. It is known that the technical difficulty associated with the use of metal compound fine particles as a cosmetic raw material and the adverse effects associated with the presence of organic ultraviolet absorbers can be eliminated (Patent Document 5). ).

Japanese Patent No. 2975682 Japanese Patent No. 3714632 JP 2005-206473 A JP 09-208437 A Japanese Patent Laid-Open No. 08-53568

  In view of the above-mentioned viewpoints, the present inventors have conducted extensive research on sunscreen cosmetics having an excellent ultraviolet absorption effect and excellent usability. As a result, a specific ultraviolet absorber and a powder of an ultraviolet scattering agent are blended. Then, it discovered that the sunscreen cosmetics which exhibit the outstanding ultraviolet-ray protective effect and have high SPF can be provided. Furthermore, it has been found that, when ultrafine titanium oxide treated with hydrophobization, particularly ultrafine titanium oxide treated with fatty acid aluminum, and an ultraviolet absorber are blended, a “squeaking sensation” peculiar to titanium oxide powder occurs. Thus, the inventors have found that this can be solved brilliantly and have completed the present invention.

  An object of the present invention is to provide a sunscreen cosmetic having an excellent feeling of use and having a high SPF due to an excellent ultraviolet absorption effect.

（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。）
（２）内部に疎水化処理された超微粒子酸化チタンを３５質量％以上含有した樹脂球状粉末と
を配合することを特徴とする日焼け止め化粧料を提供するものである。 That is, the present invention
(1) 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.)
(2) Provided is a sunscreen cosmetic characterized in that it contains a spherical resin powder containing 35% by mass or more of ultrafine titanium oxide that has been hydrophobized.

  In the present invention, the benzotriazole derivative may be 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.

  Furthermore, the present invention provides the sunscreen cosmetic described above, wherein the hydrophobized ultrafine titanium oxide is treated with fatty acid aluminum.

  In addition, the present invention provides (3) the sunscreen cosmetic described above, which further comprises (3) 2-ethylhexyl p-methoxycinnamate.

  Furthermore, the present invention provides the sunscreen cosmetic described above, wherein the blending mass ratio of the benzotriazole derivative and 2-ethylhexyl p-methoxycinnamate is 8: 2 to 2: 8. is there.

  The present invention also provides the sunscreen cosmetic described above, wherein the sunscreen cosmetic is a water-in-oil emulsified cosmetic.

  The sunscreen cosmetic of the present invention has an excellent feeling of use and an excellent ultraviolet absorption effect. In particular, the sunscreen cosmetic of the present invention has an excellent feeling of use that is less powdery and squeaky, even when a powder of an ultraviolet scattering agent is blended in order to exhibit an excellent UV protection effect. Have

It is an absorbance curve of an example and a comparative example. It is an absorbance curve of an example and a comparative example.

  Hereinafter, the present invention will be described in detail.

（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。）
（Ａ法）
第１工程

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。） “(1) A benzotriazole derivative represented by the following general formula (I)”
A benzotriazole derivative represented by the following 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.

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

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 generated inorganic substances, and further purified to give 2- [4 -(2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole is obtained in high yield.

  In the present invention, the benzotriazole derivative is 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole and / or 2- (2-hydroxy-4-isobutoxyphenyl). ) -2H-benzotriazole. Particularly preferred is 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole, which has excellent dissolution stability for cosmetic bases.

  Although the sum total of the compounding quantity of the benzotriazole derivative of said (1) is not specifically limited, It is 0.1-20 mass% normally with respect to the total amount of sunscreen cosmetics, and it may be 0.5-10 mass%. Preferably, it is 1.0-3.0 mass%.

"Resin spherical powder"
The spherical resin powder used in the present invention is a spherical resin powder containing 35% by mass or more of ultrafine titanium oxide hydrophobized inside.
In the present invention, ultrafine titanium oxide is ultrafine titanium oxide powder having an average particle size of 10 nm to 100 nm. The average particle diameter is a value measured by a conventional method using a laser particle size distribution meter.
The resin of the spherical resin powder is a resin powder containing 35% by mass or more of ultrafine titanium oxide hydrophobized inside the spherical resin. A resin powder in which ultrafine titanium oxide is encapsulated in a spherical resin powder is known, but if the content is 34% by mass or less, the content is too small. For example, a resin powder containing ultrafine titanium oxide is used as a cosmetic. Even when blended to give UV protection ability to cosmetics, a large amount of resin powder must be blended in order to achieve sufficient performance, and the blending design of the cosmetics becomes extremely difficult.
In addition, with ultrafine titanium oxide that has not been hydrophobized, the viscosity of the dispersion becomes very high at the stage of producing the dispersion before polymerization, and the dispersion energy is effectively given to the fine particles of the metal compound. However, it becomes difficult to make the metal compound fine particles highly dispersed. For this reason, aggregates of the metal compound remain or become non-uniform, making it impossible to produce a uniform resin powder.
A powder encapsulating ultrafine titanium oxide at a high content of 35% by mass or more has never been used as a cosmetic raw material.
<Production method of spherical resin powder>
In order to produce a resin spherical powder, a suspension polymerization method, an emulsion polymerization method, a method of mechanically dispersing or emulsifying a resin solution, a method of depositing fine particles from the resin solution, and the like are known. The method for dispersing the hydrophobized fine particle titanium oxide having a content of more than 40% by weight inside the base material particles is, for example, when the base material particles are nylon resin, heating and dissolving the cyclic lactam in paraffin or the like, A desired amount of titanium dioxide fine powder is added to this, and while stirring, a polymerization accelerator such as phosphorus trichloride is added to cause alkali polymerization, and the resulting particles are filtered off, and an organic solvent such as benzene or isopropyl is added. A method of washing with alcohol and drying is exemplified.
When the base material particle is a silicone resin, a fine powder of titanium dioxide or zinc oxide is added to and mixed with an aqueous solution of ammonia or amine, and further hydrolyzable silane such as chlorosilane, hydrogensilane, alkoxysilane, acetoxy Examples of the method include adding silane to cause hydrolysis and condensation reaction, filtering the obtained particles, washing with water, and drying.
When the base material particles are silicon oxide, first, a suspension is prepared by adding fine powder of titanium dioxide or zinc oxide to sodium silicate, and further, a surfactant and an oily dispersant such as benzene are added. After adding the above-mentioned suspension to this mixture and emulsifying it to obtain a water-in-oil dispersion emulsion, it is added with a salt such as ammonium sulfate or ammonium chloride to add sodium silicate and Examples include a method of reacting and filtering the obtained particles, washing with water, washing with an organic solvent such as methanol, and drying.
Further, as a suitable production method, a water-insoluble thermoplastic resin is made into a liquid at a high temperature of about 200 ° C., and the fine particle titanium oxide hydrophobized is dispersed therein. For example, there may be mentioned a method in which water-soluble materials are removed by washing with water to obtain true spherical fine particles composed of a water-insoluble thermoplastic resin and hydrophobized fine particle titanium oxide.

The average particle diameter of the resin spherical powder is 1 to 10 μm, preferably 1 to 5 μm. The average particle diameter is a value measured by a conventional method using a laser particle size distribution meter.
The treatment agent for the hydrophobic treatment is not limited, but aluminum stearate, methylhydrogenpolysiloxane, alkyltriethoxysilane and the like are preferable, and the hydrophobic treatment is performed by a conventional method.

  As for the compounding quantity of resin spherical powder, 1-40 mass% is normally mix | blended with respect to the sunscreen cosmetics whole quantity. 3-30 mass% is preferable and 5-20 mass% is further more preferable.

“(3) p-methoxycinnamic acid-2-ethylhexyl”
The sunscreen cosmetics of the present invention include p-methoxycinnamic acid-2-acid in addition to the above-mentioned specific benzotriazole derivative of an ultraviolet absorber and the ultrafine particle titanium oxide which is the above-mentioned specific resin spherical powder of an ultraviolet scattering agent. It is preferable to combine ethylhexyl in combination. p-Methoxycinnamic acid-2-ethylhexyl is a known ultraviolet absorber, and a commercially available product can be used. For example, “PARSOL MCX” (DSM Nutritional Products) is commercially available.

(1) The blending amount of p-methoxycinnamic acid-2-ethylhexyl is preferably 1 to 20% by mass, and more preferably 3 to 10% by mass with respect to the total amount of the sunscreen cosmetic.

  Moreover, it is preferable that the mixing | blending mass ratio of the said specific (1) benzotriazole derivative and (3) 2-ethylhexyl p-methoxycinnamate is 8: 2 to 2: 8.

  In addition to the above essential components, the sunscreen cosmetics of the present invention include components usually used in cosmetics, such as whitening agents, moisturizers, antioxidants, oily components, surfactants, thickeners, alcohols, A coloring agent, an aqueous component, water, various skin nutrients and the like can be appropriately blended as necessary, and can be produced by a conventional method. 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, teaseed oil, rice bran oil, jojoba oil, cacao butter, palm 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 such as vitamin E nicotinate, 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, loofima) Various drugs such as saponin, muclodisaponin, etc.), pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, cephalanthin, placenta extract.
Bark, Clara, Kouhone, Orange, Sage, Thyme, Yarrow, Zeniahoi, Senkyu, Assembly, Spruce, Spruce, Birch, Horsetail, Loofah, Marronie, Yukishinoshita, Arnica, Lily, Mugwort, Peonies, Aloe, Gardenia, Sawara 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.

Preferred bases blended in the sunscreen cosmetics of the present invention are decamethylcyclopentasiloxane, isononyl isononanoate, dimethylpolysiloxane, heptamethyloctyltrisiloxane, trimethylsiloxysilicic acid, liquid paraffin, squalane, cetyl isooctanoate, Oils such as isooctanoic acid triglyceride and succinic acid di-2-ethylhexyl. It is preferable to blend one or more of these oils together with the benzotriazole derivative represented by the above general formula (I).
Especially this invention is preferably utilized for the sunscreen cosmetics which have decamethylcyclopentasiloxane as a main component base.

  The sunscreen cosmetic of the present invention is preferably a water-in-oil emulsified cosmetic (W / O emulsion), and can be preferably used as a sunscreen cream, sunscreen emulsion, sunscreen lotion and the like.

The present invention will be specifically described with reference to examples. The present invention is not limited to these examples.
The blending amount is mass% unless otherwise specified.

  The sunscreen cosmetics of Examples and Comparative Examples (water-in-oil emulsion composition: sunscreen) were produced by conventional methods, and the feeling of use and the ultraviolet absorption effect were evaluated. In addition, (1) 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole of Synthesis Example 1 was used as the benzotriazole derivative represented by the general formula (I).

"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, Add 4.0 g of dimethylformamide and stir. 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 is recovered at normal pressure, and the remaining oil is washed with water to remove excess sodium carbonate and generated inorganic substances. This oil was distilled under reduced pressure to purify a yellow transparent fraction of 220 to 225 ° C./0.2 to 0.3 mmHg to give 2- [4- (2-ethylhexyloxy) -2-hydroxyphenyl] -2H— Benzotriazole is obtained.

"Synthesis Example 2: Synthesis of 2- (2-hydroxy-4-isobutoxyphenyl) -2H-benzotriazole"
Synthesis is carried out in the same manner as in Synthesis Example 1 using the same molar amount of isobutyl bromide instead of 2-ethylhexyl bromide to obtain 2- (2-hydroxy-4-isobutoxyphenyl) -2H-benzotriazole.

<Production of resin spherical powder>
[Production Example 1]
After 25 parts by weight of polyamide 12 and 25 parts by weight of aluminum stearate-treated fine particle titanium oxide (average particle size 15 nm, TTO S4 Ishihara Sangyo Co., Ltd.) were dispersed using an ultrasonic disperser, 100 parts by weight of oligosaccharide and 200 ° C. The mixture was heated and mixed, and extruded into a strand while melt-kneading with an extruder. This was transported and supplied into a container containing 450 parts by weight of water to dissolve the oligosaccharide in water to obtain an aqueous dispersion of titanium oxide-containing polyamide particles.
Next, the obtained aqueous dispersion was continuously filtered through 5C filter paper. The recovered filtrate was again dispersed in water to 5% by weight and further filtered. This operation was repeated 3 times for washing and drying to obtain titanium oxide-containing polyamide particles (average particle size 5 μm).

[Production Example 2]
Resin monomer phase Aluminum stearate-treated fine particle titanium oxide (average particle size 15 nm MT-100T manufactured by Teica) 45 parts by weight Vinyl acetate (resin monomer) 10 parts by weight Methyl methacrylate (resin monomer) 34.8 parts by weight Ethylene glycol dimethacrylate ( Resin monomer) 10 parts by weight
2,2 Azobis 2,4 dimethylvaleronitrile (polymerization initiator) 0.2 parts by weight Aqueous phase Water 500 parts by weight Polyvinyl alcohol (saponification degree 87%) 10 parts by weight

The resin monomer phase was dispersed using an ultrasonic disperser, and then added to the aqueous phase and stirred with a homomixer to adjust the monomer particles to 4 μm. Next, this dispersion was transferred to a reactor equipped with a stirrer and a thermometer, and the temperature was raised to 55 ° C. to initiate polymerization. Furthermore, after making it superpose | polymerize at this temperature for 5 hours, it cooled to room temperature and isolate | separated the resin powder obtained by suction filtration. After washing with an appropriate amount of warm water and methanol, it was dried at room temperature to obtain a spherical resin powder containing 45% aluminum stearate-treated titanium oxide.

＊１：ABIL EM90 (ゴールドシュミット社製）
＊２：酸化チタンTTO-V4（石原産業株式会社製）
＊３：超微粒子（平均粒子径１５ｎｍの脂肪酸アルミニウムで疎水化処理された酸化チタンを５０質量％内包したナイロン粉末（平均粒子径５μｍ）

* 1: ABIL EM90 (Gold Schmidt)
* 2: Titanium oxide TTO-V4 (Ishihara Sangyo Co., Ltd.)
* 3: Ultrafine particles (nylon powder containing 50% by mass of titanium oxide hydrophobized with fatty acid aluminum having an average particle size of 15 nm (average particle size 5 μm)

＊１：製造例２で得られた内部にステアリン酸アルミニウムで疎水化処理された超微粒子酸化チタンを４５質量％含有したポリアクリル酸球状粉末
（平均粒子径４μｍ、内包されている超微粒子酸化チタンの平均粒子径１５ｎｍ）
＊２：酸化チタンTTO-V4（石原産業株式会社製）

* 1: Polyacrylic acid spherical powder containing 45% by mass of ultrafine particle titanium oxide hydrophobized with aluminum stearate obtained in Production Example 2 (average particle size 4 μm, encapsulated ultrafine particle titanium oxide Average particle diameter of 15 nm)
* 2: Titanium oxide TTO-V4 (Ishihara Sangyo Co., Ltd.)

<Usage feeling (squeak and stickiness)>
An actual use test was conducted with a special panel to evaluate the feeling of use (squeak and stickiness). The evaluation criteria are shown below. All the examples of the present invention have an excellent feeling in use.
"Squeaking"
A: 15 or more responded that there was no squeaky feeling.
○: 10 or more and less than 15 responded that there was no squeaky feeling.
Δ: 5 or more and less than 10 responded that there was no squeaky feeling.
X: Less than 5 people answered that there was no squeaky feeling.
"Sticky"
◎: More than 15 people answered that they were not sticky.
○: 10 or more and less than 15 responded that they were not sticky.
Δ: 5 or more and less than 10 people answered that they were not sticky.
×: Less than 5 responded that they were not sticky.

<Ultraviolet absorption effect>
50 μL of the samples of Examples and Comparative Examples were uniformly applied to a nylon film (5 × 5 cm) at a rate of ² mg / cm ² , and allowed to stand for 15 minutes, and then the absorbance was measured with a spectrophotometer (U-4100: Hitachi, Ltd.). It was measured.
The results are shown in FIGS. It can be seen that the UV absorption ability of the examples is far superior to the comparative examples.
In addition, since the SPF (Sun Protection Factor) of Comparative Example 1 has a function of 34 and PA (Protection Grade of UVA) has a function of +++, the UV absorption ability of each Example is SPF 30 or higher and PA ++ or higher, and a high SPF. It can be said that it is a UV protective cosmetic having the function of PA.

  Next, the sunscreen cosmetics of the present invention are listed. All of these are sunscreen cosmetics that have excellent usability and ultraviolet absorption, and are excellent in emulsion stability.

Example 9: Sunscreen emulsion (W / O)
mass%
(1) Decamethylcyclopentasiloxane 20
(2) Polyoxyethylene / methylpolysiloxane copolymer 1
(3) Olefin oligomer 10
(4) Dimethylpolysiloxane 5
(5) p-methoxycinnamic acid-2-ethylhexyl 7.5
(6) Dimethicodiethylbenzalmalonate 5
(7) Diethylaminohydroxybenzoyl hexyl benzoate 3
(8) Fragrance 0.5
(9) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 2
(10) Benzotriazole derivative (Synthesis example 1) 2
(11) Resin spherical powder * 1 10
(12) 1.3 Butylene glycol 5
(13) Ion exchange water Residual (14) Glycerin 3
(15) Edetate Appropriate amount * 1: Polyacrylic acid spherical powder containing 45% by mass of ultrafine titanium oxide hydrophobized with aluminum stearate inside obtained in Production Example 2 (average particle size 4 μm, inclusion The average particle diameter of the ultrafine titanium oxide that is used is 15 nm)
Production method:
(1) to (9) are mixed and dissolved at room temperature, and the oil phase is adjusted in advance. Next, (10) is added and dispersed and mixed with a disper. (11) to (15) are mixed and dissolved, and then gradually added to the oil phase while stirring with a disper, and mixed and dissolved sufficiently uniformly to obtain the desired sunscreen emulsion.

Example 10: Sunscreen emulsion (W / O)
mass%
(1) Decamethylcyclopentasiloxane 15
(2) Polyoxyethylene / methylpolysiloxane copolymer 1
(3) Olefin oligomer 10
(4) Dimethylpolysiloxane 10
(5) p-methoxycinnamic acid-2-ethylhexyl 7.5
(6) Diethylaminohydroxybenzoyl hexyl benzoate 5
(7) Methylenebisbenzotriazole tetramethylbutylphenol aqueous dispersion * 1
2
(8) Fragrance 0.5
(9) Dimethicodiethylbenzalmalonate 5
(10) Benzotriazole derivative (Synthesis example 2) 2
(11) Resin spherical powder * 2 5
(12) Hydrophobized fine particle zinc oxide 10
(13) Paraben 5
(14) Ion exchange water Residual (15) Glycerin 3
(16) Edetate salt * 1 Z-COTE HP1 (BASF) commercially available from Ciba under the name “Chinosorb M”
Production method:
(1) to (10) are mixed and dissolved at room temperature, and the oil phase is adjusted in advance. Next, (11) to (12) are added and dispersed and mixed with a disper. (11) to (16) are mixed and dissolved and then gradually added to the oil phase while stirring with a disper, and mixed and dissolved sufficiently uniformly to obtain the desired sunscreen emulsion.

Example 11: Sunscreen cream (O / W)
mass%
(1) Carboxyvinyl polymer 0.3
(2) Purified water Residual (3) Xanthan gum 0.1
(4) edetate trisodium 0.1
(5) Dipotassium glycyrrhizinate 0.05
(6) 1,3-butylene glycol 5
(7) Polyoxyethylene glyceryl isostearate 1.5
(8) Polystearic acid polyoxyethylene glycerol 1
(9) L-ascorbic acid 2-glucoside 2
(10) Appropriate amount of phenoxyethanol (11) Decamethylcyclopentasiloxane 3
(12) Methylphenylpolysiloxane 3
(13) Behenyl alcohol 1
(14) p-methoxycinnamic acid-2-ethylhexyl 7
(15) Diethylaminohydroxybenzoyl hexyl benzoate 2
(16) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 2
(17) Benzotriazole derivative (Synthesis example 1) 3
(18) Perfume appropriate amount (19) Resin spherical powder * 15
* 1: Polyacrylic acid spherical powder containing 45% by mass of ultrafine particle titanium oxide hydrophobized with aluminum stearate obtained in Production Example 2 (average particle size 4 μm, encapsulated ultrafine particle titanium oxide Average particle diameter of 15 nm)
Production method:
(1) to (10) are heated and mixed and dissolved at 70 ° C. to adjust the aqueous phase. Next, (11) to (18) are heated and mixed and dissolved to adjust the oil phase, and (19) is dispersed with disper and gradually added to the aqueous phase while stirring with a disper, and mixed and dissolved sufficiently uniformly. To get the desired sunscreen cream.

Example 12: Sunscreen cream (W / O)
mass%
(1) Decamethylcyclopentasiloxane 20
(2) Polyoxyethylene / methylpolysiloxane copolymer 3
(3) Cetyl isooctanoate 10
(4) Dimethylpolysiloxane 5
(5) p-methoxycinnamic acid-2-ethylhexyl 5
(6) Diethylaminohydroxybenzoyl hexyl benzoate 1
(7) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine 3
(8) Benzotriazole derivative (Synthesis example 1) 3
(9) Octocrylene 3
(10) Distearyl diammonium chloride 0.001
(11) Phenoxyethanol 0.5
(12) Fragrance 0.5
(13) Organically modified clay mineral 2.5
(14) Resin spherical powder * 2 5
(15) Phenylbenzimidazolesulfonic acid 3
(16) Triethanolamine 1.8
(17) Ion exchange water Residual (18) 1.3 Butylene glycol 2
(19) Edetic acid salt appropriate amount * 2 Z-COTE HP1 (BASF)
Production method:
(1) to (12) are heated and mixed and dissolved at 70 ° C., and the oil phase is adjusted in advance. Next, (13) to (14) are added and dispersed and mixed with a disper. (15) to (19) are mixed and dissolved, and then gradually added to the oil phase while stirring with a disper, and mixed and dissolved sufficiently uniformly to obtain the intended sunscreen cream.

  ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding ultraviolet protection effect and can provide the sunscreen cosmetics which have the very outstanding feeling of use. The present invention is particularly useful as a water-in-oil type emulsion sunscreen cosmetic.

Claims (6)

(1) 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.)
(2) A sunscreen cosmetic comprising a resin spherical powder containing 35% by mass or more of ultrafine titanium oxide hydrophobized inside.   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, wherein the external preparation is one type or two or more types.   The sunscreen cosmetic according to claim 1 or 2, wherein the hydrophobized ultrafine titanium oxide is treated with fatty acid aluminum.   The sunscreen cosmetic according to any one of claims 1 to 3, further comprising (3) 2-ethylhexyl p-methoxycinnamate.   The sunscreen cosmetic according to any one of claims 1 to 4, wherein a blending mass ratio of the benzotriazole derivative and 2-ethylhexyl p-methoxycinnamate is 8: 2 to 2: 8.   The sunscreen cosmetic according to any one of claims 1 to 5, wherein the sunscreen cosmetic is a water-in-oil emulsified cosmetic.

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