Ultraviolet absorber-containing composition, microcapsule containing ultraviolet absorber-containing composition, and cosmetic

Abstract

Provided are: a composition containing an ultraviolet light absorber, which is characterized by containing a citric acid ester or a salicylic acid-based oil agent and an ultraviolet light absorber that is solid at 25 DEG C, and in which the composition containing the ultraviolet light absorber is encapsulated as a core material; the present invention relates to a cosmetic which is characterized by comprising a composition or a microcapsule containing an ultraviolet light absorber, and which exhibits a high UVA / UVB defense function by means of a highly poorly soluble organic ultraviolet light absorber without incorporating ethylhexyl methoxycinnamate or the like, the use of which is limited by regulations of various countries or the like. The composition has excellent long-term stability and shows a feeling of use.

Description

Technical Field

[0001] The present invention relates to a composition containing an ultraviolet absorber used in cosmetics, quasi-drugs, and the like. The present invention also relates to microcapsules encapsulating the composition containing the ultraviolet absorber, and a cosmetic containing the composition containing the ultraviolet absorber or the microcapsules. Background Art

[0002] In recent years, the demand for sunscreen cosmetics has increased, and various sunscreen cosmetics have been developed according to the purpose of use. In particular, as the influence of UVA (long-wavelength ultraviolet rays with a wavelength of 320 to 400 nm) on the skin has been understood, it is important not only to prevent UVB (medium-wavelength ultraviolet rays with a wavelength of 290 to 320 nm) but also to prevent UVA as a requirement for sunscreen cosmetics. However, as a UVA absorber, there are many substances that are solid at room temperature and hardly soluble in both water and non-polar oils. In particular, the following problems have arisen: the stability of the preparation over time is impaired due to crystal precipitation in the low-temperature region, and the expected ultraviolet protection effect cannot be obtained due to aggregation of the active ingredient.

[0003] Therefore, various studies have been conducted on the stable formulation of poorly soluble organic ultraviolet absorbers. For example, Japanese Patent Application Laid-Open No. 2009-235046 (Patent Document 1) discloses an oil-in-water emulsified cosmetic that further contains alkyl PEG / PPG polydimethylsiloxane ethyl polydimethylsiloxane in a composition formed from a water-insoluble ultraviolet absorber, i.e., a benzotriazole derivative having a specific structure, and a highly polar oil component that dissolves it, thereby stably formulating a high content of the benzotriazole derivative. In addition, Japanese Patent Application Laid-Open No. 2014-118383 (Patent Document 2) discloses that a specific dialkyl ether of isosorbide exhibits good solubility in a solid ultraviolet absorber, and describes providing a topical skin composition that contains isosorbide dialkyl ether and an oil-soluble ultraviolet absorber that is solid at 25°C, stably dissolves the oil-soluble ultraviolet absorber, and has a good feel in use. Furthermore, in Japanese Patent Application Laid-Open No. 2009-091307 (Patent Document 3), an ultraviolet-absorbing powder and a cosmetic containing the ultraviolet-absorbing powder are disclosed. The ultraviolet-absorbing powder contains a large amount of a poorly soluble ultraviolet absorber by encapsulating the ultraviolet absorber, which is poorly soluble in the cosmetic formulation oil component, inside polymer particles during the polymerization stage. However, although these cosmetics and topical skin compositions are described as being able to provide a good feel in use, due to an increase in the content of oils and surfactants, stickiness and the like are likely to occur, and the feel in use is sometimes not satisfactory.

[0004] On the other hand, it is considered that ethylhexyl methoxycinnamate and octocrylene, which are liquid UVB absorbers, are effective in dissolving poorly soluble organic UV absorbers. For example, Japanese Patent No. 5247029 (Patent Document 4) describes the use of a mixture of 2-ethylhexyl methoxycinnamate and N-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate as a UVA absorber in cosmetics and pharmaceutical preparations, and it is described that crystal precipitation of N-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate can be prevented in this use.

[0005] However, regarding ethylhexyl methoxycinnamate and octocrylene, it has also been reported that they have an adverse impact on marine organisms, and the number of countries and regions that restrict or prohibit the sale of cosmetics containing these UVB absorbers is increasing. In recent years, the intention of being beach-friendly, which complies with regulations and is friendly to the marine environment, has also been spreading among consumers.

[0006] Regarding sunscreen cosmetics containing poorly soluble organic UV absorbers like this, it is desired not only to exhibit high UVA and UVB protection functions, but also to develop a sunscreen cosmetic that can dissolve the poorly soluble organic UV absorber at a high concentration without containing ethylhexyl methoxycinnamate, octocrylene, etc., whose use is restricted due to regulations in various countries, has excellent stability over time, and exhibits excellent usability that meets the needs in recent years.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2009-235046

[0010] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2014-118383

[0011] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2009-091307

[0012] Patent Document 4: Japanese Patent No. 5247029 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] Therefore, the subject of the present invention is to provide a composition containing a UV absorber, which while exhibiting high UVA and UVB protection functions, dissolves a poorly soluble organic UV absorber at a high concentration, has excellent stability of the preparation over time, inhibits crystal precipitation, and can be formulated into various dosage forms of sunscreen cosmetics, exhibits excellent usability after formulation, and furthermore does not contain ethylhexyl methoxycinnamate, octocrylene, etc., whose use is restricted due to regulations in various countries.

[0015] Another object of the present invention is to provide a microcapsule encapsulating the composition containing an ultraviolet absorber, which can be incorporated into sunscreen cosmetics in various dosage forms, exhibits high UVA and UVB protection functions and excellent usability, and has excellent temporal stability without crystal precipitation over a long period of time.

[0016] A further object of the present invention is to provide a cosmetic (sunscreen cosmetic) characterized by incorporating the composition containing an ultraviolet absorber or the microcapsule, which exhibits high UVA and UVB protection functions by dissolving a poorly soluble organic ultraviolet absorber at a high concentration without incorporating ethylhexyl methoxycinnamate, octocrylene, etc. whose use is restricted due to regulations in various countries, etc., and has excellent temporal stability without crystal precipitation over a long period of time, and exhibits excellent usability meeting recent demands.

[0017] Means for Solving the Problems

[0018] The present inventors repeatedly conducted studies to solve the above problems, and as a result, found that by incorporating a specific citrate ester and a salicylic acid-based oil agent, a composition containing an ultraviolet absorber with excellent temporal stability can be obtained, which can dissolve a poorly soluble organic ultraviolet absorber at a high concentration while exhibiting high UVA and UVB protection functions, and further significantly suppresses crystal precipitation over time.

[0019] The present inventors also found that a microcapsule encapsulating the composition containing an ultraviolet absorber and having a copolymer of a silylated peptide or a silylated amino acid and a silane compound as a wall material can be incorporated into sunscreen cosmetics in various dosage forms, exhibits high UVA and UVB protection functions and excellent usability, and exhibits excellent temporal stability.

[0020] The present inventors further found that by incorporating the composition containing an ultraviolet absorber or the microcapsule, various dosage forms of sunscreen cosmetics having high UVA and UVB protection functions, excellent usability, and excellent temporal stability can be obtained, thus completing the present invention.

[0021] That is, a first aspect of the present invention is a composition containing an ultraviolet absorber, characterized by containing component (A): a citrate ester or a salicylic acid-based oil agent, and component (B): an ultraviolet absorber that is solid at 25°C.

[0022] A second aspect of the present invention is a composition containing an ultraviolet absorber as one of the specific aspects of the first aspect of the present invention, characterized in that component (A) is a citrate ester.

[0023] The third aspect of the present invention is a composition containing an ultraviolet absorber, which is a preferred aspect of the second aspect of the present invention, and is characterized in that the citrate ester is tributyl citrate or acetyl tributyl citrate.

[0024] The fourth aspect of the present invention is a composition containing an ultraviolet absorber, which is one of the specific embodiments of the first aspect of the present invention, and is characterized in that component (A) is a salicylic acid-based oil agent.

[0025] The fifth aspect of the present invention is a composition containing an ultraviolet absorber, which is a preferred aspect of the fourth aspect of the present invention, and is characterized in that the salicylic acid-based oil agent is homosalate or ethylhexyl salicylate.

[0026] The sixth aspect of the present invention is a microcapsule, which uses a copolymer of a silylated peptide or a silylated amino acid and a silane compound as a wall material, and encapsulates the composition containing an ultraviolet absorber according to the first aspect of the present invention as a core substance.

[0027] The seventh aspect of the present invention is a microcapsule, in which a copolymer of a silylated peptide or a silylated amino acid and a silane compound is used as a wall material, and the composition containing an ultraviolet absorber according to the second or third aspect of the present invention is encapsulated as a core substance. The seventh aspect of the present invention is a preferred aspect of the sixth aspect of the present invention.

[0028] The eighth aspect of the present invention is a microcapsule, in which a copolymer of a silylated peptide or a silylated amino acid and a silane compound is used as a wall material, and the composition containing an ultraviolet absorber according to the fourth or fifth aspect of the present invention is encapsulated as a core substance. The eighth aspect of the present invention is a preferred aspect of the sixth aspect of the present invention.

[0029] The ninth aspect of the present invention is a cosmetic, which is characterized by containing the composition containing an ultraviolet absorber according to any one of the first to fifth aspects of the present invention.

[0030] The tenth aspect of the present invention is a cosmetic, which is characterized by containing the microcapsule according to any one of the sixth to eighth aspects of the present invention.

[0031] Advantages of the Invention

[0032] The composition containing an ultraviolet absorber according to the present invention can exhibit high UVA and UVB defense functions, dissolve poorly soluble organic ultraviolet absorbers at a high concentration, and inhibit the precipitation of their crystals, and also has excellent preparation stability over time. In addition, it can be easily incorporated into various dosage forms of sunscreen cosmetics, and shows excellent usability after incorporation. Furthermore, it does not contain ethylhexyl methoxycinnamate, octocrylene, etc., whose use is restricted due to regulations in various countries.

[0033] The composition containing an ultraviolet absorber of the present invention can also be stably incorporated as the core material of microcapsules having a copolymer of a silylated peptide or a silylated amino acid and a silane compound as the wall material. Moreover, the microcapsules can provide a sunscreen cosmetic incorporated in various dosage forms, a cosmetic having excellent usability, and excellent stability over time.

[0034] Therefore, the cosmetic of the present invention incorporating the composition containing an ultraviolet absorber of the present invention or the microcapsules exhibits high UVA and UVB protection functions, excellent stability over time, and also inhibits the precipitation of crystals of the ultraviolet absorber. In addition, since the usability is also excellent, it is suitable as a sunscreen cosmetic in various dosage forms. Furthermore, it does not incorporate ethylhexyl methoxycinnamate, octocrylene, etc. whose use is restricted due to regulations in various countries. Detailed Description

[0035] [Component (A)]

[0036] First, the citrate or salicylic acid-based oil agent as Component (A) constituting the composition containing an ultraviolet absorber of the present invention will be specifically described below.

[0037] (Citrate)

[0038] The citrate of Component (A) is not particularly limited as long as it is a substance commonly used in cosmetics, and can be any of monoesters, diesters, and triesters. Among them, triesters are preferred.

[0039] More specifically, triethyl citrate, tributyl citrate, acetyltriethyl citrate, acetyltributyl citrate, etc. can be cited. Among them, from the viewpoint of further improving the solubility of the solid ultraviolet absorber, tributyl citrate and acetyltributyl citrate are particularly preferred.

[0040] (Salicylic acid-based oil agent)

[0041] The salicylic acid-based oil agent of Component (A) is not particularly limited as long as it is a substance commonly used in cosmetics. Specifically, homosalate, ethylhexyl salicylate, TEA salicylate, dipropylene glycol salicylate, benzyl salicylate, amyl salicylate, phenyl salicylate, ethylene glycol salicylate, methyl salicylate, myristyl salicylate, etc. can be cited. Among them, from the viewpoint of further improving the solubility of the solid ultraviolet absorber, homosalate and ethylhexyl salicylate are preferred, and homosalate is particularly preferred.

[0042] In the composition containing an ultraviolet absorber of the present invention, one kind of the citrate or salicylic acid-based oil agent of Component (A) can be used, or two or more kinds can be mixed and used.

[0043] The content of component (A) in the present invention is not particularly limited and varies depending on the selection of component (B). It is preferably 30 to 90% by mass in the composition containing the ultraviolet absorber, and particularly preferably 50 to 85% by mass. When it is in this range, the crystal precipitation of component (B) can be further suppressed, and the processability of the composition is also good, so the blending in cosmetics becomes easy.

[0044] [Component (B)]

[0045] Next, the ultraviolet absorber which is solid at 25 °C as component (B) will be specifically described below.

[0046] The ultraviolet absorber which is solid at 25 °C as component (B) used in the present invention is not particularly limited as long as it is a component for cosmetics. For example, diethylamino hydroxybenzoyl benzoic acid hexyl ester, ethyl p-aminobenzoate, benzophenone-1, benzophenone-3, benzophenone-6, benzophenone-9, ethylhexyl triazone, dioctyl butylamide triazone, tert-butyl methoxydibenzoylmethane, bis-ethylhexyloxyphenol methoxyphenyl triazine, etc. can be cited, and one or more of them can be used. Among them, from the viewpoint of obtaining a high ultraviolet defense effect, diethylamino hydroxybenzoyl benzoic acid hexyl ester, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, and tert-butyl methoxydibenzoylmethane are preferred.

[0047] The content of component (B) in the present invention is not particularly limited and varies depending on the selection of component (A). It is preferably 0.5 to 50% by mass in the composition, and more preferably 10 to 45% by mass. When it is in this range, the solid ultraviolet absorber can be stably blended in cosmetics, and a high ultraviolet defense effect can be obtained, so it is preferred.

[0048] In the present invention, the mass ratio (A) / (B) of component (A) to component (B) is preferably 0.1 to 50, further preferably 1.0 to 20, and most preferably 1.5 to 10. When it is in this range, the solubility of each component becomes good, so it is preferred.

[0049] Next, microcapsules encapsulating the composition containing the ultraviolet absorber of the present invention as a core material will be described.

[0050] The microcapsules of the present invention are capsules in which a copolymer of a silylated peptide or silylated amino acid and a silane compound is used as a wall material, and the composition containing the ultraviolet absorber is encapsulated therein. Since the composition containing the ultraviolet absorber is encapsulated, it has the effect of preventing ultraviolet rays. These microcapsules can be produced by a method described in Japanese Patent No. 4562050 (particularly claim 3 thereof, etc.) and Japanese Patent No. 6733322 (particularly paragraphs 0029 to 0052), while copolymerizing the silylated peptide or silylated amino acid and the silane compound and encapsulating the composition containing the ultraviolet absorber, but the production methods are not limited thereto.

[0051] Examples of the silane compound that is a raw material for the wall material of the microcapsules include tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, octyltriethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, hexyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, etc.

[0052] Examples of the silylated peptide that is a raw material for the wall material of the microcapsules include N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed protein, N-[2-hydroxy-3-(3'-dihydroxymethylsilyl)propoxy]propyl hydrolyzed protein, etc.

[0053] The hydrolyzed protein that is a constituent of the N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed protein and N-[2-hydroxy-3-(3'-dihydroxymethylsilyl)propoxy]propyl hydrolyzed protein is obtained by partially hydrolyzing a protein using an acid, a base, an enzyme, or a combination thereof. Examples of the protein source include animal proteins and plant proteins. Examples of animal proteins include collagen (including gelatin as its modified product), keratin, fibroin, sericin, casein, conchiolin, elastin, protamine, yolk proteins such as those of chicken, ovalbumin, etc. Examples of plant proteins include proteins contained in soybeans, wheat, rice (rice bran), sesame, peas, corn, potatoes, etc. From the viewpoint of improving the feel when applying the cosmetic in the form of microcapsules to the skin, the protein source is preferably fibroin or sericin.

[0054] Examples of the silylated amino acid as a raw material for the wall material of the microcapsules include N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl amino acid, N-[2-hydroxy-3-(3'-dihydroxymethylsilyl)propoxy]propyl amino acid, and the like.

[0055] The α-amino acid as a constituent of N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl amino acid and N-[2-hydroxy-3-(3'-dihydroxymethylsilyl)propoxy]propyl amino acid is not particularly limited as long as it is a substance used in cosmetics. For example, any of acidic amino acids such as aspartic acid and glutamic acid, neutral amino acids such as glycine, alanine, serine, threonine, methionine, cysteine, valine, leucine, isoleucine, phenylalanine, tyrosine, proline, hydroxyproline, tryptophan, asparagine, and glutamine, and basic amino acids such as arginine, lysine, histidine, and ornithine can be used.

[0056] In the production of microcapsules encapsulating an ultraviolet absorber using a copolymer of a silylated amino acid and a silane compound as the wall material, in order to obtain microcapsules with higher stability, the α-amino acid as a constituent of the silylated amino acid is preferably a hydrophilic amino acid. Here, a hydrophilic amino acid refers to an amino acid having a solubility of 10% or more in water at 25°C, and examples include aspartic acid, glutamic acid, glycine, alanine, and serine. Among hydrophilic amino acids, if a neutral amino acid without a charge is used, more stable and stronger capsules can be obtained, so it is more preferred. That is, serine, glycine, alanine, proline, etc. as neutral amino acids are more preferred.

[0057] In the case of producing microcapsules in which the silane compound is copolymerized with a silylated peptide or a silylated amino acid and the copolymer of the silylated peptide and the silane compound or the copolymer of the silylated amino acid and the silane compound is used as the wall material and encapsulates a composition containing an ultraviolet absorber, the composition containing the ultraviolet absorber can be encapsulated in the range of 0.01 to 99% by mass relative to the total mass of the microcapsules. However, considering the ease of preparation of the microcapsules and the ultraviolet protection effect of the prepared microcapsules, the encapsulation rate of the composition containing the ultraviolet absorber is preferably 80 to 95% of the total mass of the microcapsules. When the encapsulation rate of the composition containing the ultraviolet absorber is low, the ultraviolet protection effect becomes low, so a large amount must be added when compounded in a cosmetic for the purpose of ultraviolet protection, which may damage the usability as a cosmetic. On the other hand, if the encapsulation rate of the composition containing the ultraviolet absorber is extremely increased, the proportion of the wall material part in the total amount of the microcapsules decreases, and there is a possibility of reducing the stability of the microcapsules.

[0058] Next, the cosmetic containing the ultraviolet absorber of the present invention or the microcapsules encapsulating them will be described.

[0059] The cosmetic of the present invention is a cosmetic containing the composition containing the ultraviolet absorber or the microcapsules encapsulating them, and its manufacturing method is not particularly limited and can be prepared by a conventional method according to the dosage form. For example, microcapsules encapsulating the composition containing the ultraviolet absorber of the present invention can be manufactured and then incorporated into the cosmetic, or the composition containing the ultraviolet absorber can be prepared in advance and directly used as the oil phase of the cosmetic, or it can be mixed and dissolved with other oil-soluble components and then used.

[0060] The blending ratio of the composition containing the ultraviolet absorber or the microcapsules encapsulating them in the cosmetic is not particularly limited and varies depending on the dosage form of the cosmetic, but as the content of component (B) in the total cosmetic, it is 0.5 to 30% by mass, preferably 1 to 15% by mass.

[0061] In the cosmetic of the present invention, in addition to this essential component, components commonly used in cosmetics can be appropriately blended, such as oily raw materials, surfactants, humectants, high molecular compounds, antioxidants, whitening agents, medicaments, ultraviolet absorbers (other than components (A), (B), ethylhexyl methoxycinnamate, and octocrylene), metal ion chelating agents, proteins, protein hydrolysates or their derivatives, amino acids or their derivatives, pH adjusters, preservatives, etc.

[0062] Examples of the oily raw materials, surfactants, humectants, high molecular compounds, antioxidants, whitening agents, medicaments, ultraviolet absorbers (other than components (A), (B), ethylhexyl methoxycinnamate, and octocrylene), metal ion chelating agents, proteins, protein hydrolysates or their derivatives, amino acids or their derivatives, pH adjusters, preservatives, etc. include the same substances as those described in JP-A-2022-028125.

[0063] The components commonly used in the cosmetic can be used alone or in combination of two or more.

[0064] The cosmetic containing the composition containing the ultraviolet absorber of the present invention or the microcapsules encapsulating them can be implemented in various forms such as liquid, emulsion, cream, solid, gel, paste, etc. In addition, the cosmetic of the present invention can be an oil-in-water type emulsion system, a water-in-oil type emulsion system, etc., and there is no particular limitation on its dosage form, and it can be implemented as various cosmetics such as skin care cosmetics such as emulsions, creams, beauty liquids, lipsticks, sunscreen agents, foundation, makeup bases, eyeshadows, lipsticks, lip glosses, etc., and hair cosmetics such as hair creams, hair styling agents, etc.

[0065] Examples

[0066] Next, examples are given to specifically illustrate the present invention, but the scope of the present invention is not limited to these examples. The values described in the following examples and the like are all in mass%.

[0067] Examples 1 to 12 and Comparative Examples 1 to 7: Compositions Containing Ultraviolet Absorbents

[0068] Compositions containing ultraviolet absorbents were prepared by the compositions shown in Tables 1, 2, and 3 and the following manufacturing method. For the obtained compositions containing ultraviolet absorbents, the presence or absence of crystal precipitation was evaluated by the following evaluation method, and the evaluation results are also shown in Tables 1, 2, and 3. In the composition shown in Table 3, an oil agent other than the component (A) was used as the component (a) to replace the component (A) of the present invention.

[0069] (Manufacturing Method)

[0070] The component (A) or (a) and the component (B) described in Tables 1, 2, and 3 were heated to 70°C and uniformly dissolved. Then, it was allowed to cool to room temperature to obtain a composition containing an ultraviolet absorbent.

[0071] (Evaluation Method)

[0072] The prepared composition containing an ultraviolet absorbent was allowed to stand in a constant temperature bath at 5°C for 2 weeks and 4 weeks, and then further allowed to stand at room temperature for 1 day, and then visually confirmed whether crystals were precipitated, and evaluated according to the following judgment criteria.

[0073] (Evaluation Criteria)

[0074] ◎: No crystals of the ultraviolet absorbent were observed at all.

[0075] ○: Slightly observed crystals of the ultraviolet absorbent.

[0076] ×: Clearly observed crystals of the ultraviolet absorbent.

[0077]

[0078]

[0079]

[0080] As can be seen from the results of Tables 1, 2, and 3, in Examples 1 to 12 containing a combination of component (A) citrate, a salicylic acid-based oil agent, and component (B) a UV absorber that is solid at 25°C, compared with Comparative Examples 3 to 6 containing tri(caprylic / capric) glycerol and glycerol (diisostearate / hydrogenated rosin acid) as oil agents other than component (A), the precipitation of crystals of the solid UV absorber was suppressed. Furthermore, it can be seen that compared with the case where ethylhexyl methoxycinnamate, which is considered to have a high property of dissolving the solid UV absorber, was used instead of component (A) (Comparative Examples 1, 2, and 7) (restricted for use in various countries as described above), the precipitation of crystals of the solid UV absorber was suppressed to an equivalent or better extent.

[0081] [Examples 13 to 15 and Comparative Examples 8 and 9: Microcapsules of a composition containing a UV absorber]

[0082] Using the manufacturing method based on the methods described in the aforementioned Japanese Patent No. 4562050 and Japanese Patent No. 6733322, microcapsules were manufactured with the composition containing a UV absorber manufactured in Tables 1, 2, and 3 as the core material.

[0083] Example 13: Manufacture of microcapsules with N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed silk, a co-condensate of methyltriethoxysilane and octyltriethoxysilane as the wall film, and encapsulating acetyl tributyl citrate and diethylamino hydroxybenzoyl benzoic acid hexyl ester

[0084] In a 2-liter glass round reaction vessel with a lid, 110.5 g of an 18.1% aqueous solution of N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed silk was added, and 89.5 g of water was added to adjust the solid component concentration to 10%. A 17% hydrochloric acid aqueous solution was added to adjust the pH to 2.0. The solution was heated to 50°C, and while stirring, a mixed solution of 32.4 g of methyltriethoxysilane [KBE-13 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] and 10.1 g of octyltriethoxysilane [A-137 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] was added dropwise over about 30 minutes. After the addition was completed, stirring was continued at 50°C for 2.5 hours. Then, an aqueous sodium hydroxide solution was added dropwise to adjust the pH to 6.0, and while stirring at 600 rpm, a mixed solution of 245.16 g of acetyl tributyl citrate and 163.44 g of diethylamino hydroxybenzoyl benzoic acid hexyl ester, which is the composition containing a UV absorber of Example 2, was added dropwise over about 2.5 hours. Then, using a homogenizer, the solution was stirred at 10,000 rpm at 50°C to finely emulsify the solution.

[0085] Next, in order to prevent the aggregation of the capsule wall film, 4.0 g of trimethylchlorosilane [LS-260 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] was added to the emulsion while stirring at 50°C and 400 rpm. After stirring for 1 hour, the pH was adjusted to 6.0 with a 5% aqueous sodium hydroxide solution. Then, the temperature of the reaction solution was raised to reflux, and while distilling off the vapor containing alcohol, reflux was continued at 400 rpm for about 2 hours. Water and a preservative were added to the reaction solution, and it was slowly cooled to room temperature while stirring at 100 rpm to obtain 719.5 g of a dispersion of microcapsules encapsulating acetyl tributyl citrate and diethylamino hydroxybenzoyl benzoic acid hexyl ester (solid content concentration 61.15%, encapsulation rate 90%).

[0086] For the obtained microcapsule dispersion, the particle size distribution of the capsules was measured using SALD-2000 (trade name) manufactured by Shimadzu Corporation. As a result, it was confirmed that the capsules with an average particle diameter of 2.202 μm were distributed in a narrow range with a standard deviation of 0.192. The smaller the value of the standard deviation, the narrower the distribution width.

[0087] Example 14: Manufacture of microcapsules with N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed silk, a co-condensate of methyltriethoxysilane and octyltriethoxysilane as the wall film, and encapsulating homosalate and diethylamino hydroxybenzoyl benzoic acid hexyl ester

[0088] The encapsulated core material was set as the composition containing the ultraviolet absorber in Example 5, that is, a mixed solution of 245.1 g of homosalate and 163.44 g of diethylamino hydroxybenzoyl benzoic acid hexyl ester. Except for this, the operation was the same as in Example 13 to obtain 723.5 g of a dispersion of microcapsules encapsulating homosalate and diethylamino hydroxybenzoyl benzoic acid hexyl ester (solid content concentration 60.58%, encapsulation rate 90%). The particle size distribution was measured in the same manner as in Example 13. As a result, the average particle diameter was 1.928 μm and the standard deviation was 0.130.

[0089] Example 15: Manufacture of microcapsules with N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl serine and a co-condensate of methyltriethoxysilane as the wall film, and encapsulating homosalate and bis-ethylhexyloxyphenol methoxyphenyl triazine

[0090] As raw materials, 104.8 g of a 22.9% aqueous solution of N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propylserine, 95.2 g of water for concentration adjustment, 34.0 g of methyltriethoxysilane (0 g of octyltriethoxysilane), and the core substance to be encapsulated was a mixed solution of 306.45 g of homosalate and 102.15 g of bis-ethylhexyloxyphenol methoxyphenyltriazine, which was the composition containing an ultraviolet absorber in Example 7. The amount of trimethylchlorosilane added to prevent the aggregation of the capsule wall film was 5.1 g. Otherwise, the operation was the same as in Example 13, and a dispersion of microcapsules encapsulating homosalate and bis-ethylhexyloxyphenol methoxyphenyltriazine (solid content concentration 60.82%, encapsulation rate 90%) of 720.5 g was obtained. The particle size distribution was measured in the same manner as in Example 13, and the results showed that the average particle size was 1.642 μm and the standard deviation was 0.119.

[0091] Comparative Example 8: Preparation of microcapsules with a copolymer of N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed silk, methyltriethoxysilane, and octyltriethoxysilane as the wall film and encapsulating ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexanoate

[0092] Except that the encapsulated substance was a mixed solution of 245.16 g of ethylhexyl methoxycinnamate and 163.44 g of diethylamino hydroxybenzoyl hexanoate, which was the composition containing an ultraviolet absorber in Comparative Example 1, the operation was the same as in Example 13, and a dispersion of microcapsules encapsulating ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexanoate (solid content concentration 60.18%, encapsulation rate 90%) of 725.6 g was obtained. The particle size distribution was measured in the same manner as in Example 13, and the results showed that the average particle size was 1.899 μm and the standard deviation was 0.150.

[0093] Comparative Example 9: Preparation of microcapsules with a copolymer of N-[2-hydroxy-3-(3'-trihydroxysilyl)propoxy]propyl hydrolyzed silk, methyltriethoxysilane, and octyltriethoxysilane as the wall film and encapsulating tri(caprylic / capric) glycerol and bis-ethylhexyloxyphenol methoxyphenyltriazine

[0094] Except that the encapsulated core substance was set as the composition containing an ultraviolet absorber in Comparative Example 3, i.e., a mixed solution of 367.74 g of glyceryl tri (caprylate / caprate) and 40.86 g of bis-ethylhexyloxyphenol methoxyphenyl triazine, the operation was carried out in the same manner as in Example 13 to obtain 740.6 g of a dispersion of microcapsules encapsulating glyceryl tri (caprylate / caprate) and bis-ethylhexyloxyphenol methoxyphenyl triazine (solid content concentration: 59.82%, encapsulation rate: 90%). The particle size distribution was measured in the same manner as in Example 13, and as a result, the average particle size was 2.506 μm and the standard deviation was 0.182.

[0095] (Evaluation of the stability of microcapsules encapsulating a composition containing an ultraviolet absorber)

[0096] The aqueous dispersions of the microcapsules prepared in Examples 13 to 15 and Comparative Examples 8 and 9 were allowed to stand in a constant temperature bath at 5°C for 2 weeks and 4 weeks, and further at room temperature for 1 day, and then visually confirmed whether crystals were precipitated, and evaluated according to the same judgment criteria as the evaluation criteria for the stability of the composition containing an ultraviolet absorber described above. The evaluation results are shown in Table 4.

[0097]

[0098] It is clearly shown from the results shown in Table 4 that the microcapsules of the present invention (the microcapsules prepared in Examples 13 to 15) are superior in the stability over time under low temperature conditions as compared with the microcapsules outside the present invention (the microcapsules prepared in Comparative Examples 8 and 9).

[0099] Examples 16 to 21 and Comparative Examples 10 to 13: Sunscreen

[0100] A sunscreen containing microcapsules was prepared, and the feel during use when applied to the skin was evaluated. The microcapsules encapsulated the composition containing an ultraviolet absorber prepared in Examples 1 to 12 and Comparative Examples 1 to 7, or the composition containing an ultraviolet absorber prepared in Examples 13 to 15 and Comparative Examples 8 and 9.

[0101] (Evaluation of the feel during use)

[0102] The prepared sunscreen was stored at 5°C for 4 weeks, and after returning to room temperature, it was applied to the skin. The degree of smoothness, stickiness, ease of spreading, dry feeling, and oily feeling at this time was evaluated by a panel of 10 members according to the following evaluation criteria.

[0103] (Evaluation criteria)

[0104] Smoothness

[0105] 3: Very smooth

[0106] 2: Slightly smooth

[0107] 1: Rough

[0108] Stickiness

[0109] 3: No stickiness

[0110] 2: Slightly sticky

[0111] 1: Very sticky

[0112] Spreading ease

[0113] 3: Spreading ease is very good

[0114] 2: Spreading ease is good

[0115] 1: Lack of spreading ease

[0116] Dry feeling

[0117] 3: High dry feeling, very good

[0118] 2: Has a dry feeling, good

[0119] 1: Lack of dry feeling

[0120] Oily feeling

[0121] 3: No oily feeling, very good

[0122] 2: Little oily feeling, good

[0123] 1: Has an oily feeling

[0124] Based on the above evaluation results, the following classification is made. The results are shown in Tables 5 and 6.

[0125] ◎: The total score of 10 people is 25 or more

[0126] ○: The total score of 10 people is 15 - 24

[0127] ×: The total score of 10 people is 14 or less

[0128]

[0129] *1 is formulated with SIMULGEL EG QD (trade name, manufactured by SEPPIC), *2 is formulated with Seisept - H (trade name, manufactured by Seiwa Kasei K.K.).

[0130]

[0131] *1 is formulated with SIMULGEL EG QD (trade name, manufactured by SEPPIC), *2 is formulated with Seisept - H (trade name, manufactured by Seiwa Kasei K.K.).

[0132] As shown in Tables 5 and 6, it is clear that the sunscreen containing the ultraviolet absorber composition of the present invention or the microcapsules encapsulating them (Examples 16 to 21) has a more excellent touch compared to the sunscreen containing the composition other than the present invention or the microcapsules encapsulating them (Comparative Examples 10 to 13). In addition, in the sunscreen containing the microcapsules with the ultraviolet absorber composition of the present invention as the core substance (Examples 19 to 21), it has a more excellent touch compared to the sunscreen containing the non-encapsulated ultraviolet absorber composition (Examples 16 to 18). Although the amount of the ultraviolet absorber added is the same, it is possible to prepare a sunscreen that suppresses the stickiness and oiliness peculiar to the ultraviolet absorber.

Claims

1. A composition containing an ultraviolet absorber, characterized in that, Comprising component (A): a citrate or a salicylic acid-based oil agent, and component (B): an ultraviolet absorber that is solid at 25°C.

2. The composition containing an ultraviolet absorber according to claim 1, characterized in that, Component (A) is a citrate.

3. The composition containing an ultraviolet absorber according to claim 2, characterized in that, The citrate is tributyl citrate or acetyl tributyl citrate.

4. The composition containing an ultraviolet absorber according to claim 1, characterized in that, Component (A) is a salicylic acid-based oil agent.

5. The composition containing an ultraviolet absorber according to claim 4, wherein The salicylic acid-based oil agent is homosalate or ethylhexyl salicylate.

6. A microcapsule that uses a copolymer of a silylated peptide or a silylated amino acid and a silane compound as a wall material, and encapsulates the ultraviolet absorber-containing composition according to claim 1 as a core material.

7. A microcapsule that uses a copolymer of a silylated peptide or a silylated amino acid and a silane compound as a wall material, and encapsulates the ultraviolet absorber-containing composition according to claim 2 or 3 as a core material.

8. A microcapsule that uses a copolymer of a silylated peptide or a silylated amino acid and a silane compound as a wall material, and encapsulates the ultraviolet absorber-containing composition according to claim 4 or 5 as a core material.

9. A cosmetic, characterized in that, Containing the ultraviolet absorber-containing composition according to any one of claims 1 to 5.

10. A cosmetic, characterized in that, Containing the microcapsule according to any one of claims 6 to 8.

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