WO2015147117A1 - Ultraviolet light-absorbing cosmetic material, cosmetic containing same, and method for blocking ultraviolet light - Google Patents

Abstract

Provided are: an ultraviolet light-absorbing cosmetic material that has effects of blocking ultraviolet light and intensifying visible light, is minimally irritating and exhibits high stability when used in cosmetics; and a cosmetic containing the ultraviolet light-absorbing cosmetic material. A method for blocking ultraviolet light from penetrating human skin, said method comprising applying a cosmetic, which contains an ultraviolet light-absorbing cosmetic material having a light absorption peak at least at 250-300 nm, to the skin. The ultraviolet light-absorbing cosmetic material is characterized by containing an ultraviolet light-absorbing compound comprising a compound with cyclic structure, which is synthesized from a coumarin pigment and arginine and has one or more cyclic structures differing from the coumarin-derived structure, together with a metal ion having an ionic radius of 30-70 pm, and thus having an excitation band at 250-430 nm and a light emission band at 320-600 nm.

Description

UV-absorbing cosmetic material, cosmetic containing the same, and UV blocking method

The present invention relates to a UV-absorbing cosmetic material, a cosmetic containing the UV-absorbing cosmetic material, and a UV-blocking method, and in particular, has UV-blocking and visible light enhancing effects, low irritation, and stability when used in cosmetics The present invention relates to an excellent UV-absorbing cosmetic material, a cosmetic containing the UV-absorbing cosmetic material, and an ultraviolet blocking method.

In recent years, many adverse effects of UV rays on the skin have been reported. For this reason, sunscreen cosmetics have become a necessity in daily life as well as in summer leisure, and are widely used not only for women but also for men and infants. In addition, such sunscreen cosmetics are required to have a higher UV protection effect. As a result, high SPF sunscreen cosmetics are required, and more UV absorbers and UV scattering agents are added.

As the above ultraviolet absorber, organic ultraviolet absorbers such as 2-ethylhexyl paramethoxycinnamate and t-butylmethoxydibenzoylmethane have been used. However, organic ultraviolet absorbers have caused skin problems such as causing inflammation when in contact with the skin. In addition, since the organic ultraviolet absorber has a strong polarity and is hardly soluble, there is a problem that crystals are formed when used in cosmetics and the stability is poor.

Therefore, Patent Documents 1 to 4 disclose techniques for preventing skin troubles caused by an organic ultraviolet absorber by encapsulating the organic ultraviolet absorber in a capsule. Patent Document 5 discloses a technique for preventing crystallization of an organic ultraviolet absorbent by blending an organic ultraviolet absorbent and polyoxyethylene hydrogenated castor oil.

On the other hand, titanium oxide, zinc oxide and the like have been used as inorganic ultraviolet scattering agents. These inorganic ultraviolet scattering agents have a problem that they aggregate and cannot provide a sufficient ultraviolet ray preventing effect, or have a sticky feel when a sunscreen cosmetic is applied.

Therefore, Patent Documents 6 and 7 disclose a technique for preventing aggregation by improving the dispersion state of the inorganic ultraviolet scattering agent. Patent Documents 8 and 9 disclose a technique for improving the stickiness of an inorganic ultraviolet scattering agent by blending specific components.

Furthermore, Patent Documents 10 to 12 disclose fluorescent compounds having a light absorption band in the wavelength range of ultraviolet to visible light using coumarin dyes as raw materials, and the use of such compounds is also considered.

JP 2012-136453 A JP 2009-167168 A JP 2009-23955 A JP 2001-106612 A JP 2013-47206 A JP 2013-221148 A JP 2013-203708 A JP 2013-224276 A JP2013-203716A JP 2008-195567 A JP 2009-179623 A JP 2012-25870 A

By the way, since organic ultraviolet absorbers convert ultraviolet rays into heat energy, there is also a problem in that they may cause skin trouble by giving hot flashes to the skin. In addition, since the technologies described in Patent Documents 1 to 4 include an organic ultraviolet absorber in the capsule, the organic ultraviolet light in the capsule is rubbed against the skin when applying the cosmetic. If the absorbent is discharged, it may cause skin troubles. Further, if the capsule coating is made strong so that the capsules are not broken even when the cosmetics are rubbed against the skin, the feel during use may be deteriorated, which may contribute to a deterioration in the feeling of use of the cosmetics. Furthermore, although the technique of the said patent document 5 can prevent crystallization of an organic type ultraviolet absorber, it cannot prevent skin trouble completely.

Moreover, although the technique of the said patent documents 6 and 7 has the fixed effect which prevents the aggregation by improving the dispersion state of an inorganic type ultraviolet scattering agent, it is not enough, and also by mix | blending an inorganic type ultraviolet scattering agent. The sticky feeling cannot be completely improved. In addition, the techniques described in Patent Documents 8 and 9 do not completely improve the stickiness and the like due to the blending of the inorganic ultraviolet scattering agent, and it is essential to blend specific components into the cosmetic. However, the effect of improving the touch is not obtained.

As described above, it is desired to develop a UV-absorbing cosmetic material that can replace conventional organic UV absorbers and inorganic UV scattering agents with low irritation and good stability when used in cosmetics.

Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, have an ultraviolet shielding effect and a visible light enhancement effect, have low irritation, and have good stability when used in cosmetics. The object is to provide a cosmetic containing a UV-absorbing cosmetic material.

As a result of intensive studies to solve the above problems, the present inventor has an ultraviolet absorbing compound having an excitation band of a specific wavelength and an emission band of another specific wavelength. The present invention has been completed.

That is, the ultraviolet blocking method of the present invention is a method of blocking the skin from ultraviolet rays by applying a cosmetic containing an ultraviolet absorbing cosmetic material having light absorption at least 250 to 300 nm to human skin, A cosmetic material is synthesized from a coumarin pigment and arginine and contains a metal ion having an ionic radius of 30 to 70 pm together with an ultraviolet absorbing compound composed of a cyclic structure compound having one or more cyclic structures different from those derived from coumarin. It has an excitation band at 430 nm and an emission band at 320 to 600 nm.

The cyclic structure compound preferably does not contain a coumarin skeleton, the coumarin dye is preferably 4-hydroxycoumarin, and the metal ion is preferably Al ³⁺ or Mg ²⁺ .

Furthermore, the ultraviolet ray absorbing cosmetic material may have excitation bands of 250 to 300 nm and 330 to 430 nm and an emission band of 400 to 600 nm.

The UV-absorbing cosmetic material may have an excitation band of 260 to 350 nm and an emission band of 320 to 550 nm.

Further, the ultraviolet-absorbing cosmetic material of the present invention is an ultraviolet ray containing a cyclic structure compound that is synthesized from coumarin pigment and arginine and has one or more cyclic structures different from those derived from coumarin and has light absorption at least 250 to 300 nm. An absorbent cosmetic material characterized by being provided with metal ions having an ionic radius of 30 to 70 pm and having an excitation band at 250 to 430 nm and an emission band at 320 to 600 nm.

The cyclic structure compound preferably does not contain a coumarin skeleton, the coumarin dye is preferably 4-hydroxycoumarin, and the metal ion is preferably Al ³⁺ or Mg ²⁺ .

Further, it may be characterized by having excitation bands of 250 to 300 nm and 330 to 430 nm and an emission band of 400 to 600 nm.

Further, it may be characterized by having an excitation band of 260 to 350 nm and an emission band of 320 to 550 nm.

Further, the cosmetic according to the present invention is characterized by containing the above-described ultraviolet absorbing cosmetic material.

The ultraviolet-absorbing cosmetic material of the present invention contains an ultraviolet-absorbing compound I having light absorption at 250 to 300 nm and a metal atom, has excitation bands at 250 to 300 nm and 330 to 430 nm, and 400 to 600 nm. It has a light emission band.

In the ultraviolet-absorbing cosmetic material according to the present invention, the metal atom is present as a metal ion, and the ion radius of the metal ion is preferably 30 to 90 pm, and the metal ion is Al ³⁺ or Mg ²⁺ . Preferably there is.

Furthermore, in the ultraviolet absorbing cosmetic material of the present invention, it is preferable that the ultraviolet absorbing compound I is a compound having no structure composed of a plurality of cyclic structures derived from coumarin.

The ultraviolet-absorbing cosmetic material of the present invention is characterized by containing an ultraviolet-absorbing compound II having an excitation band at 260 to 330 nm and an emission band at 320 to 550 nm.

Furthermore, the ultraviolet-absorbing cosmetic material of the present invention preferably contains the ultraviolet-absorbing compound II and a metal atom.

Furthermore, in the ultraviolet-absorbing cosmetic material of the present invention, it is preferable that the metal atom is present as a metal ion, and the ion radius of the metal ion is 30 to 90 pm, and the metal ion is Al ³⁺ or Mg ^2+. It is preferable that

Furthermore, the ultraviolet-absorbing cosmetic material of the present invention preferably contains the ultraviolet-absorbing compound II in addition to the ultraviolet-absorbing compound I and the metal atom.

The cosmetic of the present invention is characterized by containing the ultraviolet absorbing cosmetic material.

According to the present invention, there are provided an ultraviolet-absorbing cosmetic material having an ultraviolet shielding effect and a visible light enhancing effect, low irritation, and good stability when used in cosmetics, and a cosmetic containing the ultraviolet-absorbing cosmetic material. Can do.

It is a light absorption spectrum of 4-hydroxycoumarin (a) and 7-hydroxy-4-methylcoumarin (b). 6 is a graph showing the pH dependence of the light absorption spectrum of a 7-hydroxy-4-methylcoumarin aqueous solution. 3 is a graph showing the absorption intensity at 320 nm (●) and 360 nm (▲) with respect to pH in a 7-hydroxy-4-methylcoumarin aqueous solution. 3 is a graph showing a fluorescence spectrum when a 7-hydroxy-4-methylcoumarin aqueous solution is excited with light of 360 nm. It is a light absorption spectrum before and after microwave irradiation to a 4-hydroxycoumarin and arginine mixture. It is the schematic of a microwave application apparatus. It is a light absorption spectrum (difference spectrum) before and after microwave irradiation to a 4-hydroxycoumarin and arginine mixture. It is an excitation emission spectrum of 4-hydroxycoumarin and arginylcoumarin. 6 is a graph showing fluorescence spectra of a mixed solution of arginyl coumarin and AlCl ₃ (in the series 1 to 9, the addition amount of AlCl ₃ is changed). It is the graph which showed the difference spectrum which subtracted Series2 from Series1. Fluorescence intensity VsAlCl ₃ amount at 475nm of arginyl coumarin is a graph showing a (280 nm excitation). ₃ is a graph showing the excitation wavelength dependence (340 to 400 nm) of a fluorescence spectrum (arginyl coumarin + AlCl ₃ ). 3 is a graph showing the excitation wavelength dependence (340 to 400 nm) of luminescence intensity (475 nm) of arginyl coumarin. Is a graph showing an emission spectrum in the case of adding AlCl ₃ to 4-hydroxy coumarin. It is a light transmission spectrum of arginyl coumarin. It is a light transmission spectrum of a mixed solution of arginyl coumarin and AlCl ₃ . It is the figure which showed the fraction of the ultraviolet absorption compound I by a high performance liquid chromatograph. 2 is a graph showing an ultraviolet absorption spectrum of an ultraviolet absorbing compound I. 2 is a graph showing a light absorption spectrum (difference spectrum) before and after addition of AlCl ₃ to the ultraviolet absorbing compound I. It is the graph which showed the fluorescence spectrum measured by excitation at 250 nm of the ultraviolet absorption compound I. It is the graph which showed the fluorescence spectrum measured by excitation of 325 nm of the ultraviolet absorption compound I. It is the graph which showed the fluorescence spectrum measured by excitation at 375 nm of the ultraviolet absorption compound I. The ultraviolet absorbing compound I is a graph showing the fluorescence and excitation spectra were excited Thus measurement at 368nm after AlCl ₃ addition. It is the figure which showed the fraction of the ultraviolet absorption compound II by a high performance liquid chromatograph. Solution containing an ultraviolet-absorbing compound II, and is a graph illustrating a light absorption spectrum of the solution containing the ultraviolet absorbing compound I and AlCl _3. The ultraviolet absorbing compound II is a graph showing the difference absorption spectra showing the difference in absorption spectrum in AlCl ₃ before and after addition. It is the graph which showed the fluorescence spectrum and excitation spectrum which were measured by excitation at 300 nm of the ultraviolet absorption compound II. The ultraviolet absorbing compound II is a graph showing the fluorescence and excitation spectra were excited Thus measurement at 300nm after AlCl ₃ addition. It is the figure which showed the fraction of the ultraviolet absorption compound III by a high performance liquid chromatograph. The solution containing the ultraviolet absorbing compound III, and is a graph illustrating a light absorption spectrum of the solution containing the ultraviolet absorbing compound III and AlCl _3. It is the graph which showed the fluorescence spectrum and excitation spectrum of the ultraviolet absorption compound III. It is the graph which showed the influence on the fluorescence spectrum by the metal ion addition of arginyl coumarin. It is the graph which showed the influence on the fluorescence spectrum by Mg ion and Cu ion addition density | concentration change of arginyl coumarin. It is a figure which shows the inflammation inhibitory effect (effect | action regarding IL-1 (alpha), IL-6, and IL-8) by UVB with respect to a normal human epidermal cell.

Hereinafter, the ultraviolet-absorbing cosmetic material of the present invention and the cosmetic containing the ultraviolet-absorbing cosmetic material will be specifically described.
The ultraviolet-absorbing cosmetic material of the present invention contains an ultraviolet-absorbing compound I having light absorption at 250 to 300 nm and a metal atom, has excitation bands at 250 to 300 nm and 330 to 430 nm, and emits light at 400 to 600 nm. It is characterized by having a belt. Thereby, it has an ultraviolet shielding effect and a visible light enhancement effect, has low irritation, and can have good stability when used in cosmetics. Here, the “excitation band” refers to a state in which a substance can take energy energetically when the lowest energy state is a ground state and a higher state is an excited state. An optical wavelength band that can go from the excited state to the excited state. The “emission band” is an optical wavelength band in which light can be emitted from the excited state to the outside and shifted to a lower energy state. That is.

In the UV-absorbing cosmetic material of the present invention, the metal atom contained together with the UV-absorbing compound I is preferably a metal ion, and the ion radius of the metal ion is preferably 30 to 90 pm (picometer). 35 to 70 pm is more preferable, and 50 to 65 pm is even more preferable. Since the metal atom is present as a metal ion, it has a charge, so that the intensity of light in the excitation band and the emission band can be further increased. Furthermore, the intensity of light in the excitation band and the emission band can be further increased by containing metal ions having the ionic radius.

The metal ion contained together with the ultraviolet absorbing compound I is not particularly limited as long as the effect of the present invention is obtained, but is preferably Al ³⁺ or Mg ²⁺ , and more preferably Al ³⁺ . Al ³⁺ can take an ionic radius of 50 pm, and Mg ²⁺ can take an ionic radius of 65 pm. Thereby, the intensity of light in the excitation band and the emission band can be further increased.

The metal ion is preferably water-soluble, and more preferably a metal that coordinates to the ultraviolet absorbing compound I. Thereby, the intensity of light in the excitation band and the emission band can be further increased.

Furthermore, in the ultraviolet absorbing cosmetic material of the present invention, it is preferable that the ultraviolet absorbing compound I is a compound having no structure composed of a plurality of cyclic structures derived from coumarin. Here, in order to distinguish between a structure composed of a plurality of cyclic structures derived from coumarin and a generally defined heterocyclic structure, the heterocyclic structure generally has an atom other than carbon in the ring structure. For example, a ring structure having atoms such as nitrogen, oxygen, sulfur and the like. However, examples of the structure composed of a plurality of cyclic structures derived from coumarin include compounds composed of a plurality of cyclic structures having a coumarin skeleton. A compound having a coumarin skeleton has a sensitization property and the like as described in “Sensitization and cross-reactivity of simple coumarins (YAKUGAKU ZASSHI 121 (1) 97-103 (2001))”. May cause irritation. In the present invention, since the ultraviolet absorbing compound I is a compound that does not have a structure composed of a plurality of cyclic structures derived from coumarin, it is possible to provide an ultraviolet absorbing cosmetic material with low irritation while suppressing the occurrence of irritation. However, if the structure is not composed of a plurality of the above-mentioned cyclic structures, it will be clearly distinguished that an ultraviolet-absorbing cosmetic material as a substance having a heterocyclic structure composed of a monocyclic ring structure may exist.

Furthermore, the ultraviolet-absorbing cosmetic material of the present invention is characterized by containing an ultraviolet-absorbing compound II having an excitation band at 260 to 330 nm and an emission band at 320 to 550 nm. By containing such UV-absorbing compound II, it is possible to increase the intensity of light in the excitation band and emission band, further increase the UV shielding and visible light enhancement effect, and when used in cosmetics with low irritation. The stability can be improved.

Furthermore, the ultraviolet-absorbing cosmetic material of the present invention preferably contains the ultraviolet-absorbing compound II and a metal atom. By containing a metal atom, the intensity of light in the excitation band or emission band can be further increased.

Furthermore, in the UV-absorbing cosmetic material of the present invention, it is preferable that the metal atom contained together with the UV-absorbing compound II is present as a metal ion, and the ion radius of the metal ion is 30 to 90 pm, 35 More preferably, it is ˜70 pm, and even more preferably 50-65 pm. Since the metal atom is present as a metal ion, it has a charge, so that the intensity of light in the excitation band and the emission band can be further increased. Furthermore, the intensity of light in the excitation band or the emission band can be further increased by containing the metal ions having the above-mentioned ion radius.

The metal ion contained together with the ultraviolet absorbing compound II is not particularly limited as long as the effect of the present invention is obtained, but is preferably Al ³⁺ or Mg ²⁺ , and more preferably Al ³⁺ . Al ³⁺ can take an ionic radius of 50 pm, and Mg ²⁺ can take an ionic radius of 65 pm. Thereby, the intensity of light in the excitation band and the emission band can be further increased.

Moreover, it is preferable that the ultraviolet absorbing cosmetic material of the present invention contains the ultraviolet absorbing compound II in addition to the ultraviolet absorbing compound I and the metal atom. As a result, the synergistic effect of the ultraviolet absorbing compound I and the ultraviolet absorbing compound II can increase the light intensity in a wider range of excitation band and wider range of emission band, thereby providing an ultraviolet shielding and visible light enhancement effect. Can be made larger.

The UV-absorbing cosmetic material is not particularly limited as long as it has the above characteristics. Specific examples of the ultraviolet absorbing cosmetic material will be described below.

<UV absorbing cosmetic material>
The ultraviolet-absorbing cosmetic material can be obtained, for example, from a complex or mixture of a compound synthesized from arginine and a coumarin dye and aluminum chloride. Hereinafter, the ultraviolet ray absorbing cosmetic material will be described.

(Coumarin dye)
4-hydroxycoumarin (hereinafter sometimes abbreviated as 4C) is a kind of simple coumarin compound having the following structure (1).

4-Hydroxycoumarin is a light yellow or light brown crystalline powder at room temperature. Today, over 1,000 kinds of coumarin compounds have been found as natural or synthetic products. Among them, 4-hydroxycoumarin has a possibility of synthesizing various substances because its structure is simple as the derivative warfarin is currently used as a blood anticoagulant or rodenticide. Simple coumarin also includes 7-hydroxy-4-methylcoumarin (hereinafter sometimes abbreviated as 7C) as shown in (2) below.

Coumarins have been applied to fragrances and used for medical purposes, but recently, many attempts have been made to apply them to organic dye laser materials that utilize the light absorption and emission characteristics of coumarins. . In addition, in recent years, examples of effective materials that can be used as sensitizers for dye-sensitized solar cells, which are attracting attention as a new form of solar energy utilization, have been realized as derivatives of coumarin. As a result, the possibility of industrial use is expanding.

4-Hydroxycoumarin has a light absorption spectrum as shown by the curve (a) in FIG. This light absorption characteristic is large in light absorption in the ultraviolet region and suitable for light absorption in the ultraviolet region of solar energy, but has a small light absorption band in the visible region. There are two major absorption peaks, and their wavelength bands are close. In the case of 7-hydroxy-4-methylcoumarin, it has a light absorption spectrum as shown in the curve (b) of FIG. This light absorption characteristic is suitable for light absorption in the ultraviolet region, and has a light absorption band slightly longer than 4-hydroxycoumarin, but still has little light absorption band in the visible region. Major absorption peaks are dense. As can be seen by comparing the above formulas (1) and (2), the difference in the position of the hydroxyl group (—OH) appears as a large difference in the spectrum. FIG. 1 shows that 7-hydroxy-4-methylcoumarin has major absorption bands at wavelengths of 290 nm and 322 nm. If you look closely, absorption at 322 nm is also in 4-hydroxycoumarin. This is from the basic molecular structure.

In order to make a UV-absorbing cosmetic material that effectively protects against UV rays, the light absorption band must be in the UV region. In addition, control of the excitation emission peak in the fluorescence spectrum is important.

FIG. 2 shows the pH dependence of the light absorption spectrum of 7-hydroxy-4-methylcoumarin aqueous solution. FIG. 3 shows the absorption intensity at 320 nm (●) or 360 nm (ｎｍ) with respect to pH. According to this, it can be seen that an absorption peak appears at around 320 nm below pH 7, and an absorption peak appears at around 360 nm above pH 7. It can also be seen that as pH increases, the absorption at 320 nm decreases, and conversely, the absorption at 360 nm increases.

FIG. 4 shows the fluorescence spectrum when a 7-hydroxy-4-methylcoumarin aqueous solution was excited with light of 360 nm. The fluorescence peak wavelength was 450 nm, and it was found that the fluorescence intensity increased as the pH increased.

(Arginine)
Arginine is a kind of basic amino acid having the following structure (3).

Arginine is an α-amino acid having a side chain R of CH ₂ CH ₂ CH ₂ NH (C═NH) NH ₂ , a charged polar side chain amino acid, and a basic amino acid. Is one of the higher classes). The structure of the side chain R means that it becomes a material that forms a polymer compound different from a normal polypeptide. That is, it means that it becomes a polymer material such as polyarginine that is polymerized through the amino group of the side chain instead of the main chain. Polyamino acids also exist in a variety of ways, including glutamic acid, which is polymerized via a carboxyl group on the side chain. Examples of applications other than food and pharmaceutical materials include biodegradable plastics, enzyme-cured hydrogels, and injections. Examples of possible biomaterials include cell scaffold materials, DDS matrices, biomedical hemostats and adhesives.

(Compound synthesized from arginine and 4-hydroxycoumarin)
The present inventor predicted that when any atomic group of the coumarin molecule main body is desorbed and arginine is bonded thereto, the electron density distribution changes greatly, and a large change appears in the energy value in the light absorption process. Alternatively, it was predicted that light was absorbed by the generation of molecular species generated by the cleavage of the coumarin molecular structure and the reorganization of the partial structure by the cleavage of the arginine molecular structure. In addition, it was predicted that the microwave synthesis method effective for the chemical synthesis of coumarin and amines would also work effectively for the reaction between arginine and 4-hydroxycoumarin. This is because amino acids have different functions from amines but structurally have amino groups.

In the present invention, as an example, the reaction between arginine and a coumarin dye was performed by irradiating microwaves. The microwave used for chemical synthesis in the present invention refers to an electromagnetic wave having a wavelength of 0.3 mm to 30 cm and a frequency of 1 GHz to 1 THz. The microwave oscillating electric field and oscillating magnetic field interact with permanent and induced dipoles or charges in the material. This generates heat at the molecular level and directly heats the material. When used in a chemical reaction system, rapid, uniform direct heating without heat conduction and convection, selective heating of only the substance that interacts with microwaves, precise control of heating mode by pulse, continuous irradiation, etc. Is possible. In addition, it is possible to perform heating that is not affected by the reactor wall and mass transfer, and that is not affected by whether heat conduction is good or not, and a precise reaction control process that cannot be obtained by heating from an external heat source can be configured.

Hereinafter, a method for producing a compound synthesized from arginine and 4-hydroxycoumarin will be described in detail with reference to the drawings. The ultraviolet-visible light absorption of an aqueous solution containing only the amino acid arginine used in the reaction has only an absorption wavelength band in the ultraviolet region near 207 nm.

When arginine and 4-hydroxycoumarin were mixed at a molar ratio of 1: 1, an experiment was conducted to confirm whether or not both would react. The light absorption spectrum of a sample in which arginine and 4-hydroxycoumarin were mixed at a molar ratio of 1: 1 (each concentration was 0.2 mM) was as shown in FIG. Only absorption maxima were observed at 205 nm, 286 nm, and 299 nm, which almost coincided with the maximum wavelengths of 206 nm, 286 nm, and 300 nm of 4-hydroxycoumarin, and the presence of 4-hydroxycoumarin was only confirmed. is there. The light absorption band of arginine and the light absorption band having a 205 nm peak of 4-hydroxycoumarin almost overlap. From this experimental result, it was found that simply mixing both would not react.

Next, a case will be described in which 5 mL of a mixed solution having three stages of concentration is placed in a high pressure glass tube (manufactured by Ace) having a volume of 15 mL and a maximum pressure resistance of 1400 kPa, and microwaves are separately applied for 4 minutes. FIG. 6 is a schematic diagram of a microwave application device. 1 is a microwave oven main body, 2 is a portion where an irradiated material is placed, 3 is a magnetron for generating microwaves, 4 is a high pressure glass tube, and 5 is a beaker. A general household microwave oven (2.45 GHz, about 900 W) was used as the microwave application device. A high pressure glass tube 4 placed in a beaker 5 was placed in a portion 2 where a substance to be irradiated of the microwave oven 1 was placed, and was irradiated with microwaves. The light absorption spectra before and after microwave irradiation are shown in FIG. As described above, line segment 1 is a spectrum before irradiation, line segment 2 is a spectrum after irradiation for 2 minutes, and line segment 3 is a spectrum after irradiation for 4 minutes. No absorption was observed in the visible wavelength region, and absorption maximums were observed at 208 nm, 287 nm, and 300 nm. This almost coincided with the maximum wavelengths of 207 nm, 286 nm, and 299 nm of 4-hydroxycoumarin, and the presence of 4-hydroxycoumarin was confirmed. As the microwave was applied, the absorbance in the absorption region peculiar to 4-hydroxycoumarin decreased, and the absorbance near 253 nm and 331 nm increased. This is probably because arginine and 4-hydroxycoumarin caused some kind of reaction and shifted the absorption maximum.

When the microwave application time was 2 minutes, as shown by line 2 in FIG. 5, a change in the absorption spectrum was observed, but the amount of change in the absorption value was small. As a spectrum, as shown in FIG. 7, when comparing the concentration at three levels and the reaction time at three levels, the absorbance decreased by 0.125 at 286 nm in the 0.05 mM sample (1 in FIG. 7). A calibration curve of a 4-hydroxycoumarin aqueous solution is experimentally obtained separately, and at a concentration of 0.01 mM to 0.04 mM, if the absorbance is y and the concentration is x, the function y is approximated by 54.44x + 0.055. I know.
Therefore, as Δy = −0.125,
Δy = −0.125 = 54.44Δx,
Δx = -2.30 × 10 ⁻³ mM

That is, in the 0.05 mM sample, 4-hydroxycoumarin decreased by 2.30 × 10 ⁻³ mM, and the total (2.30 × 10 ⁻³ /0.05)×100=4.6. % Are considered to have reacted. Similarly, the 0.1 mM sample (line 3 in FIG. 7) is 4.2%, and the 0.2 mM sample (line 5 in FIG. 7) is 3.1% (absorbance is 0.25 to 0.00). It is considered that 4-hydroxycoumarin reacted nearly 4% by microwave irradiation for 2 minutes. When microwave irradiation is performed for 4 minutes, dramatic changes as shown in line segment 3 in FIG. 5 and line segment 6 in FIG. 7 occur, and it is considered that 90% or more reacted.

FIG. 7 shows a graph obtained by calculating the difference spectrum from the light absorption spectrum data before and after this reaction. FIG. 7 is a graph showing the ultraviolet-visible light absorption difference spectrum of an aqueous solution containing arginine and 4-hydroxycoumarin before and after irradiation with microwaves for 2 minutes and 4 minutes. Lines 1 and 2 have a concentration of 0.05 mM, lines 3 and 4 have a concentration of 0.1 mM, and lines 5 and 6 have a concentration of 0.2 mM. No absorption was observed in the visible wavelength region, and absorption maximums were observed in the vicinity of 208 nm, 253 nm, and 330 nm. Compared with the maximum wavelengths of 207 nm, 286 nm, and 299 nm of 4-hydroxycoumarin, only the short wavelength of 208 nm almost coincides, and the others do not coincide, and a shift of the absorption maximum is observed.

In the case of irradiation for 2 minutes, about 4% is considered to have reacted. However, in the case of irradiation for 4 minutes, the absorption bands near 286 nm and 300 nm, which are the absorption regions of 4-hydroxycoumarin, are almost shifted. It is thought that most of the reaction occurred, and the reaction rate greatly increased between the irradiation time of 2 minutes and 4 minutes. From this, it is considered that this reaction process proceeds rapidly under certain high temperature and high pressure conditions.

When this reaction was further continued for more than 4 minutes, it was confirmed that even the high pressure glass tube 4 could not withstand the pressure, and the destruction phenomenon occurred. When the experiment was tried under various conditions, the following events were confirmed.

When the high pressure glass tube 4 is put in the beaker 5 as it is, almost all of the reaction product becomes a product after irradiation for 4 minutes, and thereafter, no energy is consumed in the chemical reaction. When the energy is full, the pressure rises all at once and the destruction occurs.

When the same reaction is carried out by spreading aluminum oxide powder in the beaker 5, the reaction product is saturated with irradiation for about half of 2 minutes, and the destruction phenomenon starts. This is thought to be due to the efficient transmission of microwave energy to the reactants.

The reaction product was stable even after being stored for a long period of 10 months or longer, and did not return to the original arginine and 4-hydroxycoumarin.

There are two major characteristics of the compound obtained by this chemical synthesis in the absorption spectrum. One is that the absorption maxima near the wavelength of 286 nm and 300 nm, which are peculiar to 4-hydroxycoumarin, disappear and shift to the long wavelength side to 324 nm, and the other is that the short wavelength shift to 253. From the consideration that when the length of the molecular chain is increased, a large change occurs in the light absorption process due to the change in electrical symmetry, and the absorption maximum wavelength shifts to the longer wavelength side. This is probably because hydroxycoumarin and arginine reacted to increase the product chain length.

Since the light absorption spectrum characteristics of the compound obtained by the above chemical synthesis are significantly different from arginine which is the original substance and 4-hydroxycoumarin, the entire substance having the light absorption spectrum characteristics of the compound obtained by the above chemical synthesis is Arginine and 4-hydroxycoumarin can be clearly distinguished from each other and can be referred to as a group of compounds synthesized from arginine and 4-hydroxycoumarin (provisionally named arginylcoumarin).

Next, when the excitation emission spectrum of the obtained product arginyl coumarin was measured, it was as shown in FIG. Line segment 1 is an excitation emission spectrum of a mixture of arginine and 4-hydroxycoumarin before microwave irradiation. Line 2 is the excitation emission spectrum of the product. Before the reaction, the light emission intensity maximum was in the vicinity of 374 nm, but it was found that the light emission intensity maximum point of the product arginylcoumarin was shifted to 348 nm by 26 nm. Thus, it was revealed that the product arginyl coumarin has the property of emitting photons with higher energy than the original 4-hydroxycoumarin.

(Complex of arginyl coumarin and AlCl ₃ )
Next, 5 μL of 0.22 mM arginylcoumarin was added to 2995 μL of distilled water to give 3000 μL, and 10 μL of 0.05 M AlCl ₃ was added, and an emission spectrum by excitation at 280 nm was measured. The results are shown in FIG. When AlCl ₃ was not added (Series 1), an emission spectrum having an emission maximum at 348 nm was obtained. However, when AlCl ₃ was added, the spectrum decreased in intensity and shifted to a long wavelength, and the emission maximum was at 363 nm and 475 nm. An emission spectrum was obtained. The long wavelength shift from 348 nm to 363 nm and the intensity decrease are caused by pH change caused by increase of chloride ions. On the other hand, the increase in emission at 475 nm is that the complex excited by light at 280 nm emits light having an emission maximum at 363 nm, and this light becomes excitation light to excite the complex, and the excited complex has an emission maximum at 475 nm. This indicates that light (light blue) is emitted. Further, FIG. 9 shows that the emission intensity of the 475 nm peak increases as AlCl ₃ is further added.

FIG. 10 shows a difference spectrum obtained by subtracting a spectrum (Series 2) obtained by adding 10 μL of AlCl ₃ to arginyl coumarin from a spectrum of only arginyl coumarin (Series 1). According to this, it can be clearly seen that the emission of the 348 nm peak peculiar to arginyl coumarin disappears by the addition of AlCl ₃ .

FIG. 11 plots the emission intensity of 475 nm obtained by exciting 280 nm light against the complex aqueous solution of arginylcoumarin and AlCl ₃ shown in FIG. 9 against the added amount of AlCl ₃ . A graph is shown. From this, it was shown that the emission intensity of the complex increases as the addition amount of AlCl ₃ increases. Moreover, when the addition amount of AlCl ₃ increased, the increase in fluorescence intensity tended to reach its peak. Than this, the complex of arginyl coumarin and AlCl _3, in a molar ratio of AlCl ₃ to arginyl coumarin, preferably be added 5000 times or more, more preferably be added 10,000 times or more, adding 20,000 times Is more preferable. In addition, since the increase in emission intensity reaches its peak, the upper limit is preferably 60,000 times or less, and more preferably 50,000 times or less.

FIG. 12 shows the emission intensity obtained by irradiating a complex aqueous solution of arginylcoumarin and AlCl ₃ with light of 340 nm to 400 nm to excite the complex. All were luminescences having a luminescence peak at 475. FIG. 13 shows an excitation spectrum in which the emission intensity at 475 nm is plotted with respect to the excited excitation wavelength of 340 to 400 nm. According to this, it was shown that the emission intensity (475 nm) was the strongest when excited at 370 nm.

To summarize the above results, the complex of arginyl coumarin and AlCl ₃ emits internal light having an emission maximum at 363 nm by excitation with external light of 280 nm. The internal light excites the complex, and the excited complex emits visible light having an emission maximum at 475 nm. At this time, the complex has the maximum emission intensity of visible light when the excitation wavelength is 370 nm as shown in FIG. That is, the closer the excitation wavelength is to 370 nm, the stronger the emission of visible light. In other words, the ultraviolet light can be efficiently converted into visible light. The complex of arginyl coumarin and AlCl ₃ emits internal light having an emission maximum at 363 nm. This is close to the above 370 nm. For this reason, it is considered that ultraviolet rays could be efficiently converted into visible light, and a very strong 475 nm blue light emission was obtained.

FIG. 14 shows an emission spectrum when AlCl ₃ is added to 4C. In this case, the complex (4C-AlCl ₃ complex) emits internal light having an emission maximum at 363 nm by irradiation with light at 280 nm. To do. However, the complex maximizes the emission of visible light (450 nm) when the excitation wavelength is 320 nm. For this reason, the emitted internal light (363 nm) cannot be fully utilized, and ultraviolet rays cannot be efficiently converted into visible light. As a result, strong light emission cannot be obtained.

<Visible light transmission>
FIG. 15 shows the wavelength dependence of the transmittance of arginyl coumarin (Arg-C) in the ultraviolet to visible light region by concentration. Line 1 is a measurement result in the case of 0.002 mM, line 2 is 0.04 mM, and line 3 is 0.02 mM. It can be seen that both are transparent in the visible light region of 400 nm or more. In the ultraviolet region, as the concentration increases, the transmittance decreases because of absorption in a region of 330 nm or less.

FIG. 16 shows the wavelength dependence of the transmittance of Arg-C + AlCl _{3 in} the ultraviolet to visible light region by concentration. Line segment 1 is a measurement result in the case of 0.02 mM Arg-C and 0.0005 M AlCl ₃ , and in such a low concentration, it is 100% transparent in a visible light region of 400 nm or more. Recognize. Line segment 2 is the measurement result in the case of 0.05 M AlCl ₃ in 2.00 mM Arg-C at a very high concentration of 100 times that. Even in this case, the transmittance in the visible light region is high, with a transmittance of about 70% at a wavelength of 400 nm, a transmittance of about 90% at a wavelength of 450 nm, and a transmittance of about 95% at a wavelength of 500 nm.

(Preparation of UV absorbing compound I)
Ultraviolet absorbing compound I was prepared from a complex of a compound synthesized from L-arginine and 4-hydroxycoumarin (arginylcoumarin) and AlCl ₃ . Details thereof will be described below.
First, 0.00025 mol of L-arginine, 0.00025 mol of 4-hydroxycoumarin, and 5 mL of water were prepared, and 5 mL was placed in a high-pressure glass tube (manufactured by Ace) having a volume of 15 mL and a maximum withstand pressure of 1400 kPa. 45 GHz, about 900 W) was applied for 60 seconds. 5 μL of the obtained solution was sampled, diluted 200 times, and the light absorption spectrum was measured. As a result, it was confirmed that the solution had a light absorption spectrum peculiar to arginyl coumarin of curve 3 in FIG. .

Next, the obtained solution was filtered with a filter (Nippon Pole Co., Ltd., GHP Acrodisc, 25 mm, 0.2 μ), and 2 mL was then subjected to a high performance liquid chromatograph (Shimadzu Corporation, SHIMADZU · LC-20AP system). The ingredients were analyzed with The chromatographic conditions at this time were a solvent of acetonitrile 80%, 10 mM formic acid 20%. FIG. 17 is a diagram showing fractionation of the ultraviolet absorbing compound I by high performance liquid chromatography. Four fractions were obtained, and when these were fractionated and AlCl ₃ was added and then irradiated with UV light at 375 nm, the fourth fraction, ie, the fraction (*) indicated by the arrow in the figure was the strongest. Visible light was emitted. From this, it was considered that this component absorbed ultraviolet rays and emitted visible light, and was designated as an ultraviolet absorbing compound I. In the figure, the horizontal axis represents the retention time (min), and the vertical value represents the detected voltage value (au).

The obtained solution was separately transferred to a glass container and covered with a resin film (parafilm) with a small hole, and then placed in a vacuum specimen dryer (Tokyo Rika Kikai Co., Ltd., VOM1000A). It was connected to a cooling trap (manufactured by Tokyo Rika Kikai Co., Ltd., UT-1000) with (Tokyo Glassware Co., Ltd. (TGK), 6 × 15 mm, 2 m). A glass condenser (Tokyo Rika Kikai Co., Ltd., 500 mL) was set in the cooling trap, and the trap was filled with methanol. Furthermore, a vacuum hose (Tokyo Glassware Co., Ltd. (TGK), 6 × 15 mm, 1 m) was connected to a vacuum pump (Tokyo Rika Kikai Co., Ltd., EVP-1000) to reduce the pressure. When the pressure was reduced for a sufficient time, a colored solid powder remained in the glass container, and an iced colorless solid (in an ice-like state) remained in the glass capacitor. Among these, the frozen, colorless solid was heated and melted, and then filtered through a filter (Nihon Pole, GHP Acrodisc, 25 mm, 0.2 μ), and then a high performance liquid chromatograph (Shimadzu Corporation). When the components were analyzed under the same conditions as described above using a SHIMADZU · LC-20AP system manufactured by Seisakusho, only the fourth fraction was detected. That is, the first to third fractions were not detected, and only the arrow fraction (*) in the figure was detected. When this component was added with AlCl ₃ and irradiated with UV light at 375 nm, it was confirmed that this component was the same as the above-mentioned UV-absorbing compound I. Also, from this result, the fractional components other than the above-mentioned (*) in FIG. 17 were obtained as a colored solid powder remaining in the glass container when subjected to the decompression process.

<Spectral characteristics of ultraviolet absorbing compound I>
FIG. 18 is a graph showing an ultraviolet absorption spectrum of the ultraviolet absorbing compound I. The ultraviolet-absorbing compound I was subjected to ultraviolet-visible absorption spectrum measurement analysis using an ultraviolet-visible spectrophotometer (SHIMADZU • UV1240, manufactured by Shimadzu Corporation), and showed ultraviolet-visible absorption spectrum characteristics as shown in FIG. Absorption was observed in the vicinity of 210 nm, 250 nm, and 325 nm. This was a characteristic close to the spectral curve 3 in FIG. In FIG. 18, it is observed that the UV-visible light absorption spectrum characteristics after adding AlCl ₃ are slightly shifted in wavelength. In order to detect this in detail, differential absorption spectrum data analysis before and after the addition of AlCl ₃ was performed. As a result, it became like FIG. FIG. 19 is a graph showing a light absorption spectrum (difference spectrum) before and after the addition of AlCl ₃ to the ultraviolet absorbing compound I. The generation of 194.5 nm absorption was thought to be due to Al. Other specific absorptions at 225.5 nm, 269 nm, and 371 nm were considered to be peculiar to the complex formed by the ultraviolet absorbing compound I and Al.

Next, excitation is performed at 250 nm, 325 nm, and 375 nm using a fluorescence spectrometer (SHIMADZU / RF5300, manufactured by Shimadzu Corporation) using the UV absorption maximum wavelength of 250 nm and 325 nm and the differential absorption maximum wavelength of 371 nm as a guide. As a result of measurement, results as shown in FIGS. 20 to 22 were obtained. 20 is a graph showing the fluorescence spectrum measured by excitation of the ultraviolet absorbing compound I at 250 nm, and FIG. 21 is a graph showing the fluorescence spectrum measured by excitation of the ultraviolet absorbing compound I at 325 nm. These are the graphs which showed the fluorescence spectrum measured by excitation at 375 nm of the ultraviolet absorbing compound I. From these, it was found that the ultraviolet absorbing compound I per se absorbs ultraviolet rays but does not emit light without being excited.

Next, after adding AlCl ₃ and measuring the fluorescence spectrum, visible light emission having a maximum at 470.6 nm was observed as shown in FIG. FIG. 23 is a graph showing a fluorescence spectrum and an excitation spectrum measured by excitation at 368 nm after adding AlCl ₃ to the ultraviolet absorbing compound I. Furthermore, when the excitation spectrum was measured by scanning at this maximum wavelength, it became clear that it had an excitation maximum at 224 nm, 267.4 nm, and 368.2 nm. Moreover when exciting with 267.4Nm, also the emission intensity of 368.2nm vicinity is slightly observed, since the most visible emission with a maximum at 470.6nm was observed, the UV absorbing compounds I AlCl ₃ In addition to absorbing 250 to 320 nm of medium wavelength ultraviolet light (UVB wave) having a maximum of 267.4 nm, and emitting 320 to 400 nm of long wavelength ultraviolet light (UVA wave) having a maximum of 368.2 nm. It has become clear that it has a characteristic of emitting visible light (Visible Light) of 400 to 600 nm having a maximum of 470.6 nm.

(Preparation of UV absorbing compound II)
First, as described above, it has been clarified that the main characteristics of the light absorption characteristics (FIG. 5) of the substance group arginylcoumarin are mostly represented by the light absorption characteristics of the ultraviolet absorbing compound I (FIG. 18). Whether there is a component that plays a major role in UV-Vis conversion is considered as follows. In view of FIG. 18, the ultraviolet absorbing compound I shows that the absorption near 300 nm is not zero, but is low, and the excitation spectrum characteristic of FIG. Although it is a central substance of the invention, it was considered that this alone could not include all the ultraviolet-visible light conversion functions of the substance group arginylcoumarin. Therefore, it was decided to search for a substance having high photoactivity with reference to the fact that the absorption and excitation characteristics in the vicinity of 300 nm greatly change by adding AlCl ₃ . Hereinafter, the process of finding and producing the second ultraviolet absorbing compound II will be described in detail.

First, in the same manner as above, 0.00025 mol of L-arginine, 0.00025 mol of 4-hydroxycoumarin, and 5 mL of water were prepared, and a high-pressure glass tube (made by Ace) with a volume of 15 mL and a maximum pressure resistance of 1400 kPa. The solution obtained by applying microwaves (2.45 GHz, about 900 W) for 60 seconds was decompressed in the same manner as described above. The colored solid powder obtained in a glass container was dissolved in a solvent of 20% acetonitrile and 80% aqueous 10 mM formic acid, and then filtered with a filter (manufactured by Nippon Pall Co., Ltd., GHP Acrodisc, 25 mm, 0.2 μ). Then, change with a high performance liquid chromatograph (SHIMADZU · LC-20AP system manufactured by Shimadzu Corporation) in proportion to the time from acetonitrile 20%, 10 mM formic acid 80% to acetonitrile 80%, 10 mM formic acid 20%. Analysis was carried out under elution conditions with a concentration gradient. The monitored fractionation status is shown in FIG. FIG. 24 is a diagram showing fractionation of the ultraviolet absorbing compound II by high performance liquid chromatography. In FIG. 24, about 12 fractions are distinguished and displayed.

After fractionation, UV-visible absorption spectrum measurement, fluorescence spectrum measurement, and excitation spectrum measurement analysis were performed on all components. As a result, the fluorescence intensity of the component (**) in FIG. 24 increased by adding AlCl _3. It turns out that there is a characteristic to do. Details will be described. FIG. 25 is a graph showing light absorption spectra of a solution containing the ultraviolet absorbing compound II and a solution containing the ultraviolet absorbing compound I and AlCl ₃ . The light absorption spectrum of this component is as shown in FIG. 25, that is, the absorption near 300 nm serving as a standard is maximized, and the maximum wavelength is changed by the addition of AlCl ₃ . In order to detect this in detail, differential absorption spectrum data analysis before and after the addition of AlCl ₃ was performed, and the result was as shown in FIG. FIG. 26 is a graph showing a differential absorption spectrum showing a difference in absorption spectrum before and after the addition of AlCl ₃ to the ultraviolet absorbing compound II. Absorption at 213 nm, 245 nm, and 317 nm was considered to be peculiar to the complex formed by ultraviolet absorbing compound II and Al.

Next, the fluorescence spectrum of itself was measured. FIG. 27 is a graph showing a fluorescence spectrum and an excitation spectrum measured by excitation at 300 nm of the ultraviolet absorbing compound II. As shown by curve 2 in FIG. 27, visible light emission having a maximum at 406.6 nm was observed. Further, when the excitation spectrum was measured by scanning at this maximum wavelength, it became clear that the curve 1 had an excitation maximum at 228.6 nm and 294.8 nm.

Next, fluorescence spectrum measurement after addition of AlCl ₃ was performed. FIG. 28 is a graph showing a fluorescence spectrum and an excitation spectrum measured by excitation at 300 nm after addition of AlCl ₃ to the ultraviolet absorbing compound II. As shown in FIG. That is, as indicated by curve 2 in the figure, the visible light emission, which had a maximum at 406.6 nm before the addition of AlCl ₃ , was observed as if it shifted to a short wavelength to 377.2 nm. Next, when the excitation spectrum was measured by scanning at this maximum wavelength, it became clear that the curve 1 had excitation maximums at 235.8 nm and 309.6 nm. The component (**) in FIG. 24 having such characteristics can thus be referred to as the second ultraviolet absorbing compound II, and is a substance that can more fully understand the ultraviolet-visible light conversion function of the substance group arginylcoumarin. I found out that there was.

This UV-absorbing compound II ideally enhances the UV-visible light conversion function in the wavelength region near 300 nm where the absorption and excitation levels of the UV-absorbing compound I are low. This is because UV-absorbing compound II absorbs 260 to 350 nm of medium wavelength ultraviolet light (UVB wave) having a maximum of 309.6 nm and 320 to 500 nm of long wavelength ultraviolet light (UVB wave) having a maximum of 377.2 nm. And visible light (Visible Light) is emitted, and the most commonly emitted ultraviolet light in the vicinity of 377.2 nm almost overlaps the absorption and excitation maximum of the ultraviolet absorbing compound I, and the maximum ultraviolet-visible light conversion function Will be strengthened. These results were completely unexpected. In this way, UV absorbing compound II was prepared.

(Preparation of UV absorbing compound III)
The ultraviolet absorbing compound I and the ultraviolet absorbing compound II described above are particularly highly functional ultraviolet-visible light converting substances. Compared with these substances, other substances having a medium wavelength ultraviolet (UVB wave) absorption ability and a long wavelength ultraviolet (UVA) emission characteristic were found in the substance group arginyl coumarin. FIG. 29 is a diagram showing a fraction of the ultraviolet absorbing compound III by high performance liquid chromatography. As shown in FIG. 29, it was able to be obtained as a component indicated by (***) in the figure in the same fractionation process by HPLC as the ultraviolet absorbing compound II. FIG. 30 is a graph showing light absorption spectra of a solution containing the ultraviolet absorbing compound III and a solution containing the ultraviolet absorbing compound III and AlCl ₃ . As shown in FIG. 30, the substance of this component had a medium wavelength ultraviolet (UVB wave) absorption spectrum characteristic having a maximum at 300 nm. Although it seemed to be very similar to the ultraviolet absorbing compound II, there was a difference, and the emission characteristics were not changed by the addition of AlCl ₃ . The fluorescence spectrum of this component itself was measured. FIG. 31 is a graph showing the fluorescence spectrum and excitation spectrum of the ultraviolet absorbing compound III. As indicated by curve 2 in FIG. 31, visible light emission having a maximum at 378 nm was observed. Next, when the excitation spectrum was measured by scanning with this maximum wavelength, it became clear that the curve 1 had excitation maximums at 230.8 nm, 289.6 nm, and 303.4 nm. In this way, UV absorbing compound III was prepared.

The cosmetic of the present invention is characterized by containing the ultraviolet absorbing cosmetic material. As a result, it is possible to provide a cosmetic product that has an ultraviolet shielding effect and a visible light enhancement effect, has low irritation, and has good stability when used in a cosmetic product. Here, the ultraviolet-absorbing cosmetic material contains the above-described ultraviolet-absorbing compound I, metal atoms, and ultraviolet-absorbing compound II, and the cosmetic is a broad concept including cosmetics, quasi-drugs, pharmaceuticals, and the like. It is. Further, it includes not only basic cosmetics but also makeup, hair cosmetics, cleaning materials and the like.

In addition, in the cosmetic of the present invention, other components and the like can be appropriately added within the range where the effects of the present invention are not impaired. Arbitrary ingredients other than the above can be blended in the qualitative and quantitative ranges, and ingredients usually blended in cosmetics, for example, oily ingredients, surfactants, thickeners, moisturizers, antioxidants, preservatives , Fragrances, various vitamin agents, chelating agents, pH adjusters, colorants, other ultraviolet absorbers, medicinal ingredients, other inorganic salts, and the like.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

Example 1
An aqueous solution containing a compound synthesized from arginine and 4-hydroxycoumarin was treated according to the procedure described above (Preparation of UV-absorbing compound I) to prepare UV-absorbing compound 1.

(Example 2)
An aqueous solution containing a compound synthesized from arginine and 4-hydroxycoumarin was treated according to the procedure described above (Preparation of UV-absorbing compound II) to prepare UV-absorbing compound 2.

Example 3
An aqueous solution containing a compound synthesized from arginine and 4-hydroxycoumarin was treated according to the procedure described above (Preparation of UV-absorbing compound III) to prepare UV-absorbing compound 3.

(SPF measurement test using SPF analyzer)
An SPF measurement sample of 2.0 mg / cm ² was applied to a transpore surge curl tape (manufactured by Sumitomo 3M), and SPF analyzer UV-1000S (manufactured by Labsphere) was used to measure 9 points to obtain SPF value and UVA. / UVB Ratio was determined. This operation was repeated three times, and the average values were taken as the SPF value and UVA / UVB Ratio.

Example 4
A 50% by mass aqueous solution of ethanol was prepared, and 2.75 g of UV absorbing compound 1, 0.00275 g of UV absorbing compound ₂ and 0.49 g of AlCl ₃ .6H ₂ O were added thereto, and UV absorbing compound 1 and UV absorbing were added. The sample of Example 4 was produced so that the compound 2 might be 5 mass%. The measurement results with the SPF analyzer are shown in Table 1 below.

(Example 5)
Adjust ethanol 50% by weight aqueous solution, to which the ultraviolet absorbing compound 1 3.036G, an ultraviolet absorbing compound 2 0.00275G, an ultraviolet absorbing compound 3 0.00275G, the AlCl ₃ · 6H ₂ O was added 5.88g Then, the sample of Example 5 was prepared so that the ultraviolet absorbing compound 1, the ultraviolet absorbing compound 2, and the ultraviolet absorbing compound 3 might be 5% by mass. The measurement results with the SPF analyzer are shown in Table 1 below.

(Comparative test example)
Mix and dissolve so that 2-ethylhexyl methoxycinnamate is 5% by mass, surfactant (EMALEX ML-158, manufactured by Nippon Emulsion Co., Ltd.) 5% by mass, ethanol 35% by mass, and purified water 50% by mass. Samples of test examples were prepared. The measurement results with the SPF analyzer are shown in Table 1 below.

From the results in Table 1, Example 4 and Example 5 showed SPF values equal to or higher than those of the comparative test example. From this, it was found that there was an ultraviolet ray prevention effect equivalent to 2-ethylhexyl methoxycinnamate.

(Skin irritation test)
Using Finn Chambers on Scampor Tape (manufactured by Smart Practice Japan Co., Ltd.), each sample was placed on the back of 20 Japanese people (6 men, 14 women) who were in good health and aged 20 to 60 years old. 30 mg was applied to the chamber and a patch test was performed. As a sample, a complex aqueous solution of a compound synthesized from L-arginine and 4-hydroxycoumarin (arginylcoumarin) and AlCl ₃ containing ultraviolet absorbing compounds I to III (hereinafter referred to as “sample of the present invention”) As a comparative sample, white petrolatum (Nikko Rica Co., Ltd.), physiological saline (Otsuka Pharmaceutical Co., Ltd.), and distilled water for injection (Otsuka Pharmaceutical Co., Ltd.) were used. The skin condition after 24 hours and 48 hours was evaluated according to the following <patch test criteria>, and further evaluated according to the following <skin irritation score> and the following skin irritation index formula (S1).

<Patch test criteria>
No response-
Karui Red Group +-
Red group +
Erythema + edema + papules ++
Erythema + edema + papules, serous papules, small blisters +++
Great blister ++++

<Skin irritation score>
No response 0
Karui Red Group 0.5
Red Group 1.0
Erythema + edema + papule 2.0
Erythema + edema + papules, serous papules, small blisters 3.0
Great blister 4.0

<Skin irritation index calculation formula (S1)>
Skin irritation index = (total score sum of responders with strong response after 24 or 48 hours / number of subjects) × 100 (S1)

The samples according to the present invention, white petrolatum, physiological saline, and distilled water for injection were evaluated according to <Patch Test Criteria> after 24 hours and 48 hours as “no reaction”. The skin irritation index was also 0. As a result, it was found that the sample of the present invention was not very irritating like white petrolatum, physiological saline, distilled water for injection and the like.

From the above, the result of the skin irritation test was good. From this, it was found that the ultraviolet absorbing compounds 1 to 3 were mild to the skin.

(Example 6)
In accordance with the formulation shown in Table 2 below, an anti-UV lotion was prepared. In addition, the numerical value in prescription shows mass% hereafter.

(Example 7)
In accordance with the formulation described in Table 3 below, an anti-ultraviolet lotion was prepared.

(Example 8)
In accordance with the formulation shown in Table 4 below, an ultraviolet protection cream was prepared.

Example 9
In accordance with the formulation shown in Table 5 below, an ultraviolet protection cream was prepared.

(Example 10)
In accordance with the formulation shown in Table 6 below, an anti-UV serum was prepared.

(Example 11)
In accordance with the prescription in Table 7 below, an anti-UV serum was prepared.

Example 12
According to the formulation shown in Table 8 below, an ultraviolet-proof cleansing foam was prepared.

(Comparative Examples 6-12)
The cosmetics of Comparative Examples 6 to 12 were prepared in the same manner as the UV-preventing cosmetics of Examples 6 to 12 except that Example 4 or Example 5 was replaced with purified water in the formulations shown in Tables 2 to 8. Produced.

In Examples 6-12 and Comparative Examples 6-12, there was no irritation and the safety was high. Further, Examples 6 to 12 had an ultraviolet ray preventing effect, but Comparative Examples 6 to 12 did not have an ultraviolet ray preventing effect.

(Comparison of fluorescence spectra due to different metal ion species)
The substance group arginyl coumarin (Arg-4C) was included in Al, and the fluorescence spectrum characteristics were compared with other metal ions. FIG. 32 is a graph showing the influence of addition of metal ions of arginylcoumarin on the fluorescence spectrum. Specifically, the fluorescence spectrum of addition of metal ions of arginylcoumarin is represented by the metal species, Mg, Cu, Ca, Co. , Al, In, K. As explained above, Al has the specificity of visible light emission. For other elements, weak emission was observed in the range of 380 to 500 nm, where Mg has a maximum near 420 nm. It was also found that in the case of Mg, the long wavelength ultraviolet (UVA) emission intensity is higher than that of Arg-4C itself. Next, even weaker light emission was observed in Ca, but no visible light emission was observed in other Cu, Co, In, and K, and the long-wavelength ultraviolet (UVA) emission intensity decreased.

Next, it was measured how the long-ultraviolet (UVA) emission intensity increased in Mg and decreased Cu in terms of concentration dependency. FIG. 33 is a graph showing the influence on the fluorescence spectrum due to the concentration change of Mg ions and Cu ions of arginyl coumarin. As shown in FIG. 33, in Mg, the fluorescence intensity remained increased even when the concentration changed, but in the case of Cu, it continued to decrease. From these results, Al reacts particularly with Arg-4C to give photoactivity, while Mg is not as much as Al, but obviously, unlike other metal ions, it reacts with Arg-4C to give a slight photoactivity. It turned out to give.

The inventor considered the following differences as follows. The ion radius of Al ³⁺ is 50 pm (picometer), the ion radius of Mg ²⁺ is 65 pm, and other metal ions are Cu ²⁺ ion radius 96 pm, Ca ²⁺ ion radius 99 pm, Co ²⁺ ion radius 72 pm. The ion radius of In ³⁺ is 81 pm and the ion radius of K ⁺ is 133 pm. From this, it was suggested that the increase in long-wavelength ultraviolet (UVA) emission intensity or the development of visible emission characteristics is a large factor due to a small ionic radius. However, even 1.5 times larger ion radius than Mg ²⁺ as Ca ^2+, to a lesser extent Mg ²⁺ but also those that result in the change of spectral characteristics is somewhat similar, but categorically is also an exception factor can not be defined, Since Al ³⁺ and Mg ²⁺ have a small ionic radius at the top, it was found that Al ³⁺ and Mg ²⁺ are preferable in this order as metal ions imparting the ultraviolet-visible light conversion function.

(Inhibition of UVB-induced inflammation of normal human epidermal cells by a solid component of a compound synthesized from arginine and 4-hydroxycoumarin)
When skin is irradiated with medium wavelength ultraviolet rays (UVB), it is known that various phenomena occur due to ultraviolet irradiation, and among them, it is well known that keratinocytes and mast cells produce and suppress cytokines. .

Cytokines are small amounts of physiologically active proteins that are released from cells and become various intercellular signal transduction molecules, and usually have low molecular weights (molecular weights are many less than 80,000 and less than 30,000) and have sugar chains. In many cases, it is known to bind to high affinity receptors on the cell surface through body fluids to express multifaceted biological activities. Many of its functions are related to immunity and inflammation. Among cytokines, it is known that inflammatory cytokines include interleukins IL-1α, IL-6 and IL-8. When the production amount of these cytokines increases, collagenase, which is a collagenolytic enzyme, is activated in the skin tissue, the important protein collagen forming the skin is decomposed, and as a result, the aging phenomenon is promoted. Therefore, if the production of these cytokines is suppressed in the skin tissue exposed to UVB, “aging due to light” can be reduced as a result.

Therefore, the present inventor has examined the interleukin (hereinafter referred to as IL) about the action of UVB to reduce the cytotoxicity and the anti-inflammatory action of UVB on the normal human epidermal cells of the compound synthesized from arginine and 4-hydroxycoumarin. Of the production of IL-1α, IL-6 and IL-8.

<Test method>
Normal human epidermis cells were seeded in a 48-well plate at a cell density of 5.0 × 10 4 cells / well using HuMedia KG2 medium. Forty-eight hours after seeding, the medium was replaced with Hanks buffer (Ca ²⁺ , Mg ²⁺ not contained), and cells were irradiated with a predetermined dose of UVB. The UVB non-irradiated group was covered with aluminum foil to shield UVB. Immediately after irradiation, the Hanks buffer was replaced with HuMedia-KB2 (KB2) containing a test sample at a non-toxic concentration and cultured for an additional 24 hours.

After culturing, the medium was collected and replaced with KB2 containing 33 μg / mL neutral red (NR) for the purpose of measuring cell viability and cultured for 2 hours. Thereafter, the cells were washed with PBS, and NR taken into the cells was extracted with a 0.1M HCl solution containing 30% ethanol, and the absorbance at 550 nm was measured. The cytotoxic effect of UVB was shown by Index (%) with respect to the absorbance of the UVB non-irradiated group at each concentration.

Measurement of IL-1α, IL-6 and IL-8 in the collected medium was performed using a commercially available ELISA kit (R & D systems) according to the attached protocol. For statistical processing, a significant difference test using a Student t test was performed, and the difference from the untreated test sample was evaluated.

<Result>
The results are shown in Tables 9 to 12 (Tables 1 to 4) and collectively shown in FIG. The cytotoxicity mitigating action by UVB by the test sample processed immediately after UVB irradiation was not recognized (Table 9). On the other hand, the increase in IL-1α, IL-6 and IL-8 by UVB was significantly inhibited by the test sample (Tables 10 to 12).

<Effects obtained>
Based on the above, it was confirmed that the reaction product of arginine and 4-hydroxycoumarin did not show the cytotoxic effect of UVB, but has an anti-inflammatory action (inhibition of IL-1α, IL-6 and IL-8). It was done. The effect is clear with respect to three kinds of inflammatory interleukins at a content of 0.1 mg / mL by weight. This effect means that there is an effect at a weight percentage of 0.01% (w / w) with respect to the cosmetic weight. Today, the conventionally known optimum blending ratio of additive substances for the purpose of anti-inflammatory effect is about 0.1 to 0.03% (w / w) and is used. Compared with this, it became clear that the reaction product of arginine and 4-hydroxycoumarin can be expected to be effective by using a smaller content.

Claims (13)

1. A method of shielding a skin from ultraviolet rays by applying a cosmetic containing an ultraviolet-absorbing cosmetic material having light absorption at least 250 to 300 nm to human skin,
   The UV-absorbing cosmetic material contains a metal ion having an ionic radius of 30 to 70 pm together with an UV-absorbing compound composed of a cyclic structure compound having one or more cyclic structures different from those derived from coumarin and synthesized from a coumarin pigment and arginine. A method for blocking ultraviolet rays, which has an excitation band at 250 to 430 nm and an emission band at 320 to 600 nm.
2. The ultraviolet blocking method according to claim 1, wherein the cyclic structure compound does not contain a coumarin skeleton.
3. 3. The ultraviolet blocking method according to claim 2, wherein the coumarin dye is 4-hydroxycoumarin.
4. 4. The ultraviolet blocking method according to claim 3, wherein the metal ion is Al3 ⁺ or Mg2 ⁺ .
5. 5. The ultraviolet blocking method according to claim 4, wherein the ultraviolet absorbing cosmetic material has excitation bands of 250 to 300 nm and 330 to 430 nm and an emission band of 400 to 600 nm.
6. 5. The ultraviolet blocking method according to claim 4, wherein the ultraviolet absorbing cosmetic material has an excitation band of 260 to 350 nm and an emission band of 320 to 550 nm.
7. An ultraviolet-absorbing cosmetic material comprising a cyclic structure compound synthesized from a coumarin dye and arginine and having one or more cyclic structures different from those derived from coumarin and having light absorption at least 250 to 300 nm,
   An ultraviolet-absorbing cosmetic material characterized by being provided with metal ions having an ionic radius of 30 to 70 pm and having an excitation band at 250 to 430 nm and an emission band at 320 to 600 nm.
8. The ultraviolet-absorbing cosmetic material according to claim 7, wherein the cyclic structure compound does not contain a coumarin skeleton.
9. The ultraviolet-absorbing cosmetic material according to claim 8, wherein the coumarin dye is 4-hydroxycoumarin.
10. The ultraviolet-absorbing cosmetic material according to claim 9, wherein the metal ion is Al ³⁺ or Mg ²⁺ .
11. The ultraviolet-absorbing cosmetic material according to claim 10, which has excitation bands of 250 to 300 nm and 330 to 430 nm and an emission band of 400 to 600 nm.
12. The ultraviolet-absorbing cosmetic material according to claim 10, having an excitation band of 260 to 350 nm and an emission band of 320 to 550 nm.
13. A cosmetic comprising the ultraviolet-absorbing cosmetic material according to any one of claims 7 to 12.
    
    
    

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