JPH0525029A - Anti-sunburn cosmetic - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a sunscreen cosmetic that protects the skin from ultraviolet rays. [Structure] A sunscreen cosmetic comprising 0.1 to 20% by weight of a di- or tri (hydroxyoxyaryl) -s-triazine compound represented by the formula (I) in a cosmetic base. [In the above formula (I), R ₁ represents hydrogen, chlorine, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxyl having 1 to 18 carbon atoms, and R ₂ and R ₃ are hydrogen, chlorine, a hydroxyl group, and carbon. Number 1
6 represents an alkyl group or the like, and n represents an integer of 2 or 3. [Effect] The compound represented by the formula (I) is UV-A, U
Not only UV rays of V-B and UV-C, but also long-wavelength absorption / shielding ability, especially UV-A absorption effect is large, and it has no adverse effect on skin and is compatible with oily bases. Since it is highly soluble, it greatly improves the skin protection effect while ensuring transparency when applied.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sunscreen cosmetic, and more particularly to a cosmetic which protects the skin against ultraviolet rays.

BACKGROUND OF THE INVENTION It is well known by the people that sunlight and light from artificial light sources, especially ultraviolet rays, have some effect on the skin. Depending on the wavelength, the light may be ultraviolet (200-400n
m), longer wavelength visible light (400-700 nm),
It is further divided into long-wave infrared rays (700 nm or more).
The shortest wavelength range of ultraviolet rays (200 to 290 nm) is called UV-C, and the shortest wavelength is 185 in a quartz mercury lamp.
nm, the germicidal ray is 253.7 nm, and UV-C is also radiated from a discharge tube of hydrogen or nitrogen, light of a nuclear reactor, or the like.
The radiant dose of 5 to ²⁰ mmJ / cm ² of this light causes erythema on the skin. UV-B for medium wavelength ultraviolet rays (290-320 nm)
It causes erythema, blisters, and burns (sunburn) by irradiation for 4 to 20 hours. This wavelength promotes melanogenesis, resulting in pigmentation (sunburn) and skin damage, but this UV-B is present in the sun, causing the greatest skin damage. In addition, in the artificial sun lamp, 312-312
It emits light with a wavelength of nm. Long-wave ultraviolet (320
To 400 nm) it is called the UV-A, which energy is about 20~50mmJ / cm ^2, a large change although degrade the skin immediately was thought not to occur.

However, due to recent advances in electron microscopy and skin histochemistry, UV-B and UV-C irradiation not only externally generate spots and freckles, but also reach the dermis of the skin and cause blood vessels. It has been found that it causes microchronic changes in elastic fibers in the wall and connective tissue, and causes skin cancer due to internal exacerbation and accelerated skin aging. It has also been found that such a phenomenon is proportional to the product of light energy and irradiation time (action energy density). Furthermore, it was found that UV-A promotes (exacerbates) the above-mentioned skin denaturation by UV-B, which is also a factor in the development of skin cancer. Therefore, recently, protection against this UV-A has become a major issue.

As described above, so-called sunscreen cosmetics containing an ultraviolet shielding agent or an ultraviolet absorbent are known for the purpose of preventing the change of the skin caused by light, especially ultraviolet rays. Known ultraviolet absorbing compounds include benzophenone derivatives (JP-A-62-108804 and JP-A-63-1391).
58), kojic acid and its derivatives (JP-A-63-
No. 188609), an esterified product of vitamin C (JP-A-62-129212), a cinnamic acid derivative or an aminobenzoic acid derivative (JP-B-52-31021 and JP-A-52-31021).
2-31023, 59-35941 and JP-A-60-2.
No. 31637, No. 62-265215, and dibenzoylmethane derivative (Japanese Patent Publication No. 63-6526, Japanese Patent Laid-Open No. 6-52626).
2-240610), ethyl rutin derivatives (JP-A-63-146810), chalcone derivatives, flavone derivatives (JP-A-62-109544 and 63-9).
6120 publications). Examples of the light-shielding agent include benzalphthalides (Japanese Patent Publication No. Sho 63-30822) and those obtained by blending hydrophobized titanium oxide powder with an oily cosmetic base (Japanese Patent Publication Nos. 58-42167 and 59-15885). is there. Further, as a combined cosmetic, an ultraviolet absorber (benzophenone type, aminobenzoic acid type, salicylate type and vitamin C) is blended inside a spongy porous body such as ethylene vinyl acetate polymer or polyethylene (Japanese Patent Publication No. 62- 51931), a cosmetic in which a UV absorber is adsorbed on a porous substance such as polystyrene to form a microcapsule (Japanese Patent Publication No. 53-31932),
A sunscreen composition comprising an ultraviolet absorber, a fatty acid, an amine base and an acrylic polymer (Japanese Patent Publication No. 61-45607), a cosmetic comprising an antioxidant, a benzophenone ultraviolet absorber and an unsaturated oil (JP-A-56). No. 22715), and cosmetics using urocanic acid, Parsol A, etc. are also known.

[0004]

The synthetic compounds used as the conventionally known ultraviolet absorbers described above are oils,
From the viewpoint of solubility with fats and aqueous bases, there is a limit to the amount added to cosmetic bases, it has irritation to the skin, it deteriorates after absorbing UV rays and its UV absorption is weak, and it is short-lived. Over time, the potency diminished and brought coloring,
There is a problem in that it is not sufficient for use as a cosmetic base in terms of hygiene. Further, the light shielding agent such as titanium oxide, zinc white, iron oxide, etc., in particular, these special fine powder products and surface activated products have a small ultraviolet absorbing effect. The substance itself does not change with time and has little irritation to the skin, but when it is used as a cosmetic raw material, it causes whitening and over-coloring during use, which reduces the transparency of the skin. Therefore, there is a limit to the amount of the basic cosmetics used as well as the foundations. In addition, the effect of blocking ultraviolet rays is small when used in an appropriate amount for cosmetic effects. The present invention has been made in view of the above-mentioned current situation, and ultraviolet rays, that is, UV-A, UV-B and U.
It is intended to provide a novel sunscreen cosmetic having a large effect of absorbing and shielding V-C.

[0005]

Means for Solving the Problems As a means for solving the above-mentioned problems, it is extremely difficult for the present inventors to blend a di- or tri (hydroxyaryl) -s-triazine compound (abbreviated as MHAT compound). Found to be effective. That is, the present invention provides a cosmetic base with di- or tri (hydroxyaryl) represented by the following structural formula (I).
A sunscreen cosmetic comprising 0.1 to 20% by weight of an -s-triazine compound.

[Chemical 2] [In the above formula (I), R ₁ is hydrogen, chlorine, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, an arylxy group having 6 to 8 carbon atoms, or an aryloxy group having 1 to 4 carbon atoms. It represents a mono- or dialkylamino group, and R ₂ and R ₃ may be the same or different, and are hydrogen, chlorine, a hydroxyl group, a salt of a sulfonato group, a carboxy group, a metal salt of a carboxy group, and a carbon number of 1 to 18 Alkoxy group with 1 carbon
~ 6 represents an alkyl group, n represents an integer of 2 or 3]

Specific examples of the di- or tri (hydroxyoxyaryl) -s-triazine compound represented by the above formula (I) used in the present invention include the followings, though not limited thereto. Not a thing. 1) 2-methoxy-4,6-di (2-hydroxyphenyl) -s-triazine [abbreviated as 2HPT]

[Chemical 3] 2) 2-hydroxy-4,6- (cresol or xylenol mixture) -s-triazine [abbreviated as 2HCT]

[Chemical 4] 3) 2-phenoxy-4,6-di (2,4-dihydroxyphenyl) -s-triazine

[Chemical 5] 4) 2-dimethylamino-4- (2-hydroxy-4-)
Methoxyphenyl) -6- (2-hydroxy-4-sodium sulfonate) -s-triazine [abbreviated as 2HST]

[Chemical 6] 5) 2-hydroxy-4- (xylinol) -6- (2
-Salicylic acid) -s-triazine

[Chemical 7] 6) 2,4,6-tri (cresol) -s-triazine [abbreviated as 3CCT]

[Chemical 8] 7) 2,4,6-tri (5'-methyl-o-cumenyl)
-S-triazine [abbreviated as 3HCT]

[Chemical 9] 8) 2,4,6-Tri (2-hydroxy-methyl benzoate) -s-triazine

[Chemical 10]

To synthesize the MHAT compound of the present invention as described above, for example, cyanuryl trichloride (C ₃ Cl
₃ N ₃ ) as a raw material is reacted with various phenols in a solvent to obtain di- or tri (oxyaryl) -s-triazine. Subsequently, the resulting alcoholic solution of oxyaryl-s-triazine is irradiated with ultraviolet rays to cause a rearrangement reaction to obtain MHAT. Di (aryl) -s-
The triazine-substituted product retains one chlorine of cyanuryl trichloride as a raw material, reacts with alcohols, amines and the like in a secondary reaction, and is finally purified by recrystallization or the like.

The sunscreen cosmetic of the present invention comprises an oily cosmetic base containing 0.1 to 20% by weight of the above MHAT compound.
It is added and mixed to obtain a preparation. The dosage form is ointment, cream, emulsion, lotion, vap, spray,
It can be an oil agent or the like.

As the oily cosmetic base of the present invention, those listed in Ministry of Health and Welfare Notification Nos. 332, 377 and 209, those listed in "Japanese Cosmetic Ingredient Dictionary" edited by Japan Cosmetic Industry Federation, etc. Known bases such as vegetable oils, synthetic oils,
Mineral oil, humectant, adhesive, preservative, solvent, emulsifier and the like can be used. Examples of the vegetable oil include olive oil, camellia oil, cottonseed oil, castor oil, soybean oil, coconut oil, cacao butter, spermaceti wax, lanolin, beeswax, carnalola wax, hydrogenated oil, stearic acid and its Zn, Ca, Mg or Al salt, or Butyl ester, etc., myristic acid and its Zn or Mg salt, isopropyl ester, etc., palmitic acid, its Zn salt, isopropyl ester, etc., ascorbic acid, behenic acid, olefinic acid and alcohols such as decylethyl, oleyl, cetyl, stearyl, laurel, etc. Is mentioned. Examples of synthetic oils include squalane monostearate glycerin, synthetic ester oils,
Examples thereof include synthetic polyether oils, malic acid esters, sorbitan monooleate, lanolin and hydrogenated products thereof. Examples of mineral oils include paraffin, petrolatum, liquid paraffin, and microcrystal wax.

Examples of the moisturizing agent include glycerin, propylene glycol, sorbit, polyethylene glycol, diethylene glycol, propylene glycol, sodium pyrrolidonecarboxylate and the like. Examples of the adhesive include polyvinyl alcohol, carboxymethyl, sodium salt of alginic acid or propylene glycol ester, rubbers, celluloses and the like.
Examples of the preservative include benzoic acid, sorbic acid, dehydroacetic acid, p-oxybenzoic acid esters, camphor and the like. Examples of the solvent include ethanol, acetone, ethyl acetate, butyl acetate, isopropyl alcohol and the like, and water is usually purified water. As the emulsifier, for example, polyglycerin fatty acid ester,
Examples thereof include polyoxyethylene lanolin derivatives, polyoxyethylene sorbitan fatty acid esters, polyoxyethyne polyoxypropylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, soaps, sucrose fatty acid esters, sorbitan fatty acid esters, and propylene glycol fatty acid esters.

The sunscreen cosmetic of the present invention is M
In addition to the HAT compound and the base for oily cosmetics, a known ultraviolet absorber, particularly an ultraviolet shielding agent may be used in combination if desired. Examples of the UV-screening agent that can be used in combination include titanium oxide (including special fine particles and surface-treated ones), similarly finely-grained or surface-treated zinc white or iron oxide. It is preferable that the addition amount in 1 is 1 part by weight or less.

Further, as the ultraviolet absorber which can be used in combination,
Examples include benzotriazoles, benzophenones, and others. Examples of benzotriazoles include 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3't-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 3 ', 5'-di-t-
Butylphenyl) -5-chlorobenzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-phenylbenzimidazole-5 -Sulfonic acid etc. can be mentioned.

Examples of benzophenones include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone,
2-hydroxy-4-octoxybenzophenone, 2,
2'-dihydroxy-4-methoxybenzophenone,
2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone and its sodium salt, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2
-Hydroxy-4-octadecyloxy-benzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-4-hydroxybenzophenone, 4-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxy Benzophenone, 4-phenylbenzophenone-2'-carboxylic acid isooctyl ester, 2,4-di-t-butylphenyl-3,5-di-t
-Butyl-4-hydroxybenzophenone and the like can be mentioned.

Examples of the benzoic acid compound include methyl o-benzoylbenzoate and p-aminobenzoic acid (PAB).
A), p-aminobenzoic acid glycerin ester, p-dimethylbenzoic acid amino ester, p-dimethylbenzoic acid-2 ethylhexyl ester (octyl PABA), 4
Examples thereof include -bis (hydroxypropyl) aminobenzoic acid ethyl ester and o-aminobenzoic acid methyl ester.

Examples of the cinnamic acid esters and other acid esters include benzyl cinnamate, p-methoxycinnamic acid diethanolamines, p-methoxycinnamic acid-2-ethylhexyl ester, p-methoxycinnamic acid isopropyl, and the like.
Gallic acid oleic acid triester, salicylic acid-2-ethylhexyl ester, salicylic acid-3,3,5-trimethylcyclohexyl ester, salicylic acid triethanolamine, p-butylphenyl salicylate, 2-
Cyano-3,3-diphenylacrylic acid 2-ethylhexyl ester, 2-ethyl-hexyl-3-cyano-
Mention may be made of 3,3'-diphenyl acrylate and the like.

Further, oxybenzene, camphor or its sodium sulfonate, 2-phenyl-5-methyl-
Benzoxazole, p-methylbenzylidene-4-
(1,1-diethanolmethylethyl) -4'-methoxy-dibenzoylmethane (trade name balsol 179
8), butylhexyl-p-dimethanaminobenzoate, α-β-di- (p-dimethanamino) benzoate, α-β-di- (p-methoxycinnamoyl) -α '
-(2-Ethylhexanoyl) glycerin, 2-phenylbenzimidazole-5-sulfonic acid, 5-benz-
4-hydroxy-2-methoxybenzene sulfonic acid, urocanic acids, etc. can also be mentioned.

As vitamins, other ascorbic acid, vitamin A oil, vitamin E acetate, vitamin A
₁ , A ₃ , B ₂ , B ₁₂ , vitamin C sulfate, vitamin C dipalmitate and the like can be mentioned.

The sunscreen cosmetics of the present invention are preferably further used in combination with known antioxidants for stabilizing the base material for oily cosmetics, such as pH adjusters, cosmetic fillers, sweeteners and colorants. , And fragrances can be used together. Examples of the antioxidant include isoascorbic acid, butylhydroxyanisole, dibutylhydroxyanisole, dibutylhydroxytoluene, BHT, propyl gallate, tocopherol, sezamol, flavone derivatives, and guaiac fat. Examples of the pH adjuster include acidic agents such as citric acid, tartaric acid, hydrochloric acid,
Examples of the alkaline agent include sodium hydroxide, potassium hydroxide, aqueous ammonia, soap and the like.
Examples of the filler for cosmetics include bentonite, talc, mica, sodium sulfate, barium sulfate, kaolin, calcium carbonate, silicic acid anhydride, magnesium carbonate and the like. Examples of the sweetener include saccharin, glucose, sucrose, synthetic sugar, and the like, and examples of the coloring agent include a photosensitizer 101 that emits a blue-green or white color and food blue Nos. 1 and 2 that produce a bluish color. If desired, a fragrance can be added.

The dosage form of the sunscreen cosmetic of the present invention, which comprises the MHAT compound used in the present invention and the base for oily cosmetics as described above, and optionally additives, is an ointment or a cream (vanishing type, neutral type). Type, cold type), emulsion (water-in-oil (w / o) type, oil-in-water (o /
w) type), water-rich emulsion (purified water 70 to 80% by weight), white powder (white powder, solid white powder, white powder, etc.), spray, lotion, and various other dosage forms.

[0020]

The compound MHAT, which is the main component of the sunscreen cosmetic of the present invention, comprises a phenol group and s-triazine (1,
3,5) groups are excited by ultraviolet rays due to the bond structure, and intramolecular proton transfer occurs rapidly between the three carbon atoms and nitrogen, hydrogen, and oxygen atoms, resulting in fast tautomerism, which lasts for a long time. Therefore, it is considered that the light wavelength is added with heat. Then, not only is the absorption (shielding) wavelength strong, but it extends to a long wavelength. That is, UV-
It is considered that not only C and UV-B but also weak UV-A is blocked and visible light is also shielded to add to thermal energy. The result of the absorbance measurement is shown in FIG. This phenomenon is slightly different from the compounds conventionally known as antiaging agents and light shielding agents. Therefore, the MHAT compound of the present invention can absorb and block not only ultraviolet rays but also long wavelength regions. And since it absorbs and shields a lot, it is less than 0.
The effect can be obtained even with the addition amount of 1% by weight. If it is less than 0.1% by weight, the effect of absorbing and blocking light becomes weaker, and 20% by weight
If it exceeds the above range, the stability of the product is lowered, and the product is separated to cause nonuniformity of the skin adhering layer, which is not preferable.

Titanium oxide has hitherto been used as a UV-A absorber in sunscreen cosmetics, but its absorption spectrum is as shown in FIG. 2, and the titanium oxide itself is a white pigment, which is opaque. Was a drawback. On the other hand, the MHAT compound according to the present invention does not affect the transparency and has a high compatibility with the oily cosmetic base as described above, and thus even if a large amount of 20 parts by weight to the base is added, for example. It does not crystallize and precipitate. Therefore, the added amount can be improved, and a greater light absorption or light shielding effect can be obtained. As described above, UV-A, which was considered not to cause a great change in the skin, is now considered to be a factor in the development of skin cancer in addition to the aging effect of the skin. This UV-A is used as the MHAT according to the present invention.
Since the compound can be absorbed and converted into heat, it not only has a great sunscreen effect, but also has a great health effect such as prevention of carcinogenesis.

[0022]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 Sunblock 2 HPT 5.0 g 2-Ethylhexyl palmitate 3.0 g Isopropyl myristate 18.0 g Mineral oil 44.0 g Polyoxyethylene (20) sorbitan monooleate 2.0 g Sorbitan monooleate 2.0 g Propylene glycol 5 0.0 g 2-Ethylhexanoic acid triglyceride 12.0 g Squalane 7.0 g BHT 2.0 g Total 100.0 g The above components were mixed, heated to about 50 ° C., and kneaded together, and then cut on a pig skin surface cut into sections of 10 ×. It is applied to an area of 10 mm and ultraviolet rays (light source: 5 kW manufactured by JASCO CRM-
Diffraction grating) was irradiated, and the irradiation light transmittance of the skin was measured.
The measurement method was based on the method described in “Skin Permeability” in the report of the 601st Dermatological Society of Japan, Tokyo Regional Convention. The results are shown in Table 1. Titanium oxide was measured by the same method and used as a comparative example. The results in Table 1 show that 2HPT of the present invention has a low light transmittance.

[0023]

[Table 1]

Example 2 Cream foundation 3 CCT 8.0 g Stearic acid 5.0 g Glycerin monostearate 2.5 g Cetostearyl alcohol 1.0 g Propylene glycol monolaurate 3.0 g Squalane 7.0 g Olive oil 13.0 g Triethanolamine 1 .5 g Solbit 4.0 g Titanium oxide 1.0 g Talc 4.0 g Polyoxyethylene sorbitan monostearate 3.0 g Purified water 47.0 g Total 100.0 g Powdered raw materials are crushed products and mixed with each other. After that, it is added to the oily raw material, stirred, warmed to a temperature of 70 ° C., and added to water to give an emulsified product. Cool and add perfume to give the product.

Example 3 Cream 2HCT 2.5 g 2-Hydroxy-4-methoxybenzophenone 2.0 g Polyoxyethylene sorbitan monostearate (60 EO) 1.0 g Polyoxyethylene sorbit tetraoleate (60 EO) 1 .5 g Glycerin monostearate 1.5 g Sarah beeswax 2.0 g Paraffin 2.0 g Stearic acid 3.0 g Pehenyl alcohol 3.0 g Almond oil 12.0 g Vitamin E 0.04 g Silicon oil 0.1 g p-Oxybenzoic acid ethyl ester 0.2 g liquid paraffin 5.0 g 1,3-butylene glycol 5.0 g citric acid 0.3 g dl-lauroyl-L-glutamic acid Na 0.5 g β-cyclodextrin 8.0 g kojic acid 2.0 g purified water 48.36 g total 100.00g The above compounds are mixed, stirred and dissolved, emulsified with purified water, cooled, and a flavor is added to adjust the pH of the cream to 5.

Example 4 Lotion 2HST 1.5g 2,4-dimethoxy-6 (2hydroxyphenyl) -striazine 0.5g Isopropyl p-methoxycinnamate 0.5g Polyoxyethylene hydrogenated castor oil (60EO) 1.0 g ethanol 15.0 g ethyl p-oxybenzoate 0.1 g citric acid 0.1 g sodium citrate 0.3 g N-lauroyl-L-glutamate Na 0.5 g 1,3-butylene glycol 4.0 g ethylenediaminetetraacetic acid Di Na 0.01 g Kojic acid 0.5 g β-Cyclotestrin 1.0 g BHT 0.5 g Purified water 74.5 g Total 100.0 g The above composition is uniformly stirred and dissolved to obtain a lotion.

Example 5 Lotion 3HCT 3.0 g Dimethylaminocinnamic acid-ethylhexyl 1.0 g Isopropanol 8.0 g Triethanolamine 0.5 g Mineral oil 27.0 g Lanolin oil 2.0 g Propylene glycol 3.0 g Cetyl alcohol 1.0 g Stearic acid 2.0 g BHT 1.0 g p-oxybenzoic acid ester 1.0 g Perfume 0.5 g Purified water 50.0 g Total 100.0 g Heat to about 60 ° C. to dissolve in purified water or oil. The oil melt is slowly added to the water melt with sufficient stirring, cooled and the perfume is added.

[0028]

The sunscreen cosmetic of the present invention has a function of protecting the skin from any wavelength of light, particularly UV-A, UV-B, and UV-C, and particularly has an absorbing effect on UV-A. Has the characteristic that is large. And since it has no adverse effect on the skin and is highly compatible with oily cosmetic bases, it is possible to freely select the compounding amount, while ensuring transparency while dramatically improving the protective effect compared to conventional products. It is an excellent one.

[Brief description of drawings]

FIG. 1 shows UV and high wavelength absorption curves of 2HPT and 3HCT, which are MHAT compounds according to the present invention.

FIG. 2 is a diagram showing a comparison of absorbance curves of 3HST which is an MHAT compound according to the present invention, a known ultraviolet absorber (isopropyl paramethoxycinnamate) and an ultraviolet shielding agent (special fine powder titanium oxide).

Claims (1)

Claim: What is claimed is: 1. A cosmetic base comprising 0.1 to 20% by weight of a di- or tri (hydroxyaryl) -s-triazine compound represented by the following structural formula (I). Sunscreen cosmetics. [Chemical 1] [In the above formula (I), R ₁ is hydrogen, chlorine, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, an arylxy group having 6 to 8 carbon atoms, or an aryloxy group having 1 to 4 carbon atoms. It represents a mono- or dialkylamino group, and R ₂ and R ₃ may be the same or different and are hydrogen, chlorine, a hydroxyl group, a salt of a sulfonato group, a carboxy group, a metal salt of a carboxy group, and a carbon number of 1 to 18 Alkoxy group with 1 carbon
~ 6 represents an alkyl group, n represents an integer of 2 or 3]