JP2024088421A - Water-in-oil emulsion composition - Google Patents

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

The present invention relates to a water-in-oil emulsion composition containing specific components, and more specifically to (A) a polyurethane-79 gel composition consisting of polyurethane-79 and a liquid oil agent, and (B) a water-in-oil emulsion composition containing a volatile oil agent, (C) a silicone-based emulsifier, and (D) a dihydric alcohol.

In the field of cosmetics, water-in-oil emulsion compositions are compositions often used in skin care cosmetics and makeup cosmetics, and because they cover the skin surface with an oil film, prevent water evaporation, and protect the skin from dryness, they are characterized by excellent emollient effects, moisturizing effects, treatment effects, etc. Furthermore, because they have superior makeup durability compared to powder cosmetics and oil-in-water cosmetics, they are often used in makeup cosmetics and sunscreen cosmetics.
Problems with water-in-oil emulsions include the difficulty of ensuring stability over time. In order to improve stability over time, it is generally effective to add waxes or oil-based thickeners to the external phase, but this tends to reduce the feeling of use, such as stickiness and slow absorption. Furthermore, compared to oil-in-water emulsion compositions in which the external phase is a water phase, the absorption is slower, and the evaporation rate of volatile matter is slow, so an oil film remains for a long time. Therefore, secondary adhesion is likely to occur on skin, clothing, containers, and other places that are touched after use other than the application area, making the usability poor. In addition, the viscosity is likely to decrease when stored at high temperatures, and in cold regions, repeated freezing and thawing causes emulsion destruction and separation, making it difficult to ensure stability over time against temperature changes.

Up until now, various efforts have been made in the field of water-in-oil emulsion cosmetics in order to satisfy both a good feeling in use and stability over time.
For example, there is a technology relating to a water-in-oil emulsion cosmetic containing hydrophobized 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 containing either or both of a glycerin branched fatty acid and/or an unsaturated fatty acid ester, a sorbitan branched fatty acid and/or an unsaturated fatty acid ester (Patent Document 2). However, water-in-oil emulsion compositions still suffer from usability problems such as a strong feeling of burden on the skin due to the oil film, difficulty in applying evenly, stickiness, and difficulty in achieving a moisturizing feeling, as well as stability problems such as a tendency for separation to occur in high-temperature stability tests and repeated freezing and thawing, and therefore there is a problem in achieving both usability and stability over time.

Polyurethane is a polymer that has urethane bonds in its structure and is known to have excellent elasticity, flexibility, adhesion, and impact resistance. In recent years, it has been incorporated into various cosmetics due to its effects such as its gelling ability in various solvents and its shape recovery. It is supplied in various forms, such as powder or chunks that are close to the pure product, gels that have been dissolved in a solvent in advance, and solutions. It also comes in a variety of molecular structures and compositions, and its properties are also diverse. Naturally, its solubility in each solvent and its gelling properties are different, and it is diverse in a wide range, from water-soluble to soluble in polar oils, non-polar oils, and silicone oils. There are several dozen types of polyurethane that are being considered for use in cosmetics (Patent Document 3).

The oil-soluble polyurethane exhibits high gel strength when dissolved in oil as a composition with excellent usability and feel, such as spreadability during application, glossiness, adhesion to the skin, and non-stickiness of the coating film after film formation, when blended into a water-in-oil emulsion composition. The composition is made by blending a powder coated with a gel in which the powder is diluted with an oil and the surface is coated with the oil-soluble polyurethane "(i) polyurethane obtained by reacting (a) hydrogenated polybutadiene having an isocyanate group at the end with (b) linear or branched C2-C6 glycol, or (ii) oil-soluble polyurethane synthesized by reacting (c) hydrogenated polybutadiene having a hydroxyl group at the end with (d) a diisocyanate compound and (b) a glycol represented by HO-R-OH (linear or branched C2-C6 alkylene group)" and a volatile oil and a fluorine-modified silicone resin are used in combination. It is also disclosed that an oil with low polarity is preferable for increasing gel strength (Patent Document 4). However, the oil-soluble polyurethane described in Patent Document 4 is intended for powder processing applications, and due to its high gel strength, it cannot be blended in large quantities, making it difficult to use it to improve the stability of the composition over time.

By blending polyurethane-79, which has good gelling properties with polar oils, with bis-ethylhexyl bis-oleyl pyromelitamide, and an oil-based component, an oil-based cosmetic that has good stability over time, is not sticky, and has a good skin-friendly feel has been disclosed (Patent Document 5). In the technology described in Patent Document 5, it is described that polyurethane-79 has an increased gelling ability with polar oils due to the addition of higher alcohols to the ends of the polyurethane molecules, but does not gel very well with non-polar oils. Polyurethane-79 alone does not fully exert the effect of improving stability over time by gelling, even with polar oils, so another oil-based gelling agent is required, and by using bis-ethylhexyl bis-oleyl pyromelitamide in combination, good stability over time can be ensured regardless of whether polar or non-polar oils are used.

On the other hand, water-in-oil emulsion makeup cosmetics that have excellent uniformity of the cosmetic film, high cosmetic retention effect, and excellent usability have been disclosed. In particular, a composition using a silicone surfactant as an emulsifier, a dextrin fatty acid ester as a gelling agent, and an acrylic-silicone graft copolymer, high viscosity oil, and volatile silicone oil as an oil-soluble film-forming agent has been disclosed (Patent Document 6). In the technology of Patent Document 6, the dextrin fatty acid ester, which is an oil-soluble gelling agent, is highly soluble in oil agents and therefore dissolves uniformly without the need for a coating treatment on the powder, and therefore can be produced by a simple manufacturing process. However, since a high viscosity oil is an essential component, the adhesiveness is strong and stickiness is not improved, and sufficient secondary adhesion prevention effect cannot be obtained.

JP 2006-160714 A JP 2002-348210 A JP 2022-152038 A JP 2020-29444 A JP 2021-155386 A JP 2010-100590 A

The present invention has been made in consideration of the above-mentioned conventional technology, and in light of usability problems with water-in-oil emulsion compositions, such as a feeling of burden on the skin, uneven application, stickiness, and difficulty in obtaining a moisturizing feeling, as well as stability problems such as a tendency for separation to occur in high-temperature stability tests and repeated freezing and thawing, the present invention has set as its objective the balancing of usability and stability over time. Furthermore, the present invention has set as its objective the provision of a water-in-oil emulsion composition for makeup cosmetics and sunscreen cosmetics that has excellent cosmetic durability and a secondary adhesion prevention effect.

As a result of intensive research and development, the present inventors have found that a water-in-oil emulsion composition which solves all of the above-mentioned problems can be obtained by blending (A) a polyurethane-79 gel composition in which polyurethane-79 is dissolved in an oil and gelled, with a combination of (B) a volatile oil, (C) a silicone-based emulsifier, and (D) a dihydric alcohol, and have thus completed the present invention.

That is, the present invention provides a water-in-oil type emulsion composition containing the following components [1]: (A) a polyurethane-79 gel composition comprising (A-1) polyurethane-79 and (A-2) a liquid oil agent; (B) a volatile oil agent; (C) a silicone-based emulsifier; and (D) a dihydric alcohol.
[2] The water-in-oil emulsion composition according to the above [1], further comprising a water-soluble active ingredient as component (E).
[3] The water-in-oil emulsion composition according to the above [2], wherein the component (D) is a dihydric alcohol having 3 to 6 carbon atoms.
[4] The water-in-oil emulsion composition according to any one of [1] to [3] above, wherein (A-1)/(C) is 0.05 to 5.

The water-in-oil composition of the present invention can form a uniform and soft cosmetic film that is gentle on the skin, has a good feel when used, and has excellent stability over time. Furthermore, the cosmetic lasts well and has the effect of preventing secondary adhesion.

The present invention will be described in detail below. In this specification, percentages are expressed by mass unless otherwise specified. In this specification, when a numerical range is expressed using ~, the range includes both ends of the numerical range.

HLB is a value that indicates the hydrophilic-hydrophobic balance usually used in the field of surfactants, and a commonly used calculation formula, such as the Kawakami formula, can be used.
In the present invention, the following Kawakami formula is adopted.
Here, Mw is the molecular weight of the hydrophilic group, and Mo is the molecular weight of the hydrophobic group.
Alternatively, the HLB value given in a catalog or the like may be used.

In the water-in-oil composition of the present invention, the continuous phase, which is the outer phase of the emulsion, is an oil component, and the inner phase is an aqueous component present in the form of emulsified droplets.

The (A) polyurethane-79 gel composition contained in the water-in-oil composition of the present invention is a gelling composition consisting of (A-1) polyurethane-79 and (A-2) a liquid oil agent.

(A-1) Polyurethane-79 is a polyurethane in which both ends of a copolymer having a hard segment block of 1,6-hexamethylene diisocyanate (HDI), a linear aliphatic diisocyanate, and 1,4-butane dihydric alcohol, a linear extendable dihydric alcohol, which is polyurethane formed by urethane bonding, and a soft segment block of hydrogenated dilinoleyl alcohol and hydrogenated polybutane dihydric alcohol, are blocked with stearyl alcohol. Due to the polarity of the polyurethane block, a physical network is formed in the oil by association via hydrogen bonds between polymer-polymer and polymer-oil. It is believed that gelation occurs when an oil is incorporated into this three-dimensional network structure. Polyurethane-79 has a higher alcohol residue at the end, which improves its 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 composition.

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

The content of (A-1) polyurethane-79 in the polyurethane-79 gel composition (A) is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.
The content of the 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 content within this range, it becomes easy to dissolve uniformly during production, the blending concentration is easy to adjust, and the effects of the invention can be obtained significantly, which is preferable.

The liquid oil (A-2) used in the polyurethane-79 gel composition (A) is not particularly limited as long as it is one that is normally used in cosmetics. There are no particular limitations on the nature of the oil, but it is preferably an oil that is liquid at 25°C. Examples of the liquid oil (A-2) used in the polyurethane-79 gel composition (A) include hydrocarbon oils, ester oils, fatty acids, silicone oils, etc., regardless of their origin, such as animal oils, vegetable oils, and synthetic oils. It is preferable to use one or more of these in the liquid oil (A-2).

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 particularly limited, but it is highly suitable to be 0.1 to 10 mass%, preferably 0.2 to 5.0 mass%, and more preferably 0.3 to 2 mass%. This range is preferable in terms of the lack of burden on the skin and the uniformity of the cosmetic film. It is also preferable in terms of excellent cosmetic durability and the effect of preventing secondary adhesion.

The volatile oil (B) contained in the water-in-oil composition of the present invention may be any oil that is generally used in cosmetics. The volatile oil (B) of the present invention has a flash point of 35 to 90°C and is liquid at 25°C. Examples of the volatile oil include volatile silicone oils and volatile hydrocarbon oils. Examples of the volatile silicone oil include linear dimethicones such as dimethicone (1cs), dimethicone (1.5cs), and dimethicone (2cs); branched siloxanes such as methyltrimethicone, 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 (1cs), dimethicone (1.5cs), methyltrimethicone, and decamethylcyclopentasiloxane are preferred, with decamethylcyclopentasiloxane being 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. Among 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 having 12 carbon atoms are more preferred.
These volatile oils (B) may be used alone or in combination of two or more.

The content of the volatile oil (B) 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 in that it provides excellent cosmetic durability and prevents secondary adhesion.

As the silicone surfactant (C) contained in the water-in-oil composition of the present invention, any of those typically used in water-in-oil emulsion compositions can be used, but polyether-modified silicones are preferred, and specific examples include polyoxyalkylene-modified silicones, polyglycerin-modified silicones, polyoxyalkylene-alkyl co-modified silicones, polyglycerin-alkyl co-modified silicones, linear copolymer type polyether-modified silicones, and the like. Examples of silicone main chains include linear types, branched types, and crosslinked types. Furthermore, examples of silicone chains branched from the silicone main chain include linear types and those further branched.

(C) As the silicone surfactant, from the viewpoints of emulsifiability, long-term storage stability, and preparation to a suitable viscosity, and from the viewpoints of providing a pleasant usability without a sticky feeling or an uncomfortable sensation when applied to the skin, polyoxyalkylene/alkyl co-modified silicones with straight silicone chains and polyoxyalkylene/alkyl co-modified silicones with branched silicone chains are preferred. These can be used alone or in combination from the viewpoints of providing a pleasant usability without a sticky feeling or an uncomfortable sensation while improving emulsifiability and long-term storage stability and maintaining excellent moisture-retaining properties.

Commercially available silicone surfactants (C) 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 Dow Corning Toray Co., Ltd.), DOWSIL BY25-337 (PEG/PPG-19/19 dimethicone/light liquid isoparaffin mixture) (manufactured by Dow Corning Toray Co., Ltd.), DOWSIL SH 3775 M Fluid (PEG-12 dimethicone) (manufactured by Dow Corning Toray Co., Ltd.), DOWSIL FZ-2233 (polysilicone 13) (manufactured by Dow Corning Toray Co., Ltd.), DOWSIL ES-5300 Formulation Aid (lauryl PEG-10 tris(trimethylsiloxy)silylethyl dimethicone) (manufactured by Dow Corning Toray Co., Ltd.), DOWSIL ES-5600 Silicone Glycerol Examples include polyether-modified silicones such as Emulsifier (cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone) (manufactured by Dow Corning Toray Co., Ltd.).

The content of the silicone surfactant (C) 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.

The ratio of (A-1) to (C) in the present invention is not particularly limited, but it is desirable to mix (A-1)/(C) at a ratio of (A-1)/(C) = 0.05 to 5. This range ensures stability and a good feel when used in the water-in-oil emulsion. It is also preferable for achieving excellent cosmetic durability and preventing secondary adhesion.

The dihydric alcohol (D) contained in the water-in-oil composition of the present invention is a polyhydric alcohol having two hydroxyl groups. Specific examples include 1,2-hexanediol and dipropylene glycol, which have six carbon atoms, 1,2-pentanediol, which have five carbon atoms, 1,3-butylene glycol, which have four carbon atoms, and 1,3-propanediol, which have three carbon atoms.

The content of the dihydric alcohol (D) in the water-in-oil composition of the present invention is preferably 0.1 to 20.0% by mass, more preferably 1 to 15% by mass. This range is preferable in terms of antibacterial properties, the effect of preventing dryness, and the feeling of use. These may be used alone or in combination of two or more types.

The water-soluble active ingredient (E) contained in the water-in-oil composition of the present invention is at least one selected from the group consisting of whitening agents, moisturizing agents, anti-wrinkle agents, anti-inflammatory agents, etc. The water-soluble active ingredient is placed in the inner aqueous phase of the water-in-oil composition, and the oil agent in the outer phase acts as a buffer to protect it from oxygen and ultraviolet rays, which are deterioration factors in the environment. Therefore, even when stored for a long period of time, deterioration such as oxidation and peroxidation is unlikely to occur, and there is little odor or coloring caused by the water-soluble active ingredient, so it is very suitable to incorporate these ingredients.
(E) Water-soluble active ingredient: Water-soluble means that 1 g or more can be dissolved in 100 ml of water at 20° C. and no separation or precipitation occurs.
Examples of whitening agents include water-soluble derivatives of ascorbic acid, arbutin, ellagic acid, and the like.
Examples of the moisturizing agent 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).
(wherein Z represents a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
EO means an oxyethylene group;
PO means an oxypropylene group;
BO means an oxybutylene group;
n is 1 to 9;
a, b and c respectively represent the average number of moles of EO, PO and BO added, and are independently 0 to 200. However, a, b and c cannot all be 0. In addition, when n is 2 or more, a, b and c may be the same or different.
In addition, EO, PO, and BO are added randomly or in block form.
Specific examples include polyoxyalkylene methyl glucoside, methyl gluceth-20, and polyoxyalkylene glyceryl ether, PEG/PPG/polybutylene glycol 8/5/3 glycerin.
Examples of anti-wrinkle agents include nicotinamide, ceramide, and retinol derivatives.
Anti-inflammatory agents include dipotassium glycyrrhizinate, ε-aminocaproic acid, and the like.

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

The water-in-oil composition of the present invention can contain component (F), an oil-soluble silicone resin. Any component typically used in cosmetics can be used as component (F). Specific 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.

The oil-soluble silicone resin (F) of the present invention may be blended without being dissolved in a liquid oil, or may be dissolved in an oil. Suitable oils to dissolve in include volatile silicone oils such as decamethylcyclopentasiloxane, dimethylpolysiloxane with a kinetic viscosity of 2 cs or less, and caprylyl methicone, as well as volatile hydrocarbon oils such as isoparaffin, isohexadecane, and isododecane.

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, more preferably 1 to 20% by mass. This range is preferable in terms of cosmetic wear and secondary adhesion prevention effect.

The water-in-oil composition of the present invention can be formulated with component (G), a nonionic surfactant with an HLB of 2 to 7. Component (G) is the component excluding (C) the silicone surfactant, and is formulated as an emulsifier for the water-in-oil composition. It is also formulated for the purpose of improving its stability over time. Furthermore, it also contributes to improving the feel of the composition when in use, such as the lack of stickiness. Examples of lipophilic surfactants with HLB 2 to 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), and sorbitan sesquiisostearate (HLB 4.5). One or more of these can be used.

The water-in-oil composition of the present invention can contain appropriate ingredients as needed. For example, it can contain solid or semi-solid oils, non-volatile liquid oils, other surfactants, other alcohols, water, water-based gelling agents and thickeners, oil-based gelling agents, UV protection agents, preservatives, powders, etc.

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.
Examples of solid oils or semi-solid oils and non-volatile liquid oils include animal and vegetable oils such as carnauba wax, candelilla wax, hardened oils, 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, stearyl a Examples of such oils include higher alcohols such as alcohol phytosterol, 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), di(phytosteryl/octyldodecyl) lauroyl glutamate, dipentaerythrityl tetra(hydroxystearate/isostearate), cetyl ethylhexanoate, and triethylhexanoin. These oils may be used alone or in combination of two or more as necessary.

The other surfactants are not particularly limited as long as they are normally used in cosmetics, and any surfactant other than (C) silicone-based surfactants and (F) nonionic surfactants with an HLB of 2 to 7 can be used. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. These can be used alone or in combination of two or more types as necessary.

There are no particular limitations on the other alcohols, so long as they are normally used in cosmetics, and any alcohol other than the dihydric alcohol (D) 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.

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

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 alone or in combination of two or more types as needed.

Examples of ultraviolet protection agents include organic ultraviolet absorbers such as ethylhexyl methoxycinnamate, octocrylene, bisethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, and diethylamino hydroxybenzoyl hexyl benzoate, and inorganic ultraviolet scattering agents such as fine titanium oxide and fine zinc oxide. The ultraviolet scattering agent may be one that has been subjected to a hydrophobic surface treatment. 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. The ultraviolet protection agents may be used alone or in combination of two or more of these as necessary.

Preservatives include antiseptics such as phenoxyethanol, paraoxybenzoic acid esters, sodium benzoate, salicylic acid, and iodopropynyl butylcarbamate. Antioxidants include tocopherol and dibutylhydroxytoluene. pH adjusters include lactic acid, citric acid, citrate salts, sodium hydrogencarbonate, and L-arginine. Chelating agents include sodium edetate, sodium polyphosphate, and sodium metaphosphate. These can be used alone or in combination of two or more types as needed.

The powder may be an inorganic powder, an organic powder, an inorganic pigment, an organic pigment, a pearl pigment, a natural colorant, or the like, and any of them may be used regardless of their particle shape (spherical, needle-like, plate-like, etc.), particle size, particle structure (porous, non-porous, etc.) or crystal structure (crystalline, non-crystalline). These may be used alone or in combination of two or more kinds, as required.

The form of the water-in-oil composition of the present invention may be a solid, stick, cream, gel, liquid, emulsion, or multi-layer separated form, and further may be a mousse or spray form using a propellant or compressed air.
The water-in-oil composition of the present invention can be suitably used in skin care cosmetics such as milky lotions and creams, makeup cosmetics such as foundations, concealers, BB, creams, makeup bases, eye colors, cheek colors, eyebrows, mascaras, and eyeliners, and sunscreen cosmetics. In particular, it is suitable for makeup cosmetics and sunscreen cosmetics because it does not cause a burden on the skin, has good makeup wear, and is free of secondary adhesion.

The present technology will be explained in more detail below with reference to examples and comparative examples. Note that these are not intended to limit the present invention in any way.

<Stability evaluation>
[Stability]
"50 degrees for one month"
30 g of the mixture was placed in a transparent PET container (30 ml) and allowed to stand in an incubator set at 50° C. for one month.
[Evaluation criteria]
No separation was observed.
Separation was observed: ×

"Freeze-thaw test"
30 g of the mixture was placed in a transparent PET container (30 ml), and the container was left to freeze in a freezer (-20°C) for 24 hours, and then left to thaw at room temperature.
The same procedure was carried out three times in total.
[Evaluation criteria]
No separation was observed.
Separation was observed: ×

<Sensory evaluation>
[Usability]
One day after preparation, the samples were evaluated on a 7-point scale by a panel of 20 experts in cosmetic evaluation for "freedom of burden on the skin,""uniformity of the cosmetic film,""freedom of stickiness," and "moisturizing feeling" in accordance with the following evaluation criteria. The scores of all the panels were then averaged and judged in accordance with the following criteria.
[Evaluation criteria]
(Evaluation result): (Score)
Very good: 6 points
Good: 5 points
Fairly good: 4 points
Normal: 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 more but less than 5.0: 〇
1.5 or more and less than 3.5: △
Less than 1.5: ×

"No makeup transfer"
Ten minutes after applying the sample to the arm, a piece of black paper was pressed against the sample, and the state of the sample attached to the black paper was evaluated. [Evaluation criteria]
◎: 16 to 20 people were judged to have no or almost no secondary adhesion.
○: 11 to 15 people were judged to have no or almost no secondary adhesion.
△: 6 to 10 people judged that there was no or almost no secondary adhesion.
×: 0 to 5 people judged that there was no or almost no secondary adhesion.

"Makeup lasts longer"
A panel of 20 experts in cosmetic evaluation evaluated the "condition 6 hours after application" by each member on a 7-point scale according to the following evaluation criteria. The average score of all the panels was then used to judge the condition according to the following criteria.
[Evaluation criteria]
(Evaluation result): (Score)
Very good: 6 points
Good: 5 points
Fairly good: 4 points
Normal: 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 more but less than 5.0: 〇
1.5 or more and less than 3.5: △
Less than 1.5: ×

Examples 1 to 5 and Comparative Examples 1 to 8 (water-in-oil moisturizing cream)
The water-in-oil moisturizing creams shown in Table 1 were produced by the following production method. Each sample was evaluated by the above evaluation method, and the results are also shown in Table 1.
[Production method]
(1): Heat ingredients 1 to 9 and mix until uniformly dissolved.
(2): Add ingredients 10 to 18 to (1) and mix until uniformly dissolved.
(3): Heat and dissolve ingredients 19 to 31 uniformly.
(4): Add (3) to (2) and emulsify.
(5): Treat (4) with a homogenizer.
(6): The mixture was defoamed to obtain a water-in-oil moisturizing cream.

*1 OILKEMIA 5S CC (containing 30% polyurethane-79: manufactured by Lubrizol Corporation)
*2 Leopard KL2 (manufactured by Chiba Flour Mills)
*3 GP-1 (manufactured by Ajinomoto Co., Inc.)
*4 ADEKA NOL GT-700 (manufactured by ADEKA CORPORATION)
*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 Dow Corning Toray Co., Ltd.)
*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 Pearleem 6 (manufactured by NOF Corp.)
*11 Cosmol 82 (manufactured by Nisshin Oillio Co., Ltd.) HLB 5.0
*12 Cosmoll 42V (Nikko Chemicals) HLB 4.0

The water-in-oil moisturizing creams of Examples 1 to 5 were water-in-oil moisturizing creams with good "usability" because they contained a polyurethane-79 gel composition, had "good stability," did not "feel burdensome on the skin," formed a "uniform coating," and had a smooth, non-sticky feel while still providing a "moisturizing feel."
In contrast, in Comparative Example 1, which does not contain the polyurethane-79 gel composition in Example 1, separation was observed in "50°C for one month" and "freeze-thaw test". Furthermore, good results were not obtained for "uniformity of coating film". In addition, the oily film remained for a long time, resulting in a poor feel when used. In Comparative Examples 2 and 3, the polyurethane-79 gel composition was replaced with dextrin palmitate or dibutyl lauroyl glutamide, which are representative oil-based gelling agents, but separation was observed in the third "freeze-thaw test". Furthermore, good results were not obtained for "uniformity of coating film". In Comparative Example 4, the polyurethane-79 gel composition was replaced with disteardimonium hectorite, which is another oil-based gelling agent, but a significant decrease in viscosity was observed at high temperatures, separation occurred in "50°C for one month", and separation occurred in the first "freeze-thaw test".
In Comparative Example 5, the polyurethane was replaced with a (PEG-240/Decyltetradeceth-20/HDI) copolymer, known as a hydrophobically modified polyether urethane. Since the (PEG-240/Decyltetradeceth-20/HDI) copolymer is a water-soluble polyurethane, even when heated with an oil agent, it was poorly soluble and did not become a uniform composition, making it impossible to evaluate. Therefore, the composition was obtained by heating and dissolving it in 1,3-butylene glycol in the water phase, and adding it to the water phase, and then evaluation was performed. No improvement in "stability" was observed. As for "usability," only the moisturizing feeling was good.
In Comparative Example 6, the volatile oil was replaced with 2-ethylhexanoate, which is a non-volatile oil, and the amount of water-soluble active ingredient (E) was reduced, but separation was observed in the third "freeze-thaw test". The product was very slippery during application and did not blend well, so the "uniformity of the applied film" was poor, and the product was strongly "sticky", but the "moisturizing feeling" was small. In Comparative Example 7, the product was not formulated with a silicone-based emulsifier, so the emulsification state was poor, and after "50°C for 1 month", separation occurred the next day. In the "freeze-thaw test", severe separation occurred in the first test. Regarding usability, the evaluations were poor in all of "stress on the skin", "uniformity of the applied film", "stickiness", and "moisturizing feeling". In Comparative Example 8, the product was not formulated with a dihydric alcohol, so the product was evaluated as having poor "moisturizing feeling".

Examples 6 to 10 and Comparative Examples 9 to 15 (water-in-oil foundation)
The water-in-oil foundations shown in Table 2 were produced by the following production method. Each sample was evaluated by the above evaluation methods, and the results are also shown in Table 2.
[Production method]
(1): Heat and dissolve ingredients 1 to 17.
(2): Add ingredients 18 to 21 to (1) and mix evenly.
(3): Treat (2) with a homogenizer.
(4): Heat and dissolve ingredients 22 to 34.
(5): Add (4) to (3) and emulsify.
(6): Treat (5) with a homogenizer.
(7): The mixture was defoamed to obtain a water-in-oil type foundation.

*1 OILKEMIA 5S CC (containing 30% polyurethane-79: manufactured by Lubrizol Corporation)
*2 Leopard KL2 (manufactured by Chiba Flour Mills)
*3 GP-1 (manufactured by Ajinomoto Co., Inc.)
*4 ADEKA NOL GT-700 (manufactured by ADEKA CORPORATION)
*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 Dow Corning Toray Co., Ltd.)
*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 Pearleem 6 (manufactured by NOF Corp.)
*11 Cosmol 82 (manufactured by Nisshin Oillio Co., Ltd.) HLB 5.0
*12 Cosmoll 42V (Nikko Chemicals) HLB 4.0
*13 DOWSIL ES-5600 Silicone Glycerol Emulsifier (manufactured by Dow Corning Toray Co., Ltd.)
*14 DOWSIL FZ-2233 (manufactured by Dow Corning Toray Co., Ltd.)
*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)
*19 MZY-203S (manufactured by Teika)
*20 KSP-100 (manufactured by Nissin Chemical Industry Co., Ltd.)
*21 Wilbride S-753 (manufactured by NOF Corp.)
*22 LIPIDURE-PMB (containing 5% Polyquaternium-51: manufactured by NOF Corporation)

The water-in-oil foundations of Examples 6 to 10 were compositions with good usability, with good stability in "50°C for one month" and "freeze-thaw test," and good "skin burden,""uniformity of applied film,""stickiness," and "moisturizing feel." Furthermore, by combining with an oil-soluble silicone resin, the water-in-oil foundations maintained a beautiful finish for a long time, and a "secondary adhesion prevention effect" was obtained in a short time, making them less susceptible to "makeup transfer."
In contrast, Comparative Example 9, which does not use the polyurethane-79 gel composition, had poor "stability" and "makeup retention" was poor because the "makeup film was uneven" and the makeup was not flexible, so the makeup was slightly broken down over time. No "secondary adhesion prevention effect" was felt. Comparative Examples 10 and 11 were formulated with dextrin palmitate and disteardimonium hectorite, which are oil-based gelling agents, instead of polyurethane-79. The "high temperature stability" was good, but separation occurred in the "freeze-thaw test." The "makeup retention" was poor because the "makeup film was uneven" and the makeup was not flexible, so the makeup was broken down over time. No "secondary adhesion prevention effect" was felt. Comparative Example 12 was formulated with ceresin, which has a high thickening effect on the oil phase, but neither "stability" nor "makeup retention" was improved. Comparative Example 13 replaced the volatile oil agent isododecane with the non-volatile oil agent isotridecyl isononanoate, and reduced the amount of (E) water-soluble active ingredient, but separation was observed in the third "freeze-thaw test." The "uniformity of the applied film" was poor because of the large slippage during application and poor compatibility, and the "stickiness" was strongly felt. The makeup was easily broken down, and the "makeup staying power" was poorly rated. For Comparative Example 14, since no silicone-based emulsifier was included, the emulsification state was poor, and separation occurred the next day after "50°C 1 month". Separation was also observed after the first "freeze-thaw test". Regarding usability, the "stress on the skin", "uniformity of the applied film", "stickiness", and "moisturizing feeling" were all rated poorly. Regarding "makeup staying power", the makeup was felt to break down over time, and the "secondary adhesion prevention effect" was also rated poorly. For Comparative Example 15, since no polyurethane-79 or oil-soluble silicone resin was included, the makeup broke down over time, and the "makeup staying power" was rated poorly, and the "secondary adhesion prevention effect" was not felt. Furthermore, the makeup was easily separated at high temperatures, and the "50°C 1 month" was also rated poorly.

Example 11: Anti-wrinkle cream ingredients (mass%)
1: Polyurethane-79, tri(caprylic/capric acid)glyceryl *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 bis(behenyl/isostearyl/phytosteryl) dimer dilinoleate 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: Retinol palmitate 0.1%
13: Caprylyl methicone 15%
14: Purified water (as needed)
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 Dow Corning Toray Co., Ltd.)
(Production method)
(1): Mix ingredients 1 to 13 and heat to dissolve.
(2): Mix ingredients 13 to 23 and heat to dissolve.
(3): Add (2) to (1) and emulsify.
(4): Process with a homogenizer.
(5): (4) was cooled and defoamed to obtain an anti-wrinkle cream.

Stability testing was performed at 50°C for one month, and a freeze-thaw test was carried out, confirming that there were no problems. This anti-wrinkle cream was easy to use, with good "skin burden," "uniformity of applied film," "stickiness," and "moisturizing feel."

Example 12: Water-in-oil foundation (no UV absorber)
＜Undiluted solution＞
Ingredients (mass%)
1: Polyurethane-79, tri(caprylic/capric acid)glyceryl *1 3%
2: Cetyl diglyceryl tris(trimethylsiloxy)silylethyl dimethicone *13 2%
3: Fine particle zinc oxide/decamethylcyclopentasiloxane dispersion (hydrophobized zinc oxide pure content 60%) 10%
4: Fine particle titanium dioxide/decamethylcyclopentasiloxane dispersion (hydrophobized titanium dioxide pure content 80%) 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 acetyl hyaluronate 0.1%
19: Arbutin 2%
20: Nicotinamide 5%
21: Ethylhexylglycerin 0.5%
22: Iodopropynyl butylcarbamate 0.01%
Total 100%
*25 XS66-B8636 (MOMENTIVE)

(Production method)
(1): Components 1 to 10 are heated and mixed, and dispersed using a roll mill.
(2): Add ingredients 11 to 14 to (1) and mix until uniform.
(3): Mix ingredients 15 to 22 and heat to dissolve.
(4): Treat (2) with a homogenizer.
(5): Add (3) to (4) and emulsify.
(6): Treat (5) with a homogenizer.
(7): The mixture was defoamed to obtain a water-in-oil type foundation.

For Example 12, a stability test was performed at 50°C for one month, and a freeze-thaw test was performed to confirm that there were no problems. The composition was easy to use and had good "skin burden,""uniformity of the applied film,""stickiness," and "moisturizing feeling."
Furthermore, the resulting water-in-oil type foundation had good "makeup staying power," remained beautifully applied even against sweat and sebum, and had a high "sunscreen effect" that was resistant to rubbing against clothing due to its "secondary adhesion prevention effect." When the SPF value of the original solution was measured using the method described below, a favorable result of SPF 55 was obtained.

<How to evaluate UV protection effect (SPF)>
The measurement sample was uniformly applied to a substrate HELIOPLATE HD6 (manufactured by Helio Screen) to a concentration of 1.3 mg/ ^cm2 , and then dried at room temperature for 30 minutes. Using an SPF analyzer UV-2000S (manufactured by Labsphere), measurements were taken at nine points on the applied surface, and the average SPF value was calculated. (Decimals were rounded down.)

Example 13: High SPF water-in-oil sunscreen spray (no cyclic silicones)
＜Undiluted solution＞
Ingredients (mass%)
1: Polyurethane-79, tri(caprylic/capric acid)glyceryl *1 5%
2: Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone *26 1%
3: Ethylhexyl methoxycinnamate 10%
4: Diethylaminohydroxybenzoylhexyl benzoate 2%
5: Octocrylene 3%
6: PEG-30 dipolyhydroxystearic acid 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 (Shin-Etsu Chemical Co., Ltd.)
*27 KSP-300 (Shin-Etsu Chemical Co., Ltd.)
*28 DOWSIL BY25-337 (manufactured by Dow Corning Toray Co., Ltd.)
*29 KP-561 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
(1): Mix ingredients 1 to 8 and heat to dissolve.
(2): Add ingredients 9 and 10 to (1) and mix until uniform.
(3): Add ingredients 11 to 13 to (2) and mix until uniform.
(4): Mix ingredients 14 to 21 and heat to dissolve.
(5): Treat (3) with a homogenizer.
(6): Add (4) to (5) and emulsify.
(7): Treat (6) with a homogenizer.
(8): The mixture was defoamed to obtain a concentrate of sunscreen spray.

In Example 13, the concentrate was non-separating, and therefore the homogeneity of the concentrate could be maintained without stirring during filling, and the composition was therefore easily filled into aerosol cans.
When the SPF value of the original solution was measured using the aforementioned "UV protection effect "SPF" evaluation method," a favorable result of SPF 68 was obtained.
<Evaluation of aerosol stability>
An aerosol test bottle (made of transparent glass) was filled with 30% <concentrate>:70% <propellant/LPG>, and the spray button was set to perform the evaluation.
[Stability]
A 40°C static test for three months and a freeze-thaw test (three times) were carried out, and the stability was confirmed by the following methods, with no particular problems found.
Quality check: After turning the product upside down in the aerosol test bottle (made of transparent glass) 10 times, it was confirmed that there was no sediment at the bottom. After that, the spray pattern on the black paper was checked, and it was found to be uniform and fine, which was good quality for a sunscreen spray.
[Usage]
The results of checking the aforementioned evaluation items of "skin burden,""uniformity of applied film,""stickiness,""moisturizingfeeling," and "makeup durability" confirmed that the composition exhibited the effects of the present invention. Furthermore, it was a water-in-oil sunscreen spray that was resistant to removal even when rubbed against clothing due to its "secondary adhesion prevention effect," and also had a high "sunscreen effect."

Claims (4)

The following components (A) to (D)
(A) a polyurethane-79 gel composition consisting of (A-1) polyurethane-79 and (A-2) a liquid oil; (B) a volatile oil; (C) a silicone-based emulsifier; and (D) a water-in-oil emulsion composition containing a dihydric alcohol. The water-in-oil emulsion composition according to claim 1, further comprising (E) a water-soluble active ingredient. The water-in-oil emulsion composition according to claim 1, wherein the component (D) is a dihydric alcohol having 3 to 6 carbon atoms. The water-in-oil emulsion composition according to any one of claims 1 to 3, wherein (A-1)/(C) is 0.05 to 5.