JP2009256213A - Stabilizer for suppressing photolysis of dibenzoylmethane derivative and its use, and stabilizing method of dibenzoylmethane derivative-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new stabilizer efficiently suppressing photolysis of a dibenzoylmethane derivative incorporated with a cosmetic and the like as an ultraviolet absorber and its use, and a stabilizing method of a dibenzoylmethane derivative-containing composition. <P>SOLUTION: The stabilizer for suppressing photolysis of a dibenzoylmethane derivative comprises fullerenes as an effective ingredient. Incorporation of the stabilizer for suppressing photolysis with the dibenzoylmethane derivative-containing composition such as a cosmetic, a skin care preparation for external use and the like stabilizes the composition against light. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a stabilizer for photodecomposition suppression of a dibenzoylmethane derivative, its use, and a method for stabilizing a dibenzoylmethane derivative-containing composition.

  Ultraviolet rays contained in sunlight are classified into 400 nm to 320 nm long wavelength ultraviolet rays (UV-A), 320 nm to 280 nm medium wavelength ultraviolet rays (UV-B), and less than 280 nm short wavelength ultraviolet rays. Among these, ultraviolet rays having a wavelength of 290 nm or less are absorbed by the ozone layer and do not reach the earth's surface.

  Ultraviolet rays in the UV-A and UV-B regions that reach the earth's surface have various effects on human skin. Among the ultraviolet rays reaching the ground, UV-B forms erythema and water bubbles on the skin and promotes melanin formation. On the other hand, UV-A causes browning of the skin, promotes the reduction of skin elasticity and wrinkles, or enhances this reaction for some patients, and further causes phototoxicity or photoallergic reaction. It can even be a cause. Various UV protection products have been developed to protect the skin from the toxicity of such UV rays.

  As such UV protection products, not only sunscreens for sunbathing but also cosmetic-type products for daily use such as lotions and skin creams are commercially available.

Currently, many UV protection agents are used in cosmetics and the like, but as organic UV-A absorbers, dibenzoylmethane derivatives, particularly avobenzone (4-tert-butyl-4′-methoxydibenzoylmethane) Is widely used in terms of functionality and safety (see Patent Documents 1 and 2).
US Pat. No. 4,387,089 US Pat. No. 4,489,057 US Pat. No. 5,576,354 US Pat. No. 5,587,150

  However, when used individually in sunscreen products, etc., most dibenzoylmethane derivatives tend to be photodegraded when exposed to ultraviolet light, so their UV-A absorption effect may be reduced. Are known.

  Therefore, products containing dibenzoylmethane derivatives are generally relatively difficult to formulate due to their insufficient light stability. In order to stabilize a product containing such a dibenzoylmethane derivative, blending of octocrylene (2-ethylhexyl 2-cyano-3,3-diphenylacrylate) has been performed (Patent Document 3). 4), further effective stabilization methods for dibenzoylmethane derivatives have been desired from the viewpoint of diversification of formulations.

  The present invention has been made in view of the circumstances as described above, a novel stabilizer capable of efficiently suppressing photodecomposition of a dibenzoylmethane derivative blended as a UV absorber in cosmetics and the like, and uses thereof It is another object of the present invention to provide a method for stabilizing a dibenzoylmethane derivative-containing composition.

  The present invention is characterized by the following in order to solve the above problems.

  1st: The stabilizer for photolysis suppression of the dibenzoylmethane derivative characterized by containing fullerene as an active ingredient.

  Second: The stabilizer for photolysis suppression of the first dibenzoylmethane derivative, wherein the dibenzoylmethane derivative is 4-tert-butyl-4-methoxydibenzoylmethane.

  Third: A dibenzoylmethane derivative-containing composition comprising an effective amount of a dibenzoylmethane derivative as an ultraviolet absorber and the first or second stabilizer for photodegradation.

  Fourth: A skin external preparation comprising the third dibenzoylmethane derivative-containing composition.

  Fifth: A cosmetic comprising the third dibenzoylmethane derivative-containing composition.

  Sixth: A method for stabilizing a dibenzoylmethane derivative-containing composition, the method comprising stabilizing a dibenzoylmethane derivative-containing composition against light, wherein the composition contains a fullerene.

  According to the stabilizer of the present invention, photolysis of a dibenzoylmethane derivative blended as a UV absorber in cosmetics and the like can be efficiently suppressed.

  According to the external preparation for skin and cosmetics of the present invention, the photodecomposition of the dibenzoylmethane derivative blended as an ultraviolet absorber can be efficiently suppressed and the photostability can be increased.

  According to the stabilization method of the present invention, the light stability of the dibenzoylmethane derivative-containing composition can be enhanced by blending fullerenes.

  Hereinafter, the present invention will be described in detail.

In the present invention, the fullerenes used as the photodecomposition suppression stabilizer for the dibenzoylmethane derivative may be one or more of fullerene, a fullerene derivative, a fullerene inclusion compound, a fullerene complex, or a salt thereof. Among these, fullerenes include C ₃₂ , C ₄₄ , C ₅₀ , C ₆₀ , C ₅₈ , C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C _96, etc. ₆₀ alone _or, it is preferably 60 mass% or more content of _{C 60.}

  Examples of the fullerene derivative include those in which a modifying group such as a hydroxyl group is bonded to a carbon atom of the fullerene skeleton.

  Examples of the compound that includes or complexs fullerene include organic oligomers, organic polymers, cyclodextrins that can form inclusion compounds and inclusion complexes, crown ethers, and similar compounds thereof. Specifically, for example, polyvinylpyrrolidone inclusion fullerene, γ-cyclodextrin inclusion fullerene, polyethylene glycol-modified fullerene can be used.

  In the present invention, the dosage form of the stabilizer for photolysis suppression of a dibenzoylmethane derivative containing fullerenes as an active ingredient is not particularly limited, and various forms containing the above fullerenes, for example, liquid, solid However, from the viewpoint of easy incorporation into the dibenzoylmethane derivative-containing composition, an aqueous solution of fullerene that is water-solubilized by inclusion or complexing is preferable.

  The stabilizer for photodegradation suppression of the present invention is useful for photostably protecting against harmful effects of ultraviolet rays particularly on human skin by blending with a composition containing a dibenzoylmethane derivative.

  Specific examples of the dibenzoylmethane derivatives include UV-A absorbing dibenzoylmethane derivatives that absorb ultraviolet rays having a wavelength of 320 to 400 nm, such as 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, and 4-isopropyldibenzoyl. Methane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropylbenzoylmethane, 4-tert-butyl-4'-methoxydibenzoyl Methane, 2-methyl-5-isopropyl-4′-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane, 2,4-dimethyl-4′-methoxydibenzoylmethane, 2,6-dimethyl-4'-tert-butyl-4 Such as methoxy dibenzoylmethane can be mentioned. Of these, 4-tert-butyl-4'-methoxydibenzoylmethane is preferable.

  The dibenzoylmethane derivative is an effective amount that protects against broad-spectrum ultraviolet radiation alone or in combination with other UV protection agents that may be present in the composition, avoiding serious side effects (such as undue toxicity or allergic reactions) When used as a skin external preparation or cosmetic, it is preferably 0.01 to 30% by mass, more preferably 0.1 to 6% by mass of dibenzoyl based on the total amount of the composition. A methane derivative is blended. The compounding amount of the dibenzoylmethane derivative is appropriately adjusted depending on the desired sun protection factor, that is, the SPF of the composition, the desired UV-A protection level, and the like.

  The blending amount of fullerenes to the dibenzoylmethane derivative-containing composition of the present invention is such that the mass ratio to the dibenzoylmethane derivative (fullerenes / dibenzoylmethane derivative) from the viewpoint of effectively suppressing photolysis of the dibenzoylmethane derivative. Is preferably 0.00001 or more, more preferably 0.001 or more.

  The dibenzoylmethane derivative-containing composition of the present invention appropriately protects against harmful effects of ultraviolet rays, particularly in skin external preparations or cosmetics. The composition of the present invention can be suitably used as a sunscreen that protects human skin from the harmful effects of ultraviolet rays such as sunburn and premature aging of the skin.

The dibenzoylmethane derivative-containing composition of the present invention is used as a skin external preparation by topically applying a safe and effective amount of the composition to the skin in order to protect the skin from ultraviolet rays. The amount applied depends on the desired degree of UV protection, but for example about 0.5 to 25 mg of composition per cm ^{2 of} skin is applied.

  The composition of the present invention contains a dibenzoylmethane derivative, fullerenes, and an appropriate carrier as an optional component. Appropriate carriers can be selected according to the purpose already known to those skilled in the art, for example, those that can be suitably used for skin, hair, nails, animal skin, fur, automobiles, cloth, ships, In addition, those that can be appropriately inserted into plastics, metals, etc. are used as the carrier.

  Such carriers can be suitably applied to the skin (eg sunscreen, cream, emulsion, lotion, mask, etc.); hair and fur (eg shampoo, hair set, treatment, etc.); nails (eg nail polish, treatment, etc.) Those are preferred.

  In a preferred embodiment, the carrier is one that can be suitably applied to the skin, i.e., toxic, incompatible, unstable, allergic reaction when the carrier and its components are in contact with the skin, hair, fur, nails. It can be used properly without causing any problems. As such carriers, those already known to those skilled in the art can be used, including one or more liquid or solid filler diluents or excipients that can be suitably used for skin, hair, fur and nails. Can be mentioned.

  The amount of the carrier depends on the concentration of the dibenzoylmethane derivative, fullerenes, and other optional components different from the carrier (for example, other active ingredients), but the composition of the present invention is preferable to the total amount of the composition. Contains 20 to 99.8% carrier, more preferably 50 to 99%.

  The compositions of the present invention are formulated into various product types such as creams, waxes, pastes, lotions, emulsions, mousses, gels, oils, tonics, sprays and the like. These product types include hand and body lotions, cold creams, facial moisturizers, acne prevention agents, topical analgesics, makeup cosmetics such as foundations, eye shadows, lipsticks, etc., and coatings (eg paints, varnishes, polishes) , Adhesives, etc.), household items (eg detergents, cleansers, fabric conditioners, etc.), car and marine care products (eg waxes), hair care and styling products (eg shampoos, conditioners, gels, mousses, sprays, etc.), Used in many applications such as topical animal care products (eg shampoos, conditioners, skin treatments, etc.).

  The composition of this invention can contain the various other components generally used in the range which does not impair the effect of this invention. Specific examples of such components include abrasives, absorbents, astringents, acne prevention agents, anti-caking agents, antifoaming agents, antibacterial agents, antioxidants, binders, biological additives, buffers, Bulking agents, chelating agents, chemical additives, colorants, cosmetic biocides, denaturants, external analgesics, polymer and other film forming agents or forming materials, opacifiers, pH adjusters, propellants, reducing agents Sequestering agents, skin bleaching and whitening agents, skin conditioning agents, skin sedation and / or treatment agents, skin treatment agents, thickeners, vitamins and their derivatives.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. In the following, “%” represents “% by mass” unless otherwise specified.
<Example 1>
The ultraviolet irradiation test of the 4-tert-butyl-4'-methoxydibenzoylmethane containing composition which mix | blended fullerene was done. As a fullerene sample, RadicalSponge (Vitamin C60 Bioresearch Corp., registered trademark) was used. Radical Sponge is a mixture of mixed fullerenes (C ₆₀ , C ₇₀ ) in PVP and then dissolved in 1,3-butylene glycol and water. The composition is 10% PVP, 75% 1,3-butylene glycol. , Water 15%, C ₆₀ 200 ppm or more. RadicalSponge1% is contained _{C 60} of about 2 ppm.

  A 2% ethanol solution of 4-tert-butyl-4′-methoxydibenzoylmethane (Wako Pure Chemical Industries, Ltd. 020-11271) was prepared, and Radical Sponge 1% and 5% were added thereto. What added 2% 2-cyanohexyl 2-cyano-3,3-diphenylacrylate (Tokyo Kasei C0968, Octocrylene) used as a stabilizer for photolysis suppression of butyl-4'-methoxydibenzoylmethane Prepared as test solution.

Each test solution was applied to a glass plate and dried, and then a UV irradiation test was performed. Using an ultraviolet irradiation light source having a wavelength of 230 to 400 nm (emission spectrum is shown in FIG. 3), UV-A irradiation was performed under the conditions of ultraviolet intensity: 365 nm, 23.6 mW / cm ² (irradiation time: 5, 10, 30 minutes).

The residual amount of 4-tert-butyl-4′-methoxydibenzoylmethane after ultraviolet irradiation was quantified by high performance liquid chromatography (HPLC). The HPLC analysis conditions are as follows.
HPLC column Cosmosil 5C18MSII (4.6 mm × 150 mm)
Developing solvent Methanol 90%
Flow rate 1mL / min
Detection UV 360nm
The result of the UV irradiation test is shown in FIG. The vertical axis | shaft of FIG. 1 has shown the relative value (%) when 4-tert-butyl-4'-methoxydibenzoylmethane (abovobenzone) 2% is set to 100. FIG. The amount of decomposition by adding 5% of Radical Sponge was decomposed by about 40% when Radical Sponge was not added (Control) to ultraviolet irradiation of 4-tert-butyl-4′-methoxydibenzoylmethane. Was suppressed to about 15%.

Moreover, Radical Sponge 5% (C ₆₀ : about 10 ppm) is superior to octocrylene at a concentration (2%) usually incorporated in sunscreens, and is superior in inhibiting decomposition to 4-tert-butyl-4′-methoxydibenzoylmethane. Showed the effect. From this result, it has been clarified that fullerene works as a decomposition inhibitor of 4-tert-butyl-4′-methoxydibenzoylmethane, which exceeds octocrylene even in a very small amount.
<Example 2>
A visible light irradiation test of a 4-tert-butyl-4′-methoxydibenzoylmethane-containing composition blended with fullerene was performed.

  A Radial Sponge was used as the fullerene sample. Prepare a 2% ethanol solution of 4-tert-butyl-4'-methoxydibenzoylmethane, and add 1% of Radical Sponge and 1% of this solution and 2% of octocrylene as test solutions. did.

  Each test solution was applied to a glass plate and dried, and then a visible light irradiation test was performed. Using a fluorescent lamp (National, Parlook FL15EX-N, 15 Watts: emission spectrum is shown in FIG. 4) as a visible light irradiation light source, visible light was irradiated from an irradiation distance of 40 cm (irradiation time: 1, 2, 3). Day).

  The residual amount of 4-tert-butyl-4'-methoxydibenzoylmethane after visible light irradiation was quantified by high performance liquid chromatography (HPLC). The HPLC analysis conditions are the same as in Example 1.

The result of the visible light irradiation test is shown in FIG. In contrast to visible light irradiation to 4-tert-butyl-4′-methoxydibenzoylmethane (Avobenzone), it was decomposed by about 20% in 3 days in the absence of Radical Sponge, whereas Radical Sponge 1% (C ₆₀ : About 10 ppm) was added to suppress decomposition. Moreover, 1% addition of Radical Sponge showed a higher decomposition inhibitory action than 2% addition of Octocrylene.
<Example 3>
An ultraviolet irradiation test was conducted under the same conditions as in Example 1 except that the fullerene concentration was changed. A 2% ethanol solution of 4-tert-butyl-4′-methoxydibenzoylmethane was prepared, to which Radical Sponge 2%, 3%, 4%, 7.5%, 10% were added, and 10% octocrylene was added. % Was added as a test solution. The UV irradiation conditions and the HPLC analysis conditions are the same as in Example 1.

The results of the UV irradiation test are shown in FIG. It has been clarified that the effect of suppressing the photolysis of 4-tert-butyl-4′-methoxydibenzoylmethane increases depending on the concentration of Radical Sponge. Octocrylene usually has a blending concentration of 10% as the upper limit, but Radical Sponge 10% gave almost the same result.
<Reference Example 1>
Since Radical Sponge contains PVP and 1,3-butylene glycol, it was examined whether these suppressed the decomposition of 4-tert-butyl-4′-methoxydibenzoylmethane. A solution containing PVP corresponding to Radical Sponge 10% and a solution containing 1,3-butylene glycol (PVP 1%, 1.3 butylene glycol 7.5%) was used under the same conditions as in Examples 1 and 3. The test was conducted.

  The result of the UV irradiation test is shown in FIG. Even when PVP corresponding to Radical Sponge 10% and 1,3-butylene glycol were added, the decomposition of 4-tert-butyl-4'-methoxydibenzoylmethane was not suppressed.

  From the above examples, the decomposition of 4-tert-butyl-4'-methoxydibenzoylmethane by UV irradiation was suppressed by 5% or 1% of Radical Sponge. Under UV irradiation, 5% Radical Sponge showed a superior decomposition inhibition effect of 4-tert-butyl-4'-methoxydibenzoylmethane than 2% octocrylene.

  In addition, under visible light (400 to 720 nm), 1% or 0.1% Radical Sponge suppresses the decomposition of 4-tert-butyl-4′-methoxydibenzoylmethane and is superior to 2% octocrylene. Degradation inhibitory effect was shown.

Moreover, 10% octocrylene and 10% Radical Sponge showed the same decomposition suppression effect of 4-tert-butyl-4′-methoxydibenzoylmethane. 10% Radical Sponge contains about 20 ppm C ₆₀ , which has the same performance as 10% octocrylene, thus protecting 4-tert-butyl-4′-methoxydibenzoylmethane in smaller amounts It became clear that it was an effective ingredient.

3 is a graph showing the results of a UV irradiation test of Example 1. 6 is a graph showing the results of a visible light irradiation test of Example 2. It is an emission spectrum of an ultraviolet irradiation light source. It is an emission spectrum of a visible light irradiation light source. 6 is a graph showing the results of a UV irradiation test of Example 3. 6 is a graph showing the results of a UV irradiation test of Reference Example 1.

Claims (6)

  A stabilizer for inhibiting photolysis of a dibenzoylmethane derivative, comprising fullerenes as an active ingredient.   The stabilizer for photolysis suppression of a dibenzoylmethane derivative according to claim 1, wherein the dibenzoylmethane derivative is 4-tert-butyl-4-methoxydibenzoylmethane.   A dibenzoylmethane derivative-containing composition comprising an effective amount of a dibenzoylmethane derivative as an ultraviolet absorber and the photolysis-inhibiting stabilizer according to claim 1 or 2.   An external preparation for skin comprising the dibenzoylmethane derivative-containing composition according to claim 3.   A cosmetic comprising the dibenzoylmethane derivative-containing composition according to claim 3.   A method for stabilizing a dibenzoylmethane derivative-containing composition, the method comprising stabilizing a dibenzoylmethane derivative-containing composition against light, comprising adding fullerenes to the composition.