JP7233684B2 - sunscreen cosmetics - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sunscreen cosmetic, and more particularly, to a sunscreen cosmetic that has a good feel and excellent stability over time while using both a powdery ultraviolet absorbent and a liquid ultraviolet absorbent.

Sunscreen cosmetics are intended to block the sun's rays and protect the skin from the harmful effects of ultraviolet rays. A sunscreen cosmetic having an ultraviolet protection effect has been developed. In recent years, the importance of sun protection in daily life has been pointed out, and even in cosmetics with a protective effect against ultraviolet rays, there is a need for sunscreen cosmetics that are suitable for daily use, have a fresh and fresh feeling, and are easy to use continuously. being developed.

Ultraviolet rays, which affect living organisms, are electromagnetic waves emitted from the sun, a kind of so-called solar radiation, which have a wavelength shorter than the visible light wavelength of 380 to 780 nm and are in the invisible region. As for the types of ultraviolet rays, in order from the shortest wavelength, C area ultraviolet rays (UV-C) have a wavelength range of 200 to 280 nm, B area ultraviolet rays (UV-B) have a wavelength range of 280 to 320 nm, A area ultraviolet rays (UV In -A), the wavelength range is classified into three from 320 to 380 nm. In general, light with a shorter wavelength has more energy, but it has the property of being refracted when it hits a substance. Conversely, the longer the wavelength, the easier it is to travel straight without being refracted. Therefore, ultraviolet rays are known to cause different health hazards depending on the wavelength. UV-C has a short wavelength and a large amount of energy, and is the most harmful ultraviolet ray that is absorbed by the DNA of living organisms. UV-B is strongly absorbed by the ozone layer existing 20 to 50 km above the ground, and part of it reaches the surface of the earth. Because it is absorbed on the surface of the skin, it causes sunburn, as well as diseases such as skin cancer and cataracts, so it is called "harmful ultraviolet rays." Almost 100% of UV-A reaches the surface of the earth because it is hardly absorbed in the atmosphere. Because of its long wavelength, it can penetrate deep into the skin and cause skin changes such as age spots and freckles, accelerated photoaging, and loss of skin elasticity.

Sunscreen cosmetics contain UV absorbers and UV scattering agents (zinc oxide, titanium dioxide, etc.) to block UV irradiation to the skin. In order to protect human skin, there is a demand for a sunscreen cosmetic that responds to a wide range of ultraviolet wavelengths. Depending on the corresponding area, combined use of a powdery UV absorber and a liquid UV absorber is required, but it has been difficult to stably mix them even in high-temperature and low-temperature environments.

In addition, if a large amount of metal oxide powder such as zinc oxide and titanium oxide, which are UV scattering agents, is contained in a large amount, not only will the powder aggregate and settle over time, but the viscosity will decrease, emulsification separation, precipitation, etc. will stabilize over time. There was a problem of declining performance. In addition, it has been difficult to obtain a sunscreen cosmetic with good usability due to problems such as a squeaky feel of the powder during use and a whitish and unnatural finish.

In the case of a system that does not contain an ultraviolet scattering agent in order to suppress whitening and increase transparency, it is notable that a sufficient ultraviolet protection effect cannot be obtained. In addition, when a large amount of ultraviolet absorber is used, the skin becomes sticky and squeaky after application, resulting in poor usability. Conversely, if the amount of the ultraviolet absorber is small, a sufficient sunscreen effect cannot be obtained.

In recent years, there is a demand for sunscreen cosmetics that respond to a wide range of UV wavelengths, and it is necessary to select and use UV absorbers according to the corresponding area. -Since the molecular weight is larger than that of the -B absorbent, many of them are hardly soluble, and in some cases the stability deteriorates, such as precipitation of crystals over time. Therefore, in order to stably contain the sparingly soluble ultraviolet absorber, it was necessary to contain a large amount of polar oil, but the polar oil sometimes caused stickiness and weight (see Patent Document 1).

In order to solve these problems, silicone oil, alcohol, and the like are contained together with a sparingly soluble ultraviolet absorber (see Patent Document 2).

However, while the addition of silicone oil gives a smooth feel and reduces stickiness, when the content is high, the emulsification stability is deteriorated, making it difficult to obtain a cosmetic with good stability. Met. In addition, while adding alcohol gives a fresh feel and reduces stickiness, if it is contained in a large amount relative to the emulsion, it generally lowers the viscosity of the system and deteriorates the emulsion stability. rice field. Therefore, there has been a demand for the development of a cosmetic that stably contains a sparingly soluble ultraviolet absorber, has an excellent non-sticky and fresh feeling in use, and has excellent stability over time.

In order to improve the feeling of use, it was necessary to limit the total content ratio of the poorly soluble UV absorber and the oil. It was thought that the protective effect could not be obtained (see Patent Document 3).

Japanese Patent Application Laid-Open No. 2004-520356 JP 2007-145722 A JP 2017-088568 A

The present invention has been made in view of the above circumstances, and its object is to prevent the skin from stickiness and creakiness after application while using both a powdery ultraviolet absorbent and a liquid ultraviolet absorbent. To provide a sunscreen cosmetic which gives a plump feeling and is stable over time.

As a result of intensive research to achieve the above object, ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate and/or bisethylhexyloxyphenol methoxyphenyltriazine, hydrogenated lecithin, alkyl acrylate/methacrylate copolymer, and The inventors have found that a sunscreen cosmetic containing a silicone derivative in a specific composition ratio can solve the above problems, and have completed the present invention.

The first invention of the present application contains the following components (A1) to (D), has a mass ratio A2/A1 of A2 to A1 of 0.1 to 1.8, and contains A1 and A2 relative to the total amount of the sunscreen cosmetic. A sunscreen cosmetic characterized by a total content of 11.0 to 26.0% by mass. (A1) Ethylhexyl methoxycinnamate (A2) Hexyl diethylaminohydroxybenzoylbenzoate and/or bisethylhexyloxyphenol methoxyphenyltriazine (B) Hydrogenated lecithin 0.5 to 5.0% by mass based on the total amount of the sunscreen cosmetic
(C) Alkyl acrylic acid/methacrylate copolymer and/or carboxyvinyl polymer 0.1 to 0.4% by mass based on the total amount of the sunscreen cosmetic
(D) Silicone derivative 0.5 to 5.0% by mass based on the total amount of sunscreen cosmetics

The second invention of the present application is the sunscreen cosmetic according to the first invention of the present application, wherein (D) the silicone derivative is a (divinyl dimethicone/dimethicone) copolymer having a molecular weight of 100,000 to 1,000,000.

The sunscreen cosmetic of the present invention does not cause stickiness on the skin when applied and does not make the skin feel squeaky after application, even though it uses both a powdery ultraviolet absorbent and a liquid ultraviolet absorbent. In addition, it imparts plumpness to the skin, and is also excellent in stability over time (high and low temperatures).

The configuration of the present invention will be described in detail below.

Component (A1) ethylhexyl methoxycinnamate used in the present invention is a liquid ultraviolet absorber active in the UV-B region. Specific examples of ethylhexyl methoxycinnamate include Ubinal MC80 and 80N (manufactured by BASF Japan) and Parasol MCX (DSM Nutrition Japan).

Although the blending ratio of the component (A1) of the present invention is not particularly limited, it is preferably determined appropriately and within the effective amount range. In terms of UV protection effect, the SPF value (Sun Protection Factor acronym) is generally used as an index representing the degree of the effect of blocking UV-B waves (wavelength 280 to 320 nm). Regarding the measurement method in , SPF is based on the measurement after applying 2 mg per 1 cm ² of the product to the skin, so the SPF value is preferably 5 or more, more preferably 25 or more. It is desirable to If the SPF value is 5 or less, the sunscreen effect is poor and not desirable.

The component (A2) used in the present invention, hexyl diethylaminohydroxybenzoylbenzoate, is a powdery ultraviolet absorber active in the UV-A region. Specific examples of hexyl diethylaminohydroxybenzoylbenzoate include Ubinal A Plus Granular (BASF Japan).

The component (A2) used in the present invention, bisethylhexyloxyphenolmethoxyphenyltriazine, is a powdery ultraviolet absorber active in both the UV-A region and the UV-B region. Specific examples of bisethylhexyloxyphenol methoxyphenyltriazine include Tinosorb S (BASF Japan Ltd.).

Although the blending ratio of the component (A2) of the present invention is not particularly limited, it is preferably determined appropriately and within the effective amount range. In terms of UV protection effect, the PA index (Protection
Abbreviation of grade of UVA) is adopted in Japan and is generally used, it is desirable to formulate so that the PA index is preferably + (effective), more preferably PA ++ or higher. If it is not PA+, it has poor sunscreen effect and is not desirable.

On the other hand, from the viewpoint of application feel and stability of the sunscreen cosmetic, the mass ratio A2/A1 of the powder UV absorber (A2) to the liquid UV absorber (A1) is in the range of 0.1 to 1.8. As such, it is preferred to incorporate a liquid UV absorber and a powder UV absorber. If it is less than 0.1, sufficient UV-A activity cannot be obtained, and the solubility of the powdered ultraviolet absorber becomes insufficient, resulting in poor high-temperature and low-temperature stability. As a result, slimy or sticky feeling is generated, which impairs the feeling of use. Also, the total content of the liquid UV absorber and the powder UV absorber is preferably 11.0 to 26.0% by mass with respect to the total amount of the sunscreen cosmetic. If it is less than 11.0% by mass, it is difficult to obtain a sufficient sunscreen effect.

The component (B) hydrogenated lecithin used in the present invention may be any one as long as it is suitable for use as a cosmetic. For example, hydrogenated lecithin obtained by hydrogenating vegetable lecithin such as soybean lecithin, rapeseed lecithin, maize lecithin and peanut lecithin, and animal lecithin such as egg yolk lecithin can be mentioned, and hydrogenated lecithin derived from soybean is preferred. The content of hydrogenated lecithin is preferably 0.5% by mass or more relative to the total amount of the sunscreen cosmetic. If the hydrogenated lecithin is less than 0.5% by mass, emulsification will be insufficient, which is undesirable. Specific examples of hydrogenated lecithin include Cortsome NC-21 (NOF Corporation), Resinol S-10EX (Nikko Chemicals), Phospholipid PCSH70 (Nippon Seika Co.), Phospholipon 80H (H-Holstein Co., Ltd.), etc. can be mentioned.

The component (C) alkyl acrylate/methacrylate copolymer and/or carboxyvinyl polymer used in the present invention is blended for the purpose of enhancing the stability of the formulation and improving the texture.

A carboxyvinyl polymer is a water-soluble vinyl polymer having a carboxyl group, and examples thereof include polyacrylic acid. Specifically, Carbopol 940, Carbopol 941, Carbopol 980, Carbopol 981 (above, Lubrizol Advanced Materials, Inc.), Syntaren (Wako Pure Chemical Industries, Ltd.), AQUPEC HV-501E (Sumitomo Seika Co., Ltd.) can be used.

Alkyl acrylate/methacrylate copolymer is also known as (alkyl)-modified carboxyvinyl polymer, (alkyl)-modified carbopol, (alkyl)-modified carbomer, (acrylates/alkyl acrylate (C10-30)) crosspolymer, etc. To tell. For example, commercially available products such as PEMULEN TR-1 and PEMUREN TR-2 (manufactured by Lubrizol Advanced Materials, Inc.) can be used.

The amount of one or more selected from the group consisting of the alkyl acrylate/methacrylate copolymer and/or the carboxyvinyl polymer is 0.1 to 0.4% by mass based on the total amount of the sunscreen cosmetic. is preferably If it is less than 0.1% by mass, dripping occurs when the sunscreen cosmetic is applied to the skin, resulting in deterioration in usability. On the other hand, if it exceeds 0.4% by mass, the formulation does not spread well and becomes sticky, which also reduces usability.

The (D) component silicone derivative used in the present invention is blended for the purpose of improving the stickiness, creaking and sliminess of the skin after application of the ultraviolet absorber.

Examples of silicone derivatives include dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hydroxyl-terminated dimethylpolysiloxane, polyether-modified silicone, highly polymerized unwoven silicone, highly polymerized amino modified silicone, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, fluorine-modified silicone and the like. Among them, highly polymerized unwoven silicone is preferred, and (divinyl dimethicone/dimethicone) copolymer having a molecular weight of 100,000 to 1,000,000 is particularly preferred.

The blending amount of component (D) in the present invention is preferably 0.2 to 5.0% by mass based on the total amount of the sunscreen cosmetic in the sunscreen composition. If the amount is less than 0.2% by mass, the stickiness, creaking and sliminess of the skin after application cannot be sufficiently improved.

The dosage form of the sunscreen cosmetic of the present invention is not particularly limited, but examples thereof include liquid, milky lotion, cream, oil, gel, aerosol, solid, stick, and aerosol.

In addition to the above-mentioned essential ingredients, the sunscreen cosmetic of the present invention can optionally contain any ingredient that is commonly used within a range that does not impair the effects of the present invention. These ingredients include anionic surfactants, cationic surfactants, nonionic surfactants, oils, UV absorbers, preservatives, moisturizers, polymers, amino acid derivatives, sugar derivatives, fragrances, water, Examples include alcohols, thickeners, colorants, sequestering agents, antioxidants, drugs, perfumes, and the like.

EXAMPLES Next, the present invention will be described in detail based on examples, but it is not limited thereto. Prior to Examples, test methods and evaluation methods employed in each Example will be described.

(1) Evaluation of skin stickiness after application A 10-person expert panel evaluated the “skin stickiness after application” of the sunscreen cosmetics by sensory evaluation using the sunscreen cosmetics of Examples and Comparative Examples. gone. In addition, the evaluation criteria are as follows.
[Skin stickiness during application]
◎: Very good
(8 or more subjects answered that there was no stickiness after application)
○: Good
(The number of subjects who answered that there was no stickiness after application was 6 or more and less than 8)
△: Slightly bad
(The number of subjects who answered that there was no stickiness after application was 4 or more and less than 6)
×: bad
(The number of subjects who answered that there was no stickiness after application was less than 4)

(2) Evaluation of skin squeakiness during application A sensory evaluation of “skin squeakiness after application” of sunscreen cosmetics at the time of application by a 10-person expert panel using the sunscreen cosmetics of Examples and Comparative Examples. was evaluated by In addition, the evaluation criteria are as follows.
[Skin creaking after application]
◎: Very good
(The number of subjects who answered that there was no squeak after application was 8 or more)
○: Good
(The number of subjects who answered that there was no squeak after application was 6 or more and less than 8)
△: Slightly bad
(The number of subjects who answered that there was no squeak after application was 4 or more and less than 6)
×: bad
(The number of subjects who answered that there was no squeak after application was less than 4)

(3) Evaluation of skin plumpness after application A sensory evaluation of the “skin plumpness after application” of the sunscreen cosmetics using the sunscreen cosmetics of Examples and Comparative Examples was performed by a 10-person expert panel. made an evaluation. In addition, the evaluation criteria are as follows.
[Feeling of plump skin after application]
◎: Very good
(The number of subjects who answered that they had a plump feeling after application was 8 or more)
○: Good
(The number of subjects who answered that they felt plump after application was 6 or more and less than 8)
△: Slightly bad
(The number of subjects who answered that they felt plump after application was 4 or more and less than 6)
×: bad
(The number of subjects who answered that they felt plump after application was less than 4)

(4) Evaluation of stability over time (high temperature) The stability over time after standing at 45°C for 6 months was evaluated according to the following criteria. [Stability over time (high temperature)]
◎: Good condition (No obvious separation, oil floating, syneresis, solidification, and no grains or lumps)
○: Good condition (No obvious separation, oil floating, water separation, solidification, and almost no grains or lumps)
△: Slightly poor condition (Slight separation, oil floating, water separation, and solidification are observed)
×: Poor condition (Remarkable separation, oil floating, water separation, and solidification)

(5) Evaluation of stability over time (low temperature) The stability over time after standing at 0°C for 6 months was evaluated according to the following criteria.
[Stability over time (low temperature)]
◎: Good condition (No obvious separation, oil floating, syneresis, solidification, and no grains or lumps)
○: Good condition (No obvious separation, oil floating, water separation, solidification, and almost no grains or lumps)
△: Slightly poor condition (Slight separation, oil floating, water separation, and solidification are observed)
×: Poor condition (Remarkable separation, oil floating, water separation, and solidification)

Examples 1-14, Comparative Examples 1-9
Sunscreen cosmetics having the formulations shown in Table 1 were prepared according to conventional methods, and the above tests were carried out. The results are also shown in Table 1.

As is clear from Table 1, all of the sunscreen cosmetics of Examples using the components of the present invention exhibited excellent performance. On the other hand, the comparative examples were inferior in any of stickiness of the skin after application, creaking of the skin at the time of application, plumpness of the skin after application, and stability over time (high temperature/low temperature). could not be achieved.

Claims (2)

Including the following component (A1) to component (D),
and the mass ratio A2/A1 of A2 to A1 is 0.1 to 1.8,
And the total content of A1 and A2 with respect to the total amount of sunscreen cosmetics is 11.0 to 26.0% by mass
A sunscreen cosmetic characterized by:
(A1) Ethylhexyl methoxycinnamate (A2) Hexyl diethylaminohydroxybenzoylbenzoate and/or bisethylhexyloxyphenol methoxyphenyltriazine (B) Hydrogenated lecithin 0.5 to 5.0% by mass based on the total amount of the sunscreen cosmetic
(C) Alkyl acrylic acid/methacrylate copolymer and/or carboxyvinyl polymer 0.1 to 0.4% by mass based on the total amount of the sunscreen cosmetic
(D) A silicone derivative that is a (divinyl dimethicone/dimethicone) copolymer with a molecular weight of 100,000 to 1,000,000 0.5 to 5.0% by mass based on the total amount of the sunscreen cosmetic The sunscreen cosmetic according to Claim 1 , further comprising dipropylene glycol .