KR102869153B1 - Sun screen composition comprising a complex formulation of bis-ethylhexyloxyphenol methoxyphenyl triazine - Google Patents

Abstract

The present specification discloses a water-in-oil type UV-blocking composition comprising microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil in an oil phase. The present invention exhibits a more improved UV-blocking effect than a composition comprising only microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed or bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, even though it contains a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine, and can provide a non-sticky and refreshing feeling when used.

Description

Sun screen composition comprising a complex formulation of bis-ethylhexyloxyphenol methoxyphenyl triazine

This specification describes a composition having excellent UV blocking efficiency.

Cross-reference to related applications

This application claims priority to Republic of Korea Patent Application No. 10-2019-0057115, filed May 15, 2019, the entire contents of which are incorporated herein by reference.

Ultraviolet rays (UV) are known to cause skin problems such as erythema, edema, and freckles, and are a major cause of skin cancer. Therefore, much research is being conducted on various skin diseases caused by UV rays. Generally, UV rays are classified into UV-C wavelengths of 240 to 280 nm, UV-B wavelengths of 280 to 320 nm, and UV-A wavelengths of 320 to 400 nm depending on their wavelength. Of these, UV-C passes through the ozone layer and disappears without reaching the Earth's surface, while UV-B penetrates the epidermis and causes erythema, freckles, and edema. UV-A penetrates the dermis and promotes wrinkles and melanin formation, causing skin aging and skin irritation, or it is known to cause skin cancer.

As the amount of UV radiation on the surface of the earth increases due to the recent destruction of the ozone layer, the market for products with the primary purpose of blocking UV rays is growing significantly every year, and consumer demand for compositions that block UV rays across the entire wavelength range is also increasing.

Generally, UV protection compositions have been proposed as W/O (Water in Oil) types with oil as the external phase and O/W (Oil in Water) types with water as the external phase. In the case of O/W types, when applied to the skin, it has the advantage of being refreshing compared to W/O types, but it still has the disadvantage of being easily washed off by sweat or water, despite continuous research to improve water resistance, so it has the disadvantage of significantly reducing the duration of the UV protection effect. On the other hand, in the case of W/O types, although it has superior duration compared to O/W types, it has the disadvantage of feeling heavy and sticky when used. This is not unrelated to the high viscosity of general W/O types. In addition, because W/O types are manufactured with a high viscosity by increasing the ratio of the inner phase to the water phase in order to adjust the feeling of use lightly, they have the disadvantage of lower emulsification stability compared to O/W types. Conversely, low-viscosity, water-on-oil (W/O) products suffer from the problem of separation between the inner and outer oil phases during long-term storage within the container, reducing product stability. Therefore, increasing viscosity to enhance stability often results in a heavy, sticky texture.

Bis-ethylhexyloxyphenol methoxyphenyl triazine is an effective organic UV filter that can effectively block both UVA and UVB rays. However, due to its poor solubility in solvents, it had to be dissolved in other organic UV filter agents that can dissolve BEMT or in oils with high polarity before being applied to the oil phase. Therefore, there was a limitation that it was difficult to apply bis-ethylhexyloxyphenol methoxyphenyl triazine to various product formulations. In addition, when bis-ethylhexyloxyphenol methoxyphenyl triazine was applied to a composition, it felt very greasy and sticky, making it difficult to provide a product that consumers demanded to be light and refreshing to apply.

Republic of Korea Patent No. 10-1773095

From one perspective, the problem that the present invention seeks to solve is to provide a composition that contains a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine, yet has excellent UV blocking efficacy and a refreshing and light feeling when used.

In one aspect, the present invention provides a W/O (Water in Oil) type UV protection composition comprising a water phase and an oil phase, wherein the oil phase comprises microparticles including a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil.

In one aspect, the present invention comprises microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed, and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, so that bis-ethylhexyloxyphenol methoxyphenyl triazine is applied to the skin in a mixed form in both the form of microparticles and the form dissolved in the oil, thereby being more evenly distributed on the skin. Therefore, the present invention exhibits a more improved UV protection effect even though it contains a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine than a composition comprising only microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed, or bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, and can provide a non-sticky and refreshing feeling when used.

FIG. 1a is a SEM (Scanning Electrom Microscopy) image of bowl-shaped microparticles according to one embodiment of the present invention.
Figure 1b is a high-magnification image of the same sample as Figure 1a.
Figure 2 is a diagram showing the observation results for the 4th week (cold and hot storage) of Example 2/Example 5/Example 3/Example 4/Comparative Example 2 sequentially from the left.
Figure 3 is a diagram showing the observation results for the 4th week (room temperature storage) of Example 2/Example 5/Example 3/Comparative Example 2/Example 4 sequentially from the left.
Figure 4 is a diagram showing the observation results of Comparative Example 2/Example 5/Example 4/Example 2/Example 3 at 8 weeks (4 weeks of cold storage followed by frozen storage) sequentially from the left.
Figure 5 is a diagram showing the observation results for the 8th week (room temperature storage) of Comparative Example 2/Example 5/Example 4/Example 2/Example 3 sequentially from the left.
Figure 6 is a diagram showing the observation results for the 9th week (4 weeks of cold storage + 4 weeks of freezing + room temperature storage) of Comparative Example 2/Example 5/Example 4/Example 2/Example 3 sequentially from the left.
Figure 7 is a diagram showing the observation results for long-term storage (4 weeks of cold storage + 4 weeks of freezing + 1 year of room temperature storage) of Comparative Example 2/Example 5/Example 4/Example 2/Example 3 sequentially from the left.

Hereinafter, embodiments of the present application will be described in more detail with reference to the attached drawings. However, the technology disclosed in this application is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present application to those skilled in the art. Furthermore, those skilled in the art will be able to implement the spirit of the present application in various other forms without departing from the technical spirit of the present application.

In one embodiment, the present invention relates to a water-in-oil (W/O) type UV-blocking composition comprising a water phase and an oil phase. In one embodiment, the oil phase may comprise microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil.

Another embodiment may provide a method for preparing a sunscreen composition, comprising: microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and a use of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, wherein the composition is a water-in-oil (W/O) type composition comprising an aqueous phase and an oil phase, and the microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and the bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil may be included in the oil phase. Another embodiment may provide a method for preparing a sunscreen composition, comprising: microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; And a method for blocking ultraviolet rays on the skin comprising applying an effective amount of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil to a subject in need thereof, wherein the microparticles include a polymer matrix in which the bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and the bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil can be applied by being included in the oil phase of a W/O type composition including an aqueous phase and an oil phase. Another embodiment provides microparticles including a polymer matrix in which the bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed as active ingredients for use in a composition for blocking ultraviolet rays; and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil, wherein the composition is a W/O type composition including an aqueous phase and an oil phase, and the microparticles include a polymer matrix in which the bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; And bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil may be included in the oil phase. In one embodiment, the use may be a non-therapeutic use.

Another chemical name of the bis-ethylhexyloxyphenol methoxyphenyl triazine included in the present invention is 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, also called bemotrininol, and its CAS registration number is 187393-00-6. As an example, the bis-ethylhexyloxyphenol methoxyphenyl triazine may be sold by BASF as Tinosorb S®. The bis-ethylhexyloxyphenol methoxyphenyl triazine is known as an organic UV blocker capable of simultaneously blocking UVA and UVB, but has low solubility, so it has been provided in a state dissolved in polar oil or manufactured in the form of microparticles. However, when provided in a state dissolved in polar oil, there is a problem that it is difficult to include a large amount in the composition due to the heavy and sticky feeling when used, so a satisfactory UV protection effect cannot be achieved. Even when provided in the form of microparticles, only a small amount can be contained due to the precipitation problem, so even if it is applied evenly to the skin, there are areas where the particles are not applied, so there is a problem that a satisfactory UV protection effect cannot be obtained. On the other hand, the present invention includes a raw material in which bis-ethylhexyloxyphenol methoxyphenyl triazine is stabilized in polymer microparticles and a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil, so that various forms of bis-ethylhexyloxyphenol methoxyphenyl triazine are mixed on the skin and applied to the skin without gaps, thereby maximizing the UV protection effect.

As an example, the bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil may be included in an amount of 0.01 to 2 wt% based on the total weight of the composition. If the bis-ethylhexyloxyphenol methoxyphenyl triazine is included in an amount of less than 0.01 wt% based on the total weight of the composition, the UV blocking effect is minimal, and if it exceeds 2 wt%, the polar oil content also increases, resulting in a sticky and heavy feeling of use, which is not suitable for producing a composition having a light feeling of use such as a W/S type. Specifically, the composition may include bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil in an amount of 0.01 wt% or more, 0.05 wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% or more, 0.9 wt% or more, 1.0 wt% or more, 1.1 wt% or more, 1.2 wt% or more, 1.3 wt% or more, 1.4 wt% or more, 1.5 wt% or more, 1.6 wt% or more, 1.7 wt% or more, 1.8 wt% or more, or 1.9 wt% or more, based on the total weight of the composition. Additionally, the composition may contain bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil in an amount of 2.0 wt% or less, 1.9 wt% or less, 1.8 wt% or less, 1.7 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1.0 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, 0.2 wt% or less, 0.1 wt% or less, 0.05 wt% or less, or 0.02 wt% or less, based on the total weight of the composition.

As an example, the polar oil in which the bis-ethylhexyloxyphenol methoxyphenyl triazine is dissolved may include any type without limitation as long as it can provide the bis-ethylhexyloxyphenol methoxyphenyl triazine in a stably dissolved state without precipitation even when stored for a long period of time. The polarity of the oil is determined by the presence or absence, type, number, or structure of the functional group of each oil, and alcohols, esters, vegetable oils, etc. with a linear structure having a hydrophilic functional group are typically classified as oils with relatively high polarity. For example, the polar oil may include an oil containing one or more polar functional groups of a carboxyl group (-COO), a ketone group (-CO), and a hydroxyl group (-OH). Specifically, the polar oil may be one of butylene glycol dicaprylate*dicaprate, ethylhexyl salicylate, ethylhexyl methoxycinnamate, homosalate, C12-15 alkyl benzoate, dibutyl adipate, dicaprylyl carbonate, caprylyl-caprylate, coco caprylate, octocrylene, propylheptyl caprylate, isopropyl palmitate, caprylic/capric triglyceride, and coco glyceride. More specifically, the polar oil may include one or more of butylene glycol dicaprylate*dicaprate, C12-15 alkyl benzoate, and dicaprylyl carbonate, wherein the oil has a less heavy feel than other polar oils while exhibiting high solubility in bis-ethylhexyloxyphenol methoxyphenyl triazine.

As one embodiment of the present invention, the composition may include microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed, in an amount of 0.1 to 30 wt% based on the total weight of the composition. If the microparticles are included in an amount of less than 0.1 wt% based on the total weight of the composition, the UV blocking effect is minimal, and if the amount exceeds 30 wt%, the microparticles, i.e., powder formulation, are excessively included, which may result in a stuffy feeling when used. Specifically, the composition may contain the microcomposition in an amount of 0.1 wt% or more, 0.5 wt% or more, 1.0 wt% or more, 2.0 wt% or more, 3.0 wt% or more, 4.0 wt% or more, 5.0 wt% or more, 6.0 wt% or more, 7.0 wt% or more, 8.0 wt% or more, 9.0 wt% or more, 10 wt% or more, 11 wt% or more, 12 wt% or more, 13 wt% or more, 14 wt% or more, 15 wt% or more, 16 wt% or more, 17 wt% or more, 18 wt% or more, 19 wt% or more, 20 wt% or more, 21 wt% or more, 22 wt% or more, 23 wt% or more, 24 wt% or more, 25 wt% or more, 26 wt% or more, 27 wt% or more, 28 wt% or more, or 29 wt% or more based on the total weight of the composition. In addition, the composition may contain the microcomposition in an amount of 30 wt% or less, 29 wt% or less, 28 wt% or less, 27 wt% or less, 26 wt% or less, 25 wt% or less, 24 wt% or less, 23 wt% or less, 22 wt% or less, 21 wt% or less, 20 wt% or less, 19 wt% or less, 18 wt% or less, 17 wt% or less, 16 wt% or less, 15 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less, 11 wt% or less, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, or 0.5 wt% or less based on the total weight of the composition.

In one embodiment, the microparticles may be at least one of non-porous and porous. As used herein, "non-porous" means that the interior of the particle does not contain pores or voids, and the surface porosity may be 0 or close to 0. As an embodiment, the shape of the microparticles may be spherical or hemispherical, and may be bowl-shaped. Alternatively, the microparticles may include at least one of spherical, hemispherical, and bowl-shaped shapes. As used herein, the "bowl-shaped" refers to a concave bowl or tubular shape, and as long as the interior is hollow, it may include all shapes without limitation on the degree of hollowness or the shape of the bowl. For example, the bowl-shaped shape may be a round bowl shape with a hollow interior, or more specifically, a semi-spherical shape with a hollow interior. In one embodiment, the microparticles included in the present invention may include nonporous bowl-shaped microparticles. In one embodiment, the bowl-shaped microparticles of the present invention may be nonporous. The bowl-shaped nonporous microparticles have superior particle durability compared to conventional porous microparticles, and can very stably disperse the poorly soluble bis-ethylhexyloxyphenol methoxyphenyl triazine within the formulation.

In one embodiment, the size of the microparticles may have an average diameter of 1 to 10 μm, but is not limited thereto as long as the microparticles have a size that can be stably dispersed within the composition formulation while containing a high content of bis-ethylhexyloxyphenol methoxyphenyl triazine therein. The average diameter of the microparticles is an average value of the particles included in the composition, and the average value of the particle size is a measurement of the hydrodynamic volume assuming that the particles in the dispersed phase are spherical. Specifically, 30 ml of an isotope nucleus solution (isotone, Beckman Coulter) was placed in a 100 ml container, a small amount of microparticle and dispersant solution (10% of Triton X-100) was added to the container, and the solution was dispersed using a 150 W sonicator, and then the particle size was analyzed using Multisizer 4 (Beckman Coulter). The analysis results were expressed as Median (d(50) 3.5-5.5 μm) in units of one decimal place. As a more specific embodiment, the average diameter of the microparticles may be 1 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, or 9.9 μm or more, and may be 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1.1 μm or less. Specifically, the average diameter of the microparticles may be 1 to 8 μm, more specifically, 2 to 6 μm.

As an example, the bis-ethylhexyloxyphenol methoxyphenyl triazine included in the microparticles may be evenly dispersed in a form close to a molecular unit without being crosslinked within the polymer matrix, specifically, within the polymer crosslinked structure. Specifically, the bis-ethylhexyloxyphenol methoxyphenyl triazine may be included in the polymer crosslinked structure of the polymer matrix by being homogeneously mixed and dispersed in a form close to a molecular unit within the network structure formed by the polymer crosslinked structure without being crosslinked with the polymer crosslinked structure, and other components included in the polymer matrix may be included without limitation as long as they can manufacture microparticles. For example, the polymer matrix included in the bowl-shaped non-porous microparticles may include bis-ethylhexyloxyphenol methoxyphenyl triazine, and a polymerization product of a polymerizable monomer and a polyfunctional crosslinking agent. More specifically, the microparticles may be manufactured by dispersion polymerization using an oil phase including bis-ethylhexyloxyphenol methoxyphenyl triazine, a polymerizable monomer, and a polyfunctional crosslinking agent.

As an example, the microparticles may be manufactured to have different shapes depending on the ratio of bis-ethylhexyloxyphenol methoxyphenyl triazine contained therein. From the above perspective, the bowl-shaped microparticles according to one example may contain bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 20 wt% to 30 wt% based on the total weight of the microparticles. More specifically, the particles may comprise bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of at least 20 wt%, at least 21 wt%, at least 22 wt%, at least 23 wt%, at least 24 wt%, at least 25 wt%, at least 26 wt%, at least 27 wt%, at least 28 wt%, at least 29 wt%, or at least 29.9 wt%, and may comprise at most 30 wt%, at most 29 wt%, at most 28 wt%, at most 27 wt%, at most 26 wt%, at most 25 wt%, at most 24 wt%, at most 23 wt%, at most 22 wt%, at most 21 wt%, or at most 20.1 wt%, based on the total weight of the microparticles.

In one embodiment, the polymerizable monomer is a radical polymerizable monomer, and is not limited thereto as long as it can copolymerize with a multifunctional crosslinking monomer, and specifically, it may be a radical polymerizable monomer containing one ethylene group. For example, it may include at least one aromatic vinyl monomer selected from the group consisting of styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene, and vinyltoluene; and at least one acrylic vinyl monomer selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, and glycidyl (meth)acrylate. As an example, the multifunctional cross-linking agent is not limited to a monomer capable of cross-linking the polymerizable monomer, and specifically, may be a cross-linking agent containing two or more ethylene groups. For example, the multifunctional cross-linking agent may include at least one cross-linking agent selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and tri(meth)acrylate.

As an example, the polymer may be a methyl methacrylate crosspolymer formed by a radical polymerization reaction between methyl methacrylate and ethylene glycol dimethacrylate, and may have a random network structure.

As an example, the weight ratio of the polymerizable monomer and the polyfunctional crosslinking agent may be varied without limitation depending on the desired degree of crosslinking. For example, based on 100 wt% of the polymerizable monomer, the polyfunctional crosslinking agent may be blended in an amount of 0.1 to 100 wt%, specifically 1 to 50 wt%, and more specifically 1 to 25 wt%.

In one embodiment, the composition may be a W/O (Water in Oil) type. Specifically, the composition may be a W/S (Water in Silicon oil) type. In the present specification, the "W/S type" refers to an emulsion having an oil containing silicone oil as a main component as a continuous phase and a dispersed phase containing water therein. That is, the W/S type composition refers to an emulsion in which an inner aqueous phase containing water is dispersed in an outer oil phase containing silicone oil. Although the preference for W/S type compositions is increasing due to their refreshing feel, there has been a disadvantage in that they cannot be applied to W/S type compositions due to the very low solubility of bis-ethylhexyloxyphenol methoxyphenyl triazine itself in silicone oil. Therefore, the present invention solves the above problem by providing bis-ethylhexyloxyphenol methoxyphenyl triazine in the form of microparticles and in the form dissolved in polar oil. The present invention can apply bis-ethylhexyloxyphenol methoxyphenyl triazine to the W/O type or W/S type trauma at a higher content than before.

According to one embodiment of the present invention, the W/S type composition may include one or more silicone oils selected from dimethicone, cyclomethicone, phenyl trimethicone, polydimethylsiloxane, methylphenylpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylhexasiloxane, octamethyltrisiloxane, etc. In one embodiment, the silicone oil may be included in an amount of 15 to 60 wt%, specifically 15 to 50 wt%, and more specifically 20 to 40 wt%, based on the total weight of the composition, but is not limited thereto. In one embodiment, the composition may include a balance of water. In a W/S type composition according to one embodiment of the present invention, the composition may further include a silicone-based surfactant containing at least one of polyethylene glycol (PEG), polypropylene glycol (PPG), and a polyglyceryl group. In a composition according to one embodiment of the present invention, a PEG-added silicone-based surfactant may be specifically used in terms of stably dispersing microparticles containing bis-ethylhexyloxyphenol methoxyphenyl triazine while not generating bis-ethylhexyloxyphenol methoxyphenyl triazine precipitated as crystals on the interface. Examples of PEG-added silicone surfactants include PEG/PPG-18/18 Dimethicone (Cyclopentasiloxane and PEG/PPG-18/18 Dimethicone), PEG-30 Dipolyhydroxystearate, PEG-7 Dimethicone, PEG-10 Dimethicone, Cyclopentasiloxane/PEG.PPG-19.19 Dimethicone, Sorbitan Isostearate, Lauryl PEG.PPG-18.18 Methicone, Cetyl PEG.PPG-10.1 Dimethicone. Examples thereof include PEG.PPG-10.1 Dimethicone), Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone, etc. In addition, one or more PEG-added silicone-based surfactants may be used in the present invention, but are not limited thereto. More specifically, the PEG-added silicone-based surfactant may be a nonionic surfactant having a hydrophilic-lipophilic group balance (HLB) of 1 to 6. In one embodiment, the surfactant may be included in an amount of 0.01 to 10 wt% based on the total weight of the composition, specifically 1 to 8 wt%, and more specifically 3 to 6 wt%. If it is less than 0.01 wt%, the dispersibility of the microparticles is reduced, and if it is more than 10 wt%, stickiness may be caused, which may hinder a refreshing feeling of use.

The water-containing portion of the W/S-type composition according to one embodiment of the present invention may include at least one of water and ethanol, and may also include all other components that can be typically included in the water-containing portion.

The composition according to the present invention is, in one embodiment, a cosmetic composition, and in one embodiment, may be formulated by containing a cosmetically or dermatologically acceptable medium or base. This may be any formulation suitable for topical application, for example, in the form of a solution, gel, solid, anhydrous paste, an emulsion obtained by dispersing an oil phase in an aqueous phase, a suspension, a microemulsion, a microcapsule, a microgranule, or an ionic (liposome) and non-ionic vesicular dispersion, or in the form of a cream, skin, lotion, powder, ointment, spray, or concealer stick. It may also be used in the form of a foam or an aerosol composition further containing a compressed propellant. These compositions may be prepared according to conventional methods in the art.

As an embodiment of the present invention, the sun protection factor (SPF) of the composition may be 10 to 50 or higher when calculated by Equation 1 below. The protection grade of UVA (PA) may be PA+ to PA++++.

[Formula 1]

SPF = (minimum erythema dose on skin area where composition is applied) / (minimum erythema dose on skin area where composition is not applied)

In one embodiment, the composition may further include an organic UV blocker or an inorganic UV blocker depending on the purpose. The organic UV blocker or the inorganic UV blocker may be included in an amount of 0.01 to 20 wt%, respectively, based on the total weight of the composition, but is not limited thereto. Specifically, examples of the organic UV blocker include octyl methoxycinnamate, octyl salicylate, octocrylene, butyl methoxydibenzoylmethane, oxybenzone, octyltriazone, menthyl anthranilate, 3,4-methylbenzylidene camphor, isoamyl-P-methoxycinnamate, methylenebisbenzotriazolidetramethylbutylphenol, and the like. Examples of the inorganic UV blocker include powders of titanium dioxide, zinc oxide, iron oxide, zinc oxide, and the like.

As an example, the composition according to the present invention may contain, in addition to the effective ingredient, other ingredients that can preferably have a synergistic effect on the main effect within a range that does not impair the main effect, and in addition to the effective ingredient of the present invention, those skilled in the art can easily select and blend other ingredients according to the formulation or purpose of use of the other composition. In addition, as an example, the composition of the present invention may contain, in addition to the above ingredients, other ingredients that are typically blended in cosmetic compositions as needed. For example, moisturizers, emollients, thickeners, organic and inorganic pigments, organic powders, preservatives, bactericides, antioxidants, plant extracts, pH regulators, alcohols, pigments, fragrances, blood circulation promoters, cooling agents, antiperspirants, purified water, etc. Other blended ingredients that may be included in the composition of the present invention are not limited thereto, and the blending amount of the above ingredients may be within a range that does not impair the purpose and effect of the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples, and Test Examples. These are presented solely as examples to more specifically illustrate the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these Examples, Comparative Examples, and Test Examples.

[Manufacturing Example 1] Manufacturing of microparticles containing bis-ethylhexyloxyphenol methoxyphenyl triazine

9 g of polyvinyl alcohol was added to a reactor and dissolved in 2000 g of distilled water to produce an aqueous phase. 200 g of methyl methacrylate (MMA) and 25 g of ethylene glycol dimethacrylate were added to an emulsifier and stirred for 5 minutes. 75 g of bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT) was additionally added and dissolved for 30 minutes to produce an oil phase. Here, 3 g of the initiator 2,2'-azobis-(2,4-dimethylvaleronitrile was added and mixed. After that, the above-mentioned water was added to the emulsifier, dispersion polymerization was performed for 30 minutes using the emulsifier, and the temperature was increased to react at 50°C for 15 hours. After dehydration using a reduced pressure filter, washing with water three times and vacuum drying were performed to obtain bowl-shaped polydisperse microparticles (Figs. 1a and 1b) containing 25 wt% of the final bis-ethylhexyloxyphenol methoxyphenyl triazine (yield = 90%, average diameter of microparticles = 2 μm).

[Experimental Example 1] Comparison of clinical results of UV protection according to the formulation of bis-ethylhexyloxyphenol methoxyphenyl triazine

As one embodiment of the present invention, a composition comprising microparticles including a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed in an oil phase; and bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) dissolved in a polar oil was prepared with the following composition. Specifically, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) was completely dissolved in a polar oil (C12-C15 alkyl benzoate*titanium oxide*aluminum stearate*polyhydroxystearic acid*alumina) by heating to 80°C, and then cooled. Other oil phase components other than the above components were sequentially added to a container and mixed, and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil was added to the container containing the oil phase components and uniformly dispersed and dissolved. After mixing and dissolving the components of the water phase in a separate container, the components were added to the container containing the components of the oil phase and emulsified using a homogenizer to prepare a W/S type UV blocking composition in the form of a sun milk formulation (Example 1).

A comparative example was prepared by the same method as Example 1, except that bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) dissolved in polar oil was not included, and the remaining oily components were sequentially added to silicone oils while dissolving and dispersing them without heating, thereby producing a W/S type UV-blocking composition in the form of a sun milk formulation (Example 1).

Example 1 Comparative Example 1 Yu Sang-bu Ethylhexyl methoxycinnamate*BHT 7 7 Ethylhexyl salicylate KSCI: Octyl salicylate 4 4 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S®) 1 - Dimethicone 15 15 Cyclopentasiloxane*cyclohexasiloxane Remaining amount Remaining amount C12-15 alkyl benzoate*C12-15 alcohols 6 6 Disteardimonium hectorite 0.3 0.3 PEG-10 Dimethicone 1.5 1.5 Tocopherol*Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 1.5 1.5 Manufacturing Example 1 (Bowl-shaped polydisperse microparticles containing 25 wt% of bis-ethylhexyloxyphenol methoxyphenyl triazine) 8 12 C12-C15 alkyl benzoate*titanium oxide*aluminum stearate*polyhydroxystearic acid*alumina 5 5 Zinc oxide*Hydrogenated dimethicone*PEG-10 dimethicone*Cyclopentasiloxane 11 11 Zinc oxide*triethoxycaprylylsilane 2.5 2.5 Award distilled water 15 15 polyol 5 5 sodium chloride 1 1 2Na EDTA 0.05 0.05 antiseptic 1.15 1.15 ethanol 5 5 Total weight (wt%) 100 100 Test results (n=3) Average SPF 41.1 Average SPF 22.6 Average PFA 8.1 Average PFA 7.7

Evaluation of Sun Protection Factor (SPF)

The amount of ultraviolet light emitted from a solar simulator lamp to the test area was adjusted to 20–100 mJ/㎠ and irradiated onto the back of the test subject. The minimal erythema dose (MED) was determined 24 hours after irradiation.

To confirm the UV blocking effect of each sample (Example 1 and Comparative Example 1), 0.1 g of the sample was uniformly applied to the back of the subject at a thickness of 2 μl/㎠ and left to dry for 15 minutes. A UV irradiation window was attached and fixed to the area where each sample was applied, and areas other than the irradiation window were blocked from UV rays using leather and a towel, and then UV rays were irradiated.

Based on the subject's MED (SPF 50), the UV exposure dose was investigated, and the test was conducted while gradually increasing the UV exposure dose. The minimum erythema dose was determined 24 hours after UV exposure, and the UV protection effect was calculated according to Equation 2 below, and is shown in Table 1 above.

[Formula 2]

SPF = (minimum erythematous dose on the skin area where the composition is applied) / (minimum erythematous dose on the skin area where the composition is not applied, MED)

Evaluation of UV Protection Factor (PFA)

The amount of UV-A (320-400 nm) irradiated from a solar simulator lamp to the test area was adjusted to 6.40-19.54 J/cm ² and irradiated to the back area of the test subject. The minimum persistent pigment darkening dose (MPPDD) was confirmed 24 hours after irradiation with UV-A.

To confirm the UV-A blocking effect of each sample (Example 1 and Comparative Example 1), 0.1 g of the sample was uniformly applied to the back of the subject at a thickness of 2 μl/㎠ and left to dry for 15 minutes. A UV irradiation window was attached and fixed to the area where each sample was applied, and areas other than the irradiation window were blocked from UV rays using leather and a towel, and then UV rays were irradiated.

Based on the MPPDD of the subject (PFA 8), the UV-A irradiation dose was investigated, and the test was conducted while gradually increasing the UV-A irradiation dose. The minimum sustained blackening amount after 24 hours of UV-A irradiation was determined, and the UV-A blocking effect was calculated according to Equation 3 below, and is shown in Table 1 above.

[Formula 3]

UVA protection factor = (minimum persistent darkening of the skin area where the composition is applied) / (minimum persistent darkening of the skin area where the composition is not applied, MPPDD)

As a result, as shown in the table above, although Example 1 contains the same amount of bis-ethylhexyloxyphenol methoxyphenyl triazine as Comparative Example 1, the SPF index and PA index confirmed through clinical trials show that the UV blocking power of Example 1 is about twice as high, confirming that the UV blocking effect of the present invention is excellent.

[Test Example 2] Comparison of the stability of bis-ethylhexyloxyphenol methoxyphenyl triazine

The presence or absence of precipitation of bis-ethylhexyloxyphenol methoxyphenyl triazine depending on the type of polar oil in the dissolved bis-ethylhexyloxyphenol methoxyphenyl triazine included in the composition of the present invention was confirmed through the following experiment. If a polar oil capable of sufficiently dissolving bis-ethylhexyloxyphenol methoxyphenyl triazine is not included, precipitation of bis-ethylhexyloxyphenol methoxyphenyl triazine occurs, making it impossible to function as a UV blocker.

In order to conduct the experiment, the oil phase of the W/S type composition was prepared with the composition shown in Table 2 below. At this time, the content of each component is expressed as weight% based on the total weight of the composition including both the water phase and the oil phase (100 weight%). In this experiment, since a transparent oil phase is required to compare the solubility of bis-ethylhexyloxyphenol methoxyphenyl triazine, all powders containing inorganic UV blockers that affect turbidity in the composition were excluded. Therefore, the total weight in the table below is 58 weight%. Specifically, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S®) was dissolved in ethylhexyl methoxycinnamate*BHT and ethylhexyl salicylate KSCI: octyl salicylate by heating to 80°C, and then cooled. Other oil phase components other than the above components were mixed in a container, and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil was added to the container containing the oil phase components and uniformly dispersed and dissolved. As a comparative example of the present invention, Comparative Example 2 was also prepared using the same method as the above method.

Comparative Example 2 Example 2 Example 3 Example 4 Example 5 Yu Sang-bu Trisiloxane*dimethicone 5 2 2 2 3 Butylene glycol dicaprylate*dicaprate - 6 - - 3 C12-C15 alkyl benzoate - - 6 - - dicaprylyl carbonate - - - 6 - Caprylyl Methicone*Phenyl Trimethicone 4 4 4 4 4 Diphenylsiloxy phenyl trimethicone 4 4 4 4 4 Dimethicone*Trisiloxane 6 3 3 3 5 Trimethylsiloxysilicate*cyclopentasiloxane 3 3 3 3 3 ethanol 5 5 5 5 5 PEG-10 Dimethicone 1.5 1.5 1.5 1.5 1.5 Tocopherol*Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 2 2 2 2 2 Cyclopentasiloxane*cyclohexasiloxane Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount C12-C15 alkyl benzoate 4 4 4 4 4 Ethylhexyl methoxycinnamate*BHT 7 7 7 7 7 Ethylhexyl salicylate KSCI: Octyl salicylate 4 4 4 4 4 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S®) 2 2 2 2 2 Total weight (wt%) 58 58 58 58 58

The manufactured Comparative Example 1 and Examples 2 to 5 were stored at room temperature, cold temperature (4°C), or frozen, and it was observed whether bis-ethylhexyloxyphenol methoxyphenyl triazine precipitated, i.e., whether it was stably dissolved in the oil phase. Immediately after manufacture, Examples 2 and 3 were relatively transparent, and the others were translucent. At room temperature the next day, all but Example 2 were translucent. After 5 days at room temperature, Examples 2 and 3 were transparent, but the others were translucent. After 3 weeks (4th week), all samples stored at room temperature were transparent, showing good stability (Fig. 3). Even after 7 weeks (8th week), all samples stored at room temperature were transparent, showing good stability (Fig. 5). Among the samples stored at a cold temperature from the next day, bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were precipitated in Comparative Example 2, and turbidity was formed in the order of Example 4 > Example 3 > Example 5 > Example 2 for the rest, showing that Example 2 had the best stability (Fig. 2). The cold-stored samples that had passed 4 weeks were continuously frozen thereafter and thawed in the 5th week, and as a result, a large amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were precipitated in Comparative Example 2, and a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were precipitated in Example 5. The turbidity of the remaining Examples 2 to 4 was similar to that after 3 weeks. In the frozen-stored samples that had passed 8 weeks (4 weeks cold + 4 weeks frozen), the degree of bis-ethylhexyloxyphenol methoxyphenyl triazine crystal precipitation was in the order of Comparative Example 2 >> Example 5 > Example 4 and Example 2 > Example 3 (Fig. 4). In the case of the 9th week sample that was thawed after 8 weeks (4 weeks of cold + 4 weeks of freezing) and stored at room temperature, a large amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were precipitated in Comparative Example 2, and a small amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were also precipitated in Example 5 (Fig. 6). Fig. 7 shows the sample that was thawed after 8 weeks (4 weeks of cold + 4 weeks of freezing) and stored at room temperature for 1 year. A large amount of bis-ethylhexyloxyphenol methoxyphenyl triazine crystals were precipitated in Comparative Example 2 and Example 5, but no precipitation was observed in Examples 4, 2, and 3 even after long-term storage.

In summary, the stability of BEMT dissolved in oil at room temperature after initial manufacturing is good, but there is a difference in the solubility of BEMT in refrigerated/frozen states between samples. This means that in addition to ethylhexyl methoxycinnamate and ethylhexyl salicylate used for dissolution in the initial oil phase, a certain amount of polar oil that can increase the solubility of BEMT in oil must be added to safely secure the solubility of BEMT in oil under various conditions.

[Test Example 3] Skin Stability Evaluation

In order to confirm the skin stability of the composition according to one embodiment of the present invention, a patch test was conducted on 18 adult women and 12 adult men (average age 32.5 years) with normal skin. Specifically, each composition of Example 1 and Comparative Example 1 prepared in Test Example 1 was directly contacted with the skin of the test subjects through a patch, and the patch was removed after 28 hours. The first reading was performed after 30 minutes, and the second reading was performed after 96 hours. Table 3 below shows the results of the second reading. In order to determine the intensity of skin irritation of Example 1 and Comparative Example 1, a weight was applied according to the degree of positive skin reaction to obtain the average skin reaction score, and the skin irritation of the samples was visually assessed. At this time, the judgment criteria were based on a 5-point scale, with less than 1 point (Grade I) being considered non-irritating, 1 to 3 points (Grade II) being mildly irritating, 3 to 5 points (Grade III) being moderately irritating, and 5 or more points (Grade IV) being strongly irritating. The average skin reactivity was calculated according to the following formula.

[Formula 4]

Average reactivity Judgment grade Example 1 0 No stimulation Comparative Example 1 0 No stimulation

As a result, as shown in the table above, the composition according to one embodiment of the present invention was determined to have excellent safety for the skin.

The present invention may provide the following embodiments as one example.

A first embodiment can provide a W/O (Water in Oil) type UV-blocking composition comprising a water phase and an oil phase, wherein the oil phase comprises microparticles including a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed; and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in a polar oil.

A second embodiment can provide a composition in which, in the first embodiment, the microparticles are included in an amount of 0.1 to 30 wt% based on the total weight of the composition.

A third embodiment can provide a composition in which, in at least one of the first embodiment and the second embodiment, the bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the polar oil is included in an amount of 0.01 to 2 wt% based on the total weight of the composition.

A fourth embodiment can provide a composition comprising, in one or more of the first to third embodiments, an oil including a polar functional group including at least one of a carboxyl group (-COO), a ketone group (-CO), and a hydroxyl group (-OH).

A fifth embodiment can provide a composition comprising at least one of the first to fourth embodiments, wherein the polar oil comprises at least one oil selected from the group consisting of butylene glycol dicaprylate*dicaprate, ethylhexyl salicylate, ethylhexyl methoxycinnamate, homosalate, C12-15 alkyl benzoate, dibutyl adipate, dicaprylyl carbonate, caprylyl-caprylate, cococaprylate, octocrylene, propylheptyl caprylate, isopropyl palmitate, caprylic/capric triglyceride, and cocoglyceride.

A sixth embodiment can provide a composition according to at least one of the first to fifth embodiments, wherein the microparticles are non-porous microparticles in a bowl shape.

A seventh embodiment can provide a composition according to at least one of the first to sixth embodiments, wherein the microparticles contain bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 20 wt% to 30 wt% based on the total weight of the microparticles.

The eighth embodiment can provide a composition in which, in at least one of the first to seventh embodiments, the average diameter of the microparticles is 1 to 10 μm.

The ninth embodiment can provide a composition according to at least one of the first to eighth embodiments, wherein the polymer matrix includes bis-ethylhexyloxyphenol methoxyphenyl triazine, and a polymerization product of a polymerizable monomer and a polyfunctional crosslinking agent.

A tenth embodiment can provide a composition comprising at least one selected from the group consisting of the first embodiment to the ninth embodiment, wherein the polymerizable monomer comprises at least one aromatic vinyl monomer selected from the group consisting of styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene, and vinyltoluene; and at least one acrylic vinyl monomer selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, octyl(meth)acrylate, stearyl(meth)acrylate, benzyl(meth)acrylate, and glycidyl(meth)acrylate.

An eleventh embodiment can provide a composition in which, in at least one of the first to tenth embodiments, the multifunctional crosslinking agent comprises at least one selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and tri(meth)acrylate.

The twelfth embodiment can provide a composition in which, in at least one of the first to eleventh embodiments, the water-containing portion includes at least one of water and ethanol.

The 13th embodiment can provide a composition in which, in at least one of the first to twelfth embodiments, the composition is of the W/S (Water in Silicon oil) type.

The 14th embodiment can provide a composition having a sun protection factor (SPF) of 30 or more in at least one of the first to 13th embodiments.

Claims (14)

Including the award and the paid award,
Microparticles comprising a polymer matrix in which bis-ethylhexyloxyphenol methoxyphenyl triazine is dispersed in the above oil phase; and bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in polar oil,
The above microparticles are included in an amount of 0.1 to 30 wt% based on the total weight of the composition,
Bis-ethylhexyloxyphenol methoxyphenyl triazine dissolved in the above polar oil is contained in an amount of 0.01 to 2 wt% based on the total weight of the composition.
W/O (Water in Oil) type UV blocking composition. delete delete In the first paragraph, the polar oil is a composition comprising an oil having at least one polar functional group among a carboxyl group (-COO), a ketone group (-CO), and a hydroxyl group (-OH). A composition according to claim 1, wherein the polar oil comprises at least one oil selected from the group consisting of butylene glycol dicaprylate*dicaprate, ethylhexyl salicylate, ethylhexyl methoxycinnamate, homosalate, C12-15 alkyl benzoate, dibutyl adipate, dicaprylyl carbonate, caprylyl-caprylate, cococaprylate, octocrylene, propylheptyl caprylate, isopropyl palmitate, caprylic/capric triglyceride, and cocoglyceride. A composition in claim 1, wherein the microparticles are non-porous microparticles in a bowl shape. A composition in claim 1, wherein the microparticles contain bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 20 to 30 wt% based on the total weight of the microparticles. A composition according to claim 1, wherein the average diameter of the microparticles is 1 to 10 μm. A composition in claim 1, wherein the polymer matrix comprises a polymer of bis-ethylhexyloxyphenol methoxyphenyl triazine and a polymerizable monomer and a polyfunctional crosslinking agent. In claim 9, the polymerizable monomer comprises at least one aromatic vinyl monomer selected from the group consisting of styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene, and vinyltoluene; and at least one acrylic vinyl monomer selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, octyl(meth)acrylate, stearyl(meth)acrylate, benzyl(meth)acrylate, and glycidyl(meth)acrylate. A composition comprising at least one selected from the group consisting of: A composition in claim 9, wherein the multifunctional crosslinking agent comprises at least one selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and tri(meth)acrylate. A composition in claim 1, wherein the water component comprises at least one of water and ethanol. In claim 1, the composition is a W/S (Water in Silicon oil) type composition. In claim 1, the composition has a sun protection factor (SPF) of 30 or more.