JP2005289916A - Ultraviolet absorber and skin external preparation containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet absorber which absorbs ultraviolet light in both the UV-A region and the UV-B region and is excellent in compatibility with an oil component used as a base of a skin external preparation; and a skin external preparation containing the absorber. <P>SOLUTION: The ultraviolet absorber is composed of a compound represented by the general formula (wherein one of R, R', and R" is hydrogen and the other two are each a methyl group, or two of them are hydrogen and the remainder is a 1-3C straight chain alkyl). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a novel ultraviolet absorber, an external preparation for skin containing the same, and a novel benzotriazole compound.
The ultraviolet absorber of the present invention has ultraviolet absorption in the UV-A and UV-B regions, and is excellent in compatibility with the oil component that is a base for external preparation for skin.

  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 a low melting point, excellent compatibility with oils of various skin external preparation bases, having ultraviolet absorption in the UV-A region, and light of the ultraviolet absorber itself. To provide an ultraviolet absorber excellent in stability and capable of sustaining an ultraviolet absorption effect over a long period of time, and a skin external preparation containing the same.

By the way, from such a viewpoint, even if a new ultraviolet absorber is developed, the synthesis method is very difficult, and the structure is complicated and requires a lot of labor and cost in actual production. There is no industrial significance.
In other words, it can be easily produced by existing facilities without investing in new facilities, with the same effort and cost as the production of conventional UV absorbers, and can be stably supplied to users such as cosmetic companies. is important.
This invention solves the said subject by the following solution means, and provides a novel ultraviolet absorber.

（式中、Ｒ、Ｒ’、Ｒ”は、いずれか一つが水素であって二つがメチル基であるか、いずれか二つが水素であって一つがＣ１〜Ｃ３の直鎖アルキル基である。） An ultraviolet absorbent comprising the following general formula (I) is provided.
Formula (I)

(In the formula, any one of R, R ′, and R ″ is hydrogen and two are methyl groups, or any two are hydrogen and one is a C1-C3 linear alkyl group. )

The present invention also provides 2- (2-hydroxy-3,5-di-secondarybutylphenyl) -2H-benzotriazole of any one of the following formulas (Ia), (Ib), and (Ic). is there.

  Furthermore, this invention provides the skin external preparation containing said ultraviolet absorber.

Moreover, this invention provides the skin external preparation containing the ultraviolet absorber of following formula (Id).

The ultraviolet absorber of the present invention is a stable compound having a large molar extinction coefficient in the UV-A region near λmax 350 nm and the UV-B region near λmax 310 nm, and excellent in heat resistance and transpiration. As a cosmetic ultraviolet absorber, there is practically no ultraviolet absorber that absorbs ultraviolet rays in the entire UV-A region and UV-B region. Therefore, it is not necessary to combine and combine two or more ultraviolet absorbers in the UV-B region and two or more ultraviolet absorbers in the UV-B region as in the prior art.
Furthermore, the ultraviolet absorber of the present invention is excellent in compatibility with various oils of the skin external preparation base. In particular, it is remarkably excellent in compatibility and stability with di-2-ethoxyethyl succinate which is important as an oil component.
Moreover, it mix | blends with various resin compositions as a ultraviolet absorber (stabilizer).

  Hereinafter, the present invention will be described in detail.

式中のＲ、Ｒ’、Ｒ”は、いずれか一つが水素であって残りの二つがメチル基である。或いは、いずれか二つが水素であって、残りの一つがＣ１〜Ｃ３の直鎖アルキル基、すなわちメチル基、エチル基、プロピル基のいずれかである。 The benzotriazole-based ultraviolet absorber of the present invention has a low melting point and can be easily added to paints, resin compositions and the like, and surprisingly, not only the UV-A region near λmax 350 nm, but also the UV around λmax 310 nm. It has been found that the compound has a large molar extinction coefficient in the -B region, is excellent in heat resistance and transpiration, is a chemically stable compound, and is an ultraviolet absorber having high compatibility with various cosmetic base materials. The result is a completed invention.
Formula (I)

In the formula, any one of R, R ′ and R ″ is hydrogen and the remaining two are methyl groups. Alternatively, any two are hydrogen and the remaining one is a straight chain of C1 to C3. It is an alkyl group, that is, a methyl group, an ethyl group or a propyl group.

In the above general formula, a compound in which R, R ′, and R ″ are any combination of the following (a), (b), and (c) is a novel 2- (2-hydroxy- 3,5-di-secondary butylphenyl) -2H-benzotriazole benzotriazole compound.
(Ia) R is CH ₃ , R ′ and R ″ are H
(Ib) R and R ′ are CH ₃ , R ″ is H
(Ic) R and R ″ are CH ₃ , R ′ is H

Specifically, it is 2- (2-hydroxy-3,5-di-secondarybutylphenyl) -2H-benzotriazole of any one of the following formulas (Ia), (Ib) and (Ic).

Although not a novel compound, the compound of the following formula (Id) when R, R ′, and R ″ are all hydrogen in the general formula (I) is excellent in heat resistance and transpiration and chemically stable. The present inventor has found that the compound is highly compatible with oils of various cosmetic bases, that is, the compound is useful as an ultraviolet absorber for a skin external preparation.

  A general process for synthesizing such benzotriazoles is a method in which o-nitroaniline is converted to a diazonium salt with sodium nitrite and the like, coupled with phenol to synthesize a monoazo compound, and then reduced to benzotriazole. There are also described in JP-A-52-113973, JP-A-52-113974, JP-A-2-134370, JP-A-4-59768, JP-A-7-18246, JP-A-2003-26668, and the like.

（Ｉａ）ＲはＣＨ₃、Ｒ’及びＲ”はＨ
（Ｉｂ）Ｒ及びＲ’はＣＨ₃、Ｒ”はＨ
（Ｉｃ）Ｒ及びＲ”はＣＨ₃、Ｒ’はＨ The novel benzotriazole compounds (Ia), (Ib) and (Ic) of the present invention are produced by a production process according to the following general formula.
First, each o-nitroaniline derivative is made into a diazonium compound (A), and then the coupler is dispersed in an alkaline aqueous solution and coupled with 2,4-di-secondary butylphenol, whereby the nitroazo compound (B) is first obtained. can get. The target compound (C) can be obtained by reducing the compound (B) by a conventional method.

(Ia) R is CH ₃ , R ′ and R ″ are H
(Ib) R and R ′ are CH ₃ , R ″ is H
(Ic) R and R ″ are CH ₃ , R ′ is H

  The above-mentioned novel compound has a low melting point and high transparency when heated and melted, has excellent heat stability, has little transpiration, and maintains an ultraviolet absorption effect over a long period of time. It is also chemically stable.

  The ultraviolet absorbers of the present invention having different R, R ', and R "can be similarly produced using o-nitroaniline derivatives having the corresponding R, R', and R".

The skin external preparation of this invention is manufactured by mix | blending the ultraviolet absorber of the said General formula (1) with skin external preparations, such as cosmetics. The blending amount is appropriately determined according to the target product, but is usually 0.01 to 10% by mass with respect to the total amount of the external preparation for skin, and is dissolved and blended in the oil for external preparation for skin.
Moreover, it is preferable to mix | blend with other ultraviolet absorbers, such as p-methoxycinnamate 2-ethylhexyl, in the skin external preparation of this invention. For example, when a benzotriazole derivative of the general formula (I) and 2-ethylhexyl p-methoxycinnamate are used in combination, 8: 2 to 2: 8 is preferable. 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.

  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, 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 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.

Example 1 Synthesis of 2- (3,5-di-secondary butyl-2-hydroxyphenyl) -5-methyl-2H-benzotriazole (Ia)
A. Preparation of diazonium salt A 500 ml four-necked flask equipped with a thermometer was charged with 4methyl-2-nitroaniline (30.4 g, 0.20 mol) and water (150 ml), and stirred with 35% hydrochloric acid (62.5 g, 0.60 mol). After cooling to 5 ° C. or lower, 38.7 g (0.20 mol) of 36% sodium nitrite aqueous solution was quickly added and stirred for 1 hour. This was filtered to obtain a clear dark purple diazonium salt aqueous solution. This aqueous solution was stored cold.
B. Coupling Add 42.1 g (0.20 mol) of 2,4-disecondary-butylphenol and 400 ml of water to a 1000 ml four-necked flask equipped with a thermometer and a reflux condenser, and stir at room temperature with 28 g of granular caustic soda. 0.7 mol) was added and stirring was continued to dissolve completely. Then, it cooled to 5 degreeC and the diazonium salt of A was dripped in the range of 5-10 degreeC over 4 hours. Stirring was continued for about 5 hours after the completion of the dropwise addition, and a red azo compound was produced. After neutralizing with hydrochloric acid, the aqueous layer was separated to obtain dark red monoazo crystals (B).
C. Reduction The total amount of the compound (B) was dissolved in xylene and 1-butanol in a four-necked flask, and further dehydrated by adding 67 g of 32% NaOH and 1.0 g of 2,3-dichloro-1,4-naphthoquinone. For 7 hours to obtain benzotriazole. Water was added to the reaction solution and neutralized with sulfuric acid. After separating the aqueous layer, the solvent was recovered, and the remaining oil layer was distilled under reduced pressure (215 to 220 ° C./0.5 mmHg). The minute was dissolved by heating by adding 500 ml of methanol. The solution was cooled to 20 ° C. and the precipitated yellow powdery crystals were filtered off and dried to obtain the desired compound.
The yield was 33.8 g and the yield was 55.8% (calculated from 4-methyl-2-nitroaniline).
m. p. 36.3 to 37.7 ° C., HPLC purity 99.0%
This yellow powdery crystal was subjected to highly sensitive elemental analysis to quantify C, H, and N.
<Measurement device>
Oxygen circulation combustion and TCD detection method NCH quantifier Sumigraph NCH-21 type (manufactured by Sumika Chemical Analysis Center)
<Measurement results>
Calculated as C ₂₁ H ₂₇ N ₃ O C (%) 74.74; H (%) 8.06; N (%) 12.45
Found C (%) 75.9; H (%) 8.33; N (%) 12.7

Example 2 Synthesis of 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5,6-dimethyl-2H-benzotriazole (Ib)
A. Preparation of Diazonium Salt A 500 ml four-necked flask equipped with a thermometer was charged with 24.4 g (0.15 mol) of 2,3-dimethyl-6-nitroaniline and 115 ml of water, and stirred with 35% hydrochloric acid 46.9 g 0.45. The mixture was cooled to 5 ° C. or lower, and 28.7 g of 0.15 mol of 36% sodium nitrite aqueous solution was quickly added and stirred for 1 hour. This was filtered to obtain a clear dark purple aqueous solution of diazonium salt. This aqueous solution was stored cold.
B. Coupling Add 31.6 g (0.15 mol) of 2,4-disecondary butylphenol and 300 ml of water to a 1000 ml four-necked flask equipped with a thermometer and reflux condenser, and 21.0 g of granular caustic soda with stirring at room temperature. (0.525 mol) was added and stirring was continued to complete dissolution. Then, it cooled to 5 degreeC and the diazonium salt of A was dripped in the range of 5-10 degreeC over 4 hours. Stirring was continued for about 5 hours after the completion of the dropwise addition, and a red azo compound was produced. After neutralization with hydrochloric acid, the aqueous layer was separated to obtain dark red monoazo crystals. (B)
C. Reduction The total amount of the compound (B) is dissolved in xylene and 1-butanol in a four-necked flask, and further dehydrated by adding 50 g of 32% NaOH and 0.8 g of 2,3-dichloro-1,4-naphthoquinone. For 7 hours to obtain benzotriazole. Water was added to the reaction solution and neutralized with sulfuric acid. The aqueous layer was separated, the solvent was recovered, 350 ml of methanol was added to the remaining oil layer and dissolved by heating, and then cooled to 20 ° C. The precipitated grayish yellow crystals were filtered off, heated and dissolved in 350 ml of methanol, 1 g of carbon was added, and the mixture was treated at 60 ° C. for 1 hour. The carbon was then removed by filtration through a microfilter, and the solution was cooled to 20 ° C. The precipitated yellow powdery crystals were filtered off and dried to obtain the target compound.
The yield was 28.0 g, and the yield was 53.1% (calculated from 2,3-dimethyl-6-nitroaniline).
m. p. 86.6-87.3 ° C., HPLC purity 99.9%
This yellow powdery crystal was subjected to highly sensitive elemental analysis to quantify C, H, and N.
<Measurement device>
Oxygen circulation combustion and TCD detection method NCH quantifier Sumigraph NCH-21 type (manufactured by Sumika Chemical Analysis Center)
<Measurement results>
Calculated as C ₂₂ H ₂₉ N ₃ O C (%) 75.18; H (%) 8.32; N (%) 11.95
Found C (%) 76.2; H (%) 8.60; N (%) 12.1

Example 3 Synthesis of 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -4,5-dimethyl-2H-benzotriazole (Ic)
A. Preparation of Diazonium Salt A 500 ml four-necked flask equipped with a thermometer was charged with 33.2 g (0.20 mol) of 4,5-dimethyl-2-nitroaniline and 150 ml of water and stirred with 35% hydrochloric acid 62.5 g 0.6. The mixture was cooled to 5 ° C. or lower, and 38.3 g (0.20 mol) of 36% sodium nitrite aqueous solution was quickly added and stirred for 1 hour. This was filtered to obtain a clear dark purple diazonium salt aqueous solution. This aqueous solution was stored cold.
B. Coupling Add 42.1 g (0.20 mol) of 2,4-disecondary butylphenol and 400 ml of water to a 1000 ml four-necked flask equipped with a thermometer and a reflux condenser and stir at room temperature with 28 g of granular caustic soda (0 g). .7 mol) was added and stirring was continued to complete dissolution. Then, it cooled to 5 degreeC and the diazonium salt of A was dripped in the range of 5-10 degreeC over 4 hours. Stirring was continued for about 5 hours after the completion of the dropwise addition, and a red azo compound was produced. After neutralization with hydrochloric acid, the aqueous layer was separated to obtain dark red monoazo crystals. (B)
C. Reduction The total amount of the compound (B) was dissolved in xylene and 1-butanol in a four-necked flask, and further dehydrated by adding 67 g of 32% NaOH and 1.0 g of 2,3-dichloro-1,4-naphthoquinone. For 7 hours to obtain benzotriazole. Water was added to the reaction solution and neutralized with sulfuric acid. The aqueous layer was separated, the solvent was recovered, 500 ml of methanol was added to the remaining oil layer, dissolved by heating, and then cooled to 20 ° C. The deposited grayish yellow crystals were filtered off, dissolved in 500 ml of methanol by heating, added with 2 g of carbon, and treated at 60 ° C. for 1 hour. The carbon was then removed by filtration through a microfilter, and the solution was cooled to 20 ° C. The precipitated yellow powdery crystals were filtered off and dried to obtain the target compound.
The yield was 30.9 g, and the yield was 44.0% (from 4,5-dimethyl-2-nitroaniline).
m. p. 108.6-109.2 ° C., HPLC purity 99.4%
This yellow powdery crystal was subjected to highly sensitive elemental analysis to quantify C, H, and N.
<Measurement device>
Oxygen circulation combustion and TCD detection method NCH quantifier Sumigraph NCH-21 type (manufactured by Sumika Chemical Analysis Center)
<Measurement results>
Calculated as C ₂₂ H ₂₉ N ₃ O C (%) 75.18; H (%) 8.32; N (%) 11.95
Found C (%) 76.5; H (%) 8.40; N (%) 12.0

Example 4 Synthesis of 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -2H-benzotriazole (Id)
The same procedure as in Example 1 was conducted except that 27.6 g (0.20 mol) of o-nitroaniline was used instead of 30.4 g (0.20 mol) of 4-methyl-2-nitroaniline. A pale yellowish white crystal was obtained in a yield of 33.6 g and a yield of 51.9% (from o-nitroaniline).
m. p. 36.5-37.0 ° C., HPLC purity 99.6%

"solubility"
Ia, Ib, Ic, Id which are benzotriazole derivatives synthesized in Examples 1-5
Was dissolved in the oil of the following cosmetic base material, and its solubility was measured.
<Oil content of cosmetic base>
Liquid paraffin: Kaneda Corporation 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.

Amount dissolved in cosmetic base (Wt / Wt%)

  None of the compounds dissolved in the above dissolution amount was precipitated as crystals or separated into oily components. Further, the dissolved colors were all slightly yellow and transparent, and no odor was felt. Moreover, regarding Ia and Id, the dissolution amount is not the upper limit.

"Comparative example"
4-tert-Butoxy-4-methoxydibenzoylmethane (trade name parsol 1789), which has a maximum absorption region in the UV-A region, is currently used as a UV absorber in the UV-A absorption region and has good cosmetic applications. Although it can be said that the UV-A absorber does not exist, the disadvantage is that the solubility in the cosmetic base is low as described above. The results of measuring the solubility in the same manner as in Table 1 are shown in Table 2.

Amount dissolved in cosmetic base (Wt / Wt%)

  The solubility is particularly bad for liquid paraffin, and the solubility of about 5% is a certain degree for squalane and CIO. The benzotriazole derivative produced in the present invention has no superiority in Ib and Ic other than liquid paraffin and CIO, but all other compounds showed excellent solubility.

  Next, the UV absorption range of each compound and p-methoxycinnamic acid-2-ethylhexyl and 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789) was measured. The maximum absorption wavelength λmax and the maximum molar extinction coefficient ε are shown in Table 3 below.

  Compared with p-methoxycinnamic acid-2-ethylhexyl ester and 4-tert-butoxy-4-methoxydibenzoylmethane (trade name parsol 1789), the molar extinction coefficient is slightly lower in each absorption region, but UV-A , Having a sufficiently high absorption in the UV-B region, it is not necessary to use the former two kinds of existing ultraviolet absorbers together for ultraviolet absorption in both regions. That is, the ultraviolet absorbent according to the present invention can absorb almost all ultraviolet rays with a single ultraviolet absorbent. Moreover, the ultraviolet absorber of this invention is excellent in the stability as a compound.

Since the ultraviolet absorbent according to the present invention has high compatibility with oils of various cosmetic bases, it is possible to produce sun care cosmetics having much higher ability to ultraviolet radiation. Moreover, the ultraviolet absorber of this invention can be provided industrially easily with good yield using the existing equipment. In addition, by using this benzotriazole compound as a cosmetic ultraviolet absorber, the following problems, which are disadvantages of conventional cosmetic ultraviolet absorbers, can be solved.
1) There is no ultraviolet absorber for cosmetics that absorbs ultraviolet radiation in the entire UV-A and UV-B regions.
2) Although parsol 1789 is a de facto standard as a cosmetic ultraviolet absorber that absorbs the UV-A region, it has poor compatibility with a cosmetic base material, and there is a problem in the stability of the compound itself.
Examples of the external preparation for skin of the present invention are shown below.

Example 5 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- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5-methyl-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 is prepared by a conventional method. The sunscreen of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 6 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) edetate trisodium appropriate amount (11) 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5,6-dimethyl-2H-benzotriazole 1.0
(12) 2- [4- (2-Ethylhexyloxy) -2-hydroxyphenyl] -2H-benzotriazole 2.0
(13) 2,4,6-trianilino-p- (carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine 0.5
(14) 4-t-butyl-4′-methoxydibenzoylmethane 1.0
(15) 2-ethylhexyl p-methoxycinnamate 7.5
(16) Carboxymethylcellulose Na 0.5
(17) Ethyl cellulose 1.0
(18) Spherical acrylic resin powder 5.0
(19) Purified water Residue (20) Perfume appropriate amount (production method)
A cream is prepared by a conventional method. The cream of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 7 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- (3,5-di-secondarybutyl-2-hydroxyphenyl) -4,5-dimethyl-2H-benzotriazole 2.0
(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 is prepared by a conventional method. The cream of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 8 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- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5-methyl-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 is prepared by a conventional method. The cream of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 9 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- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5-methyl-2H-benzotriazole 1.0
(7) 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5,6-dimethyl-2H-benzotriazole 1.0
(8) 2-ethylhexyl p-methoxycinnamate 7.5
(9) Dipropylene glycol 5.0
(10) Fine zinc oxide (hydrophobized 60 nm) 15.0
(11) Paraben appropriate amount (12) Phenoxyethanol Appropriate amount (13) Trisodium edetate Appropriate amount (14) Dimethyl distearyl ammonium hectorite 0.5
(15) Spherical polyalkyl acrylate powder 5.0
(16) Purified water residue (17) Perfume appropriate amount (production method)
An emulsion is prepared by a conventional method. The emulsion of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 10 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- (3,5-di-secondarybutyl-2-hydroxyphenyl) -4,5-dimethyl-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 is prepared by a conventional method. The emulsion of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 11 Two-layer type cream
Blending amount (% by mass)
(1) Dimethylpolysiloxane 5.0
(2) Decamethylcyclopentasiloxane 25.0
(3) Trimethylsiloxysilicic acid 5.0
(4) 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5-methyl-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 is prepared by a conventional method. The two-layer type cream of this formulation has good stability and feel when used, and the solubility of the UV absorber is also good.

Example 12 Protector
Blending amount (% by mass)
(1) Dimethylpolysiloxane 3.0
(2) Methylphenylpolysiloxane 2.0
(3) Ethanol 5.0
(4) 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5,6-dimethyl-2H-benzotriazole 0.5
(5) 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -4,5-dimethyl-2H-benzotriazole 0.5
(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 is prepared by a conventional method. The protector of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 13 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- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5-methyl-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 is prepared by a conventional method. The hair styling agent of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 14 Shampoo
Blending amount (% by mass)
(1) Dimethylpolysiloxane 1.5
(2) 2-ethylhexyl p-methoxycinnamate 0.2
(3) 2- (3,5-di-secondarybutyl-2-hydroxyphenyl) -5-methyl-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 is prepared by a conventional method. The shampoo of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

Example 15 Rinse
Blending amount (% by mass)
(1) Polyoxyethylene / methylpolysiloxane copolymer 6.0
(2) 2- (3,5-Di-secondarybutyl-2-hydroxyphenyl) -5,6-dimethyl-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 is prepared by a conventional method. The rinse of this formulation has good stability and feel in use, and the solubility of the UV absorber is also good.

  The ultraviolet absorbent according to the present invention does not require new capital investment and can be industrially produced with high yield. And it has ultraviolet absorption in the UV-A and UV-B regions, has a low melting point, excellent transpiration and light resistance, and has a skin external preparation or resin composition in any range from low to high temperatures. It can be easily added to products. Moreover, it turns out that the light resistance after a heating is also large. Therefore, it can be used in a wide range from low temperature to high temperature, and various organic materials with good performance can be provided.

2 is an ultraviolet absorption spectrum of the compound (Ia) obtained in Example 1. 2 is an ultraviolet absorption spectrum of the compound (Ib) obtained in Example 2. 2 is an ultraviolet absorption spectrum of the compound (Ic) obtained in Example 3. It is an ultraviolet absorption spectrum of compound (Id) obtained in Example 4. 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. (Product name parsol 1789) 2 is an infrared absorption spectrum of the compound (Ia) obtained in Example 1. 2 is an infrared absorption spectrum of the compound (Ib) obtained in Example 2. 2 is an infrared absorption spectrum of the compound (Ic) obtained in Example 3.

Claims (4)

The ultraviolet absorber which consists of the following general formula (I).
Formula (I)

(In the formula, any one of R, R ′, and R ″ is hydrogen and two are methyl groups, or any two are hydrogen and one is a C1-C3 linear alkyl group. ) 2- (2-hydroxy-3,5-di-secondarybutylphenyl) -2H-benzotriazole of any one of the following formulas (Ia), (Ib) and (Ic).

  The skin external preparation containing the ultraviolet absorber of Claim 1. A skin external preparation containing an ultraviolet absorber of the following formula (Id).

Images