JP5731452B2 - Novel benzotriazole derivative compound and water-soluble ultraviolet absorber containing the same - Google Patents

Description

  The present invention relates to a novel benzotriazole derivative that absorbs ultraviolet rays in the UV-A region, an ultraviolet absorbent containing the same, particularly a water-soluble benzotriazole derivative, an ultraviolet absorbent using the same, and a skin external preparation containing the same. It relates to agents or cosmetics. More specifically, the present invention relates to a benzotriazol-2-ylresorcinol derivative compound into which polyethylene glycol is introduced.

In cosmetics, an ultraviolet absorber is blended in order to increase the light stability of the components of the cosmetics themselves or to protect the human skin.
The ultraviolet 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). Never reach the ground. In addition, UV rays in the UV-A region (320 to 400 nm) invade the skin blackly, but it is not considered to cause sunburn like the UV-B region (290 to 320 nm) 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 that it causes.
Cosmetic UV absorbers used to date are classified according to structure from (a) benzoic acid derivatives, (b) cinnamic acid derivatives, (c) benzophenone derivatives, (d) dibenzoylmethane derivatives, (e ) Salicylic acid derivatives and the like, and (b) and (d) are examples of ultraviolet absorbers frequently used in recent years.

However, the ultraviolet absorbers listed above have their respective problems as follows from a practical viewpoint.
In the compound of (a), for example, p-dimethylaminobenzoic acid-2-ethylhexyl ester is liquid and transparent, and has advantages that it is easy to handle, but there is a suspicion of carcinogenicity including these derivatives. not being used. Further, the maximum absorption wavelength is in the vicinity of 290 nm, and absorbs ultraviolet rays only in the UV-B region.
In the compound (b), p-methoxycinnamic acid-2-ethylhexyl ester is the most commonly used UV absorber for sun care cosmetics currently on the market, but the maximum absorption wavelength is around 310 nm, and absorption The area does not reach the UV-A area. Moreover, it is deteriorated by sunlight, and there is a problem in the colorability and the durability of the UV protection effect.
In the compound of (c), for example, 2-hydroxy-4-methoxybenzophenone has absorption over the UV-A and UV-B regions and has relatively good solubility in a cosmetic base, but the maximum absorption wavelength is slightly UV- Located near the B region, the absorbance is not so high. In recent years, a basic skeleton structure (benzophenone) has been pointed out as an environmental hormone and its use has been avoided.
As the compound (d), 4-tert-butoxy-4-methoxydibenzoylmethane is often used. 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, absorption in the UV-B region is small, and it is said that there is a problem in light stability. There is also a problem in that the compatibility with the decorative base material is poor and only a small amount can be mixed.
In the salicylic acid derivative (e), octyl salicylate is used. It has a maximum absorption wavelength in the UV-B region, is oily, and has excellent compatibility with paraffin oil or the like, but is not practically used because of its low absorbance (see Non-Patent Document 1 above).

  Therefore, in the UV-B region, (b) p-methoxycinnamic acid-2-ethylhexyl ester is used, and in the UV-A region, (d) 4-tert-butoxy-4-methoxydibenzoylmethane is used. Often used. Moreover, both are often used together to cover the entire area.

  As for the UV-A region, as a UV absorber for cosmetic use, a good UV absorber other than 4-tert-butoxy-4-methoxydibenzoylmethane (trade name Parsol 1789) described above has been found. In particular, it is to provide an ultraviolet absorber which is excellent in compatibility with a cosmetic base material particularly in the UV-A region, has excellent light stability, and the compound itself is hardly decomposed or deteriorated over a long period of time.

However, the ultraviolet absorbers listed above are generally oil-soluble, and it is very difficult to mix them with aqueous skin external preparations. In addition to aqueous skin external preparations, for example, in the field of toiletries, deodorants, fragrances, hair care, body care, etc. are also required for water-based paints and water-based polymers in industrial fields. Wide range.
However, at present, no water-soluble UV absorber having sufficient performance has been researched and developed. Among those currently used, 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone sodium (manufactured by Cypro Kasei Co., Ltd.) is known. However, since this substance is a sulfonate, it affects the pH when blended into cosmetics, the ultraviolet absorption region changes, and the solubility in water is only about 6% (25 ° C), Patent Document 1 suggests that there is a problem that the blending amount into the product cannot be increased.
Moreover, when mix | blending a ultraviolet absorber with a skin external preparation, it must be a highly safe compound without the sensitization to skin. In addition, it is important that the compound itself has a so-called light-resistant stability that is not decomposed by exposure to sunlight.

In addition to the above-mentioned sodium 2-hydroxy-4-methoxy-5-sulfoxonium benzophenone, various compounds have been proposed, but none of them have been put into practical use or limited in part. It is only used for small quantities.
For example, in Patent Document 2 and Patent Document 3, a sugar chain is introduced into a cinnamic acid derivative to make it water-soluble, but the ultraviolet absorption region is only about 350 nm, and the UV-B region is targeted. Is. Further, there is no example regarding solubility and solubility in water, and no mention is made.
In Patent Document 8, cinnamic acid is used as an acid amide and then a glycoside in which a sugar is introduced into an amino group. Furthermore, Patent Document 9 reports an attempt to introduce a quaternary ammonium group into a benzalmalonate derivative. Although it has excellent light resistance in the UV-B region, its solubility in water is small.
Patent Document 4 proposes a compound in which an alkylcarboxylic acid is introduced into the 1-position of a benzylidenehydantoin derivative and a sugar is further esterified to form a glycoside.
However, in the reaction scheme (3) of paragraph 0017 of the same document, there are two NH functional groups at the 1-position and the 3-position, and the basis for the selective reaction at the 1-position is not specified. Although NMR, FTIR, and UV spectrum measurement data are described, it is impossible to make a structure judgment that reacts selectively to the 1st position only with these data, and the described structure itself in the literature is incorrect. There is even a possibility.

  In general, a 4-benzylidene derivative has a large molar extinction coefficient in the UV-A region due to the influence of a continuous conjugated double bond of a vinyl group and an aromatic ring bonded to the vinyl group. Light resistance is poor compared to 2H-benzotriazole and the like, and it is considered that there is a problem in the stability of the compound itself to light. In addition, also in patent document 4, there is no Example regarding the solubility and solubility in water, and nothing is mentioned. These are the same in Patent Document 5.

  In Patent Document 6, an attempt has been made to introduce a sugar chain via an alkyl group into the hydroxyl group at the 4-position of a 2,4-dihydroxybenzophenone derivative, and water-soluble ultraviolet absorption having an ultraviolet absorption region in the UV-B region. However, since the absorbance of benzophenone is generally small, it is necessary to increase the amount of the benzophenone, which is disadvantageous in terms of cost and performance as a preparation, and also has a problem in the safety of benzophenone itself.

  In Patent Document 7, a 2,4-dihydroxybenzophenone derivative or a dibenzoylmethane derivative is condensed with a maleic anhydride copolymer via an alkyloxy group to form a water-soluble ultraviolet absorber. Since the absorbance in the -A region is very small, it is difficult to use this region as an ultraviolet absorber.

  Patent Document 10 suggests a compound in which polyethylene glycol is ether-bonded to a 2,4-dihydroxybenzophenone derivative. Examples of water-soluble benzotriazole derivatives are described in Patent Document 11, Patent Document 12, and Patent Document 13. However, Patent Document 11 merely lists sulfonic acid, carboxylic acid, phosphoric acid, and the like as ionic groups, which are general benzotriazole derivatives that can be considered in Marcouche, and describes the introduction of polyethylene glycol to the hydroxyl group. However, the compound which condensed polyethylene glycol through the carboxylic acid of this application is not contained. In addition, what is actually used in the examples is 4-benzotriazol-2-yl-benzene-1,3-diol, which is a two-stage precursor of the present compound, and can be easily obtained as an industrial product. And only slightly soluble in water.

Patent Documents 12 and 13 propose benzotriazol-2-ylphenol in which polyethylene glycol is ester-bonded via propionic acid.
However, since the ultraviolet absorption range is slightly different from the benzotriazol-2-ylresorcinol of the present application, the absorption range in the UV-A region is small, especially the absorption close to 400 nm is very small. There's a problem. About this difference, the data which compared with both most basic structures are shown in (Table 1) and (FIG. 5). In Table 1, ε is the molar extinction coefficient (ε) at the maximum absorption wavelength (λmax).

Further, while resorcinol as a raw material is easily available, the phenol raw materials of Patent Documents 12 and 13 are special raw materials that are generally difficult to obtain and are considered to be expensive.
Therefore, it is very difficult to provide these compounds at low cost and to put them into practical use.

JP 2007-332084 A JP-A-9-268194 JP-A-9-263596 JP-A-8-127589 JP-A-9-241289 JP-A-9-255696 JP-A-10-231467 Japanese Patent Laid-Open No. 10-120698 JP 7-330693 A JP 7-109447 A Japanese Patent No. 4463114 JP-A-7-246773 JP 2001-39028 A

Masamitsu Ichihashi et al., Skin Aging and Sun Care Science, Fragrance Journal, Inc.

The problem to be solved by the present invention is that it has a low melting point, is excellent in compatibility with various cosmetic base materials, particularly purified water, has absorption in almost all regions of UV-A and UV-B, and is photostable. It is an object to provide a water-soluble ultraviolet absorber that is excellent in resistance to degradation and degradation of the compound itself over a long period of time.
In view of the current situation where water-soluble UV absorbers are not necessarily developed in terms of performance and cost in cosmetic and industrial applications, low-cost, high-performance water-soluble UV absorbers are designed. Develop and provide stable.

  In the field of so-called engineering plastics such as polycarbonate, the present inventor efficiently absorbs ultraviolet rays over a long period of time even under harsh use conditions, hardly causes material deterioration, and as a compound, it has excellent stability and is well-established. Attention was paid to a derivative of 2H-benzotriazol-2-ylphenol.

  However, 2H-benzotriazol-2-ylphenol, which is a basic structure as a benzotriazole ultraviolet absorber, has a problem in that it is generally highly fat-soluble and has a very low ability to distribute water. This is because biodegradation by microorganisms does not proceed and continues to exist in the environment forever. As a result, the concentration is expected to be high when taken into the living body of a living body such as a human body. Further, although UV rays are widely absorbed from the UV-B to the UV-A region, the absorption wavelength region in the UV-A region is not always satisfactory because the entire region cannot be covered and the absorbance is small.

  On the other hand, 2H-benzotriazol-2-ylresorcinol has a smaller ultraviolet absorption capacity in the UV-B region than 2H-benzotriazol-2-ylphenol, but the above 2H-benzotriazol-2-ylphenol. It absorbs a wider UV-A wavelength range and has a larger molar extinction coefficient. In addition, it is slightly soluble in water.

  On the other hand, in introducing the side chain for imparting water solubility, in view of the prior art mentioned above, 1. introduction of sulfonate; 2. introduction of monosaccharides or sugar chains; 3. Introduction of polyethylene glycol or polypropylene glycol. The introduction of quaternary amine salts was considered.

Among them, the present inventor decided to select 3.
The reason is that it is considered that it has superior cost and safety, is easy to synthesize, has high stability of the compound even at high temperatures, and can be easily added to industrial products.

In particular, polyethylene glycol is also used as a raw material for cosmetics and skin external preparations.
As an introduction method, two methods of conjugating an ether bond to the 3-position hydroxyl group of resorcinol or introducing an ester bond by introducing a carboxyl group were considered. In the former, it is necessary to react once by converting the hydroxyl group of polyalkylene glycol to haloalkyl. In the latter case, the intermediate is targeted quantitatively without any by-product by adding the lactone by ring opening It was thought that the final target product can be easily obtained by esterification in the next step. Therefore, we decided to adopt the latter. Specifically, polyalkylene glycol monoalkyl ether was used as the polyalkylene glycol. This is because the hydroxyl group on one side is blocked with an alkyl group such as a methyl group or an ethyl group, whereby the selectivity of the reaction is improved and the cost can be reduced.

In addition, the final target compound precursor alkylcarboxylic acid itself has some water-soluble properties and is very useful as an intermediate compound. In this way, the molecular design of the compounds, the actual synthesis and evaluation, surprisingly found that some compounds have a solubility in water of 30% or more at room temperature.
Therefore, further investigations were made on the purification methods of these novel compounds, and as a result of repeated various efforts aimed at establishing an efficient production method using general-purpose equipment at a low cost, the present invention was completed. It has come.

（I）

式中、Ｒ_１は、水素原子または塩素原子を示す。Ｒ_２は、水素原子またはメチル基を示す。ｎの数は、８から２２の整数である。 The present invention is a novel benzotriazole derivative compound represented by the following general formula (I).

(I)

In the formula, R ₁ represents a hydrogen atom or a chlorine atom. R ₂ represents a hydrogen atom or a methyl group. The number of n is an integer of 8 to 22.

ｂ) Ｒ_１＝Ｈ、Ｒ_２＝Ｈ、ｎ＝１２

ｃ) Ｒ_１＝Ｈ、Ｒ_２＝Ｈ、ｎ＝８

In particular, at least one benzotriazole derivative compound represented by the following a) to c) in the general formula (I) is preferable.
a) R ₁ = H, R ₂ = H, n = 22

b) R ₁ = H, R ₂ = H, n = 12

c) R ₁ = H, R ₂ = H, n = 8

  The derivative compound represented by the general formula (I) can be used as an ultraviolet absorber. In particular, a compound specified by at least one of the compounds a) to c) can be used favorably as an ultraviolet absorber. The compound containing the derivative represented by the general formula (I) can also be used as a skin external preparation.

  The present invention can provide a novel ultraviolet absorber that is rich in water solubility and has a stable benzotriazole structure and an efficient ultraviolet absorption region in the UV-A region. Therefore, by using the water-soluble ultraviolet absorber that is the 2H-benzotriazol-2-ylresorcinol derivative of the present invention, a high-performance water-soluble cosmetic preparation that could not be produced in the past, particularly inexpensive and high It can be stably added to toiletries such as external skin preparations, hair care products, body care products, deodorants, and fragrances that require raw materials with high performance and safety. In addition, high-performance industrial products can be supplied by addition to water-based paints for vehicles and water-based polymers.

2 is an ultraviolet absorption spectrum of the compound (a) obtained in Example 1. 2 is an ultraviolet absorption spectrum of the compound (b) obtained in Example 2. 2 is an ultraviolet absorption spectrum of the compound (c) obtained in Example 3. 2 is an ultraviolet absorption spectrum of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate shown in Comparative Example 1. FIG. It is the ultraviolet absorption spectrum of 2H-benzotriazol-2-ylresorcinol derivative (Exemplary Compound 1) having the most basic structure and the ultraviolet absorption spectrum of 2H-benzotriazol-2-ylphenol (Exemplary Compound 2).

（I）
式中、Ｒ_１は、水素原子または塩素原子を示す。Ｒ_２ は、水素原子またはメチル基を示す。ｎの数は、８から２２の整数である。 Hereinafter, a suitable manufacturing method is described in detail about the 2H-benzotriazol-2-ylresorcinol derivative compound represented by the general formula (I) according to the present invention.

(I)
In the formula, R ₁ represents a hydrogen atom or a chlorine atom. R ₂ represents a hydrogen atom or a methyl group. The number of n is an integer of 8 to 22.

Hereinafter, the compound of the present invention can be synthesized according to Scheme 1.
The outline of the method for synthesizing the compounds will be described in order below.
First, 4-benzotriazol-2-ylbenzene-1,3-diol (G-1) was synthesized based on the synthesis examples of JP-A-2005-206473 and JP-A-2005-290240. The intermediate compound (M-1) of butyric acid can be obtained using the method described.

（スキーム１）

(Scheme 1)

  Subsequently, the target polyethylene glycol derivative (G-2) can be obtained by utilizing a condensation reaction by reflux dehydration using an acidic catalyst such as methanesulfonic acid in a toluene solvent. Examples of acidic catalysts other than methanesulfonic acid include Bronsted acids such as sulfuric acid and paratoluenesulfonic acid, and Lewis acid catalysts such as metal complexes.

  The ratio of (M-1) to the target polyethylene glycol monomethyl ether in the reaction is 1: 1 to 1: 3, preferably about 1: 2 in terms of molar ratio, and the catalyst is based on (M-1). 0.01 to 20% by weight, preferably about 1 to 2% by weight. The reaction temperature is stirred for about 24 to 48 hours while vigorously refluxing in the range of about 110 to 115 ° C., and is carried out until the theoretical amount of water produced by the reaction is distilled. Thereafter, washing with water is repeated to remove unreacted excess polyethylene glycol monomethyl ether. At this time, most of the target product is distributed to the toluene layer. Further, after the activated carbon treatment and the column treatment are performed several times, the toluene solvent containing water is distilled off under reduced pressure and dried in a dryer at 60 ° C. for about 170 hours to obtain the target yellow liquid. When this oily substance is stored at 10 ° C., it solidifies into a yellow waxy substance.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. The final object was measured and evaluated for purity, melting point and absorbance by HPLC. Moreover, about the compound of the Example, < ¹ > H-NMR and FT-IR were measured and it confirmed that it was the structure of the target object.

<Absorbance measurement conditions>
Measuring device: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500 nm
Sample concentration: 10 ppm / chloroform

<HPLC surface 100 purity measurement conditions>
Measuring device: LC-6A (manufactured by Shimadzu Corporation)
Column: SUMPAX ODS-A-212 6 μm, 6 mm × 15 cm
Column temperature: 40 ° C
Mobile phase: acetonitrile: water = 8: 2, 0.3% phosphoric acid added (to water)
Measurement wavelength: 254 nm

<FTIR measurement conditions>
Apparatus: FTIR-8400S (manufactured by Shimadzu Corporation)
Sample: Liquid film method (KBr plate)

^<1 H-NMR measurement conditions>
Instrument: Varian Mercury-300 (300 MHz) SC-NMR spectrometer
Resonance frequency: 300 MHz ( ¹ H-NMR)
Solvent: DMSO-d6

Tetramethylsilane was used as an internal standard substance for ¹ H-NMR, the chemical shift value was represented by δ value (ppm), and the coupling constant was represented by Hertz. Further, s is a singlet, d is a doublet, t is a triplet, q is a quintet, dd is a doublet doublet, br s is a broad singlet, and m is an abbreviation for multiplet.

[Example 1]
Synthesis Example of Compound a) A 500 mL four-necked flask was equipped with a thermometer, a condenser with a ball, and a water separator, and 4- [4- (2H-benzotriazol-2-yl) -3-hydroxyphenoxy] butyric acid 8.146 g (0.026 mol), monomethoxypolyethylene glycol n = 22 (trade name UNIOX M-1000: manufactured by NOF CORPORATION), 52.0 g (0.052 mol), 100 mL of toluene were added, and the reflux temperature was stirred. Heated until reached. The mixture reached the reflux temperature at 113 to 114 ° C., and reacted for 24 hours while removing the distilled water with a water separator. The whole became a dark red transparent oil, and after confirming the formation of the target product and the disappearance of the raw material butyric acid by thin layer chromatography, the mixture was cooled to 80 ° C., added with 30 mL of hot water, stirred and allowed to stand. The lower aqueous layer was separated. Similarly, wash the oil layer 4 times (total 5 times) with 30 mL of warm water, add 1 g of activated carbon and 0.5 g of ascorbic acid, treat at 80 ° C. for 0.5 hours, filter through a membrane filter, Undissolved material was removed. Similarly, after the activated carbon treatment was performed 4 times (5 times in total), it was passed through column chromatography packed with Wakogel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.). The obtained yellow liquid is concentrated with an evaporator, and the solvent is further distilled off under conditions of 150 ° C./20 Pa. Finally, it is dried with a constant temperature dryer at 60 ° C. for about 170 hours to obtain 18.61 g of pale yellow oil. Obtained.

FIG. 1 shows the ultraviolet absorption spectrum of the compound (a) obtained in Example 1.
HPLC 97.8%; yellowish wax; yield: 55.81% (based on M-1).
¹ H-NMR (300 MHz, DMSO-d ₆ ) δ: 10.6, (br s, OH), 8.00, (dd, 2H, J = 6.6 Hz, J = 3.3 Hz, J = 3.0 Hz, Benzotriazol-H), 7.71 (d, 1H, J = 9Hz, Phenol-H), 7.50 (dd, 2H, J = 6.6Hz, J = 3.0Hz, Benzotriazol-H), 6.65 (d, 2H, J = 2.4Hz, Phenol-H ), 6.60 (dd, 2H, J = 9.0Hz, J = 2.7 Hz, J = 2.4Hz, Phenol-H), 4.14 (t, 2H, J = 9.3Hz, COO-CH 2 -H), 4.04 (t , 2H, J = 12.6Hz, Ph -O-CH 2 -H), 3.61-3.58 (m, 2H, COO-CH 2 CH 2 -H), 3.50-3.38 (m, 84H, polyethylene-H), 3.22 (s, 3H, OCH ₃ -H), 2.00 (q, 2H, PhO-CH ₂ CH ₂ -H), .FT-IR (Liquid Thin Film) cm ^-1 ; 3550 (OH), 2880 (CH), 1730 (C = O), 1630, 1600, 1500, 1470, (C = C), 1350 (CH), 1280 (Ph-O), 1110 (CO),.

[Example 2]
Synthesis example of compound b) In Example 1, instead of UNIOX M-1000, monomethoxypolyethylene glycol n = 12 (trade name UNIOX M-550: NOF Corporation) 29.15 g (0.052 mol) And performed similarly. 13.8 g of pale yellow oil was obtained.
FIG. 2 shows the ultraviolet absorption spectrum of the compound (b) obtained in Example 2.
HPLC 90.5%; yellowish wax; yield: 62.0% (based on M-1).
¹ H-NMR (300 MHz, DMSO-d ₆ ) δ: 10.6, (br s, OH), 8.00, (dd, 2H, J = 6.6 Hz, J = 3.3 Hz, Benzotriazol-H), 7.73 (d, 1H , J = 8.7Hz, Phenol-H), 7.50 (dd, 2H, J = 6.6Hz, J = 3.0Hz, Benzotriazol-H), 6.66 (d, 2H, J = 2.7Hz, Phenol-H), 6.60 ( dd, 2H, J = 9.0Hz, J = 2.7Hz, J = 2.4Hz, Phenol-H), 4.14 (t, 2H, J = 9.3Hz, COO-CH ₂ -H), 4.04 (t, 2H, J = 12.9Hz, Ph-O-CH 2 -H), 3.61-3.58 (m, 2H, COO-CH 2 CH 2 -H), 3.50-3.30 (m, 44H, polyethylene-H), 3.21 (s, 3H , OCH ₃ -H), 2.00 (q, 2H, PhO-CH ₂ CH ₂ -H) ,.
FT-IR (Liquid Thin Film) cm ^-1 ; 3520 (OH), 2880 (CH), 1730 (C = O), 1630,1600,1510,1470,1450, (C = C), 1350 (CH), 1290 (Ph-O), 1110 (CO) ,.

[Example 3]
Synthesis Example of Compound c) In Example 1, instead of UNIOX M-1000, monomethoxypolyethylene glycol n = 8 (trade name UNIOX M-400: manufactured by NOF Corporation) 20.0 g (0.052 mol) And performed similarly. 12.0 g of pale yellow oil was obtained.

FIG. 3 shows the ultraviolet absorption spectrum of the compound (c) obtained in Example 3.
HPLC 93.5%; yellowish wax; yield: 67.9% (based on M-1).
¹ H-NMR (300 MHz, DMSO-d ₆ ) δ: 10.6, (br s, OH), 8.00, (dd, 2H, J = 6.6 Hz, J = 3.3 Hz, J = 3.0 Hz, Benzotriazol-H), 7.72 (d, 1H, J = 8.7Hz, Phenol-H), 7.50 (dd, 2H, J = 6.6Hz, J = 3.0Hz, Benzotriazol-H), 6.66 (d, 2H, J = 2.4Hz, Phenol- H), 6.61 (dd, 2H, J = 8.7Hz, J = 2.7Hz, J = 2.4Hz, Phenol-H), 4.14 (t, 2H, J = 9.3Hz, COO-CH ₂ -H), 4.04 ( t, 2H, J = 12.3Hz, Ph-O-CH ₂ -H), 3.61-3.58 (m, 2H, COO-CH ₂ CH ₂ -H), 3.53-3.38 (m, 28H, polyethylene-H), 3.21 (s, 3H, OCH ₃ -H), 1.99 (q, 2H, PhO-CH ₂ CH ₂ -H) ,.
FT-IR (Liquid Thin Film) cm ^-1 ; 3520 (OH), 2880 (CH), 1730 (C = O), 1630,1600,1510,1480,1440 (C = C), 1350 (CH), 1290 (Ph-O), 1110 (CO) ,.

[Example 4]
For the compounds a) to c) synthesized in Examples 1 to 3, the maximum absorption wavelength (λmax), the molar extinction coefficient (ε) at that time, and the solubility in water at room temperature (25 ° C.) were measured. The results are summarized in “Table 2”.

備考）* は、一般式Ｉにおいて、Ｒ_１＝Ｈ、Ｒ_２＝Ｈであり、そのときのｎの数を示す。

Remarks) * is R ₁ = H, R ₂ = H in the general formula I, and indicates the number of n at that time.

[Comparative Example 1]
UV absorption of 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid trihydrate (Cipro Kasei Co., Ltd .: (Chemical Formula 3)), an existing water-soluble UV absorber, was measured, and λmax and molar absorption were measured. The coefficient was calculated. The results are shown in (Table 3).

From this result, it can be seen that the ultraviolet absorption region does not cover the UV-A region as compared with the compound of the present invention, and in addition, the molar extinction coefficient is small.
Although the solubility in water was very good, it showed strong acidity, and it was found that the use of this compound was limited.

測定濃度 ５ｐｐｍ ／ メタノール

Measurement concentration 5ppm / methanol

Claims (4)

A novel benzotriazole derivative compound represented by the following general formula (I).

(I)

In the formula, R ₁ represents a hydrogen atom or a chlorine atom. R ₂ represents a hydrogen atom or a methyl group. The number of n is an integer of 8 to 22. The benzotriazole derivative compound according to claim 1, wherein in the general formula (I), at least one of the following a) to c):
a) R ₁ = H, R ₂ = H, n = 22

b) R ₁ = H, R ₂ = H, n = 12

c) R ₁ = H, R ₂ = H, n = 8

  The ultraviolet absorber containing the derivative compound shown by Claim 2. A skin external preparation containing the derivative compound of the general formula I shown in claim 1.

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