Sunscreen cosmetics and mist-type sunscreen products

Abstract

This product provides a sunscreen cosmetic that, while being water-based, achieves a high SPF effect and also offers excellent usability, stability, and separation / redispersion properties. [Solution] A sunscreen cosmetic comprising an aqueous component and an oily component, wherein the aqueous formulation comprises the following components (A) to (D): (A) an organic ultraviolet absorber, (B) a polyvalent metal salt of octenyl succinate starch (powder), (C) an associative thickener, and (D) ethanol.

Description

[Technical Field]

[0001] This invention relates to an aqueous sunscreen cosmetic formulation containing an aqueous component and an oily component, and a mist-type sunscreen cosmetic using the said sunscreen cosmetic. [Background technology]

[0002] Mist-type sunscreens, which are formulated by filling a spray bottle with sunscreen, are popular with many consumers due to their portability and ease of use. Traditionally, most commercially available mist-type sunscreens were based on oil-based ingredients.

[0003] Sunscreens based on oil-based ingredients offer good skin compatibility and long-lasting protection, but they have the drawback of leaving a sticky or greasy feeling when sprayed on the skin, resulting in an unpleasant user experience. While incorporating powder into the cosmetic is effective in reducing stickiness and greasiness, mist-type sunscreens based on oil-based ingredients often use low-viscosity oil components for ease of spraying. This makes it difficult to stably disperse the powder in the liquid, leading to sedimentation, caking, or clumping. Furthermore, oil-based ingredients themselves may be unsuitable for some individuals.

[0004] Therefore, in recent years, sunscreen cosmetics based on water-based components have attracted attention. For example, a two-layer type sunscreen cosmetic has been developed in which the upper layer is a water-based layer and the lower layer is an emulsion layer containing powder (see, for example, Patent Document 1). The sunscreen cosmetic described in Patent Document 1 contains, as its main components, an organic ultraviolet absorber, a volatile silicone oil, a lipophilic powder with an average particle size of 5.0 to 20 μm, and polyvinylpyrrolidone, and is used by filling it into a spray container. In this two-layer type sunscreen cosmetic, the water-based layer and the emulsion layer are separated in the spray container before use, but by shaking the spray container before use, the water-based layer and the emulsion layer are mixed, and the organic ultraviolet absorber and lipophilic powder are dispersed throughout the liquid. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2023-85020 [Overview of the project] [Problems that the invention aims to solve]

[0006] Incidentally, sunscreen cosmetics that protect the skin from ultraviolet rays are required to have not only a high SPF effect, but also excellent stability and usability. In this regard, the sunscreen cosmetic described in Patent Document 1 is based on water-based components, so there is room for improvement in its performance as a sunscreen (achieving a high SPF effect). Furthermore, when the spray container is shaken before use, the emulsion layer containing the lower layer of powder disperses into fine emulsion particles throughout the liquid, but when sprayed onto the skin in this state, the area of ​​skin to which the sunscreen cosmetic is applied turns white, a phenomenon known as "white cast," which is a concern as it negatively affects the usability. Moreover, it is ideal for sunscreen cosmetics to maintain their initial state even after opening and be usable for a long period of time (excellent stability), but the sunscreen cosmetic described in Patent Document 1 has room for improvement in terms of separation when not in use (during storage) and redispersibility when used, and further improvement is desired in terms of appearance, which affects the product value.

[0007] This invention has been made in view of the above-mentioned problems, and aims to provide a sunscreen cosmetic that is based on aqueous components, yet achieves a high SPF effect, and furthermore, is excellent not only in terms of usability and stability but also in terms of separation / redispersion properties, as well as a mist-type sunscreen cosmetic using said sunscreen cosmetic. [Means for solving the problem]

[0008] The characteristic configuration of the sunscreen cosmetic according to the present invention, which solves the above problems, is as follows: A sunscreen cosmetic containing water-based components and oil-based components, The following components (A) to (D): (A) Organic UV absorbers (B) Octenyl succinate starch polyvalent metal salt (powder) (C) Associative thickener (D) Ethanol The key feature is that it is an aqueous formulation containing [specific ingredient].

[0009] According to this sunscreen cosmetic composition, which contains both an aqueous component and an oily component, by using an aqueous formulation (water-based) containing (A) an organic UV absorber, (B) a polyvalent metal salt of starch octenyl succinate (powder), (C) an associative thickener, and (D) ethanol, when the container is shaken before use to mix the aqueous and oily components, the organic UV absorber (oily component) containing the polyvalent metal salt of starch octenyl succinate disperses throughout the aqueous component as fine droplets. As a result, the organic UV absorber and the polyvalent metal salt of starch octenyl succinate are evenly dispersed throughout the liquid. Here, the droplets (oily component) formed in the aqueous component are not emulsified with a surfactant, and are therefore larger than the size of typical emulsion particles. This makes it possible to provide a sunscreen cosmetic that achieves a high SPF effect while having excellent usability and stability, eliminating white cast, and also having excellent separation and redispersibility.

[0010] In the sunscreen cosmetic composition according to the present invention, The above-mentioned component (A) preferably has an overall specific gravity of 1.01 or higher.

[0011] According to the sunscreen cosmetic of the present constitution, since the specific gravity of component (A) as a whole is 1.01 or more, when the sunscreen cosmetic is allowed to stand after use, droplets formed in the aqueous component settle, and a layer (oil phase) of an organic ultraviolet absorber containing octenyl succinate starch polyvalent metal salt is formed below the layer (aqueous phase) containing ethanol and water. As described above, the sunscreen cosmetic of the present constitution has good separability between the aqueous phase and the oil phase when allowed to stand, while the oil phase is uniformly redispersed in the aqueous phase when shaken (when used). Therefore, while having good stability and feeling of use during use, it exhibits a clean appearance with a clear interface between the aqueous phase and the oil phase when not in use, and can be said to have high value as a commercial product.

[0012] In the sunscreen cosmetic according to the present invention, The content of component (D) is preferably 20% by mass or less.

[0013] According to the sunscreen cosmetic of the present constitution, by setting the content of ethanol to 20% by mass or less, the octenyl succinate starch polyvalent metal salt can be stabilized in the oil phase in a state where the aqueous component and the oily component are mixed. In addition, by doing so, the SPF value boosting effect of the octenyl succinate starch polyvalent metal salt can be stably exhibited. Furthermore, by reducing the content of ethanol, it becomes difficult for users to feel dryness, and moreover, even people with sensitive skin or people sensitive to alcohol can use the sunscreen cosmetic with peace of mind.

[0014] In the sunscreen cosmetic according to the present invention, (E) It is preferable that the content of water is 50% by mass or more.

[0015] According to the sunscreen cosmetic of the present constitution, it can be made into a high water content type containing 50% by mass or more of water, and can provide a sunscreen cosmetic excellent in use feeling such as "freshness", "light spreadability" and "good skin compatibility".

[0016] The characteristic configuration of the mist-type sunscreen cosmetic according to the present invention, which solves the above problems, is as follows: The product consists of filling a spray bottle with any one of the sunscreen cosmetics described above.

[0017] This mist-type sunscreen cosmetic, being water-based, is easy to use, achieves a high SPF effect, offers excellent feel and stability, eliminates white cast, and provides a sunscreen cosmetic with excellent separation and redispersibility properties.

[0018] In the mist-type sunscreen cosmetic according to the present invention, When the spray container containing the sunscreen cosmetic is held and shaken 20 times, it is preferable that the oily component disperses the powder by forming droplets containing the powder (excluding emulsion particles) in the aqueous component.

[0019] In this mist-type sunscreen cosmetic, the oily component forms droplets (excluding emulsion particles) containing powder (polyvalent metal octenyl succinate starch salt) in the aqueous component, allowing the powder to be dispersed throughout the liquid. This improves the feel and stability of the product while efficiently providing the SPF booster effect of the polyvalent metal octenyl succinate starch salt.

[0020] In the mist-type sunscreen cosmetic according to the present invention, When the spray container containing the sunscreen cosmetic is held and shaken 20 times, and then placed on a horizontal surface, it is preferable that the mixture of the aqueous component and the oily component separates again within 60 minutes.

[0021] With this mist-type sunscreen cosmetic composition, the mixture of water-based and oil-based components separates again within 60 minutes (i.e., an interface between the upper and lower layers is established), thus achieving good separation and redispersion properties. Furthermore, when the mixture separates again, there is less cloudiness, and the interface between the water-phase and oil-phase presents a clear and beautiful appearance, resulting in a product with high value. [Brief explanation of the drawing]

[0022] [Figure 1] Figure 1 is a magnified photograph of droplets formed when a container (sunscreen cosmetic) filled with the sunscreen cosmetic of the present invention is shaken. [Figure 2] Figure 2 shows photographs of (a) the sunscreen cosmetic of the present invention and (b) a conventional cosmetic, both applied to the skin. [Modes for carrying out the invention]

[0023] The following describes embodiments of the sunscreen cosmetic composition according to the present invention and a mist-type sunscreen cosmetic product using the sunscreen cosmetic composition. However, the present invention is not limited to the following description, and various modifications are possible as long as they do not depart from the technical concept of the present invention.

[0024] <Sunscreen cosmetics> The sunscreen cosmetic according to the present invention is a water-based cosmetic formulation containing an aqueous component (aqueous phase) and an oily component (oil phase), the main components being (A) an organic ultraviolet absorber, (B) octenyl succinate starch polyvalent metal salt (powder), (C) an associative thickener, and (D) ethanol. The sunscreen cosmetic according to the present invention can achieve a high SPF effect without using surfactants, and furthermore, it has excellent usability, stability, and separation / redispersion properties. In addition, it exhibits a beautiful appearance without clumping or caking, making it a highly valuable product. Each component contained in the sunscreen cosmetic according to the present invention is described below.

[0025] In the following explanation, aqueous components refer to components that form the aqueous phase, and oily components refer to components that form the oil phase. However, aqueous components and the aqueous phase may be treated as synonymous, and oily components and the oil phase may be treated as synonymous.

[0026] [(A) Organic UV absorbers] The organic ultraviolet absorber, which is component (A), is included in the oil phase of the sunscreen cosmetic. The water-based sunscreen cosmetic according to the present invention is mixed with the water-based and oil-based components by shaking before use. At this time, the organic ultraviolet absorber, which is the oil-based component, is in a state containing (coexisting with) the polyvalent metal salt of starch octenyl succinate (powder), which is component (B) described later and is also an oil-based component. The oil-based component (oil phase) disperses throughout the liquid as fine droplets in the water-based component (aqueous phase), and as a result, the organic ultraviolet absorber and the polyvalent metal salt of starch octenyl succinate are evenly dispersed throughout the liquid.

[0027] Figure 1 shows an example of a magnified photograph of droplets formed when a container filled with sunscreen cosmetic is shaken. Figure 1 shows that droplets (oil phase) consisting of an oily component incorporating powder are formed in the aqueous component (aqueous phase) which appears black in the background. Since these droplets are not emulsified with a surfactant, they are visible to the naked eye (for example, about 100 μm to several hundred μm). The size of these droplets is larger than the size of emulsion particles that are not visible to the naked eye (for example, about several μm to several tens of μm). As demonstrated in the examples described later, the sunscreen cosmetic according to the present invention, which can form such droplets, achieves a high SPF effect while also having excellent usability, stability, and separation / redispersibility.

[0028] The organic UV absorber preferably has an overall specific gravity of 1.01 or higher. Here, "overall" means the organic UV absorber as a whole. For example, if multiple types of organic UV absorbers are included, it is acceptable even if the specific gravity of one of them is less than 1.01, as long as the overall specific gravity of the organic UV absorbers is 1.01 or higher. The specific gravity is the value at 20°C. When the type of organic UV absorber is selected so that the overall specific gravity of the organic UV absorber is 1.01 or higher, when the sunscreen cosmetic is left to stand after use, the droplets formed in the aqueous component will settle, and the oil phase containing the organic UV absorber will form below the aqueous phase. In such a sunscreen cosmetic, the separation of the aqueous phase and oil phase is good when left to stand, but when shaken (during use), the oil phase is evenly redispersed in the aqueous phase. Therefore, while it has good stability and feel when used, when not in use (during storage), it exhibits a clean appearance with a clear interface between the aqueous phase and the oil phase, resulting in a product with high value.

[0029] The types of organic UV absorbers are not particularly limited as long as they can be incorporated into cosmetics. For example, cinnamic acid derivatives such as ethylhexyl methoxycinnamate, ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate; PABA derivatives such as para-aminobenzoic acid, ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, glyceryl PABA; salicylic acid derivatives such as homosalate, ethylhexyl salicylate, dipropylene glycol salicylate, TEA salicylate; benzophenone-1, benzophenone-2, Benzophenone derivatives such as benzophenone-3 or oxybenzone, benzophenone-4, benzophenone-5, benzophenone-6, benzophenone-8, benzophenone-9, benzophenone-12; benzylidene derivatives such as 3-benzylidene, 4-methylbenzylidene, benzylidene sulfonic acid, benzalkonium methosulfate, terephthalylidene disulfonic acid, polyacrylamide methylbenzylidene; ethylhexyl Triazine derivatives such as triazone, anisotriazine, diethylhexylbutamide triazone, 2,4,6-tris(diisobutyl-4'-aminobenzalmalonate)-s-triazine, ethylhexyltriazone, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine; phenylbenzimidazole derivatives such as phenylbenzimidazole sulfonic acid and phenyldibenzimidazole tetrasulfonate disodium; drometrizole trisiloxane Phenylbenzotriazole derivatives such as methylenebis(benzotriazolyltetramethylbutylphenol); anthranil derivatives such as menthyl anthranilate; imidazoline derivatives such as 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate; benzalmalonate derivatives such as polyorganosiloxanes having a benzalmalonate functional group; 4,4-diarylbutadiene derivatives such as 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene;Examples of organic UV absorbers include octocrylene, 2-[4-(diethylamino)-2-hydroxybenzoyl]hexyl benzoate, diethylamino hydroxybenzoyl hexyl benzoate, 4-tert-butyl-4'-methoxydibenzoylmethane, and bis-ethylhexyloxyphenol methoxyphenyl triazine. These organic UV absorbers can be used individually, or two or more organic UV absorbers may be used in combination. Preferred organic UV absorbers include, for example, ethylhexyl methoxycinnamate, diethylamino hydroxybenzoyl hexyl benzoate, dimethoxybenzylidene dioxoimidazolidine propionate octyl, and t-butyl methoxydibenzoylmethane. From the viewpoint of UV protection function and safety for the skin, ethylhexyl methoxycinnamate (UVB absorber), which has high UVB protection function, is particularly preferred. Furthermore, to provide UV protection across a wide wavelength range, it is possible to use ethylhexyl methoxycinnamate in combination with diethylamino hydroxybenzoyl hexyl benzoate (a UVA absorber) which has high UVA protection capabilities. The specific gravity of ethylhexyl methoxycinnamate at 20°C is 1.01, while the specific gravity of diethylamino hydroxybenzoyl hexyl benzoate at 20°C is 1.03-1.05.

[0030] The UVB absorber content in sunscreen cosmetics is preferably 3 to 10% by mass, and more preferably 5 to 8% by mass. The UVA absorber content in sunscreen cosmetics is preferably 0.3 to 3% by mass, and more preferably 1 to 2% by mass. If the content of organic ultraviolet absorbers is within the above ranges, it is possible to maintain practical ultraviolet protection function as a sunscreen cosmetic while avoiding a decrease in usability due to stickiness or greasiness when applied to the skin.

[0031] [(B) Starch octenyl succinate polyvalent metal salt] (B) Component octenyl succinate starch polyvalent metal salt is in powder form and is included in the oily component (oil phase) of sunscreen cosmetics.

[0032] Examples of polyvalent metal salts of starch octenyl succinate include calcium starch octenyl succinate and aluminum starch octenyl succinate. These polyvalent metal salts of starch octenyl succinate may be used individually or in combination.

[0033] The content of polyvalent metal salt of starch octenyl succinate in sunscreen cosmetics is preferably 1 to 7% by mass, more preferably 2 to 5% by mass, and even more preferably 2 to 3% by mass. If the content of polyvalent metal salt of starch octenyl succinate is within the above range, it is possible to avoid a decrease in the feel of the product due to stickiness or greasiness when applied to the skin. Furthermore, when the sunscreen cosmetic remaining after use is stored, for example, by standing on a dressing table, the cloudiness of the liquid due to the powder is not noticeable, and a clean interface is formed between the aqueous phase and the oil phase. Sunscreen cosmetics exhibiting such a clean appearance have excellent separation / redispersibility and have high commercial value.

[0034] Incidentally, while the inventors were conducting numerous trials and errors in search of a higher-performance sunscreen cosmetic, they surprisingly discovered that when an organic UV absorber is used in combination with a polyvalent metal salt of starch octenyl succinate, the SPF value of the organic UV absorber is specifically increased (SPF booster effect). In particular, a very high SPF booster effect was observed with calcium starch octenyl succinate and / or aluminum starch octenyl succinate. This SPF booster effect is an unknown phenomenon that has not been known to those skilled in the art until now. It is thought that polyvalent metal salts of starch octenyl succinate can function as efficacy enhancers that enhance the UV protection performance (SPF value) of organic UV absorbers. The SPF booster effect will be explained in detail in the examples described below.

[0035] [(C) Associative thickener] (C) The associative thickener is a viscous semi-solid or jelly-like substance that is included in the aqueous phase of sunscreen cosmetics. The associative thickener is given by the following formula (1): R1 -{(O-R 2 ) k -OCONH-R 3 [-NHCOO-(R 4 -O) n -R 5 h} m ···(1) (wherein R 1 , R 2 and R 4 are the same or different hydrocarbon groups from each other, R 3 is a hydrocarbon group that may have a urethane bond, R 5 is a linear, branched or secondary hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, and k and n are independently numbers from 0 to 1000.) It is preferably a hydrophobically modified polyether urethane represented by the above formula. By using a hydrophobically modified polyether urethane, when the sunscreen cosmetic is left standing, the aqueous phase and the oil phase are clearly separated. On the other hand, when the aqueous component and the oily component are mixed, the oily organic ultraviolet absorber contains the polyvalent metal salt of starch octenylsuccinate, which is also an oily powder (in a coexisting state), the oily components (oil phase) form fine droplets in the aqueous component (aqueous phase) and disperse throughout the entire liquid. As a result, the organic ultraviolet absorber and the polyvalent metal salt of starch octenylsuccinate are uniformly dispersed throughout the entire liquid. When the sunscreen cosmetic is sprayed (applied) onto the skin in this state, the droplets in the aqueous component are not as fine as those in an emulsion (emulsified particles), so the "whitening" phenomenon, where the area of the skin with the sunscreen cosmetic looks white, does not occur, and a beautiful finish can be obtained. In addition, in the spray pattern when the sunscreen cosmetic is sprayed onto the skin, the variation in the spray amount between the central area and the peripheral area of the spray pattern is small, so uniform application to the skin can be achieved. Figure 2 exemplifies photographs of (a) the sunscreen cosmetic of the present invention and (b) a conventional cosmetic, each in a state sprayed onto the skin. According to Figure 2, it can be confirmed that the spray pattern of the cosmetic applied to the skin is more uniform for the sunscreen cosmetic of the present invention compared to the conventional cosmetic.

[0036] ​ As the hydrophobic modified polyether urethane, polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer ((PEG-240 / decyltetradeceth-20 / HDI) copolymer) is preferred. Cosmetics containing (PEG-240 / decyltetradeceth-20 / HDI) copolymer are easy to use and have further improved stability and feel.

[0037] The content of the associative thickener in the sunscreen cosmetic is preferably 0.3 to 0.75% by mass. If the content of the associative thickener is within the above range, it is possible to maintain a clean appearance (a clear interface between the aqueous and oil phases) when the sunscreen cosmetic is left to stand, while suppressing a decrease in usability due to increased viscosity and the occurrence of a white cast when applied to the skin.

[0038] [(D) Ethanol] (D) Ethanol, which is component of sunscreen cosmetics, is included in the aqueous phase.

[0039] The ethanol content in sunscreen cosmetics is preferably 20% by mass or less. By limiting the ethanol content to 20% by mass or less, the polyvalent metal salt of starch octenyl succinate can be stabilized in the oil phase when the aqueous and oily components are mixed. This also allows the SPF booster effect of the polyvalent metal salt of starch octenyl succinate to be stably exerted. Furthermore, by reducing the ethanol content, the product is less likely to cause dryness, and even people with sensitive skin or those sensitive to alcohol can use the sunscreen cosmetic with peace of mind. The lower limit of the ethanol content is not particularly limited as long as it is valid as an aqueous sunscreen cosmetic, but for example, it can be 7% by mass or more.

[0040] [(E)Water] Since the sunscreen cosmetic composition according to the present invention is an aqueous formula, it is preferable that it contains 50% by mass or more of water. In this case, it becomes a high-water-content cosmetic composition, and it is possible to realize a sunscreen cosmetic composition with excellent usability, such as "freshness," "lightness of spreadability," and "skin compatibility." As the water for the cosmetic composition, it is preferable to use purified water, which is designated as a Class 3 pharmaceutical product in the Japanese Pharmacopoeia, as well as highly purified water such as distilled water or ion-exchanged water.

[0041] [(F) Other ingredients] The sunscreen cosmetic composition according to the present invention may contain, as (F) other ingredients, ingredients that can be used as cosmetics in addition to the above ingredients. Examples of other ingredients include moisturizing ingredients such as PEG / PPG / polybutylene glycol-8 / 5 / 3 glycerin and butene glycol, fragrance ingredients such as L-menthol, and preservatives.

[0042] <Sunscreen cosmetics> The sunscreen cosmetic according to the present invention can be configured as a mist-type sunscreen cosmetic (in the form of a product distributed on the market) by filling a spray container with the sunscreen cosmetic composition according to the present invention described above. As the spray container, a push-type spray container equipped with a push button, a trigger-type spray container equipped with a lever, etc. The appearance of the spray container is preferably transparent or semi-transparent so that the state of the sunscreen cosmetic composition (separation / redispersion state) of the contents can be confirmed. The capacity of the spray container is preferably about 30 to 300 mL, considering daily use and portability. The mist-type sunscreen cosmetic according to the present invention is easy to use because it is an aqueous formula, achieves a high SPF effect, and is a sunscreen cosmetic that is excellent in terms of usability, stability, and separation / redispersion properties.

[0043] <Evaluation of Cosmetics (Makeup)> As explained in "Problems the Invention Aims to Solve," sunscreen cosmetics (cosmetics) must not only have a high SPF effect but also a good feel and high stability. Furthermore, excellent separation / redispersibility, and the clear interface between the aqueous and oil phases when separated, are also important elements for a product. The inventors of this invention investigated criteria for evaluating sunscreen cosmetics (cosmetics) and found that the state of the cosmetic (visual appearance) when the sunscreen cosmetic (spray container) is shaken before use, and the state of the cosmetic (visual appearance) when the sunscreen cosmetic is placed on a horizontal surface after use (after shaking), can affect not only separation / redispersibility but also the stability and feel of the cosmetic. In this invention, sunscreen cosmetics in state (1) below are evaluated as having excellent stability and feel, and sunscreen cosmetics in state (2) below are evaluated as having excellent separation / redispersibility.

[0044] (1) When a spray container containing sunscreen cosmetics is held and shaken 20 times, the oily components form droplets containing powder (excluding emulsion particles) in the aqueous components, resulting in a dispersed state of powder. (2) When the spray container containing the sunscreen cosmetic is held and shaken 20 times, and then left to stand on a horizontal surface, the mixture of the aqueous component and the oily component will separate again within 60 minutes (i.e., an interface between the upper and lower layers will be formed).

[0045] The sunscreen cosmetic (makeup) according to the present invention can achieve states (1) and (2) by being an aqueous formulation containing at least the above components (A) to (D). As a result, the sunscreen cosmetic according to the present invention is evaluated to have excellent usability, stability, separation / redispersion properties, and a beautiful appearance.

[0046] The evaluation method described above is a simple method that allows for evaluation of sunscreen cosmetics (spray containers) based on their appearance, yet it is extremely useful because it allows for accurate assessment of the quality and properties of sunscreen cosmetics. The evaluation results of the sunscreen cosmetic composition according to the present invention will be explained in detail in the examples. [Examples]

[0047] A sunscreen cosmetic was prepared by appropriately blending components (A) to (D) described in the embodiment, water, and other components, and this was filled into a spray bottle to produce a mist-type sunscreen cosmetic. Examples and comparative examples are described below.

[0048] [Example 1] <Preparation of sunscreen cosmetics> As component (A), 7 parts by mass of ethylhexyl methoxycinnamate (Uvinul MC80, manufactured by BASF Japan Ltd.) and 1.5 parts by mass of diethylamino hydroxybenzoyl hexyl benzoate (Uvinul A Plus Granular, manufactured by BASF Japan Ltd.) and as component (B), 2 parts by mass of powdered calcium starch octenyl succinate (Octie NS-1, manufactured by Nippon Denko Chemical Co., Ltd.) were combined to form an oily component. Furthermore, as component (C), 0.5 parts by mass of polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer (Adekanol GT-700, manufactured by ADEKA Corporation), 20 parts by mass of ethanol (Traceable 95 Grade 1, manufactured by Nippon Alcohol Industry Co., Ltd.), and 2% by mass of PEG / PPG / polybutylene glycol-8 / 5 / 3 glycerin (Wilbride S-753D, manufactured by NOF Corporation) were combined to form an aqueous component. These oily and aqueous components were mixed, and water (purified water) was added to make a total of 100 parts by mass to obtain the sunscreen cosmetic composition of Example 1.

[0049] [Comparative Examples 1-5] To compare with the sunscreen cosmetic composition according to the present invention, cosmetic compositions (Comparative Examples 1-5) were prepared by incorporating various silica powders instead of the calcium starch octenyl succinate used in Example 1. Comparative Example 1 contained 2 parts by mass of porous spherical silica [average particle size 30 μm] (Godball E-90C, manufactured by Suzuki Oil & Fat Industry Co., Ltd.), Comparative Example 2 contained 2 parts by mass of non-porous spherical silica [average particle size 13 μm] (Premium Silica 150H, manufactured by Sunjing Co., Ltd.), Comparative Example 3 contained 2 parts by mass of dimethicone-treated porous spherical silica [average particle size 5 μm] (SA-SB-300, manufactured by Miyoshi Chemicals Co., Ltd.), Comparative Example 4 contained 2 parts by mass of hydrophobically treated non-porous spherical silica [average particle size 10 μm] (MiyoFEEL NHS-SB-N1, manufactured by Miyoshi Chemicals Co., Ltd.), and Comparative Example 5 contained 2 parts by mass of porous spherical silica [average particle size 5 μm] (Sunsphere H-53, manufactured by AGC SI-TEC Inc.). These silica powders are conventional cosmetic powders that have been used for a long time.

[0050] <Evaluation of separability / redispersibility> The separation and redispersibility of sunscreen cosmetics were evaluated based on their everyday use. First, the sunscreen cosmetic was filled into a 50 mL transparent spray bottle to create a mist-type sunscreen cosmetic. This sunscreen cosmetic (spray bottle) was placed on a horizontal surface, and the separation of the cosmetic was observed visually. Next, the spray bottle was held and shaken 20 times, then placed back on the horizontal surface, and the redispersion of the cosmetic was observed visually after 60 minutes. The separation and redispersibility of the cosmetic were then evaluated based on the following evaluation criteria.

[0051] [Separability Evaluation Criteria] A: The upper layer (water-based component) and the lower layer (oil-based component containing powder) are clearly separated. B: The interface between the upper and lower layers is not clear. C: It is not separated into upper and lower layers.

[0052] [Redistribution Assessment Criteria] A + The whole thing is finely and uniformly dispersed. A The whole is evenly distributed. B There is some inconsistency in the distribution. C The distribution is uneven.

[0053] Furthermore, in conjunction with the above evaluation of separability / redispersibility, the state of the powder contained in the cosmetic was evaluated based on the following evaluation criteria.

[0054] [Powder state evaluation criteria] A + No clumps of powder are visible at all. A No clumps of powder are visible. B Some clumping or caking of powder may be observed. C The powder is caking (it is not redispersing).

[0055] Table 1 shows the formulation and evaluation of the sunscreen cosmetic of Example 1, as well as the formulation and evaluation of the cosmetics of Comparative Examples 1 to 5. Regarding the formulations in Table 1, "(PEG-240 / decyltetradeceth-20 / HDI) copolymer" listed in the ingredients column refers to polyethylene glycol-decyltetradeceth-20-hexamethylene diisocyanate copolymer. A blank space indicates that the ingredient was not included (the same applies to subsequent examples and comparative examples).

[0056] [Table 1]

[0057] As shown in Table 1, the sunscreen cosmetic of Example 1 has separation properties of A and redispersibility properties of A. + , powder state A +The sunscreen cosmetic composition according to the present invention exhibits excellent separation and redispersibility even in an aqueous formulation with an ethanol content of 20% by mass or less, and the powder does not clump, making it a very convenient product for daily use. In contrast, the cosmetic compositions of Comparative Examples 1 to 5, which contained various silica powders other than calcium octenyl succinate, were evaluated as having A for separation, but B to C for redispersibility. Regarding the powder state, clumping and caking were observed in the cosmetic compositions of Comparative Examples 2 to 5. Thus, in aqueous formulations of cosmetic compositions with an ethanol content of 20% by mass or less, it is difficult to redisperse the various silica powders that have been commonly used in the past, and they cannot be said to be convenient to use as sunscreen cosmetics.

[0058] [Examples 2-6, Comparative Example 6] As shown in Table 2, the sunscreen cosmetics of Examples 2 to 6 were prepared by changing the amount of polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer, which is component (C). Comparative Example 6 was a cosmetic that did not contain polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer. In addition to "separability / redispersibility" and "powder state" as performed in Example 1 and Comparative Examples 1 to 5, "stability" and "feel" as described below were also evaluated.

[0059] <Stability Evaluation> Assuming that sunscreen cosmetics are used across both summer and winter seasons, the stability of the cosmetics at low and high temperatures was evaluated. The sunscreen cosmetics were filled into 50 mL transparent spray bottles to create a mist-type sunscreen cosmetic. These sunscreen cosmetics (spray bottles) were left undisturbed for one month in low temperature (5°C) or high temperature (40°C) environments, and the stability of the cosmetics was evaluated based on the following evaluation criteria. Stability was judged comprehensively based on appearance, redispersibility, mist quality, and feel.

[0060] [Stability Evaluation Criteria] A: Almost no changes were observed from the day after the cosmetic preparation, which is excellent. B: There were no significant changes observed from the day after the cosmetic preparation, indicating good results. C: Changes can be observed from the day following the preparation of the cosmetic product.

[0061] <Evaluation of user experience> Assuming that sunscreen cosmetics are used daily, the user experience of the cosmetic was evaluated. The sunscreen cosmetic was filled into a 50mL transparent spray bottle to create a mist-type sunscreen cosmetic. First, the sunscreen cosmetic (spray bottle) was placed on a horizontal surface to separate the cosmetic into two layers. Then, the spray bottle was held and shaken 20 times before use. The user experience of the cosmetic was evaluated based on the following criteria: "whiteness when applied to the skin (white cast)", "stickiness of the applied film", and "glossiness of the applied film". The evaluation test was conducted by three panelists (sensory evaluation specialists), and the evaluation was decided after each panelist exchanged opinions on the skin condition they independently evaluated.

[0062] [Evaluation Criteria for User Experience] A + : Absolutely none. A Almost none. B : There is a little. C :be.

[0063] Table 2 shows the formulation and evaluation of the cosmetic composition of Comparative Example 6, as well as the formulation and evaluation of the sunscreen cosmetic compositions of Examples 2 to 6.

[0064] [Table 2]

[0065] As shown in Table 2, the sunscreen cosmetic of Example 2, which contained 0.2 parts by mass of polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer, was evaluated as having a separation property of B, a redispersibility of B, and a powder state of B. The sunscreen cosmetic of Example 6, which contained 1 part by mass of polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer, was evaluated as having a separation property of A, a redispersibility of B, and a powder state of A. Although there was a slight decrease in some evaluation items, the sunscreen cosmetics of Examples 3 to 5, which contained amounts in the range of 0.3 to 0.75 parts by mass, were all evaluated as having an A for separation property, redispersibility, and powder state, demonstrating excellent separation and redispersibility. In contrast, the cosmetic of Comparative Example 6, which did not contain polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer, was evaluated as having a C for separation property, redispersibility, and powder state, indicating inferior performance as a cosmetic and poor usability. Based on these results, the amount of polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer in sunscreen cosmetics can be varied within the range of 0.2 to 1 part by mass (mass%), with 0.3 to 0.75 parts by mass (mass%) being preferred. Regarding stability and usability, there was almost no effect observed due to differences in the amount of polyethylene glycol / decyltetradeceth-20 / hexamethylene diisocyanate copolymer.

[0066] [Examples 7-12] As shown in Table 3, sunscreen cosmetics of Examples 7-12 were prepared by changing the type and amount of the polyvalent metal salt of starch octenyl succinate, which is component (B). For the polyvalent metal salt of starch octenyl succinate, aluminum starch octenyl succinate (Examples 7-9) and calcium starch octenyl succinate (Examples 10-12) were used. The amount was changed within the range of 2-5 parts by mass. Evaluations were performed on "separability / redispersibility" and "powder state," as well as "stability" and "feel."

[0067] Table 3 shows the formulations and evaluations of the sunscreen cosmetics in Examples 7 to 12.

[0068] [Table 3]

[0069] As shown in Table 3, the sunscreen cosmetics of Examples 7-9 using aluminum starch octenyl succinate, and the sunscreen cosmetics of Examples 10-12 using calcium starch octenyl succinate, all have a separation property of A and a redispersibility property of A. + It was evaluated as having excellent separation and redispersibility properties. It also received an A rating in powder form. + The sunscreens were rated ~A, and no clumping or caking of the powder was observed, indicating good performance. Regarding stability, the sunscreens of Examples 9 and 12, which contained 5 parts by mass, showed slight decreases in some evaluation items, but this was not a practical problem. Regarding usability, the sunscreens of Examples 7 to 12 were all rated A or higher, indicating excellent usability. Based on these results, the amount of aluminum starch octenyl succinate or calcium starch octenyl succinate in the sunscreens can be changed within a range of at least 2 to 5 parts by mass (mass%), and considering stability, 2 to 3 parts by mass (mass%) is preferable.

[0070] [Examples 13-15, Comparative Examples 7-12] Next, the UV protection function of the sunscreen cosmetic according to the present invention was verified. As shown in Table 4, sunscreen cosmetic compositions of Examples 13 and 14 were prepared, containing (A) ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexyl benzoate, along with (B) calcium starch octenyl succinate, and their SPF values ​​were measured. For comparison, cosmetic compositions without calcium starch octenyl succinate (Comparative Example 7) and cosmetic compositions containing various silica powders instead of calcium starch octenyl succinate (Comparative Examples 8-10) were also prepared, and their SPF values ​​were measured.

[0071] Furthermore, as shown in Table 5, we prepared cosmetics containing calcium starch octenyl succinate along with ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexyl benzoate (Example 15), and cosmetics containing calcium starch octenyl succinate but without ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexyl benzoate (Comparative Examples 11 and 12), and verified whether calcium starch octenyl succinate itself has UV protection properties.

[0072] SPF values ​​were measured in vitro using an SPF analyzer (UV-2000S, Labsphere). The measurement method involved applying 2 mg / cm of sunscreen cosmetic to Blenderm® surgical tape (3M). 2 The material was uniformly applied, and the SPF value in the 290-400 nm range was measured using an SPF analyzer. Evaluation was conducted on "separability / redispersibility" and "ease of use."

[0073] Table 4 shows the formulations and evaluations of the sunscreen cosmetics of Examples 13 and 14, and the formulations and evaluations of the sunscreen cosmetics of Comparative Examples 7 to 10. Table 5 shows the formulations and evaluations of the sunscreen cosmetics of Example 15, and the formulations and evaluations of the sunscreen cosmetics of Comparative Examples 11 and 12. Regarding the formulations in Table 4, "L-menthol" listed in the ingredients column is a commonly used fragrance ingredient in cosmetics. Regarding the formulations in Table 5, "isotridecyl isononanoate" listed in the ingredients column is available as "Sarakos 913," and "triethylhexanoin" is available as "TIO," both of which are cosmetic raw materials manufactured by Nisshin Oillio Group Ltd. and are commonly used as bases in cosmetics.

[0074] [Table 4]

[0075] [Table 5]

[0076] As shown in Table 4, the sunscreen cosmetics of Examples 13 and 14, and the cosmetics of Comparative Examples 7 to 10, all contain ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexyl benzoate as organic ultraviolet absorbers. However, the sunscreen cosmetics of Examples 13 and 14, which also contain calcium starch octenyl succinate, have an SPF value of 50. + High UV protection performance was confirmed. On the other hand, the cosmetics in Comparative Examples 7-10, which did not use calcium octenyl succinate starch or used other powders instead of calcium octenyl succinate starch, had low SPF values ​​of 12-16, indicating insufficient UV protection performance.

[0077] Furthermore, as shown in Table 5, in a comparison between the sunscreen cosmetic of Example 15, which contains ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexyl benzoate, calcium starch octenyl succinate, and polyethylene glycol decyltetradeceth-20 hexamethylene diisocyanate copolymer, and the cosmetic of Comparative Examples 11 and 12, which do not contain ethylhexyl methoxycinnamate and diethylamino hydroxybenzoyl hexyl benzoate, but contain calcium starch octenyl succinate and polyethylene glycol decyltetradeceth-20 hexamethylene diisocyanate copolymer, the sunscreen cosmetic of Example 15 has an SPF value of 50 + However, the cosmetics in Comparative Examples 11 and 12 had very low SPF values.

[0078] From the above results, it was found that calcium starch octenyl succinate does not exhibit ultraviolet protection performance (ultraviolet absorption effect) on its own, but when used in combination with an organic ultraviolet absorber, it surprisingly showed a specific effect of increasing the SPF value of the organic ultraviolet absorber (SPF booster effect). This SPF booster effect was also observed with aluminum starch octenyl succinate, although the data is not presented here. Furthermore, as shown in Comparative Examples 8-10, this SPF booster effect was not observed with powders other than polyvalent metal salts of starch octenyl succinate. Thus, the inventors have newly discovered that polyvalent metal salts of starch octenyl succinate, which are component (B), function as an efficacy enhancer that strengthens the ultraviolet protection performance (SPF value) of the organic ultraviolet absorber, which is component (A).

[0079] [Examples 16-21] As shown in Table 6, the sunscreen cosmetics of Examples 16-21 were prepared by changing the amount of ethanol, which is component (D). The amount of ethanol was varied within the range of 4.6 to 29.6% by mass. Evaluations were performed on "separability / redispersibility," "powder state," "stability," and "feel."

[0080] Table 6 shows the formulations and evaluations of the sunscreen cosmetics in Examples 16-21.

[0081] [Table 6]

[0082] As shown in Table 6, the sunscreen cosmetics of Example 16, which contained 4.6 parts by mass of ethanol, and Example 21, which contained 29.6 parts by mass of ethanol, were rated C for separation performance, but no major problems were observed in other areas. The sunscreen cosmetics of Examples 17 to 20, in which the amount of ethanol was varied within the range of 7.6 to 19.6 parts by mass, generally received good evaluations in terms of separation / redispersibility, stability, and feel. Regarding the powder state, some clumping (caking) was observed in the cosmetics of Examples 16 and 17, but overall it was generally good. From these results, it can be said that the amount of ethanol in sunscreen cosmetics can be varied within the range of at least approximately 5 to 30 parts by mass (mass%), and approximately 8 to 20 parts by mass (mass%) is preferable considering separation performance.

[0083] [Examples 22-25] Next, the properties of the sunscreen cosmetic composition according to the present invention, which does not contain the moisturizing ingredient PEG / PPG / polybutylene glycol-8 / 5 / 3 glycerin, were evaluated. As shown in Table 7, the sunscreen cosmetic compositions of Examples 22 to 25 were prepared by changing the type and amount of the polyvalent metal salt of starch octenyl succinate, which is component (B). For the polyvalent metal salt of starch octenyl succinate, aluminum starch octenyl succinate (Examples 22 and 23) and calcium starch octenyl succinate (Examples 24 and 25) were used. The amount used was 2 parts by mass or 3 parts by mass. The evaluation was performed on "separability / redispersibility" and "powder state", as well as "stability" and "feel".

[0084] Table 7 shows the formulations and evaluations of the sunscreen cosmetics in Examples 22-25.

[0085] [Table 7]

[0086] As shown in Table 7, even without PEG / PPG / polybutylene glycol-8 / 5 / 3 glycerin, the sunscreen cosmetics of Examples 22-25 all received an A rating for separation and a A rating for redispersibility, demonstrating excellent separation and redispersibility. Regarding the powder state, the sunscreen cosmetics of Examples 22-25 all received an A rating, with no problems such as clumping or caking. Regarding stability, the sunscreen cosmetics of Examples 22-25 all received an A rating, demonstrating excellent stability regardless of temperature. Regarding usability, the sunscreen cosmetics of Examples 22-25 all received an A or higher rating, indicating excellent usability. These results confirm that PEG / PPG / polybutylene glycol-8 / 5 / 3 glycerin does not affect the performance or usability of the sunscreen cosmetics. [Industrial applicability]

[0087] The sunscreen cosmetic composition according to the present invention can be used as a mist-type sunscreen cosmetic.

Claims

1. A sunscreen cosmetic containing water-based components and oil-based components, The following components (A) to (D): (A) Organic UV absorbers (B) Octenyl succinate starch polyvalent metal salt (powder) (C) Associative thickener (D) Ethanol A water-based sunscreen cosmetic containing [ingredient name].

2. The sunscreen cosmetic composition according to claim 1, wherein the component (A) has a specific gravity of 1.01 or more overall.

3. The sunscreen cosmetic composition according to claim 1, wherein the content of component (D) is 20% by mass or less.

4. (E) The sunscreen cosmetic composition according to claim 1, comprising 50% by mass or more of water.

5. A mist-type sunscreen cosmetic comprising filling a spray container with the sunscreen cosmetic composition described in any one of claims 1 to 4.

6. The mist-type sunscreen cosmetic according to claim 5, wherein when the spray container containing the sunscreen cosmetic is held and shaken 20 times, the oily component forms droplets containing powder (excluding emulsion particles) in the aqueous component, thereby dispersing the powder.

7. The mist-type sunscreen cosmetic according to claim 5, wherein when the spray container containing the sunscreen cosmetic is held and shaken 20 times, and then placed on a horizontal surface, the mixture of the aqueous component and the oily component is separated again within 60 minutes.

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