WO2014189230A1

WO2014189230A1 - Regenerative sunblock composition comprising photochromic substance or photochromic substance-protein complex

Info

Publication number: WO2014189230A1
Application number: PCT/KR2014/004354
Authority: WO
Inventors: 정세채; 박연일
Original assignee: 한국표준과학연구원; 충남대학교산학협력단
Priority date: 2013-05-20
Filing date: 2014-05-15
Publication date: 2014-11-27
Also published as: KR101494208B1; KR20140136345A

Abstract

A sunblock composition according to the present invention is a sunblock composition comprising a photochromic substance which, when exposed to ultraviolet (UV-A) light, absorbs the UV-A light and is converted to a visible-light or near-infrared (IR-A)-light receptor (Z-form) showing an absorption band of visible light or IR-A light, and which absorbs visible light or IR-A light and is converted to a UV-A-light receptor (E-form) showing an absorption band of UV-A light, when the converted visible-light or IR-A-light receptor is exposed to the visible light or IR-A light.

Description

Regenerative sunscreen composition comprising a photochromic material or photochromic material-protein complex

The present invention relates to a novel regenerative sunscreen composition having a large blocking effect of UVA on skin aging and based on photochromic biological photoreceptors.

Ultraviolet or UV radiation generally refers to light rays having a wavelength of 400 nm or less. Ultraviolet rays are classified into roughly three kinds according to their wavelengths. UV A rays have a wavelength range of 320 to 400 nm, UV B rays have a wavelength range of 280 to 320 nm, and UV C rays have a wavelength of 280 nm or less. It has a wavelength and is mainly absorbed by the ozone layer in the atmosphere and does not reach the earth's surface. Excessive contact with UV A or UV B rays can cause various skin damage and burning. Therefore, various kinds of cosmetics have been developed and used to solve and protect various skin damages caused by UV rays. Many cosmetics prefer products that can simultaneously block UV A and UV B for effective protection against UV damage that can damage the skin.

Dibenzoylmethane and its derivatives are relatively sensitive to ultraviolet light, so they decompose rapidly under sunlight. In the presence of UV B blockers, especially in the presence of p-methoxycinnamic acid and its derivatives, the decomposition process is further accelerated. Since such dibenzoylmethane and its derivatives are optically unstable in the presence of p-methoxycinnamic acid and its derivatives, the prolonged exposure to the sun does not guarantee sustained protection of the skin.

In general, there are two ways to block ultraviolet rays, one of which is to effectively scatter the ultraviolet rays that are part of the sunlight, thereby reducing the amount of ultraviolet rays that reach the skin. Another form of sun protection is to reduce the amount of ultraviolet light that reaches the skin using lotions, creams, powders, emulsions, and sprays, including materials that can effectively absorb ultraviolet light. To date, UV absorbers having a sunscreen effect and ensuring stability include organic substances such as benzophenol derivatives, p-aminobenzoic acid derivatives, p-methoxy cinnamic acid derivatives and salicylic acid derivatives. Specific examples include drometrizole, 4-methylbenzylidene camphor, menthyl anthranilate, benzophenone-3, benzophenone-8, butylmethoxydibenzoylmethane, ethylhexyl dimethylpava, ethylhexylmethoxycinnamate, paraamino Benzoic acid, phenylbenzimidazolesulfonic acid, isoamyl p-methoxycinnamate, diethexyl butyaminotrione zone, methylenebis-benzotriazolyl tetramethylbutylphenol, terephthalylidene dicamphor sulfonic acid and the like. . Ultraviolet energy absorbed by these organic substances is released after being converted into thermal energy, so it is safe to minimize contact with the skin. Such an ultraviolet absorber often absorbs UV B, and little absorbs UV A.

On the other hand, according to US Patent Publication No. US2013-0004440, dibenzoylmethane and its derivatives, which are mainly used as a sunscreen to block UV A, have properties that decompose very rapidly upon exposure to sunlight and thus cannot be expected for a long time. For this reason, sunscreen compositions must be used repeatedly for effective screening.

According to U.S. Patent Application Publication No. US2002-0022008, photochromic property or photochromicity means that a color changes when a substance is exposed to light of a certain wavelength, and spontaneously returns to its original color when the irradiation is completed. , Or when changing the wavelength of light to be irradiated means that the changed color is returned to the original color. In particular, according to US Patent Publication US6361763 has been reported for a sunscreen composition comprising a photochromic compound related to the spiropyrans (spiropyrans) and the pericyclic reaction (spiroxazine) series of pericyclic reactions (pericyclic reactions). These photochromic substances are mainly substances absorbing ultraviolet B, and since they are organic substances that are insoluble in water, their use is limited. The UV absorption effect of these materials can be estimated by measuring the UV transmittance or absorbance, but it is difficult to accurately estimate the effect according to skin conditions specific to each person.

The present invention provides a photochromic material or optical arc comprising absorbing ultraviolet rays when exposed to ultraviolet rays to cause absorption bands in visible or near infrared rays and causing absorption bands in the ultraviolet region when exposed to visible or near infrared rays. It is intended to develop a sunscreen composition comprising a denaturing protein complex.

The composition for blocking ultraviolet rays according to the present invention absorbs ultraviolet rays when exposed to ultraviolet rays (UV A) and is converted into photoreceptors that exhibit absorption bands of visible or near infrared rays (IR-A), and the converted visible and near infrared ray photoreceptors. Is characterized in that it comprises a photochromic material that absorbs visible light or near infrared light when exposed to visible light or near infrared light is converted into a photoreceptor that represents the absorption band of the ultraviolet region.

The photochromic material may represent a Z-form having an absorption band maximum in the UV region and an E-form having an absorption band maximum in the visible region, wherein the photoreceptor of the Z-form is exposed to ultraviolet rays. When exposed to E-form, the photoreceptor of the E-form contains a photochromic material that is converted to Z-form upon exposure to visible or near infrared light.

The photochromic material includes those derived from living organisms.

Specifically, the photochromic substance is phycocyanobilin, phycoerythrobilin, phycourobilin, phycoviolobilin.

Picocyanobilirin

The photochromic material includes ultraviolet photoreceptor-visible and near-infrared photoreceptors characterized by ultraviolet-orange, ultraviolet-blue, and ultraviolet-green.

The photochromic substance protein complex is characterized in that it is a complex of protein and at least one selected from picocyanobilirin, picoerythrobilin, picourovilin, picoviolobilin. The photochromic material alone is converted to a photoreceptor that absorbs ultraviolet rays when exposed to ultraviolet rays (UV A) and exhibits absorption bands of visible or near infrared rays (IR-A), and the converted visible and near infrared photoreceptors When exposed to visible or near infrared light, the visible light or near infrared light may be absorbed and converted into a photoreceptor representing an absorption band in the ultraviolet region. However, the conversion process is effectively performed by forming a complex with a protein.

The protein that binds to the photochromic material is preferably a GAF protein found in cyanobacteria, and the GAF protein forms a double thioester linkage with a chromophore of the photochromic material so that photochromatility is effectively achieved. do.

The GAF protein-photochromic substance complex, in particular the GAF protein-phycocyanobilin complex, can be obtained separately from cyanobacteria, and can also be produced and isolated using recombinant E. coli in another method. (Gamberta GA, Lagarias JC 2001. Genetic engineering of phytochrome biosynthesis in bacteria.Proc. Natl. Acad. Sci. USA 98: 10566-10571).

In order to employ | adopt said photochromic material or photochromic material protein complex as a composition for sunscreen, it is preferable that it is water-soluble.

The photochromic substance or photochromic substance-protein complex is in a formulation selected from lotions, creams, powders, emulsions and sprays. The sunscreen composition of the formulation may contain any of the ingredients conventionally used in general cosmetics. The components are especially chosen from fats, preservatives, stabilizers, neutralizers, water thickeners, fatty phase thickeners, fillers, fragrances, active agents, surfactants, antioxidants, film-forming polymers, plasticizers and mixtures thereof.

The regenerative sunscreen composition comprising the photochromic material or the photochromic material protein complex according to the present invention has the effect of overcoming the limitation of the use time through irreversible photoreaction of the material causing the existing sunscreen effect and maximizing the practical use time. Seems. In addition, by using materials obtained from proteins derived from living organisms rather than using general organic materials, by securing the stability of the sunscreen composition and facilitating cleaning by retaining water-soluble properties in water, existing environmental aspects Effective compared to the product. This results in a remarkably improved reproducibility, environmentally friendly, and excellent products that can also be seen as an effective barrier to UV A.

1 is a diagram illustrating a potential energy diagram in which a photoreaction of a photochromic material occurs.

2 is a diagram showing two absorbance spectra according to the state of the GAF protein-phycocyanobilin complex.

Figure 3 is a diagram showing the change in absorbance spectrum with irradiation time at the irradiation light wavelength of the GAF protein-phycocyanobilin complex.

The present invention relates to the development of a new type of regenerative sunscreen composition comprising a photochromic material or a photochromic material protein complex, and uses a material having a modification upon irradiation with light. The photochromic material or the photochromic material protein complex absorbs it when exposed to ultraviolet rays as shown in FIG. 1 and induces an absorption band in visible or near infrared rays, and on the contrary, induces an absorption band in ultraviolet rays when exposed to visible or near infrared rays. It has This method overcomes the limitations of the use time of the sunscreen composition due to permanent alteration of the photochromic material or photochromic material protein complex caused by the irreversible reaction of the material causing the sunscreen effect. It aims to maximize the use time.

As mentioned above, the regeneration in the present invention indicates that absorption band-induced phenomena at the time of exposure to ultraviolet light, visible light, and near infrared light of the photochromic material or the photochromic material protein complex is not an irreversible reaction but a reversible characteristic. It means a phenomenon. In everyday outdoor activities, the skin is rarely exposed to ultraviolet light for a long time and is often exposed repeatedly for a short time. In this condition, namely, when the UV A exposure is limited, the photoreceptor applied to the skin is often exposed to the visible region, and at this time, the conversion from the E-form to the Z-form is performed to regenerate the sunscreen composition. Have.

One example of the sunscreen composition according to the present invention to achieve the above object is that by using a photochromic material or a photochromic material protein complex, the absorption band is induced in visible or near infrared by absorbing ultraviolet light when exposed to ultraviolet light and visible Absorption bands are induced in the ultraviolet region when exposed to light or near infrared rays.

When irradiating UV A or visible light, the change in absorbance (OD) according to the exposure time can be expressed by the following differential equation.

dOD _Z-form / dt = 1 / τ OD _Z-form

OD _Z-form to exp (-t / τ)

Therefore, if the constant τ at this time is determined experimentally, the effective amount of UV protection can be calculated, and the appropriate exposure time can be derived using this.

The present inventors have developed a sunscreen composition comprising a photochromic substance or photochromic substance protein complex derived from an organism, thereby obtaining a long-term sunscreen effect. It was confirmed that this is due to the intrinsic characteristics of the photochromic material for the wavelength of light, thereby completing the present invention. A sunscreen composition comprising a photochromic substance or photochromic substance protein complex derived from an organism is water soluble and is very easy to clean, and its utilization may be very excellent due to the increased blocking effect of UV A related to skin aging.

Looking in more detail with respect to the sunscreen composition used in the present invention can be used in the configuration of a commonly used sunscreen composition as follows.

In general, the sunscreen composition used together with the photochromic colorant and the ultraviolet absorbent including the derivative may include various components together according to the purpose of use. The absorbent may be present in an amount of 0.01 to 30% by weight based on the total weight of the composition. Monochromatic colorants selected from monochromatic dyes, monochromatic pigments, and combinations thereof used in the sunscreen composition may be present in a proportion of 0.01 to 60% by weight of the total weight of the composition.

It may also contain any ingredients conventionally used in general cosmetics. These ingredients are especially fatty substances, preservatives, stabilizers, neutralizers, water thickeners (polysaccharide biopolymers, synthetic polymers) or fatty thickeners such as clays, fillers, fragrances, hydrophilic or lipophilic active agents, surfactants, oxidation Inhibitors, film-forming polymers and mixtures thereof. The amount of the various components is in the amount conventionally used in the art, for example 0.01 to 30% by weight relative to the total weight of the composition. The composition may also contain water in a concentration ranging from 0 to 95% by weight relative to the total weight of the composition, or an organic solvent that may be up to 90%. The filler can be introduced to modify the texture of the composition. They may be present in a proportion of 0 to 35% by weight relative to the total weight of each composition. Film-forming polymers include nitrocellulose, cellulose acetobutyrate, polyvinyl butyral, alkyd resins, which may be present in amounts ranging from 0 to 40% by weight relative to the total weight of the composition. The composition may also contain a plasticizer that can be added to the film-forming polymer to adjust the flexibility of the polymer film without weakening its physical strength. Plasticizers include dimethoxyethyl phthalate, glyceryl benzoate and mixtures thereof, and can generally be present in amounts ranging from 0 to 30% by weight relative to the total weight of the composition.

The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and variations without departing from the essential characteristics of the present invention.

The sunscreen compositions of the invention may be prepared in the lotion, cream, powder, emulsion and spray formulations that are conventionally prepared. Hereinafter, the present invention will be described in detail with reference to preferred embodiments. However, the scope of the present invention is not limited to these examples.

(Example)

In this example, GAF protein-phycocyanobilin (PCB) complex was extracted from cyanobacteria and used. In addition, the GAF protein-phycocyanobilin complex was produced and isolated using recombinant Escherichia coli as another method. (Gamberta GA, Lagarias JC 2001. Genetic engineering of phytochrome biosynthesis in bacteria.Proc. Natl. Acad Sci. USA 98: 10566-10571).

Absorbance measurement in this Example was carried out using a UV-1601 spectrometer manufactured by Shimadzu, Japan, at a concentration of about 10 μM based on phycocyanobilin.

(Example 1)

In order to confirm the regeneration of the GAF protein-phycocyanobilin complex extracted from the organism, the photoreceptor of the Z-form of the GAF protein-phycocyanobilin complex is identified as E-form when it receives light corresponding to UV A. While the quantum efficiency is changed with Φ _Z-to-E , when it is exposed to visible light, the absorbance spectrum is investigated by irradiating UV A light and visible light in order to confirm that it is changed to the original Z-form with Φ _E-to-Z . Was measured and shown in FIG.

2 is an absorbance spectrum of two states of phycocyanobilin as described above. In Figure 2 (a) shows a thermally stable state Z-form, Figure 2 (b) shows an E-form state. In the case of Z-form, it can be seen that the absorption band reaches the maximum value in the ultraviolet A (UV A) region corresponding to 320 to 400 nm to be implemented in the present invention. On the other hand, in the case of E-form, the absorption band developed well around 560 nm, which is the visible light region, showing the maximum value, and also it can be seen that there is some light absorption in the UV A region.

(Example 2)

Absorbance spectra in two states of the GAF protein-phycocyanobilin complex and the absorbance spectra according to the irradiation time versus the wavelength of the irradiated light were measured and shown in FIG. 3.

In the case of irradiating UV A in FIG. 3 (a), it can be seen that the absorbance of the ultraviolet region decreases with time and the absorbance of the visible region increases, and in the case of irradiating visible rays in FIG. As a result, the absorbance of the ultraviolet region increases and the absorbance of the visible region decreases.

Table 1 shows the results of measuring the change in OD _Z-form over time at 325 nm wavelength UV.

Table 1

Time (sec)	OD (wavelength: 325 nm)
0	0.415
20	0.400
40	0.395
60	0.390
120	0.380
240	0.370
480	0.350
960	0.320
1920	0.300
2520	0.295

From the results of Examples 1 and 2 above, the photochromic material or photochromic material-protein complex is self-renewal and the limit of the use time through the irreversible photoreaction of the material causing the existing UV blocking effect To overcome the problem and to maximize the practical use time, including a photochromic material, it is possible to secure biological stability as a protein derived from the organism.

In addition, the results of light absorption measurement and absorbance measurement of the UV A region and the visible light region using the photochromic material having the reproducibility of Example 1 and Example 2 include the photochromic material used according to the present invention. In the case of the sunscreen composition, it means that the use time of the irreversible photoreaction compared to the conventional sunscreen composition is overcome, and that the actual use time is surprisingly increased.

Claims

It includes a photochromic substance that absorbs ultraviolet rays when exposed to ultraviolet rays (UV A) and is converted into visible and near infrared photoreceptors, and the converted visible and near infrared photoreceptors are converted to ultraviolet photoreceptors when exposed to visible or near infrared rays. UV blocking composition.
The method of claim 1,

The photochromic material is a UV-blocking composition exhibiting a Z-form having an absorption band maximum in the UV region and an E-form having an absorption band maximum in the visible region.
The method of claim 2,

The photoreceptors of the visible and near-infrared photoreceptors are converted to E-form when exposed to ultraviolet rays, and the photoreceptors of the E-form are converted to Z-form upon exposure to visible or near-infrared rays. Composition.
The method of claim 1,

The photochromic material is a composition for sun protection, characterized in that derived from living organisms.
The method of claim 4, wherein

A composition for blocking sun, characterized in that to form a complex of the photochromic material and GAF protein.
The method of claim 5,

The complex of the photochromic substance and GAF protein is at least one selected from phycocyanobilin, phycoerythrobine, pico eurobline, picoviolobiline and a complex of GAF protein.
The method of claim 4, wherein

The photochromic material is a UV-blocking composition wherein the ultraviolet light receptor-visible light and the near-infrared light receptor are ultraviolet-orange, ultraviolet-blue, and ultraviolet-green.
The method of claim 6,

The complex of the photochromic material and GAF protein is a sunscreen composition wherein the GAF protein found in cyanobacteria has a double thioester linkage with the chromophore of the photochromic material.
The method of claim 6,

The photochromic substance or photochromic substance and GAF protein complex is a water-soluble composition, characterized in that the water-soluble.
The method of claim 6,

The photochromic material or photochromic material and GAF protein complex is a composition for sun protection, characterized in that included in the formulation selected from lotions, creams, powders, emulsions and sprays.