HK1161541B - Water-in-oil-type emulsion sunscreen cosmetic - Google Patents

Description

Water-in-oil type emulsified sunscreen cosmetic

Technical Field

The present invention relates to a water-in-oil type emulsified sunscreen cosmetic. More specifically, the present invention relates to a low viscosity water-in-oil type emulsion sunscreen cosmetic composition having an extremely excellent ultraviolet protection promoting effect over a wide ultraviolet range and excellent in usability (smoothness, refreshing feeling, non-stickiness, etc.).

Background

The main ultraviolet absorption wavelength regions of the sunscreen cosmetic are UV-A region (320-400 nm) and UV-B region (290-320 nm). It has been thought that ultraviolet rays in the UV-A region blacken the skin, but do not cause sunburn and promote skin aging as does ultraviolet rays in the UV-B region. However, in recent years, it has been found that ultraviolet rays in the UV-B region stay relatively on the surface portion of the skin, whereas ultraviolet rays in the UV-a region reach the deep portion of the skin, causing not only skin aging but also skin cancer. Therefore, a sunscreen cosmetic exhibiting an ultraviolet ray protection effect in a wide ultraviolet ray region including a UV-B region and a UV-a region is required.

In particular, whitening hot flashes have been prevalent in recent years, and recently, sunscreen cosmetics having an excellent ultraviolet protection effect have been demanded more than ever. Further, products having excellent usability (non-stickiness and the like) are more preferable. Furthermore, low viscosity products which are spread well upon application are desirable.

Examples of technologies close to the sunscreen cosmetic of the present invention include the technologies described in patent documents 1 to 3 below.

That is, japanese patent application laid-open No. 2008-162930 (patent document 1) describes an oil-in-water emulsion sunscreen cosmetic which contains an oil-soluble ultraviolet absorber, a water-soluble thickener (e.g., an acrylic water-soluble polymer), a water-soluble ultraviolet absorber, and a specific hydrophilic nonionic surfactant, and which is excellent in ultraviolet protection ability and stability without impairing the usability of moisture. The sunscreen cosmetic described in patent document 1 is excellent in usability and water-retention because of its oil-in-water emulsion type, but it is undeniable that the water resistance is insufficient compared with the water-in-oil emulsion type.

Jp 2007-217379 a (patent document 2) describes a water-in-oil type emulsion sunscreen cosmetic which exhibits an excellent ultraviolet blocking effect and an effect of preventing/suppressing a smell with time by neutralizing phenylbenzimidazole sulfonic acid to prepare a salt, and then blending the salt into an oil phase (external phase) and using a water-in-oil type emulsion system in which octocrylene and hydrophobized titanium dioxide and/or zinc oxide are blended. However, in patent document 2, there is no description or suggestion that the ultraviolet absorption ability (boost effect of ultraviolet absorption ability) is significantly improved by using an ultraviolet absorber and a water-soluble polymer in combination in a water-in-oil emulsion sunscreen cosmetic.

Jp 2007-291094 a (patent document 3) describes a water-in-oil emulsion sunscreen cosmetic which contains a surface-treated zinc oxide whose surface is coated with a (polydimethylsiloxane/polymethylsiloxane) copolymer and an organotitanate and/or trialkoxyalkylsilane, and which is excellent in extensibility, dispersion stability of powder with time, and ultraviolet protection effect. However, patent document 3 does not describe and mention a case where ultraviolet absorption ability (acceleration effect of ultraviolet absorption ability) is significantly increased by using an ultraviolet absorber and a water-soluble polymer in combination in a water-in-oil emulsion sunscreen cosmetic.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2008-162930

Patent document 2: japanese patent laid-open publication No. 2007-217379

Patent document 3: japanese patent laid-open publication No. 2007-291094

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a low-viscosity water-in-oil emulsion sunscreen cosmetic composition which has an extremely excellent ultraviolet protection promoting effect over a wide ultraviolet range and is excellent in usability (smoothness, refreshing feeling, non-stickiness, etc.).

Means for solving the problems

Conventionally, in a water-in-oil emulsion system, when an aqueous component having a large molecular weight such as a water-soluble polymer is added to an aqueous phase as a dispersed phase, the water-soluble polymer is not always positively added to the aqueous phase from the viewpoints of easiness of stickiness due to the water-soluble polymer in use, system stability (balance), and the like.

However, as a result of intensive studies to solve the above-mentioned conventional problems, the present inventors have unexpectedly found that when a water-soluble polymer is blended in an aqueous phase in a water-in-oil emulsion sunscreen cosmetic system in which an ultraviolet absorber is blended, the ultraviolet absorption ability is remarkably improved in a wide range of ultraviolet region (i.e., acceleration effect of ultraviolet absorption ability) and the usability is excellent, thereby completing the present invention.

Namely, the present invention provides a water-in-oil type emulsion sunscreen cosmetic composition comprising 0.01 to 10 mass% of (a) a water-soluble polymer and 0.01 to 30 mass% of (B) an ultraviolet absorber, wherein the viscosity of the cosmetic composition is 10,000 mPas (type B viscometer: 30 ℃) or less, and the aqueous phase is 45 mass% or less.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides a low viscosity water-in-oil type emulsion sunscreen cosmetic composition which has an extremely excellent ultraviolet protection promoting effect (ultraviolet absorption promoting effect) in a wide ultraviolet range and is excellent in usability (smoothness, refreshing feeling, non-stickiness, etc.).

Detailed Description

The water-in-oil emulsion sunscreen cosmetic of the present invention will be described in detail below.

The water-soluble polymer as the component (a) is not particularly limited, and examples thereof include natural water-soluble polymers, semisynthetic water-soluble polymers, synthetic polymers, and inorganic water-soluble polymers.

Examples of the natural water-soluble polymer include plant-based water-soluble polymers such as gum arabic, tragacanth gum, galactan, guar gum, locust bean gum, tamarind gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (marmelo), seaweed gum (seaweed extract), starch (rice, corn, potato, wheat), and glycyrrhizic acid; water-soluble polymers of microorganisms such as xanthan gum, dextran, succinoglycan and pullulan; animal-based water-soluble polymers such as collagen, casein, albumin, and gelatin.

Examples of the semisynthetic water-soluble polymer include starch-based water-soluble polymers such as carboxymethyl starch and methylhydroxypropyl starch; cellulose-based water-soluble polymers such as methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, carboxymethylcellulose (CMC), crystalline cellulose, and cellulose powder; alginic acid-based water-soluble polymers such as sodium alginate and propylene glycol alginate.

Examples of the synthetic water-soluble polymer include vinyl water-soluble polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, and carboxyvinyl polymer (carbopol); polyoxyethylene-based water-soluble polymers such as polyethylene glycol 20,000, polyethylene glycol 4,000,000, and polyethylene glycol 600,000; a copolymer-based water-soluble polymer such as a polyoxyethylene-polyoxypropylene copolymer; acrylic water-soluble polymers such as sodium polyacrylate, polyethylacrylate and polyacrylamide, and also polyethyleneimine and cationic polymers.

Examples of the inorganic water-soluble polymer include bentonite, magnesium aluminum silicate (Veegum), laponite, hectorite, and silicic anhydride.

(a) The components can be 1 or more than 2. In the present invention, a natural water-soluble polymer is preferably used from the viewpoint of enhancing the ultraviolet protection effect, and a plant-based water-soluble polymer and a microorganism-based water-soluble polymer are preferably used. Among them, agar and succinoglycan are particularly preferably used.

The amount of component (a) blended in the cosmetic composition of the present invention is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and more preferably 0.1 to 1% by mass. When the amount is less than 0.01% by mass, the effect of improving the ultraviolet protection is difficult to obtain, while when the amount is more than 10% by mass, the usability and the stability of the preparation may be impaired.

The ultraviolet absorber as component (b) is not particularly limited as long as it can be blended in a cosmetic, and any of oil-soluble and water-soluble ones can be used.

Examples of the oil-soluble ultraviolet absorber include benzoic acid-based ultraviolet absorbers such as p-aminobenzoic acid (PABA), PABA monoglyceride, N-dipropoxypaba ethyl ester, N-diethoxypaba ethyl ester, N-dimethylpaba butyl ester, and diethylaminohydroxybenzoylbenzoic acid hexyl ester; anthranilic acid-based ultraviolet absorbers such as trimethylcyclohexyl (homomenthyl) -N-acetyl anthranilate; salicylic acid-based ultraviolet absorbers such as amyl salicylate, menthyl salicylate, trimethylcyclohexanol salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2, 5-diisopropyl cinnamate, ethyl-2, 4-diisopropyl cinnamate, methyl-2, 4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, p-isopropyl-methoxy cinnamate, isopentyl-p-methoxy cinnamate, octyl-p-methoxy cinnamate [ (2-ethylhexyl-p-methoxy cinnamate ], 2-ethoxyethyl-p-methoxy cinnamate, cyclohexyl-p-methoxy cinnamate, ethyl- α -cyano- β -phenyl cinnamate, 2-ethylhexyl- α -cyano- β -phenyl cinnamate, glycerol mono-2-ethylhexanoyl-di-p-methoxy cinnamate, methyl-2, 5-diisopropyl cinnamate, ethyl-2, 4-diisopropyl cinnamate, methyl-2, 4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, p-isopropyl-methoxy cinnamate, isopentyl-p-, Cinnamic acid-based ultraviolet absorbers such as 3-methyl-4- [ methylbis (trimethylsiloxy) silyl ] butyl 3, 4, 5-trimethoxycinnamate; 2-phenyl-5-methylbenzoxazole, 2 ' -hydroxy-5-methylphenylbenzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, dibenzylazine (dibenzazine), dianisiloylmethane, 4-tert-butyl-4 ' -methoxydibenzoylmethane, 4- (1, 1-dimethylethyl) -4 ' -methoxydibenzoylmethane, 5- (3, 3-dimethyl-2-norbornenyl) -3-pentan-2-one, octocrylene [ (-. 2-cyano-3, 3-diphenyl-2-propenoic acid-2-ethylhexyl ], and mixtures thereof, Polysiloxane-15 [ (] dimethicodiethylbenzylzalmanatate ], and the like. But are not limited to these examples. Among them, benzoic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, octocrylene, polysiloxane-15, and the like are preferably used from the viewpoint of promoting the ultraviolet ray protection ability by the combination with the component (a).

Examples of the water-soluble ultraviolet absorber include 2, 4-dihydroxybenzophenone, 2 ' -dihydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ', 4, 4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4 ' -methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4 ' -phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxybenzophenone, and the like, Benzophenone-based ultraviolet absorbers such as 4-hydroxy-3-carboxybenzophenone; benzimidazole-based ultraviolet absorbers such as phenylbenzimidazole-5-sulfonic acid and salts thereof, phenylene-bis-benzimidazole-tetrasulfonic acid and salts thereof; benzotriazole-based ultraviolet absorbers such as methylenebis-benzotriazole-tetramethylbutylphenol; 3- (4' -methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, ethyl urocanic acid, and the like. But are not limited to these examples. Among them, from the viewpoint of promoting the ultraviolet ray protection ability by the combined use with the component (a), a benzimidazole-based ultraviolet ray absorber, a benzotriazole-based ultraviolet ray absorber, and the like are preferably used.

The amount of component (b) blended in the cosmetic composition of the present invention is 0.01 to 30% by mass, preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass. When the amount is less than 0.01% by mass, it is difficult to obtain a sufficient ultraviolet protection ability, while when it is blended in an amount exceeding 30% by mass, usability, stability of the preparation, and safety may be impaired. (b) The component (A) may be 1 or more than 2.

The water-in-oil emulsion sunscreen cosmetic of the present invention contains the component (a) and the component (b), but from the viewpoint of usability (stickiness and the like), the component (a) has not been positively blended in a water-in-oil emulsion system. In the present invention, the water-in-oil emulsion system exhibits an extremely excellent effect that could not be expected in the past by blending the component (a) in combination with the component (b) to further enhance the ultraviolet absorption ability of the component (b) (i.e., an ultraviolet absorption ability-enhancing effect). Thus, even if the component (b) is blended at a relatively low level as compared with the conventional one, a superior ultraviolet protection effect can be obtained at a higher level than the conventional one. Further, the usability of the water-in-oil emulsion system, such as greasy or sticky feeling upon application, can be improved. That is, both of a remarkable improvement in the ultraviolet protection effect and usability can be sought.

The water-in-oil type emulsion sunscreen cosmetic of the present invention may further contain a hydrophobic powder from the viewpoint of improving water resistance and the like. The hydrophobic powder is not limited to a powder itself that is hydrophobic, and includes a hydrophobized powder in which the surface of the powder is hydrophobized even if it is hydrophilic.

Specific examples of the hydrophobic powder include organic powders such as polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, and cellulose powder, and silicone powder such as trimethylsiloxane powder.

Examples of the powder component of the hydrophobized powder include inorganic powders such as talc, kaolin, mica, sericite (serite), muscovite, phlogopite, synthetic mica, lepidolite, biotite, lepidolite, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate, etc.), boron nitride, etc.; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (red iron oxide) and iron titanate; inorganic brown pigments such as gamma-iron oxide; inorganic yellow pigments such as yellow iron oxide and yellow soil; inorganic black pigments such as black iron oxide, carbon black, and low-dimensional titanium dioxide; inorganic violet pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate; ultramarine blue pigments, berlin blue pigments, and the like; pearl pigments such as titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, colored titanium dioxide-coated mica, bismuth oxychloride, and fish scale foil; and metal powder pigments such as aluminum powder and copper powder. In the present invention, those obtained by subjecting these powder components to a hydrophobic treatment can also be used.

The hydrophobizing treatment method is not limited as long as it can impart hydrophobicity, and, for example, a general surface treatment method such as a gas phase method, a liquid phase method, an autoclave method, a mechanochemical method, or the like can be used.

For example, when the hydrophobizing agent is added to the raw material powder to perform the treatment, the raw material powder may be diluted with an appropriate solvent (dichloromethane, chloroform, hexane, ethanol, xylene, volatile silicone, or the like) and added, or may be added as it is. For mixing and stirring of the powder and the treating agent, a ball mill, a faujasite ball mill, a vibratory ball mill, an attritor, a ball mill, a rod mill, a pan mill, a homomixer (homomixer), a disperser (Homo Disper), a henschel mixer, a nauta mixer, or the like can be used. In addition, the following method may also be used: a method of polymerizing a cyclic organosiloxane on the surface of a powder at a low temperature of 100 ℃ or lower by a gas phase reaction using the activity of the surface of the powder (Japanese examined patent publication No. 1-54380); a method of adding a pendant group of glycerol monoallyl ether or the like to the Si-H portion of the silicon polymer of the surface after the aforementioned method (Japanese examined patent publication No. 1-54381), and the like.

Specific examples of the hydrophobic treatment include treatments using silicones such as methylhydrogenpolysiloxane, a methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer, and dimethylpolysiloxane; treatment with a silane compound such as octyltriethoxysilane or hexyltrimethoxysilane; treatment with fatty acids such as palmitic acid and stearic acid; a metal saponification treatment using an alkali metal salt or an alkaline earth metal salt of the fatty acid; fluorine treatment using perfluoroalkyl phosphoric acid diethanolamine salt, perfluoroalkyl trimethoxysilane, or the like. But are not limited to these examples.

The hydrophobic powder has high hydrophobicity, and when it is practically used in an emulsion, it has high resistance to water and sweat, and is least likely to cause makeup, and therefore, the effect is excellent in persistence. Further, the emulsified particles are dense and have the most excellent long-term stability.

These hydrophobic powders may be used in 1 kind or in 2 or more kinds. The hydrophobic powder is not limited to the above-mentioned components as long as it is a hydrophobic powder that can be generally used in cosmetics. In the present invention, from the viewpoint of ultraviolet protection, hydrophobized titanium dioxide, zinc oxide, and the like are preferred examples. Examples of the titanium dioxide subjected to the hydrophobic treatment include "TTO-S-4", "TTO-V-4" (all manufactured by stone industries, Ltd.), "MT-100 TV", "MT-014V" (all manufactured by TAYCA CORPORATION) and the like as commercially available products, and examples of the zinc oxide subjected to the hydrophobic treatment include "FZO-50" (manufactured by stone industries, Ltd.), "MZ-700" (manufactured by TAYCA CORPORATION) and "Z-Cote HP-1" (manufactured by BASF CORATION) as commercially available products.

When the hydrophobic powder is blended, the blending amount thereof in the cosmetic of the present invention is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and particularly preferably 3 to 20% by mass. When the amount is less than 0.1% by mass, it is difficult to sufficiently improve the effect of blending the hydrophobic powder, while when it exceeds 50% by mass, the usability and stability of the preparation may be impaired.

The viscosity of the water-in-oil type emulsion sunscreen cosmetic of the present invention is low at 10,000 mPas (30 ℃ C., B-type viscometer) or less, preferably 6,000 mPas or less. When the viscosity exceeds 10,000 mPas, the viscosity becomes too high, and the spreading at the time of application becomes difficult, and a good feeling of handling cannot be obtained.

The formulation of the water-in-oil type emulsion sunscreen cosmetic of the present invention is not particularly limited, and is in the form of cream, liquid or the like, and a two-layer dispersion type formulation which is separated into two layers when left to stand and is used after shaking when used is particularly preferable in the present invention. Such a low viscosity emulsified system is not known in the past, particularly when a water-soluble polymer having a large molecular weight is actively blended in an aqueous phase.

The water-in-oil type emulsified sunscreen cosmetic of the present invention can be prepared by a conventional method, and the method of emulsification is not particularly limited. Examples of the method include the following: respectively heating the water phase and the oil phase to about 70 ℃, slowly adding the heated water phase into the oil phase, emulsifying by using an emulsifying machine, and then cooling to room temperature; but is not limited thereto. In the present invention, the water phase is blended in a proportion of 45 mass% or less with respect to the total amount of the cosmetic. When the water phase exceeds 45 mass%, the viscosity of the cosmetic tends to be high.

Other optional additives used in general external skin preparations such as cosmetics and pharmaceuticals, for example, oils and fats, waxes, hydrocarbon oils, higher alcohols, higher fatty acids, synthetic ester oils, surfactants, metal ion chelating agents (sequestrant agents), lower alcohols, polyhydric alcohols, powder components, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, perfumes, and water may be appropriately blended in the water-in-oil emulsion sunscreen cosmetic of the present invention as necessary within a range not to impair the effects of the present invention.

In addition, an organically modified clay mineral may be blended. Examples of the organically modified clay mineral include distearyldimethylammonium hectorite (═ quaternary ammonium salt-18 hectorite), distearyldimethylammonium bentonite (═ quaternary ammonium salt-18 bentonite), distearylbenzyldimethylammonium hectorite, dioctadecyl dimethylammonium salt-modified montmorillonite, octadecyl dimethylbenzylammonium salt-modified montmorillonite, and dihexadecyl dimethylammonium salt-modified montmorillonite. When the organically modified clay mineral is blended, the blending amount is preferably 1% by mass or less in the cosmetic.

Examples of other ingredients that can be blended include preservatives (ethyl paraben, butyl paraben, etc.); anti-inflammatory agents (e.g., glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (e.g., saxifrage extract, arbutin, etc.); various extracts (e.g., phellodendron amurense, coptis chinensis, japanese swingletop, japanese peony, birch, sage, loquat, ginseng, aloe, mallow, iris, grape, coix seed, luffa, lily, saffron, ligusticum wallichii, ginger, hypericum erectum, formononetin, garlic, capsicum, dried orange peel, angelica, seaweed, etc.), activators (e.g., royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoters (e.g., vanillylamide nonanoate (nonionics), benzyl nicotinate, β -butoxyethyl nicotinate, capsaicin, zingerone, tincture of cantharides, ichthammol, tannic acid, α -borneol, tocopheryl nicotinate, inositol hexanicotinate, cyclamate, cinnamylphenylpiperazine, tolylazoline, acetylcholine, verapamil, cepharanthine, γ -oryzanol, etc.); anti-lipemic agents (e.g., sulfur, dithioanthracene, etc.); and anti-inflammatory agents (e.g., tranexamic acid, thiotaurine, hypotaurine, etc.). But are not limited to these examples.

Examples

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to the following examples. The amounts to be blended are all expressed in mass%.

1. Ultraviolet ray protection promoting effect and viscosity

Examples 1 to 8 and comparative examples 1 to 8

The effect of increasing the ultraviolet absorption capacity (i.e., the effect of promoting the ultraviolet absorption capacity) by combining a water-soluble polymer with an ultraviolet absorber was evaluated by performing a test using a low-viscosity sample having a composition shown in tables 2 to 3 below. In tables 2 to 3, "comparative example" is a system containing an ultraviolet absorber but no water-soluble polymer, and "example" is a system using both an ultraviolet absorber and a water-soluble polymer.

< Effect of promoting ultraviolet protection >

(test method)

At 2mg/cm²The samples were applied to a substrate for coating in the proportions described above using a spectrophotometer ("U-4100"; Hitach)i High-Technologies Corporation) measures the ultraviolet absorbance (abs.) at the maximum absorption wavelength (λ max) (nm) of the ultraviolet absorption spectrum of each ultraviolet absorber contained in the sample. The measured values are shown in tables 2 to 3. The greater the value of ultraviolet absorbance, the more excellent the ultraviolet protection effect. The λ max (nm) of each ultraviolet absorber contained in the sample is shown in table 1 below.

TABLE 1

(ultraviolet absorption Capacity increasing rate)

The increase rate of ultraviolet absorbance (abs.) of each example relative to each control example was calculated from the measured values. The examples and comparative examples were compared with each other using the same ultraviolet absorber. The results are shown in tables 2 to 3.

(ultraviolet ray protection effect)

The ultraviolet protection effect was evaluated from the above-mentioned ultraviolet absorption capacity increase rate of each example by the following criteria.

A⁺⁺: the rate of increase in ultraviolet absorptivity was 20% or more higher than that of the control example

A⁺: the increase rate of the ultraviolet absorption capacity is more than 10 to 20 percent higher than that of the comparative example

A: the increase rate of the ultraviolet absorption capacity is more than 5 percent to 10 percent higher than that of the comparative example

B: the increase rate of the ultraviolet absorption capacity is more than 0 percent to 5 percent higher than that of the comparative example

C: the rate of increase in the ultraviolet absorbability was the same as or smaller than that of the comparative example.

< viscosity >

The viscosity of each sample after the shaking preparation was measured at 30 ℃ using a type B viscometer (model B viscometer) (SHIBAURASSYSTEMS CO., LTD) and a rotational speed of 12 rpm.

The following compounds shown in tables 2 to 3 were used.

Polysiloxane-15 (Dimethico diethyl diazalmalonate)^(*1): "ParsolSLX" (manufactured by DSM Nutrition Japan K.K),

Phenylbenzimidazole sulfonic acids^(*2): "Eusolex 232" (manufactured by Merck Co., Ltd.),

Benzylbenzimidazole tetrasulfonic acid disodium salt^(*3): "Neoheliopan AP" (manufactured by Haarmann and Reimer Co., Ltd.),

Methylene bis-benzotriazole-tetramethylbutylphenol^(*4): "TINOSORB M" (manufactured by Ciba Specialty Chemicals Holding Inc.).

From the results shown in tables 2 to 3, it is understood that even when an ultraviolet absorber having any one of ultraviolet absorption wavelength regions of the UV-A region (320 to 400nm) and the UV-B region (290 to 320nm) is used, the ultraviolet protection promoting effect is exhibited by using the water-soluble polymer in combination with the ultraviolet absorber, as compared with the case where the ultraviolet absorber is used alone.

2. Usability

Example 9 and comparative example 9

The usability of example 9 (agar formula) and comparative example 9 (no agar formula) shown in table 4 were evaluated by using 10 female panelists.

For each evaluation item, whether the usability of example 9 is improved as compared with comparative example 9 was evaluated according to the following evaluation criteria. The results are shown in Table 5. In addition, the usability of example 9 was not evaluated lower than that of comparative example 9.

(evaluation criteria)

A⁺: the answers of more than 7 of 10 are improved

A: the answers of more than 5 of 10 are improved

B: the answers of more than 3 of 10 are improved

C: the responses of 2 out of 10 are improved

TABLE 4

	Example 9	Comparative example 9
			Distearyldimethylammonium hectorite	0.15	0.15
Decamethylcyclopentasiloxane	45.8	45.8
			Lauryl PEG-9 polydimethylsiloxyethyl dimethicone	0.6	0.6
Trimethylsiloxy silicic acid	0.05	0.05
			Polyoxybutylene polyoxypropylene glycol	0.1	0.1
2-ethylhexyl 2-ethylhexanoate	2	2
			Isostearic acid	0.3	0.3
Octyl methoxycinnamate	5	5
			Ochrolin	1	1
Hydrophobizing (silane treatment) cationic treatment of zinc oxide	20	20
			Phenylbenzimidazole sulfonic acids	1.5	1.5
Triethanolamine	0.9	0.9
			Ion exchange water	21.2	22.2
Ethylenediaminetetraacetic acid trisodium salt	0.05	0.05
			Agar-agar	1	-
Phenoxyethanol	0.35	0.35

TABLE 5

Evaluation item	Evaluation (usability improvement of example 9)
		Harmonious feeling during application	A
Light after paintingSlippery feel	A+
		Refreshing feeling after application	A+
Has no sticky feeling after being applied	A
		No film feeling after coating	A

From the results shown in Table 5, it is clear that example 9 containing agar (water-soluble polymer) is improved in usability as compared with comparative example 9 containing no agar.

Prescription examples are further shown below.

Example 10 Water-in-oil emulsion sunscreen emulsion

(production method)

(ii) mixing and dissolving (7) and (8) at 80 ℃ and adding the mixture to the oil phases of (1) to (6). Next, (9) to (11) were added, and dispersed and mixed by using a disperser. After (12) to (16) were mixed and heated at 95 ℃ to dissolve them, they were slowly added to the oil phase with stirring by a disperser, and after sufficiently and uniformly mixing, they were quenched to 25 ℃ to obtain the desired sunscreen emulsion.

Example 11 Water-in-oil emulsion sunscreen emulsion

(production method)

The components (1) to (11) were dispersed and mixed by using a disperser. After (12) to (16) were mixed and heated to dissolve at 95 ℃, they were slowly added to the oil phase with stirring by a disperser, and after sufficiently and uniformly mixing, they were quenched to 25 ℃ to obtain the desired sunscreen emulsion.

Example 12 Water-in-oil emulsion sunscreen emulsion

(production method)

Dispersing and mixing (1) - (10) by using a disperser. After mixing and dissolving (11) to (15), the mixture was slowly added to the oil phase with stirring by a disperser to obtain the desired sunscreen emulsion.

Example 13 Multi-phase sunscreen emulsion

(production method)

The oil phases of (1) to (4) were slowly added to the water phases of (11) to (19) to obtain O/W preparations. The preparation was slowly added to the oil phases of (5) to (10), and then stirred by a homomixer to obtain a target sample.

Example 14 Water-in-oil emulsion Foundation

(production method)

The oil phases (7) to (13) were dispersed and mixed by a disperser into the oil phases (1) to (6) mixed by the disperser. After mixing and heating to dissolve (14) to (19) at 95 ℃, the mixture was slowly added to the oil phase with a disperser while stirring, and after sufficiently and uniformly mixing, the mixture was cooled to 25 ℃ to obtain the desired emulsified foundation.

Industrial applicability

The low-viscosity water-in-oil emulsion sunscreen cosmetic composition of the present invention has an extremely excellent ultraviolet protection promoting effect over a wide ultraviolet range and is excellent in usability (smoothness, refreshing feeling, non-stickiness, etc.).

Claims (2)

1. A water-in-oil type emulsified sunscreen cosmetic composition comprising 0.05 to 5 mass% of agar and/or succinoglycan (a), and 0.1 to 20 mass% of an ultraviolet absorber (B) selected from the group consisting of octyl methoxycinnamate, octocrylene, polysiloxane-15, phenylbenzimidazole sulfonic acid, disodium phenylbenzimidazole tetrasulfonate, methylenebis-benzotriazole-tetramethylbutylphenol, 4-tert-butyl-4 '-methoxydibenzoylmethane and 4- (1, 1-dimethylethyl) -4' -methoxydibenzoylmethane, wherein the viscosity of the cosmetic composition is 10,000 mPas (30 ℃, B-type viscometer) or less, and the aqueous phase is 45 mass% or less.

2. A water-in-oil emulsion sunscreen cosmetic according to claim 1, which is a double-layer dispersion type cosmetic that is used after shaking at the time of use.