Water-in-oil emulsion composition

Abstract

To provide a composition that causes no burden on the skin, ensures superior uniformity of a coating layer, delivers a sensation that is moisturizing without being sticky, and maintains stability over time.SOLUTION: A water-in-oil emulsion composition comprises (A) a polyurethane-79 gel composition in which polyurethane-79 is dissolved in an oily agent and gelled, in combination with (B) a volatile oil agent, (C) a silicone-based emulsifier, and (D) a divalent alcohol.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a water-in-oil emulsified composition containing specific components. More specifically, it relates to a water-in-oil emulsified composition comprising (A) a Polyurethane-79 gel composition composed of Polyurethane-79 and a liquid oil, (B) a volatile oil, (C) a silicone-based emulsifier, and (D) a dihydric alcohol.

Background Art

[0002] In the field of cosmetics, water-in-oil emulsified compositions are commonly used in skin care cosmetics and makeup cosmetics. They cover the skin surface with an oil film, prevent moisture transpiration, and protect the skin from dryness, so they are characterized by excellent emollient effect, moisturizing effect, and treatment effect on the skin. In addition, since they have better makeup durability than powder cosmetics and oil-in-water cosmetics, they are often used in makeup cosmetics and sunscreen cosmetics. A problem with water-in-oil emulsions is that it is difficult to ensure stability over time. To improve stability over time, it is generally effective to incorporate waxes or oily thickeners into the outer phase; however, this tends to degrade the usage sensation, such as causing stickiness and slowing skin absorption. Furthermore, compared with oil-in-water emulsified compositions whose outer phase is an aqueous phase, water-in-oil emulsions have slower skin absorption and leave an oil film on the skin for a long time due to the slow evaporation rate of volatile components. For this reason, secondary adhesion easily occurs to contacted areas after application, such as skin other than the application site, clothing, and containers, resulting in poor usability. In addition, the viscosity tends to decrease when stored at high temperatures, and repeated freeze-thaw cycles in cold regions promotes emulsion breakage and causes separation, making it difficult to ensure stability over time against temperature changes.

[0003] Various efforts have been made so far to satisfy both good usage sensation and stability over time in water-in-oil emulsified cosmetics. For example, there is a technology relating to a water-in-oil emulsion cosmetic containing hydrophobic silica, a water-soluble polymer, a lipophilic surfactant with an HLB value of 7 or less, oil, and water (Patent Document 1), and a technology relating to a water-in-oil emulsion cosmetic containing polyether-modified silicone, a water-soluble polymer electrolyte, an inorganic salt and / or an organic salt, and characterized by containing either or both of glycerin branched fatty acid and / or unsaturated fatty acid ester, or sorbitan branched fatty acid and / or unsaturated fatty acid ester (Patent Document 2). However, water-in-oil emulsion compositions still have usability problems such as a strong feeling of burden on the skin due to the oil film, difficulty in uniform application, stickiness, and difficulty in obtaining moisturizing effects, as well as stability problems such as separation occurring easily in high-temperature stability tests and with repeated freeze-thawing, thus posing a challenge in achieving both usability and long-term stability.

[0004] Polyurethane is a polymer containing urethane bonds in its structure, and is known for its excellent elasticity, flexibility, adhesion, and impact resistance. In recent years, its gelling ability in various solvents and shape recovery properties have attracted attention, and it is being incorporated into various cosmetics. It is supplied in various forms, such as a powder or lump close to its pure form, a gel pre-dissolved in a solvent, or a solution. Furthermore, there are various molecular structures and compositions, and their properties vary accordingly. Naturally, its solubility in each solvent and gelling characteristics also differ, ranging from water-soluble types to those soluble in polar oils, non-polar oils, and silicone oils. Dozens of types of polyurethane are known to be under consideration for use in cosmetics (Patent Document 3).

[0005] A water-in-oil emulsion composition has been disclosed that incorporates oil-soluble polyurethane into an emulsion composition to create a composition with excellent usability and feel, such as spreadability during application, gloss, adhesion to the skin, and non-stickiness of the coating after film formation. This composition involves creating a powder by coating the surface of an oil-soluble polyurethane that exhibits high gel strength when dissolved in oil, specifically "(i) a polyurethane obtained by the reaction of (a) hydrogenated polybutadiene having an isocyanate group at the terminus and (b) a linear or branched C2-C6 glycol, or (ii) an oil-soluble polyurethane synthesized by the reaction of (c) hydrogenated polybutadiene having a hydroxyl group at the terminus, (d) a diisocyanate compound, and (b) a glycol represented by HO-R-OH (linear or branched C2-C6 alkylene group)," with an oil-based solvent pre-diluted to create a gel, and then incorporating a volatile oil and a fluorine-modified silicone resin. Furthermore, it has been stated that a less polar oil is preferable to further increase gel strength (Patent Document 4). However, the oil-soluble polyurethane described in Patent Document 4 is for powder processing applications, and furthermore, due to its high gel strength, it cannot be incorporated in large quantities, making it difficult to apply to improve the long-term stability of compositions.

[0006] Patent Document 5 discloses an oily cosmetic composition that has good stability over time, is non-greasy, and has a pleasant feel on the skin, achieved by combining polyurethane-79, which has good gelling properties with polar oils, bis-ethylhexylbisoleyl pyromelitamide, and an oily component. In the technology described in Patent Document 5, polyurethane-79 has enhanced gelling ability with polar oils by adding higher alcohols to the ends of the polyurethane molecule, but it is described that it does not gel well with non-polar oils. Polyurethane-79 alone does not sufficiently exhibit the effect of improving stability over time through gelation even with polar oils, so another oily gelling agent is required, and by using bis-ethylhexylbisoleyl pyromelitamide in combination, good stability over time can be ensured regardless of whether the oil is polar or non-polar.

[0007] On the other hand, an oil-in-water emulsion type makeup cosmetic has been disclosed that exhibits excellent uniformity of the cosmetic film, high makeup longevity, and a superior feel. In particular, a composition is disclosed that uses a silicone-based surfactant as an emulsifier, a dextrin fatty acid ester as a gelling agent, and an acrylic-silicone graft copolymer, a high-viscosity oil, and a volatile silicone oil as an oil-soluble film-forming agent (Patent Document 6). In the technology described in Patent Document 6, the dextrin fatty acid ester, which is an oil-soluble gelling agent, dissolves uniformly in oils without the need for coating treatment of the powder, so it can be produced in a simple manufacturing process. However, because a high-viscosity oil is an essential component, the adhesion is strong and stickiness is not improved, and a sufficient secondary adhesion prevention effect cannot be obtained. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2006-160714 [Patent Document 2] Japanese Patent Publication No. 2002-348210 [Patent Document 3] Japanese Patent Publication No. 2022-152038 [Patent Document 4] Japanese Patent Publication No. 2020-29444 [Patent Document 5] Japanese Patent Publication No. 2021-155386 [Patent Document 6] Japanese Patent Publication No. 2010-100590 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0009] This invention has been made in view of the above-mentioned prior art, and addresses problems related to usability of water-in-oil emulsion compositions, such as burden on the skin, uniformity of application, stickiness, and difficulty in obtaining moisturizing effects, as well as problems related to stability, such as separation easily occurring in high-temperature stability tests and repeated freeze-thawing, with the aim of achieving both usability and stability over time. Furthermore, for makeup cosmetics and sunscreen cosmetics, the aim was to provide a water-in-oil emulsion composition that has excellent makeup retention and an effect of preventing secondary adhesion. [Means for solving the problem]

[0010] As a result of diligent research and development, the inventors have discovered that by blending (A) a polyurethane-79 gel composition, in which polyurethane-79 is dissolved and gelled in an oil, with a combination of (B) a volatile oil, (C) a silicone-based emulsifier, and (D) a divalent alcohol, a water-in-oil emulsion composition that solves all of the aforementioned problems can be obtained, thus completing the present invention.

[0011] In other words, the present invention comprises the following components [1] (A) Polyurethane-79 gel composition consisting of (A-1) Polyurethane-79 and (A-2) Liquid oil (B) Volatile oils (C) Silicone-based emulsifier (D) Divalent alcohol This is a water-in-oil emulsion composition containing [a specific ingredient]. [2] The water-in-oil emulsion composition described in [1] further contains component (E) a water-soluble active ingredient. [3] The water-in-oil emulsion composition described in [2] above, wherein component (D) is a dihydric alcohol having 3 to 6 carbon atoms. [4] The water-in-oil emulsion composition described in [1] to [3] above, wherein (A-1) / (C) is 0.05 to 5. [Effects of the Invention]

[0012] In the water-in-oil composition of the present invention, a cosmetic film that is uniform, flexible, imposes less burden on the skin can be formed, whereby a water-in-oil composition having good usability and excellent stability over time can be obtained. Furthermore, the composition has good makeup longevity and also has an effect of preventing secondary adhesion. BEST MODE FOR CARRYING OUT THE INVENTION

[0013] Hereinafter, the present invention will be described in detail. In the present specification, percentages are expressed by mass unless otherwise specified. In the present specification, when a numerical range is expressed using ~, the range includes the numerical values at both ends.

[0014] HLB is a numerical value representing the hydrophilic-hydrophobic balance commonly used in the field of surfactants, and commonly used calculation formulas, such as the Kawakami formula, can be used. In the present invention, the following Kawakami formula is adopted. [Formula] Here, Mw is the molecular weight of the hydrophilic group, and Mo is the molecular weight of the hydrophobic group. Furthermore, the HLB values described in catalogs or the like may also be used.

[0015] In the water-in-oil composition of the present invention, the continuous phase serving as the outer phase of the emulsion is an oily component, and an aqueous component exists in the state of emulsified droplets in the inner phase.

[0016] The (A) polyurethane-79 gel composition contained in the water-in-oil composition of the present invention is a gelled composition composed of (A-1) polyurethane-79 and (A-2) liquid oil.

[0017] (A-1) Polyurethane-79 is a polyurethane copolymer having hard segment blocks of polyurethane formed by urethane bonding between a linear aliphatic diisocyanate, 1,6-hexamethylene diisocyanate (HDI), and a linear bulking divalent alcohol, 1,4-butane divalent alcohol, and soft segment blocks of hydrogenated dilinoleyl alcohol and hydrogenated polybutane divalent alcohol, with both ends blocked with stearyl alcohol. Due to the polarity of the polyurethane blocks, a physical network is formed in the oil through association via hydrogen bonding between polymer-polymer and polymer-oil. It is thought that gelation occurs when the oil is incorporated into this three-dimensional network structure. By having higher alcohol residues at the ends, polyurethane-79 has improved solubility in various oils, thereby improving the stability of water-in-oil emulsions. Preferably, (A-1) Polyurethane-79 used in the present invention can be easily and uniformly dissolved by dissolving it in (A-2) liquid oil to form a gel-like composition.

[0018] The polyurethane-79 gel composition of the present invention (A) can be the commercially available OILKEMIA 5S CC (manufactured by LUBRIZOL). Its composition is (A-1) polyurethane-79 gel composition containing 30% polyurethane-79 and (A-2) tri(caprylic / capric acid) glyceryl as a liquid oil. When incorporated into cosmetics in Japan, it is common to list the ingredients as 70% tri(caprylic / capric acid) glyceryl, 25% hydrogenated polyolefin (C6-20), and 5% (HDI / trimethylol hexyllactone) crosspolymer.

[0019] The content of (A-1) polyurethane-79 in the polyurethane-79 gel composition of (A) is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass. The content of liquid oil (A-2) in the polyurethane-79 gel composition (A) is preferably 50 to 90% by mass, and more preferably 60 to 80% by mass. By setting the concentration within this range, uniform dissolution during manufacturing becomes easier, the blending concentration can be easily adjusted, and the effects of the invention can be significantly enhanced, which is therefore preferable.

[0020] The liquid oil (A-2) used in the polyurethane-79 gel composition of (A) is not particularly limited as long as it is commonly used in cosmetics. While its properties are not particularly limited, it is preferably a liquid oil at 25°C. Examples of liquid oils (A-2) used in the polyurethane-79 gel composition of (A) include hydrocarbon oils, ester oils, fatty acids, and silicone oils, regardless of their origin, such as animal oils, vegetable oils, or synthetic oils. It is preferable to use one or more of these in the liquid oil (A-2).

[0021] The content of (A) polyurethane-79 gel composition in the water-in-oil composition of the present invention is not particularly limited. The content of (A-1) polyurethane-79 in the water-in-oil composition of the present invention is not limited, but it is very preferable to be 0.1 to 10% by mass, preferably 0.2 to 5.0% by mass, and more preferably 0.3 to 2% by mass. This range is preferable in terms of not feeling burdensome on the skin and uniformity of the cosmetic film. Furthermore, it is preferable in terms of excellent makeup retention and the ability to prevent secondary adhesion.

[0022] The volatile oil agent (B) contained in the water-in-oil composition of the present invention can be any of those commonly used in cosmetics. The volatile oil agent (B) of the present invention has a flash point of 35 to 90°C and is liquid at 25°C. Examples of volatile oil agents include volatile silicone oils and volatile hydrocarbon oils. Examples of volatile silicone oils include linear dimethicones such as dimethicone (1 cs), dimethicone (1.5 cs), and dimethicone (2 cs); branched siloxanes such as methyl trimethicone, tris(trimethylsilyl)methylsilane, and tetrakis(trimethylsilyl)silane; alkyl-modified silicones such as caprylyl methicone; and cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Of these, dimethicone (1 cs), dimethicone (1.5 cs), methyl trimethicone, and decamethylcyclopentasiloxane are preferred, and decamethylcyclopentasiloxane is more preferred. Examples of volatile hydrocarbon oils include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; and isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene. Of these, hydrocarbon oils having 8 to 16 carbon atoms are preferred, hydrocarbon oils having 10 to 16 carbon atoms are more preferred, and hydrocarbon oils having 12 carbon atoms are even more preferred. Among these, isoparaffinic hydrocarbon oils are preferred, and isododecane and hydrogenated polyisobutene with 12 carbon atoms are more preferred. These (B) volatile oils can be used individually or in combination of two or more types.

[0023] The content of (B) volatile oil agent in the water-in-oil composition of the present invention is preferably 1.0 to 40% by mass, and more preferably 5 to 30% by mass. This range is preferable because it provides excellent makeup retention and prevents secondary adhesion.

[0024] As the (C) silicone-based surfactant included in the water-in-oil composition of the present invention, any silicone-based surfactant commonly used in water-in-oil emulsion compositions can be used, but polyether-modified silicones are preferred. Specifically, examples include polyoxyalkylene-modified silicones, polyglycerin-modified silicones, polyoxyalkylene-alkyl copolymerized silicones, polyglycerin-alkyl copolymerized silicones, and linear copolymer-type polyether-modified silicones. As for the silicone main chain, examples include linear types, branched types, and cross-linked types. Furthermore, silicone chains branched from the silicone main chain can be linear or further branched.

[0025] (C) As for silicone-based surfactants, polyoxyalkylene alkyl copolymerized silicones with straight silicone chains and polyoxyalkylene alkyl copolymerized silicones with branched silicone chains are preferred from the viewpoint of emulsification, long-term storage stability, and adjusting to a suitable viscosity, as well as from the viewpoint of providing a good feel without stickiness or discomfort when applied to the skin. One or more of these can be used from the viewpoint of improving emulsification and long-term storage stability, maintaining excellent moisture-clotting properties, and providing a good feel without stickiness or discomfort.

[0026] Examples of commercially available (C) silicone-based surfactants include KF-6015 (PEG-3 dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6017 (PEG-10 dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6028 (PEG-9 polydimethylsiloxyethyl dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6038 (lauryl PEG-9 polydimethylsiloxyethyl dimethicone) (manufactured by Shin-Etsu Chemical Co., Ltd.), KSG-210 ((dimethicone / (PEG-10 / 15)) crosspolymer / dimethicone mixture) (manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL BY11-030 (PEG / PPG-19 / 19 dimethicone / cyclopentasiloxane mixture) (manufactured by Toray Dow Corning), DOWSIL BY25-337 (PEG / PPG-19 / 19 Examples of polyether-modified silicones include dimethicone / light liquid isoparaffin mixture (manufactured by Toray Dow Corning), DOWSIL SH 3775 M Fluid (PEG-12 dimethicone) (manufactured by Toray Dow Corning), DOWSIL FZ-2233 (polysilicone 13) (manufactured by Toray Dow Corning), DOWSIL ES-5300 Formulation Aid (lauryl PEG-10 tris(trimethylsiloxy)silylethyl dimethicone) (manufactured by Toray Dow Corning), and DOWSIL ES-5600 Silicone Glycerol Emulsifier (cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone) (manufactured by Toray Dow Corning).

[0027] The content of (C) silicone-based surfactant in the water-in-oil composition of the present invention is preferably 1.0 to 10.0% by mass, and more preferably 2.0 to 6.0% by mass. This range is preferable in terms of the stability of the water-in-oil emulsion and good usability.

[0028] The ratio of (A-1) to (C) in this invention is not particularly limited, but it is preferable that (A-1) / (C) be blended in a ratio of (A-1) / (C) = 0.05 to 5. Within this range, stability of the water-in-oil emulsion and a good feel can be obtained. Furthermore, it is preferable for obtaining excellent makeup retention and a secondary adhesion prevention effect.

[0029] dihydric alcohol The (D) dihydric alcohol contained in the water-in-oil composition of the present invention refers to polyhydric alcohols that have two hydroxyl groups. Specifically, examples include 1,2-hexanediol (6 carbon atoms), dipropylene glycol, 1,2-pentanediol (5 carbon atoms), 1,3-butylene glycol (4 carbon atoms), and 1,3-propanediol (3 carbon atoms).

[0030] The content of (D) divalent alcohol in the water-in-oil composition of the present invention is preferably 0.1 to 20.0% by mass, and more preferably 1 to 15% by mass. This range is preferable in terms of antibacterial effect, anti-drying effect, and usability. These may be used individually or in combination of two or more.

[0031] The (E) water-soluble active ingredient contained in the water-in-oil composition of the present invention is at least one selected from the group consisting of whitening agents, moisturizers, wrinkle inhibitors, anti-inflammatory agents, etc. Since the water-soluble active ingredient is placed in the internal aqueous phase of the water-in-oil composition, the oil in the external phase acts as a buffer, protecting it from degradation factors in the environment such as oxygen and ultraviolet rays. Therefore, even with long-term storage, degradation such as oxidation and peroxidation is less likely to occur, and there is little odor change or discoloration caused by the water-soluble active ingredient, making it highly preferable to incorporate these ingredients. (E) For water-soluble active ingredients, water solubility means that 1 g or more can be dissolved in 100 ml of water at 20°C, and that there is no separation or precipitation. Examples of skin whitening agents include water-soluble derivatives of ascorbic acid, arbutin, and ellagic acid. Examples of humectants include sugars, sodium hyaluronate and its derivatives, amino acids and their derivatives, phosphocholine group-containing polymers, and alkylene oxide derivatives represented by the following general formula (I). [ka] (In the formula, Z represents a residue obtained by removing n hydroxyl groups from a hydroxy compound having 1 to 30 carbon atoms; EO stands for oxyethylene group; PO stands for oxypropylene group; BO stands for oxybutylene group; n means 1 through 9; a, b, and c represent the average number of moles added of EO, PO, and BO, respectively, and are independently between 0 and 200. However, a, b, and c cannot all be 0. Also, when n is 2 or greater, multiple a, b, and c may be the same or different. (Note that EO, PO, and BO are added in a random or blocky form.) Specifically, examples include methyl gluceth-20, a polyoxyalkylene methyl glucoside, and PEG / PPG / polybutylene glycol 8 / 5 / 3 glycerin, a polyoxyalkylene glyceryl ether. Examples of wrinkle-preventing agents include nicotinamide, ceramides, and retinol derivatives. Examples of anti-inflammatory agents include dipotassium glycyrrhizinate and ε-aminocaproic acid.

[0032] Particularly suitable ingredients include magnesium ascorbate phosphate, arbutin, sodium hyaluronate, trehalose, trimethylglycine, methyl gluceth-20, PEG / PPG / polybutylene glycol 8 / 5 / 3 glycerin, polyquaternium-51, nicotinamide, and dipotassium glycyrrhizinate.

[0033] The water-in-oil composition of the present invention may contain component (F), an oil-soluble silicone resin. Component (F) can be any of those commonly used in cosmetics. Specifically, examples include trimethylsiloxysilicate, trifluoropropyldimethyl / trimethylsiloxysilicate, polymethylsilsesquioxane, acrylic-silicone graft copolymer, alkyl-modified acrylic-silicone graft copolymer, polyvinylpyrrolidone-modified methylpolysiloxane, etc., and one or more of these can be used.

[0034] The component (F) oil-soluble silicone resin of the present invention may be incorporated without being dissolved in a liquid oil, or it may be used after being dissolved in an oil. Suitable oils for dissolving it include volatile silicone oils such as decamethylcyclopentasiloxane, dimethylpolysiloxane with a kinematic viscosity of 2 cs or less, and caprylyl methicone, as well as volatile hydrocarbon oils such as isoparaffin, isohexadecane, and isododecane.

[0035] The content of component (F), oil-soluble silicone resin, in the water-in-oil composition of the present invention is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This range is preferable in terms of makeup retention and secondary adhesion prevention effect.

[0036] The water-in-oil composition of the present invention may contain nonionic surfactants of component (G) HLB 2 to 7. Component (G) is the same as (C) silicone-based surfactant and is added as an emulsifier to the water-in-oil composition. It is also added to improve its stability over time. Furthermore, it contributes to improving the user experience, such as reducing stickiness during use. Examples of lipophilic surfactants with an HLB of 2-7 include diglyceryl monostearate (HLB 5), diglyceryl monooleate (HLB 6.5), diglyceryl monoisostearate (HLB 5.5), diglyceryl diisostearate (HLB 4), polyglyceryl-2 triisostearate (HLB 3), decaglyceryl pentastearate (HLB 3.5), decaglyceryl pentaisostearate (HLB 3.5), sorbitan sesquistearate (HLB 4.5), sorbitan sesquioleate (HLB 4), sorbitan monoisostearate (HLB 5), sorbitan sesquiisostearate (HLB 4.5), etc., and one or more of these can be used.

[0037] The water-in-oil composition of the present invention may contain various components as needed. For example, it may contain solid or semi-solid oils, non-volatile liquid oils, other surfactants, other alcohols, water, water-based gelling agents and thickeners, oily gelling agents, UV inhibitors, preservatives, powders, and the like.

[0038] Examples of solid oils, semi-solid oils, and non-volatile liquid oils include natural animal and vegetable oils, hydrocarbon oils, silicone oils, higher alcohols, higher fatty acids, and ester oils. As solid oils or semi-solid oils, and non-volatile liquid oils, the following are used: animal and vegetable oils such as carnauba wax, candelilla wax, hydrogenated oil, shea butter, olive oil, jojoba oil, and squalane; hydrocarbons such as ceresin, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, Fischer-Tropsch wax, polybutene, liquid paraffin, and hydrogenated polyisobutene; silicones such as stearyl dimethicone and alkyl (C30-45) methicone; behenyl alcohol, cetyl alcohol, and stearyl alcohol. Examples of higher alcohols include phytosterols, isostearyl alcohol, and octyldodecanol; higher fatty acids such as stearic acid, behenic acid, and isostearic acid; and ester-based oils such as dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), dilauroyl glutamate (phytosteryl / octyldodecyl), tetra(hydroxystearic acid / isostearic acid) dipentaerythrityl, cetyl ethylhexanoate, and triethylhexanoin. These can be used individually or in combination of two or more as needed.

[0039] Other surfactants are not particularly limited as long as they are commonly used in cosmetics, and any surfactant other than (C) silicone-based surfactants and (F) nonionic surfactants with HLB 2-7 can be used. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. These can be used individually or in combination of two or more as needed.

[0040] Other alcohols are not particularly restricted as long as they are commonly used in cosmetics, and any alcohol other than (D) dihydric alcohols can be used. Specifically, monohydric alcohols such as ethanol and isopropyl alcohol, trihydric or higher alcohols such as glycerin, diglycerin, sorbitol, maltitol, maltose, and trehalose, sugar alcohols, and sugars can be used.

[0041] Examples of water-based gelling agents and thickeners include natural polymers such as agar, plant-derived polymers such as locust bean gum, microbial polymers such as xanthan gum and gellan gum, and cellulosic polymers such as hydroxypropyl methylcellulose and hydroxypropyl methylcellulose stearoxy ether; synthetic polymers such as vinyl polymers such as carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer, polyoxyethylene polymers, acrylic polymers such as acrylic acid / acryloyldimethyltaurate sodium copolymer, sodium polyacrylate, polyethyl acrylate, and polyacrylamide, and water-soluble urethane polymers such as (PEG-240 / decyltetradeceth-20 / HDI) copolymer; and inorganic thickeners such as bentonite, synthetic hectorite, and anhydrous silicic acid. These can be used individually or in combination of two or more as needed.

[0042] Examples of oily gelling agents include dextrin fatty acid esters such as dextrin palmitate and dextrin 2-ethylhexanoate palmitate, amino acid derivatives such as dibutyl lauroyl glutamide, sucrose fatty acid esters such as sucrose stearate, and organically modified clay minerals such as disteardimonium hectorite. These can be used individually or in combination of two or more as needed.

[0043] Examples of UV-blocking agents include organic UV absorbers such as ethylhexyl methoxycinnamate, octocrylene, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, and diethylamino hydroxybenzoyl hexyl benzoate, as well as inorganic UV scattering agents such as fine-particle titanium dioxide and fine-particle zinc oxide. UV scattering agents may be hydrophobically treated. Examples of hydrophobic surface treatments include silicone treatment agents, fluorine compound treatment agents, amino acid treatment agents, fatty acid treatment agents, fatty acid soap treatment agents, and fatty acid ester treatment agents. UV-blocking agents can be used individually or in combination of two or more as needed.

[0044] Examples of preservatives include phenoxyethanol, parahydroxybenzoic acid esters, sodium benzoate, salicylic acid, and iodide propynyl butylcarbamate. Examples of antioxidants include tocopherol and dibutylhydroxytoluene, pH adjusters include lactic acid, citric acid, citrate, sodium bicarbonate, and L-arginine, and chelating agents include sodium edetate, sodium polyphosphate, and sodium metaphosphate. These can be used individually or in combination of two or more as needed.

[0045] Examples of powders include inorganic powders, organic powders, inorganic pigments, organic pigments, pearl pigments, and natural pigments. Any type of powder can be used, regardless of its particle shape (spherical, needle-shaped, plate-shaped, etc.), particle size, particle structure (porous, non-porous, etc.), or crystalline structure (crystalline, amorphous). These can be used individually or in combination of two or more types as needed.

[0046] The forms of the water-in-oil composition of the present invention include solid, stick, cream, gel, liquid, emulsion, and multilayer separation forms, and further, mousse and spray forms using propellants or compressed air can also be included. Furthermore, the water-in-oil composition of the present invention can be suitably used in skincare cosmetics such as lotions and creams, makeup cosmetics such as foundations, concealers, BB creams, creams, makeup bases, eye colors, cheek colors, eyebrow products, mascaras, and eyeliners, and sunscreen cosmetics. In particular, it is suitable for makeup cosmetics and sunscreen cosmetics because it does not leave a heavy feeling on the skin, has good staying power, and does not cause secondary adhesion. [Examples]

[0047] The present technology will be described in more detail below with reference to examples and comparative examples. However, these examples do not limit the present invention in any way.

[0048] <Stability Evaluation> [Stability] "50℃ for one month" 30g was filled into a transparent PET container (30ml) and left to stand in an incubator set to 50°C for one month. [Evaluation Criteria] No separation was observed. :○ Separation was observed: ×

[0049] "Freeze-thaw test" 30g was filled into a transparent PET container (30ml), frozen in a freezer (-20℃) for 24 hours, and then thawed at room temperature. I performed the same operation a total of three times. [Evaluation Criteria] No separation was observed. :○ Separation was observed: ×

[0050] <Sensory evaluation> [Usability] For samples prepared one day prior to the preparation, a panel of 20 cosmetic evaluation specialists evaluated the following aspects on a 7-point scale according to the evaluation criteria below: "lack of burden on the skin," "uniformity of the cosmetic film," "lack of stickiness," and "moisturizing effect." Furthermore, the average score of all panel members was used to make a final judgment according to the following criteria. [Evaluation Criteria] (Evaluation result): (Score) Very good: 6 points Good: 5 points Fairly good: 4 points Average: 3 points Slightly poor: 2 points Defective: 1 point Very poor: 0 points [Judgment criteria] (Average score): (Judgment) 5.0 or higher: ◎ 3.5 or higher but less than 5.0: ○ 1.5 or higher but less than 3.5: △ Less than 1.5: × "No makeup transfer" Ten minutes after applying the sample to the arm, a piece of black drawing paper was pressed against it, and the state of the sample adhering to the black drawing paper was evaluated. [Judgment criteria] ◎: 16-20 people were determined to have no or very little secondary adhesion. ○: 11-15 people were determined to have no or very little secondary adhesion. △: 6-10 people were determined to have no or very little secondary adhesion. ×: Determined that 0-5 people had no or very little secondary adhesion. "Makeup longevity" Twenty cosmetic evaluation panel members evaluated the "condition 6 hours after application" on a 7-point scale according to the following evaluation criteria. The average score of all panel members was then used to make a final judgment according to the following criteria. [Evaluation Criteria] (Evaluation result): (Score) Very good: 6 points Good: 5 points Fairly good: 4 points Average: 3 points Slightly poor: 2 points Defective: 1 point Very poor: 0 points [Judgment criteria] (Average score): (Judgment) 5.0 or higher: ◎ 3.5 or higher but less than 5.0: ○ 1.5 or higher but less than 3.5: △ Less than 1.5: ×

[0051] Examples 1-5 and Comparative Examples 1-8 (Water-in-Oil Moisturizing Cream) The water-in-oil moisturizing creams shown in Table 1 were manufactured using the following manufacturing method. Each sample was evaluated using the evaluation method described above, and the results are also shown in Table 1. [Manufacturing method] (1): Heat ingredients 1-9 and mix and dissolve them uniformly. (2): Add components 10-18 to (1) and mix and dissolve uniformly. (3) Heat and dissolve components 19-31 uniformly. (4): Add (3) to (2) and emulsify. (5): Process (4) in a homomixer. (6): The foam was removed to obtain a water-in-oil moisturizing cream.

[0052] [Table 1] *1 OILKEMIA 5S CC (contains 30% polyurethane-79: manufactured by Lubrizol) *2 Leopard KL2 (manufactured by Chiba Flour Milling Co., Ltd.) *3 GP-1 (manufactured by Ajinomoto Co., Inc.) *4 Adekanol GT-700 (manufactured by Adeka) *5 KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.) *6 KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.) *7 DOWSIL BY11-030 (manufactured by Toray Dow Corning) *8 KSG-210 (contains 24.2% dimethicone / PEG-10 / 15 crosspolymer: manufactured by Shin-Etsu Chemical Co., Ltd.) *9 KSG-16 (contains 25% dimethicone / vinyl dimethicone crosspolymer: manufactured by Shin-Etsu Chemical Co., Ltd.) *10 Pearl Ream 6 (manufactured by NOF Corporation) *11 Cosmoll 82 (manufactured by Nisshin Oillio Co., Ltd.) HLB 5.0 *12 Cosmoll 42V (manufactured by Nikko Chemicals Co., Ltd.) HLB4.0

[0053] The water-in-oil moisturizing creams of Examples 1-5, by incorporating a polyurethane-79 gel composition, were water-in-oil moisturizing creams with "good stability," "no burden on the skin," a "uniform application film," a smooth and non-greasy feel, yet "moisturizing effect," and thus "good usability." In contrast, Comparative Example 1, which did not contain the polyurethane-79 gel composition compared to Example 1, showed separation in the "50°C for 1 month" and "freeze-thaw test." Furthermore, good results were not obtained for "uniformity of the coated film." In addition, an oily film remained for a long time, resulting in poor usability. In Comparative Examples 2 and 3, the polyurethane-79 gel composition was replaced with dextrin palmitate or dibutyl lauroyl glutamide, which are typical oily gelling agents, but separation was observed on the third "freeze-thaw test." Furthermore, good results were not obtained for "uniformity of the coated film." In Comparative Example 4, the polyurethane-79 gel composition was replaced with disteardimonium hectorite, another oily gelling agent, but a significant decrease in viscosity was observed at high temperatures, separation occurred at "50°C for 1 month," and separation also occurred on the first "freeze-thaw test." Comparative Example 5 was modified by replacing the polyurethane with (PEG-240 / decyltetradeceth-20 / HDI) copolymer, known as a hydrophobic modified polyether urethane. Since (PEG-240 / decyltetradeceth-20 / HDI) copolymer is a water-soluble polyurethane, heating it with an oil-based agent did not result in a uniform composition, making evaluation impossible. Therefore, the composition was obtained by heating and dissolving it in 1,3-butylene glycol in the aqueous phase and adding it to the aqueous phase for evaluation. No improvement in "stability" was observed. In terms of "usability," only the moisturizing effect was good. In Comparative Example 6, the volatile oil was replaced with the non-volatile oil cetyl 2-ethylhexanoate, and the amount of (E) water-soluble active ingredient was reduced. However, separation was observed on the third attempt in the "freeze-thaw test." Due to significant slipperiness during application and poor adhesion, the "uniformity of the applied film" was poorly evaluated, and a strong "stickiness" was felt, but the "moisturizing effect" was low. In Comparative Example 7, because no silicone-based emulsifier was included, the emulsification state was poor, and separation occurred the day after "50°C for 1 month." Severe separation was also observed on the first attempt in the "freeze-thaw test." In terms of usability, the evaluation was poor in all aspects: "burden on the skin," "uniformity of the applied film," "stickiness," and "moisturizing effect." In Comparative Example 8, because no dihydric alcohol was included, the evaluation was that the "moisturizing effect" was poor.

[0054] Examples 6-10 and Comparative Examples 9-15 (Water-in-Oil Foundation) The water-in-oil foundations shown in Table 2 were manufactured using the following manufacturing method. Each sample was evaluated using the evaluation method described above, and the results are also shown in Table 2. [Manufacturing method] (1): Heat and dissolve components 1-17. (2): Add ingredients 18-21 to (1) and mix uniformly. (3): Process (2) in a homomixer. (4): Heat and dissolve components 22-34. (5): Add (4) to (3) and emulsify. (6): Process (5) in a homomixer. (7): The foam was removed to obtain a water-in-oil foundation.

[0055] [Table 2] *1 OILKEMIA 5S CC (contains 30% polyurethane-79: manufactured by Lubrizol) *2 Leopard KL2 (manufactured by Chiba Flour Milling Co., Ltd.) *3 GP-1 (manufactured by Ajinomoto Co., Inc.) *4 Adekanol GT-700 (manufactured by Adeka) *5 KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.) *6 KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.) *7 DOWSIL BY11-030 (manufactured by Toray Dow Corning) *8 KSG-210 (contains 24.2% dimethicone / PEG-10 / 15 crosspolymer: manufactured by Shin-Etsu Chemical Co., Ltd.) *9 KSG-16 (contains 25% dimethicone / vinyl dimethicone crosspolymer: manufactured by Shin-Etsu Chemical Co., Ltd.) *10 Pearl Ream 6 (manufactured by NOF Corporation) *11 Cosmoll 82 (manufactured by Nisshin Oillio Co., Ltd.) HLB 5.0 *12 Cosmoll 42V (manufactured by Nikko Chemicals Co., Ltd.) HLB4.0 *13 DOWSIL ES-5600 Silicone Glycerol Emulsifier (manufactured by Toray Dow Corning) *14 DOWSIL FZ-2233 (manufactured by Toray Dow Corning) *15 KF-7312L (Contains 50% trimethylsiloxysilicate: Manufactured by Shin-Etsu Chemical Co., Ltd.) *16 KP-561P (manufactured by Shin-Etsu Chemical Co., Ltd.) *17 NIKKOL DGMIS (manufactured by Nikko Chemicals Co., Ltd.) HLB 5.5 *18 MT-100TV (manufactured by Teika Co., Ltd.) *19 MZY-203S (manufactured by Teika Co., Ltd.) *20 KSP-100 (manufactured by Nisshin Chemical Industry Co., Ltd.) *21 Willbride S-753 (manufactured by NOF Corporation) *22 LIPIDURE-PMB (contains 5% polyquaternium-51: manufactured by NOF Corporation)

[0056] The water-in-oil foundations of Examples 6-10 exhibited good stability in "50°C for 1 month" and "freeze-thaw tests," and were compositions with good usability, exhibiting good "skin burden," "uniformity of applied film," "stickiness," and "moisturizing effect." Furthermore, by combining them with oil-soluble silicone resin, the foundations provided a long-lasting, beautiful finish, achieved a "secondary adhesion prevention effect" in a short time, and were less prone to "makeup transfer." In contrast, Comparative Example 9, which did not use the polyurethane-79 gel composition, had poor "stability," and its "makeup longevity" was poor due to the "uneven makeup film" and lack of flexibility, resulting in slight makeup breakdown over time. No "secondary adhesion prevention effect" was observed. Comparative Examples 10 and 11 contained dextrin palmitate and disteardimonium hectorite, which are oily gelling agents, instead of polyurethane-79. "High-temperature stability" was good, but separation occurred in the "freeze-thaw test." "Makeup longevity" was poor due to the "uneven makeup film" and lack of flexibility, resulting in makeup breakdown over time. No "secondary adhesion prevention effect" was observed. Comparative Example 12 contained ceresin, which has a high viscosity-enhancing effect on the oil phase, but neither "stability" nor "makeup longevity" improved. In Comparative Example 13, the volatile oil agent isododecane was replaced with the non-volatile oil agent isotridecyl isononanoate, and the amount of (E) water-soluble active ingredient was reduced, but separation was observed on the third "freeze-thaw test." The first comparative example had poor "uniformity of the applied film" due to significant slipperiness during application and poor adhesion, and a strong feeling of "stickiness." It was prone to makeup breakdown, resulting in a poor evaluation of "makeup longevity." For comparative example 14, the lack of a silicone-based emulsifier resulted in poor emulsification, leading to separation the day after the "50°C for 1 month" test. Separation was also observed in the first "freeze-thaw test." Regarding usability, it received poor evaluations in all aspects: "skin burden," "uniformity of the applied film," "stickiness," and "moisturizing effect." For "makeup longevity," makeup breakdown was noticeable over time, and the "secondary adhesion prevention effect" was also poorly rated. For comparative example 15, the lack of polyurethane-79 and oil-soluble silicone resin resulted in breakdown over time, leading to a low evaluation of "makeup longevity" and no perceived "secondary adhesion prevention effect." Furthermore, it was prone to separation at high temperatures, resulting in a poor evaluation after "50°C for 1 month."

[0057] Example 11: Wrinkle-fighting cream Ingredients (mass%) 1: Polyurethane-79 Caprylic / Capric Triglyceride *1 3% 2: (Dimethicone / (PEG-10 / 15)) Crosspolymer Dimethicone *8 2% 3: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone *23 1% 4: Dextrin palmitate 2% 5: Ceramide NP 0.01% 6: Dimer dilinoleyl dimer dilinoleate bis(behenyl / isostearyl / phytosteryl) 2% 7: Triethylhexanoin 10% 8: Macadamia nut fatty acid phytosteryl 5% 9: Carnauba wax 1% 10: Highly polymerized methylpolysiloxane / light liquid isoparaffin *24 3% 11: Tocopherol 0.1% 12: Retinyl palmitate 0.1% 13: Caprylyl Methicone 15% 14: Purified water (appropriate amount) 15: Hydroxypropyl methylcellulose stearoxy ether 0.05% 16: Nicotinamide 5% 17: Dipropylene glycol 3% 18: Glycerin 10% 19: Dipotassium glycyrrhizinate 0.1% 20: Trimethylglycine 2% 21: Sodium hyaluronate 0.1% 22: Water-soluble collagen 0.1% 23: Phenoxyethanol 0.5% Total 100% *23 KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.) *24 DOWSIL BY 25-320 (manufactured by Toray Dow Corning) (Manufacturing method) (1): Mix ingredients 1-13 and heat until dissolved. (2): Mix components 13-23 and heat until dissolved. (3): Add (2) to (1) and emulsify. (4): Process in a homomixer. (5):(4) was cooled and degassed to obtain a wrinkle-treating cream.

[0058] Stability testing was conducted at 50°C for one month, and freeze-thaw tests were performed, confirming that there were no problems. It was a wrinkle-treating cream with good usability, exhibiting good "skin burden," "uniformity of application film," "stickiness," and "moisturizing effect."

[0059] Example 12: Water-in-oil foundation (without UV absorbers) <Undiluted solution> Ingredients (mass%) 1: Polyurethane-79 Caprylic / Capric Triglyceride *1 3% 2: Cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone *13 2% 3: Fine particle zinc oxide / decamethylcyclopentasiloxane dispersion (60% pure hydrophobized zinc oxide) 10% 4: Fine particle titanium dioxide / decamethylcyclopentasiloxane dispersion (80% pure hydrophobically treated titanium dioxide) 4% 5: Hydrophobized iron oxide 5% 6: Hydrophobized titanium dioxide (pigment grade) 4% 7: Cetyl ethylhexanoate 7% 8: Sorbitan sesquioleate 2% 9: Ceresin 2% 10: Stearyl glycyrrhetinate 0.05% 11: Polymethylsilsesquioxane (powder) 3% 12: Talc 4% 13: Trifluoroalkyldimethyltrimethylsiloxysilicate dimethicone *25 1% 14: Decamethylcyclopentasiloxane 13% 15: Purified water (appropriate amount) 16:1,3-Butylene Glycol 10% 17: (Acryloyldimethyltaurate Ammonium / VP) Copolymer 0.1% 18: Sodium acetylated hyaluronate 0.1% 19: Arbutin 2% 20: Nicotinamide 5% 21: Ethylhexylglycerin 0.5% 22: Propynyl iodide butylcarbamate 0.01% Total 100% *25 XS66-B8636 (MOMENTIVE) (Manufacturing method) (1): Components 1 to 10 are heated and mixed, then dispersed using a roll mill. (2): Add ingredients 11-14 to (1) and mix until uniform. (3) Mix ingredients 15-22 and heat until dissolved. (4): Process (2) in a homomixer. (5): Add (3) to (4) and emulsify. (6): Process (5) in a homomixer. (7): The foam was removed to obtain a water-in-oil foundation.

[0060] Regarding Example 12, a stability test was conducted at 50°C for 1 month, and a freeze-thaw test was performed, confirming that there were no problems. It was a composition with good usability, exhibiting good "skin burden," "uniformity of applied film," "stickiness," and "moisturizing effect." Furthermore, a water-in-oil foundation was obtained that offers excellent "makeup longevity," remains flawless even with sweat and sebum, and maintains a beautiful application. It also has a "secondary adhesion prevention effect," making it resistant to rubbing against clothing and providing high "sunscreen protection." Additionally, when the SPF value of the undiluted solution was measured using the method described below, a favorable result of SPF 55 was obtained. <Method for evaluating UV protection effect "SPF"> The measurement sample was applied to the HELIOPLATE HD6 substrate (manufactured by Helio Screen) at a concentration of 1.3 mg / cm³. 2 The surface was coated evenly and dried at room temperature for 30 minutes. An SPF analyzer UV-2000S (Labsphere) was used to measure the SPF at nine points on the coated surface, and the average SPF value was calculated. (Decimal places were rounded down.)

[0061] Example 13: High SPF water-in-oil sunscreen spray (cyclic silicone-free) <Undiluted solution> Ingredients (mass%) 1: Polyurethane-79 Caprylic / Capric Triglyceride *1 5% 2: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone *26 1% 3: Ethylhexyl Methoxycinnamate 10% 4: Diethylamino hydroxybenzoyl hexyl benzoate 2% 5: Octocrylene 3% 6: PEG-30 Dipolyhydroxystearate 2% 7: Isotridecyl isononanoate 5% 8: (VP / Eicosene) Copolymer 3% 9: (Diphenyl Dimethicone / Vinyl Diphenyl Dimethicone / Silsesquioxane) Crosspolymer *27 3% 10: Spherical anhydrous silicic acid 3% 11:PEG / PPG-19 / 19 Dimethicone / Light Liquid Isoparaffin *28 5% 12: (Acrylates / Stearyl Acrylate / Dimethicone Methacrylate) Copolymer *29 4% 13: Isododecane 10% 14: Purified water (appropriate amount) 15:1,2-pentanediol 1% 16: Ethanol 10% 17: Xanthan gum 0.03% 18: Polyquaternium-51·Water *22 1% 19:PEG / PPG / Polybutylene Glycol 8 / 5 / 3 Glycerin *20 2% 20: Methyl Gluceth-10 1% 21: Ethylhexylglycerin 0.5% Total 100% *26 KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.) *27 KSP-300 (manufactured by Shin-Etsu Chemical Co., Ltd.) *28 DOWSIL BY25-337 (manufactured by Toray Dow Corning) *29 KP-561 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Manufacturing method) (1): Mix ingredients 1-8 and heat until dissolved. (2): Add ingredient 9.10 to (1) and mix until uniform. (3): Add ingredients 11-13 to (2) and mix until uniform. (4): Mix components 14-21 and heat until dissolved. (5): Process (3) in a homomixer. (6): Add (4) to (5) and emulsify. (7): Process (6) in a homomixer. (8) The foam was removed to obtain the concentrate for the sunscreen spray.

[0062] Regarding Example 13, since the stock solution is non-separable, it was a composition that could be filled into aerosol cans well because its uniformity could be maintained without stirring during filling. When the SPF value of the undiluted solution was measured using the aforementioned "UV protection effect (SPF) evaluation method," a favorable result of SPF 68 was obtained. <Evaluation of aerosol stability> Aerosol test bottles (made of clear glass) were filled with a 30% concentrate and 70% propellant (LPG), a spray button was attached, and the results were evaluated. [Stability] Stability was confirmed using the following methods after conducting a 3-month static test at 40°C and a freeze-thaw test (3 times), and no particular problems were found. Quality check: After inverting the aerosol test bottle (made of clear glass) 10 times, it was confirmed that there was no sediment at the bottom. Subsequently, the spray pattern on black paper was checked, and it showed a uniform and fine spray pattern, indicating good quality for a sunscreen spray. [Usability] Based on the evaluation criteria mentioned above—"skin burden," "uniformity of the applied film," "stickiness," "moisturizing effect," and "makeup longevity"—the composition demonstrated the effects of the present invention. Furthermore, it was an oil-in-water type sunscreen spray that was resistant to rubbing against clothing due to its "secondary adhesion prevention effect" and also had a high "sunscreen effect."

Claims

1. The following components (A) to (D) (A) Polyurethane-79 gel composition comprising (A-1) Polyurethane-79 and (A-2) Liquid oil (B) Volatile oils (C) Silicone-based emulsifier (D) Divalent alcohol A water-in-oil emulsion composition containing (A-1) polyurethane-79 in an amount of 0.15% to 4.5% of the total composition.

2. Furthermore, the water-in-oil emulsion composition according to claim 1, further containing (E) a water-soluble active ingredient.

3. The water-in-oil emulsion composition according to claim 1, wherein the component (D) is a dihydric alcohol having 3 to 6 carbon atoms.

4. The water-in-oil emulsion composition according to claims 1 to 3, wherein (A-1) / (C) is 0.05 to 5.

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