JP2008214341A - Ultraviolet-screening composition and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet-screening composition having a wide wavelength range of ultraviolet ray absorbing performance together with high safety and a high efficiency of the ultraviolet ray absorbing performance. <P>SOLUTION: The composition comprises a specific organic compound combined with an ultraviolet ray absorbing compound (excluding the specific organic compound) and/or an inorganic ultraviolet ray scattering compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ultraviolet protection composition, and cosmetics for use, and further to a novel organic compound.

  Inorganic compounds and organic compounds having ultraviolet absorbing ability and scattering ability are known, and in particular, inorganic compounds have been blended in a wide variety of cosmetics.

  As inorganic ultraviolet scattering agents, fine particles such as zinc oxide and titanium oxide are used. They have the ability to absorb ultraviolet rays over a wide wavelength range of UV-A and UV-B, are insoluble in water and cosmetic general-purpose oils, and have high safety due to low transdermal absorbability. However, when such an inorganic compound is blended in a large amount, whitening occurs or the skin becomes unsuitable, and wrinkles and spots on the skin are caused by free radicals generated by the catalytic action of the compound. A problem that an aging phenomenon occurs has been reported (Non-Patent Document 1).

  On the other hand, as organic ultraviolet absorbers, compounds such as salicylic acid, benzophenone, paraaminobenzoic acid, and methoxycinnamic acid are used. They have absorption ability in the UV-B region of 280 to 320 nm, are liquid or soluble in general-purpose oils, and are relatively easy to be formulated into preparations, and have a high extinction coefficient, that is, UV absorption efficiency. Is characterized by high. However, it has been reported that the above compounds cause skin irritation and allergy (Non-patent Document 1).

There has been a demand for an ultraviolet protection composition that has both ultraviolet absorption ability and high safety in a wide wavelength range, which is a feature of inorganic ultraviolet scattering agents, and high ultraviolet absorption efficiency, which is a feature of organic ultraviolet absorbers (patents). References 1, 2).
International Publication No. 99/66896 Japanese Patent Laid-Open No. 11-116457 “Sunscreen and Dermatology”, Fragrance Journal, 1993, p359

  An object of the present invention is to provide an ultraviolet protection composition having ultraviolet absorption ability in a wide wavelength range, high safety, and high efficiency ultraviolet absorption ability.

  As a result of intensive studies, the present inventors have found that the above problem can be achieved by combining a specific organic compound with an ultraviolet absorbing compound (excluding a specific organic compound) and / or an inorganic ultraviolet scattering compound. The present invention has been completed.

That is, the present invention includes the following aspects.
[1] An ultraviolet ray containing an organic compound represented by the following general formula (1) and / or (2) and an organic ultraviolet absorbing compound (excluding the general formulas (1) and (2)) and / or an inorganic ultraviolet scattering compound Defensive composition.

(In the formula, each R ₁ independently represents an OH group, a halogen atom, a linear or branched C _1-6 alkyl group optionally containing a silicon atom, and a linear or branched C _1-6 alkoxy optionally containing a silicon atom. Represents a straight-chain or branched C _1-5 alkoxycarbonyl group, or a linear or branched C _1-6 alkylsulfonamide group optionally containing a silicon atom or an amino functional group, q is an integer of 0 to 4 R ₂ represents hydrogen or an OH group, R ₃ represents a linear or branched saturated alkyl having 2 to 8 carbon atoms, M ^{n +} represents a polyvalent metal ion, and n is an integer of 2 to 3 Represents.)
[2] The ultraviolet protection composition according to [1], wherein the inorganic ultraviolet scattering compound is selected from titanium oxide and zinc oxide.
[3] The ultraviolet protection composition according to [1], wherein the organic ultraviolet absorbing compound (excluding the general formulas (1) and (2)) is selected from cinnamic acid derivatives.

[4] The ultraviolet protective agent according to [1] to [3], further comprising an organic powder represented by the following general formula (3).
(In the formula, R4 represents linear saturated alkyl having 11 to 17 carbon atoms.)
[5] A cosmetic comprising the ultraviolet protection composition according to [1] to [4].

[6] An organic compound represented by the following general formula (1).
(In the formula, each R ₁ independently represents an OH group, a halogen atom, a linear or branched C _1-6 alkyl group optionally containing a silicon atom, and a linear or branched C _1-6 alkoxy optionally containing a silicon atom. Represents a straight-chain or branched C _1-5 alkoxycarbonyl group, or a linear or branched C _1-6 alkylsulfonamide group optionally containing a silicon atom or an amino functional group, q is an integer of 0 to 4 R ₂ represents hydrogen or an OH group, M ^{n +} represents a polyvalent metal ion, and n represents an integer of 2 to _3. )

  The UV protection composition of the present invention exhibits a synergistic effect on UV protection (SPF value or PFA value) when used in combination with a specific organic compound and a conventional inorganic UV scattering agent and / or organic UV absorber. Therefore, it is possible to prepare an ultraviolet protective agent such as a cosmetic with a smaller blending amount than before. For this reason, whitening that is a defect of the conventional inorganic ultraviolet scattering agent and irritation to the skin that is a defect of the conventional organic ultraviolet absorber are reduced. Furthermore, by using a specific organic powder in combination, it is possible to provide a cosmetic powder that does not aggregate at the time of formulation and has a high UV-blocking effect, and a cosmetic that contains it and has good stability and a feeling of use. .

The organic compound of the present invention is represented by the following general formulas (1) and (2).

(In the formula, each R ₁ independently represents an OH group, a halogen atom, a linear or branched C _1-6 alkyl group optionally containing a silicon atom, and a linear or branched C _1-6 alkoxy optionally containing a silicon atom. Represents a straight-chain or branched C _1-5 alkoxycarbonyl group, or a linear or branched C _1-6 alkylsulfonamide group optionally containing a silicon atom or an amino functional group, q is an integer of 0 to 4 R ₂ represents hydrogen or an OH group, R ₃ represents a linear or branched saturated alkyl having 2 to 8 carbon atoms, M ^{n +} represents a polyvalent metal ion, and n is an integer of 2 to 3 Represents.)
In the general formulas (1) and (2), R ₁ is an OH group, a linear or branched C _1-6 alkoxy group containing a silicon atom, or a linear chain, from the viewpoint of good ultraviolet absorption ability in a wide range. Or a branched C _1-5 alkoxycarbonyl group is preferable, an OH group or a linear chain optionally containing a silicon atom or a branched C _1-6 alkoxy group is more preferable, and a linear chain optionally containing a silicon atom from the viewpoint of insolubility. Or a branched C _1-6 alkoxy group is particularly preferred. Among “the linear or branched C _1-6 alkoxy group optionally containing a silicon atom” referred to by R ₁ , a C _1-3 alkoxy group is more preferable, and a methoxyl group is particularly preferable.

The “amino functional group” in the “linear or branched C _1-6 alkylsulfonamido group containing an amino functional group” referred to by R ₁ in the general formulas (1) and (2) is, for example, a methylamino group, diethyl A tilamino group, a 2-ethylhexylamino group, and the like.

  Q in the general formulas (1) and (2) is preferably 0 to 3 from the viewpoint of good ultraviolet absorption ability in a wide range, and more preferably 0 to 2 from the viewpoint of availability of raw materials and insolubility.

R ₂ in the general formulas (1) and (2) is preferably a hydrogen atom from the viewpoint of availability of raw materials and ease of preparation.

  M in the general formula (1) is preferably magnesium, calcium, titanium, zirconium, zinc or iron, and more preferably magnesium, zinc or calcium from the viewpoint of good ultraviolet absorption ability in a wide range, and is insoluble. In view of the above, zinc is particularly preferable. N in the general formula (1) is selected from integers of 2 to 3, and 2 is preferable.

R ₃ in the general formula (2) includes an ethyl group, a butyl group, a t-butyl group, an isobutyl group and a 2-ethylhexyl group, and a 2-ethylhexyl group is preferable.

  R4-CO in the general formula (3) includes a lauroyl group, a myristoyl group, a palmitoyl group, and a stearoyl group, but a lauroyl group is preferable from the viewpoint of dispersibility and feeling of use.

The organic compound of the general formula (1) (hereinafter also referred to as the compound (1)) can be produced, for example, by the following steps.
(Step 1) A step of subjecting a benzylidene hydantoin as a raw material to a Michael addition reaction with an alkyl acrylate using a catalyst to obtain a benzylidene dioxoimidazolidine propionic acid alkyl ester.
(Step 2) A step of heating a benzylidene dioxoimidazolidine propionate alkyl ester with a base in a solution to obtain a benzylidene dioxoimidazolidine propionate solution.
(Step 3) A step of obtaining a compound (1) by mixing a benzylidene dioxoimidazolidine propionate solution with an inorganic polyvalent metal salt / or organic polyvalent metal salt solution and performing crystal separation.

  The benzylidene hydantoin used in Step 1 is a known compound. You may refer suitably for a well-known technique for the reaction conditions of a Michael addition reaction.

  The base used in step 2 is not particularly limited as long as the desired reaction proceeds, and specific examples include metal hydroxides such as sodium hydroxide and potassium hydroxide, and organic salts such as ethanolamine and diethanolamine. . You may use these 1 type or in mixture of 2 or more types. In view of easy salt exchange with the polyvalent metal salt in the next step, sodium hydroxide and potassium hydroxide are preferable.

  Various conditions for the reaction in step 2 are not particularly limited as long as the target compound can be obtained. For example, the pH is about 8.0 to 12.0. For example, the solvent is not particularly limited, and is preferably water or methanol. Further, for example, the reaction temperature is not limited and is usually room temperature to 100 ° C., and preferably 50 to 80 ° C. in consideration of the reaction time and the solvent used for the reaction.

  In Step 3, an inorganic polyvalent metal salt or an organic polyvalent metal salt can be used without any particular limitation. Specifically, an inorganic polyvalent metal salt such as zinc sulfate, zinc chloride, calcium chloride, magnesium sulfate, zinc acetate, Examples include organic polyvalent metal salts such as zinc gluconate and zinc lactate. These may be used singly or in combination of two or more. In view of obtaining a metal salt having low solubility in water or an organic solvent, it is preferable to use zinc acetate or zinc sulfate. The method for adding zinc acetate and zinc sulfate salt is not particularly limited as long as salt exchange proceeds, and it may be charged as a solid or may be dissolved in water or an organic solvent in advance. From the viewpoint of allowing the salt exchange reaction to proceed rapidly, a method in which a basic solution of benzylidene dioxoimidazolidine propionic acid is introduced into a zinc acetate or zinc sulfate salt solution is preferred.

  The organic compound of the general formula (2) (hereinafter also referred to as compound (2)) can be obtained in the above-mentioned step 1, but soft shade DH (3,4-dimethoxybenzylidene dioxoimidazolidine) manufactured by Ajinomoto Co., Inc. 2-ethylhexyl propionate can be used.

  Compounds (1) and (2) are difficult to dissolve in a solvent. Since compounds (1) and (2) have an organic chromophore, they absorb ultraviolet rays. Compounds (1) and (2) have a solubility in water and organic solvents of less than 1% by mass. Examples of organic solvents here include polyhydric alcohols, higher alcohols, liquid paraffins, silicone oils, and fatty acid triglycerides. It is done. When measuring the solubility, the compound (1) or (2) is added to the solvent in such an amount that undissolved matter is generated. After reaching the equilibrium state, the solubility of the organic compound dissolved in the solvent can be measured immediately in a laboratory or the like by using HPLC or the like.

  In particular, compound (1) has an ability to absorb ultraviolet rays, and a composition containing this can be used alone as an organic ultraviolet absorber. Further, the compound (1) is extremely useful because it is hardly soluble in a solvent and has a characteristic that the transdermal absorbability is poor and is safe.

  The ultraviolet protective composition of the present invention is characterized in that the compound (1) and / or (2) is used in combination with another organic ultraviolet absorbing compound or an inorganic ultraviolet scattering compound. When used in combination, the UV absorber of the present invention exhibits a synergistic effect in a wide wavelength range with respect to UV protection ability. As will be described later in the examples, the ultraviolet protection ability is quantified by parameters such as SPF value and PFA value.

  The organic ultraviolet absorbing compound that may be used in combination with the compounds (1) and (2) is an organic compound that can absorb ultraviolet rays, and is not particularly limited as long as it is other than the compounds (1) and (2). For example, ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, potassium paramethoxycinnamate, glyceryl di-2-methoxycinnamate mono-2-ethylhexanoate, diparamethoxy Cinnamic acid derivatives such as glyceryl octyl cinnamate and methylbis (trimethylsiloxy) silylisopentyl trimethoxy; dibenzoylmethane derivatives such as 4-tert-butyl-4′-methoxydibenzoylmethane; 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, dihydroxydimethoxybenzophenone, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone, etc. Benzophenone derivatives; benzoic acid derivatives such as paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, octyl paradimethylaminobenzoate; amyl salicylate, octyl salicylate, phenyl salicylate, homomentyl salicylate, diethyl salicylate Examples include salicylic acid derivatives such as propylene glycol, ethylene glycol salicylate, and myristyl salicylate; vegetable ultraviolet absorbers such as shea butter. Any one or two or more of these can be used. Of these, cinnamic acid derivatives, dibenzoylmethane derivatives, and benzophenone derivatives are preferable, and cinnamic acid derivatives are more preferable, and paramethoxycinnamon is preferable from the viewpoint that the synergistic effect of UV protection is excellent when used in combination with the compound of formula (1). Ethyl acetate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2-ethoxyethyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, potassium paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, glyceryl octyl diparamethoxycinnamate Further, methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate is more preferred, and 2-ethylhexyl paramethoxycinnamate is particularly preferred.

  The inorganic ultraviolet scattering compound that may be used in combination with the compounds (1) and (2) is not particularly limited as long as it is an inorganic compound that can scatter ultraviolet rays. For example, titanium oxide, fine particle titanium oxide, zinc oxide, fine particle zinc oxide, iron oxide, fine particle iron oxide, cerium oxide and the like can be mentioned. The inorganic ultraviolet scattering compound is preferably various types such as silicone treatment using methyl hydrogen polysiloxane or silane coupling agent, fluorine treatment such as metal soap treatment, perfluoroalkylsilane, or hydrophobic treatment using dextrin fatty acid ester or the like. Processing is performed. Moreover, arbitrary 1 type, or 2 or more types can be used for an inorganic ultraviolet-ray scattering compound. Of these, titanium oxide (particularly fine particle titanium oxide) and zinc oxide are preferred from the viewpoint that the synergistic effect of the UV protection ability is extremely excellent.

  The weight ratio of the organic compound (compound (1) (2)) of the present invention to the inorganic ultraviolet scattering agent is usually from 1/40 to 5/1, preferably from the viewpoint of a remarkable UV protection synergistic effect. 1/30 to 3/1, more preferably 1/20 to 3/1.

  The weight ratio of the organic compound of the present invention (compound (1) (2)) to the organic ultraviolet scattering agent (excluding general formulas (1) and (2)) is usually 1/20 to 5/1, From the viewpoint of a remarkable UV protection synergistic effect, it is preferably 1/15 to 4/1, and more preferably 1/4 to 4/1.

By containing the organic powder of the following general formula (3) (hereinafter also referred to as compound (3)) in the UV protection composition of the present invention, UV protection that does not agglomerate during formulation and has a high UV blocking effect. The composition, and the stability and usability of using the composition can be imparted.
(In the formula, R4 represents linear saturated alkyl having 11 to 17 carbon atoms.)

  The compound (3) of the present invention can be prepared by a conventional method such as heat condensation of lysine and a long chain fatty acid. As long-chain fatty acids, straight chain saturated C 12-18 ones can be used. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, coconut oil fatty acid and the like, and these may be used alone or in combination of two or more. As the compound (3), lauroyl lysine is preferable from the viewpoint that it is versatile and can efficiently improve the feeling of use of the ultraviolet protection composition.

  There is no restriction | limiting in particular as a method of making the compound (3) of this invention contain in a ultraviolet protection composition. Although a method of stirring and mixing may be used, the compound (1) and / or the compound (2) is surface-treated with the compound (3) from the viewpoint that the effect of preventing aggregation and the effect of enhancing the stability and the feeling of use are further exhibited. Thereafter, a method of mixing with an organic ultraviolet absorbing compound (excluding the general formulas (1) and (2)) and / or an inorganic ultraviolet scattering compound is preferred, and the compound (1) and / or the compound (2) and the inorganic ultraviolet scattering compound are preferred. On the other hand, the method of surface-treating with a compound (3) is more preferable.

  The method for surface treatment with the compound (3) may be either a dry method or a wet method. The dry method is a simple and effective method, and can be easily processed by mixing the compound (1) and / or (2) and the compound (3) and then co-grinding. In the case of the wet method, the compound (3) is dissolved in an organic solvent using calcium chloride as a solubilizer, and then contacted with the compound (1) and / or (2), followed by washing with water and calcium chloride. Surface treatment can be performed by removing and drying. From the viewpoint of UV protection ability and usability, co-grinding by a dry method or a wet method is particularly preferable.

  The organic compound of the present invention (compounds (1) and (2)) is used as a powder and the particle size is not particularly limited, but the upper limit of the particle size is preferably 30 microns from the viewpoint of good usability, and 10 microns. Is more preferably 5 microns, and particularly preferably 1 micron. From the viewpoint of easy handling in terms of formulation, the lower limit of particle size is preferably 10 nanometers, more preferably 50 nanometers, and particularly preferably 100 nanometers.

The weight ratio of the organic compound of the present invention (compounds (1) and (2)) to the organic powder (3) is usually 97/3 to 3/97, and is 95/5 from the viewpoint of usability and dispersibility. ~ 5/95 is preferable, and 93/7 to 10/90 is more preferable. The ratio of the surface treatment of the organic compound of the present invention (compounds (1) and (2)) with the organic powder (3) is 65/35 to 97 from the viewpoint of usability, dispersibility, and effective UV protection. / 3, preferably 75/25 to 95/5. Most preferably, it is 80 / 20-93 / 7. If it is the said range, sufficient effect is exhibited in a dispersibility and a usability | use_condition.

  The dosage form of the ultraviolet-absorbing protective composition of the present invention is not particularly limited as long as it can be applied to the outer skin such as liquid, emulsion, ointment, cream, gel, and aerosol. In order to obtain a desired form of the UV protection composition, it can be prepared by a conventional method by appropriately blending base components and the like as necessary.

  The ultraviolet protection composition of the present invention is suitably used as a cosmetic. Examples of cosmetics include sunscreens, foundations, lipsticks, lip glosses, hair styling agents, and mascaras.

  In the ultraviolet protection composition of the present invention, if necessary, various components generally blended in hair cosmetics and skin external preparations can be blended as long as the effects of the present invention are not impaired. Examples of such components include oily components, surfactants, humectants, higher alcohols, sequestering agents, natural and synthetic polymers, water-soluble and oil-soluble polymers, various extracts, inorganic and organic pigments, Inorganic and organic clay minerals, inorganic and organic pigments treated with metal soaps or silicones, colorants such as organic dyes, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, cooling sensates, Examples include antiperspirants, bactericides, skin activators, and other drugs.

  The content of the ultraviolet protection composition of the present invention in the cosmetic is not particularly limited, and is usually 0.5 to 30% by mass of the total amount of the cosmetic. If it is in the above-mentioned range, sufficient UV protection ability is exhibited. From the viewpoint of showing a clear UV protection effect and being economical, the blending amount is preferably 1 to 20% by mass, more preferably 2 to 15% by mass.

  EXAMPLES Hereinafter, although a production example and an Example demonstrate this invention further in detail, this invention is not limited to these. The blending amount is mass% unless otherwise specified.

[Powder feel evaluation method]
Five professional panelists evaluated the feel of the powder, such as a smooth, sticky, squeaky, and rough feeling. The average value of each panelist's evaluation according to the following evaluation criteria is calculated, ◎ when the average value is 1.5 to 2.0, ○ when the average value is less than 1.0 to 1.5, 0.5 to 1.0 A case of less than Δ was judged as Δ, and a case of less than 0.5 was judged as ×.

Evaluation criteria for smooth feeling:
2: There is a smooth feeling 1: There is a little smooth feeling 0: There is not much smooth feeling -1: There is no smooth feeling

Evaluation criteria for squeakiness:
2: There is no squeaking feeling 1: There is not much squeaking feeling 0: There is a slight squeaking feeling -1: There is a squeaking feeling

[Solubility test]
20 mg of the powder to be measured is added to 100 mL of the solvent, stirred with a magnetic stirrer at room temperature for 4 hours, and then allowed to stand. The supernatant is filtered with a 0.45 μm filter, and the solubility of the filtrate is determined by HPLC analysis. Determined (unit: ppm).

[Diffusion reflectance measurement]
The diffuse reflectance was measured using an ultraviolet-visible spectrophotometer (V-570 manufactured by JASCO Corporation). The measurement range was 300 to 500 nm.

[SPF, PFA measurement]
SPF and PFA were determined using an SPF analyzer manufactured by Optometrics.
SPF value (Sun Protection Factor): A value representing the protection level against UV-B.
PFA value (Protection Factor of UV-A) is a value representing the protection level against UV-A.

[Production Example 1] 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid zinc salt (powder 1, 2)
3,4-Dimethoxybenzylidenehydantoin (manufactured by Showa Denko KK) was subjected to a Michael addition reaction with 2-ethylhexyl acrylate using a catalyst (potassium carbonate) to give 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid 2 -Ethylhexyl was obtained.
The obtained ester was heated with a base (sodium hydroxide) in a solution at 80 ° C. for 3 hours to obtain 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid.
The obtained methanol solution containing 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid is mixed with a methanol solution containing zinc acetate, and the resulting crystals are separated and dried to give plate crystals of the title compound. A powder (powder 1) was obtained. Particle size 27 microns (Figure 1: SEM photo)
[Production Example 2]
The powder 1 obtained in Production Example 1 was jet milled to obtain a powder 2 having a particle size of 2 microns.

[Production Example 3] Benzylidenedioxoimidazolidinepropionic acid zinc salt (powder 3)
Hydantoin and benzaldehyde were heated at 90 ° C. for 5 hours in water containing monoethanolamine and sodium hydroxide. After cooling, the precipitated crystals were separated to obtain benzylidenehydantoin.
The obtained benzylidene hydantoin was subjected to a Michael addition reaction with 2-ethylhexyl acrylate using a catalyst (potassium carbonate) to obtain 2-ethylhexyl benzylidene dioxoimidazolidine propionate.
The obtained ester was treated in the same manner as in Production Example 1 to obtain a powder of the title compound (powder 3). Particle size 1.5 microns

[Production Example 4] 2,4-Dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl (powder 4)
“Soft shade” DH (particle size: 22 microns) manufactured by Ajinomoto Co., Inc. was pulverized with a jet mill to a particle size of 2 microns.

[Production Example 5] Nε-lauroyllysine-treated 3,4-dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl (powder 5)
5 parts of Nε-lauroyllysine and 95 parts of 3,4-dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl (“soft shade” DH) were mixed and obtained by co-grinding with a jet mill in a dry process. The average particle size of the mixture is 2 microns.
Nε-lauroyllysine: Ajinomoto Co., Inc. trade name “Amihope” LL
3,4-Dimethoxybenzylidenedioxoimidazolidine 2-ethylhexyl propionate: Ajinomoto Co., Inc. trade name “Soft Shade” DH

[Production Example 6] Nε-lauroyllysine-treated 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid zinc salt (powder 6)
10 parts of Nε-lauroyllysine and 90 parts of 3,4-dimethoxybenzylidenedioxoimidazolidine propionate (powder 1) were mixed and obtained by co-grinding with a jet mill in a dry process. The average particle size of the mixture is 3 microns.

[Solubility evaluation]
As shown in Table 1, it was found that the solubility of 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid zinc salt (powder 1) in each solvent was extremely low.

[Evaluation of UV protection]
The diffuse reflectance of 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid zinc salt (powder 1) was measured.
0.5 g of the powder to be measured was weighed on an integrating sphere attachment of a spectrophotometer, and the diffuse reflectance in the range of 260 to 500 nm was measured. The measurement results are shown in FIG.
From this result, it can be seen that the powder of 3,4-dimethoxybenzylidenedioxoimidazolidinepropionic acid zinc salt (powder 1) is excellent in absorption in a wide ultraviolet region up to around 400 nm.

[Synergistic effect of UV protection]
Tables 2 to 5 show the results of measuring SPF and PFA of the mixtures, focusing on the synergistic effect of the combined use of the compounds (1) and (2) with the conventional organic ultraviolet absorber and inorganic ultraviolet scattering compound. The measurement was carried out as a dispersion mixture using the compounds (1) and (2) and a conventionally used organic ultraviolet absorbing compound or inorganic ultraviolet scattering compound. From the table, it can be seen that the effect is synergistically higher in the mixed system than the value of each alone.

* 1) OMC: 2-ethylhexyl methoxycinnamate
* 2) Common components [cyclomethicone: 30.0%, dextrin palmitate: 4.5%, dimethicone polyol: 1.5%, dialkyl carbonate (14,15): remaining]

* 3) Titanium oxide: MT-100Z Takeca Co., Ltd.

* 4) Zinc oxide: MZ-3S Teika Co., Ltd.

[Radical inhibition ability evaluation]
The degree to which the additive suppressed the generation of radicals was investigated. For measurement of ESR, an apparatus manufactured by JEOL Ltd. was used, and Nt-butyl-α-phenylnitrone (PBN) was used as a spin trap agent. The measurement conditions for ESR are as follows. Samples were diluted with olive oil (40 mM).
Central magnetic field 335.9mT
Magnetic field modulation 100kHz 0.1mT
Amplification 400
Time constant 0.1 seconds Microwave output 1.0 mW
Magnetic field sweep width 7.5mT
Sweep time 1 minute Measurement temperature Room temperature Calibration Mn ²⁺ supported on magnesium oxide was used.

  The measurement results are as follows. Here, the amount of radicals generated in additive-free olive oil was taken as 1, and the amount of radicals generated in each sample was expressed as a relative value. It shows that radical suppression ability is so high that a value is small. Titanium oxides A and B are commercially available surface-treated titanium oxides. The results show that the compound of the present invention has a radical suppressing effect.

Additive-free olive oil 1.0
Dimethoxybenzylidene dioxoimidazolidine propionic acid zinc salt 0.8
Dimethoxybenzylidene dioxoimidazolidine propionate calcium salt 0.7
Dimethoxybenzylidene dioxoimidazolidine propionate magnesium salt 0.7
Titanium oxide (silica coat) Company A 2.0
Titanium oxide (silica coat) Company B 0.8

[Powder feel evaluation]
Table 6 shows the evaluation results of the powders 1 to 6. In the table, DH is 2-ethylhexyl 3,4-dimethoxybenzylidenedioxoimidazolidinepropionate (trade name, “soft shade” DH average particle size: 22 microns).

A cosmetic was produced according to a conventional method. The numerical value in the formulation example is a blending amount (% by weight).

[Formulation Example 1] Solid powder foundation Powder 2 4.0
2. Silicone-treated powder Talc 20.0
Mica residue Titanium oxide 10.0
Bengala 1.0
3. N-lauroyl-L-lysine 5.0
4). Nylon powder 2.0
5. Dimethylpolysiloxane 9.0
5. Octyl methoxycinnamate 1.0
6). Monooleic acid POE sorbitan 1.0
7). Isocetyl octoate 2.0
8). Preservative 0.3
9. Fragrance 0.1
This solid powder foundation had good spreading and stickiness on the skin, a natural finish, and excellent UV protection.

[Prescription Example 2] Sunscreen Cosmetic (W / O Cream)
1. Octamethylcyclotetrasiloxane 10.5
2. Dimethylpolysiloxane (100cs) 5.0
3. Dimethylpolysiloxane (2.5 million cs) 3.0
4). Liquid paraffin 15.0
5. Polyether modified silicone 6.0
6). 2-ethylhexyl methoxycinnamate 4.0
6). Powder 5 1.0
7). Zinc oxide 4.0
8.1,3-Butylene glycol 5.0
9. Preservative 0.2
Ten. Purified Water Residue This cream stretched, blended well into the skin, and was excellent in UV protection.

2 is an SEM photograph of dimethoxybenzylidene dioxoimidazolidine propionate zinc salt (powder 1) synthesized in Production Example 1. 2 represents the relationship between the ultraviolet wavelength and the diffuse reflectance of dimethoxybenzylidene dioxoimidazolidine propionate zinc salt (powder 1) synthesized in Production Example 1.

Claims (6)

An ultraviolet protection composition comprising an organic compound represented by the following general formula (1) and / or (2) and an organic ultraviolet absorbing compound (excluding the general formulas (1) and (2)) and / or an inorganic ultraviolet scattering compound .
(In the formula, each R ₁ independently represents an OH group, a halogen atom, a linear or branched C _1-6 alkyl group optionally containing a silicon atom, and a linear or branched C _1-6 alkoxy optionally containing a silicon atom. Represents a straight-chain or branched C _1-5 alkoxycarbonyl group, or a linear or branched C _1-6 alkylsulfonamide group optionally containing a silicon atom or an amino functional group, q is an integer of 0 to 4 R ₂ represents hydrogen or an OH group, R ₃ represents a linear or branched saturated alkyl having 2 to 8 carbon atoms, M ^{n +} represents a polyvalent metal ion, and n is an integer of 2 to 3 Represents.) The ultraviolet protective composition according to claim 1, wherein the inorganic ultraviolet scattering compound is selected from titanium oxide and zinc oxide. 2. The ultraviolet protective composition according to claim 1, wherein the organic ultraviolet absorbing compound (excluding the general formulas (1) and (2)) is selected from cinnamic acid derivatives. Furthermore, the organic powder represented by following General formula (3) is contained, The ultraviolet protection composition in any one of Claim 1 to 3 characterized by the above-mentioned.
(In the formula, R4 represents linear saturated alkyl having 11 to 17 carbon atoms.) Cosmetics containing the ultraviolet protection composition according to any one of claims 1 to 4. An organic compound represented by the following general formula (1).
(In the formula, each R ₁ independently represents an OH group, a halogen atom, a linear or branched C _1-6 alkyl group optionally containing a silicon atom, and a linear or branched C _1-6 alkoxy optionally containing a silicon atom. A linear or branched C _1-5 alkoxycarbonyl group, or a linear or branched C _1-6 alkylsulfonamide group optionally containing a silicon atom or an amino functional group, q is an integer of 0 to 4 R ₂ represents hydrogen or an OH group, M ^{n +} represents a polyvalent metal ion, and n represents an integer of 2 to _3. )