Water-in-oil emulsion composition

Abstract

To provide a water-in-oil emulsion composition with excellent emulsion stability and usability.SOLUTION: A water-in-oil emulsion composition containing (A) an ether type nonionic surfactant having HLB of 5 to 10, or nonionic surfactant having HLB of 11 to 14, (B) nonionic surfactant having HLB of 1 to 4.5, (C) oil solution and (D) water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water-in-oil emulsion composition suitable for cosmetics and the like. [Background technology]

[0002] Water-in-oil emulsion compositions have advantages such as a high occlusive effect due to the presence of an oily component in the continuous phase, high moisturizing properties, etc. However, water-in-oil emulsion compositions may have usability problems such as an inability to ensure emulsion stability or an oily feel when used.

[0003] Patent Documents 1 and 2 propose an attempt to improve emulsion stability and usability by combining two surfactants with different HLB values. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-102078 [Patent Document 2] WO2016 / 080270 Summary of the Invention [Problem to be solved by the invention]

[0005] However, there is a demand for a water-in-oil emulsion composition that is even more excellent in emulsion stability and ease of use. Therefore, an object of the present invention is to provide a water-in-oil emulsion composition that is excellent in emulsion stability and ease of use. [Means for solving the problem]

[0006] The present inventors have conducted studies to solve the above problems and have found that a water-in-oil emulsion composition with excellent emulsion stability and ease of use can be obtained by using a combination of specific surfactants, thereby completing the present invention. That is, the gist of the present invention relates to the following.

[0007] [1] (A) An ether-type nonionic surfactant having an HLB of 5 to 10, or a nonionic surfactant having an HLB of 11 to 14, (B) a nonionic surfactant having an HLB of 1 to 4.5; (C) oil solution, and (D) Water; A water-in-oil emulsion composition comprising: [2] The water-in-oil emulsion composition according to [1], wherein the ether-type nonionic surfactant having an HLB of 5 to 10 in (A) is a polyoxyalkylene alkyl ether. [3] The water-in-oil emulsion composition according to [1] or [2], wherein the nonionic surfactant having an HLB of 11 to 14 in (A) is an ester-type nonionic surfactant or an ether-type nonionic surfactant. [4] The water-in-oil emulsion composition according to any one of [1] to [3], wherein the (B) nonionic surfactant having an HLB of 1 to 4.5 is an ester-type nonionic surfactant or an ether-type nonionic surfactant. [5] The water-in-oil emulsion composition according to any one of [1] to [4], further comprising (E) an organically modified clay mineral. [6] The water-in-oil emulsion composition according to any one of [1] to [5], which does not contain a silicone component. [7] The (A) ether-type nonionic surfactant having an HLB of 5 to 10, or The water-in-oil emulsion composition according to any one of [1] to [6], wherein the content of the nonionic surfactant having an HLB of 11 to 14 is 0.01 to 10% by mass based on the total mass of the composition. [8] The water-in-oil emulsion composition according to any one of [1] to [7], wherein the content of the (B) nonionic surfactant having an HLB of 1 to 4.5 is 0.01 to 10% by mass based on the total mass of the composition. [9] The water-in-oil emulsion composition according to any one of [1] to [8], wherein the content of the (C) oil agent is 1 to 50% by mass based on the total mass of the composition.

[10] The water-in-oil emulsion composition according to any one of [5] to [9], wherein the content of the (E) organically modified clay mineral is 1 to 20 mass % based on the total mass of the composition.

[11] The water-in-oil emulsion composition according to any one of [1] to

[10] , wherein the water-in-oil emulsion composition is a skin external preparation.

[12] The water-in-oil emulsion composition according to

[11] , wherein the topical skin preparation is a cosmetic. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a water-in-oil emulsion composition that is excellent in emulsion stability and ease of use. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described below. <Water-in-oil emulsion composition> One aspect of the present invention is (A) an ether-type nonionic surfactant having an HLB of 5 to 10, or a nonionic surfactant having an HLB of 11 to 14, (B) a nonionic surfactant having an HLB of 1 to 4.5; (C) oil solution, and (D) Water; The present invention relates to a water-in-oil emulsion composition (hereinafter, sometimes referred to as "the water-in-oil emulsion composition of the present invention") comprising:

[0010] The present inventors have conducted various investigations in search of a technique for improving the emulsion stability and usability of water-in-oil emulsion compositions. In this context, the present inventors have succeeded in creating a water-in-oil emulsion composition with excellent emulsion stability and ease of use by using a specific combination of nonionic surfactants with different HLB (Hydrophile-Lipophile Balance).Based on this finding, the present invention has been completed.

[0011] <Component (A) Nonionic Surfactant> The water-in-oil emulsion composition of the present invention contains an ether-type nonionic surfactant having an HLB of 5 to 10 as one of the nonionic surfactants of component (A). The ether-type nonionic surfactant having an HLB of 5 to 10 used in the present invention may be one or more surfactants appropriately selected from those commonly used in cosmetics, etc. The ether-type nonionic surfactant having an HLB of 5 to 10 of component (A) can be appropriately selected using HLB as an indicator. Specific examples of the ether-type nonionic surfactant include polyglycerin alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, and alkyl glycosides.

[0012] More specifically, for example, Polyoxyethylene (hereinafter referred to as POE) (2) polyoxyalkylene alkyl ethers such as cetyl ether (Ceteth-2, etc.) (HLB 8.0); Polyoxyalkylene alkylphenol ethers such as POE(3) nonylphenyl ether (HLB 7.4); Examples include alkyl glycosides such as decyl glucoside (HLB 10.0).

[0013] The water-in-oil emulsion composition of the present invention includes, as another type of nonionic surfactant of component (A), a nonionic surfactant having an HLB of 11 to 14. The nonionic surfactant having an HLB of 11 to 14 used in the present invention may be one or more types appropriately selected from those commonly used in cosmetics, etc. The nonionic surfactant having an HLB of 11 to 14 of component (A) can be appropriately selected using HLB as an indicator. Specific examples include ether-type nonionic surfactants, fatty acid alkanolamide-type nonionic surfactants, and ester-type nonionic surfactants. Examples of ether-type nonionic surfactants include polyglycerin alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, and alkyl glycosides. Examples of ester-type nonionic surfactants include polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, (poly)glycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters.

[0014] More specifically, for example, Polyglycerin alkyl ethers such as polyglyceryl-4 lauryl ether (HLB 12.3); Polyoxyalkylene alkylphenol ethers such as POE(12) dodecyl phenyl ether (HLB 13.6); Alkyl glycosides such as cetearyl glucoside (HLB 13.0); (Poly)glycerin fatty acid esters such as polyglyceryl-6 laurate (HLB 13.4); Sucrose fatty acid esters such as sucrose stearate (e.g., Ryoto (trademark) Sugar Ester S-1170) (HLB 11.1); Examples include:

[0015] <Component (B) Nonionic Surfactant> In the water-in-oil emulsion composition of the present invention, the nonionic surfactant of component (B) includes a nonionic surfactant having an HLB of 1 to 4.5. The nonionic surfactant having an HLB of 1 to 4.5 used in the present invention may be one or more surfactants appropriately selected from those commonly used in cosmetics, etc. The nonionic surfactant of component (B) can be appropriately selected using HLB as an indicator. Specific examples include ether-type nonionic surfactants, fatty acid alkanolamide-type nonionic surfactants, and ester-type nonionic surfactants. Examples of ether-type nonionic surfactants include polyglycerin alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, and alkyl glycosides. Examples of ester-type nonionic surfactants include polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, (poly)glycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters.

[0016] More specifically, for example, Polyoxyalkylene alkyl ethers such as POE(2) stearyl ether (steareth-2, etc.) (HLB 4.4); Polyoxyalkylene fatty acid esters such as ceteth-3 stearate (HLB 3.0); (Poly)glycerin fatty acid esters such as polyglyceryl-10 pentastearate (HLB 3.5) and glyceryl stearate (HLB 4.2); Sucrose stearate (e.g., Ryoto (trademark) Sugar Ester S-270) (H LB2.0) and other sucrose fatty acid esters; Sorbitan fatty acid esters such as sorbitan tristearate (HLB 2.1); Examples include:

[0017] In the present invention, the content of the nonionic surfactant as component (A) is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 1 to 2 mass%, based on the total mass of the composition. In addition, in this embodiment, the content of the nonionic surfactant as component (B) is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 1 to 2 mass%, based on the total mass of the composition.

[0018] Furthermore, the total content of the nonionic surfactants of components (A) and (B) is preferably 0.02 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, based on the total mass of the composition. From the viewpoint of solubilization stability, it is preferably 0.02% by mass or more, and from the viewpoint of formulation flexibility, it is preferably 20% by mass or less.

[0019] Furthermore, the mass ratio of the nonionic surfactant of component (A) to the nonionic surfactant of component (B) used in the present invention is preferably 3:1 to 1:3, more preferably 1:1 to 1:2. By combining the two specific surfactants of the present invention and using them preferably in such a mass ratio, it is possible to obtain a water-in-oil emulsion composition that is stable and has an excellent feel when used, even when it contains an oily component.

[0020] In the water-in-oil emulsion composition of the present invention, an appropriate HLB value can be obtained by combining surfactants having different HLB values, such as the nonionic surfactants of component (A) and component (B). In the water-in-oil emulsion composition of the present invention, the HLB of the combination of the nonionic surfactants of component (A) and component (B) may be 5 or more, 6 or more, or 7 or less, 6 or less, or any combination thereof that is not contradictory. The HLB may be, for example, 5 to 7 or 5 to 6. The HLB can be adjusted based on the HLB of each surfactant, the content of the surfactant, etc. The HLB value was calculated by the Griffin method described below.

[0021] HLB = 20 x (molecular weight of hydrophilic group / total molecular weight)

[0022] <Component (C) Oil> The water-in-oil emulsion composition of the present invention contains an oil as component (C). The oil used in the present invention may be one or more oils appropriately selected from those commonly used in cosmetics and the like. Specific examples of such oils and waxes include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated coconut oil, hydrogenated oil, Japan wax, hydrogenated castor oil, beeswax, candelilla wax, carnauba wax, Ibota wax, lanolin, reduced lanolin, hard lanolin, and jojoba wax; isododecane, hydrogenated polyisobutene, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, microcrystalline cellulose, and the like. hydrocarbons such as tarin wax; higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, behenic acid, and undecylenic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol, and ethylhexyl palmitate; cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, and diisopropyl adipate. Examples of oils include synthetic ester oils such as glycerin, di-2-ethylhexyl sebacate, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentane erythritol tetra-2-ethylhexanoate, and cetyl 2-ethylhexanoate; and silicone oils such as linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexanesiloxane; and modified polysiloxanes such as amino-modified polysiloxanes, polyether-modified polysiloxanes, alkyl-modified polysiloxanes, and fluorine-modified polysiloxanes. In one embodiment of the present invention, from the viewpoint of improving compatibility with the skin, the composition may be free of silicone components such as silicone oil.

[0023] In the present invention, the content of the oil agent as component (C) is preferably 1 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 20 to 40 mass %, based on the total mass of the composition.

[0024] <Component (E) organically modified clay mineral> In order to further improve emulsification performance, the water-in-oil emulsion composition of one embodiment of the present invention may further comprise an organically modified clay mineral as component (E). The organically modified clay mineral used in the present invention may be one or more types appropriately selected from those typically used in cosmetics and the like. Specific examples include known clay minerals such as hectorite, montmorillonite, saponite, hectorite, bentonite, and smectite that have been treated with an organic cation. More specific examples include dimethyl distearyl ammonium hectorite (quaternium-18 hectorite, etc.), dimethyl distearyl ammonium bentonite (quaternium-18 bentonite, quaternium-90 bentonite, etc.), benzyl dimethyl stearyl ammonium hectorite, dioctadecyl dimethyl ammonium salt-modified montmorillonite, octadecyl dimethyl benzyl ammonium salt-modified montmorillonite, dihexadecyl dimethyl ammonium salt-modified montmorillonite, and dimethyl distearyl ammonium smectite.

[0025] In the present invention, the content of the organically modified clay mineral as component (E) is preferably 1 to 20 mass %, more preferably 2 to 10 mass %, and even more preferably 3 to 5 mass %, based on the total mass of the composition.

[0026] <Other ingredients> The water-in-oil emulsion composition of the present invention may contain other optional ingredients as long as the effects of the composition are not impaired. The optional components are not particularly limited as long as they are components that can normally be blended into cosmetics and the like, and examples thereof include solvents, polyhydric alcohols, surfactants other than the essential components (cationic surfactants, anionic surfactants, silicone surfactants, etc.), various active ingredients, moisturizers, pH adjusters, thickeners, preservatives, powders, antibacterial agents, ultraviolet light scattering / absorbing agents, etc. One or a combination of two or more optional components may be used in the present invention. Preferred examples of the antibacterial agent include natural antibacterial substances such as phenoxyethanol, caprylyl glycol, glyceryl caprylate, ethylhexylglycerin, and caprylhydroxamic acid. The active ingredients include moisturizing ingredients, whitening ingredients, wrinkle-reducing ingredients, anti-inflammatory ingredients, and extracts derived from animals and plants, and only one kind may be contained, or two or more kinds may be contained.

[0027] Optional components include, but are not limited to, polyhydric alcohols such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, and 1,2-pentanediol; moisturizing ingredients such as sodium pyrrolidone carboxylate, lactic acid, and sodium lactate; powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, and barium sulfate, which may be surface-treated; inorganic pigments such as red iron oxide, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, iron blue, titanium oxide, and zinc oxide, which may be surface-treated; pearling agents such as titanium dioxide, fish phosphate foil, and bismuth oxychloride, which may be surface-treated; and laked pigments. Preferred examples of the ultraviolet absorber include organic dyes such as Red No. 202, Red No. 228, Red No. 226, Yellow No. 4, Blue No. 404, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, and Red No. 204, which may be present in the ultraviolet absorbing agent; organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, and organopolysiloxane elastomer; ultraviolet absorbers such as para-aminobenzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, sugar-based ultraviolet absorbers, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 4-methoxy-4'-t-butyldibenzoylmethane; and lower alcohols such as ethanol and isopropanol.

[0028] These optional components can be added in any step of the present invention or before or after the step. The water-in-oil emulsion composition of the present invention can be produced by a conventional emulsification method, except that it contains the above-mentioned essential components.

[0029] <External skin preparations and cosmetics> The topical skin preparation of the present invention contains the water-in-oil emulsion composition of the present invention and is suitable for use in, for example, cosmetics including pharmaceuticals and quasi-drugs. Cosmetics are particularly preferred. The dosage form is not particularly limited as long as it is a water-in-oil emulsion, and preferred examples include lotions, emulsions, etc. Except for using the water-in-oil emulsion composition of the present invention, the production of external skin preparations, medicines, and cosmetics including quasi-drugs can be carried out using conventionally known production methods. [Example]

[0030] The present invention will be specifically described below with reference to examples, but these are merely examples of the present invention and the scope of the present invention is not limited to these examples.

[0031] Water-in-oil emulsion compositions of Examples and Comparative Examples were prepared and evaluated according to the formulations shown in Table 1. Specifically, the procedure was as follows: The oil phase was heated to 70°C and dissolved. The aqueous phase, which had also been heated and dissolved at 70°C, was added to the oil phase, and the mixture was emulsified while stirring with a homomixer to obtain the desired water-in-oil emulsion compositions.

[0032] [Table 1]

[0033] [Table 2]

[0034] 1. Appearance stability Each sample was left at room temperature for 4 weeks and then evaluated for appearance. ◎: No separation was observed and the mixture was stable. 〇: Slight separation has occurred, but it does not affect the quality. △: Some separation occurred. ×: Separation was clearly observed by visual inspection.

[0035] 2. Softness of the skin after application Each prepared sample was used by a female expert panel (N=10) and evaluated the softness of the skin after application. ◎: More than 9 out of 10 people answered that their skin was soft. ○: More than 7 out of 10 people answered that their skin is soft. △: More than 5 out of 10 people answered that their skin felt soft. ×: Fewer than 4 out of 10 people answered that their skin was soft.

[0036] 3. No stickiness on the skin after application Each of the prepared samples was used by a female expert panel (N=10) to evaluate the non-stickiness of the skin after application. ◎: More than 9 out of 10 people answered that their skin did not feel sticky after use. ○: More than 7 out of 10 people answered that "it doesn't leave a sticky feeling on the skin after use." △: More than 5 out of 10 people answered that "it doesn't leave a sticky feeling on the skin after use." ×: Less than 4 out of 10 people answered that their skin did not feel sticky after use.

[0037] The water-in-oil emulsion compositions of Examples 1 and 8, which contain an ether-type nonionic surfactant having an HLB of 5 to 10 as component (A) and an ester-type nonionic surfactant having an HLB of 1 to 4.5 as component (B), were found to be excellent in stability and usability. On the other hand, the water-in-oil emulsion composition of Comparative Example 1, which contained an ester-type nonionic surfactant with an HLB of 10.4 and an ester-type nonionic surfactant with an HLB of 3.5, had insufficient stability and usability. The water-in-oil emulsion composition of Example 2, which contains an ether-type nonionic surfactant having an HLB of 5 to 10 as component (A) and an ether-type nonionic surfactant having an HLB of 1 to 4.5 as component (B), was found to be excellent in stability and usability.

[0038] The water-in-oil emulsion compositions of Examples 3 and 4, which contain an ester-type nonionic surfactant having an HLB of 11 to 14 as component (A) and an ester-type nonionic surfactant having an HLB of 1 to 4.5 as component (B), were found to be excellent in stability and usability. On the other hand, the water-in-oil emulsion composition of Comparative Example 2, which contained an ester-type nonionic surfactant with an HLB of 14.7 and an ester-type nonionic surfactant with an HLB of 3.5, had insufficient stability and usability. The water-in-oil emulsion composition of Example 5, which contains an ether-type nonionic surfactant having an HLB of 11 to 14 as component (A) and an ester-type nonionic surfactant having an HLB of 1 to 4.5 as component (B), was found to be excellent in stability and usability. The water-in-oil emulsion composition of Example 6, which contains an ester-type nonionic surfactant having an HLB of 11 to 14 as component (A) and an ether-type nonionic surfactant having an HLB of 1 to 4.5 as component (B), was found to be excellent in stability and usability. The water-in-oil emulsion composition of Example 7, which contains an ether-type nonionic surfactant having an HLB of 11 to 14 as component (A) and an ether-type nonionic surfactant having an HLB of 1 to 4.5 as component (B), was found to be excellent in stability and usability. [Industrial Applicability]

[0039] The present invention can be applied to cosmetics, quasi-drugs, pharmaceuticals, etc.

Claims

1. (A) an ether-type nonionic surfactant which is a polyoxyalkylene alkyl ether and has an HLB of 5 to 10, or a nonionic surfactant which is a polyglycerin alkyl ether and has an HLB of 11 to 14; (B) a nonionic surfactant having an HLB of 1 to 4.5 selected from (poly)glycerin fatty acid esters, sorbitan fatty acid esters, and polyoxyalkylene alkyl ethers; (C) an oil agent containing at least an ester oil and a hydrocarbon; (D) water, and (E) an organically modified clay mineral selected from dimethyl distearyl ammonium hectorite and dimethyl distearyl ammonium bentonite; A water-in-oil emulsion composition containing the above and not containing any silicone component.

2. 2. The water-in-oil emulsion composition according to claim 1, wherein the ether-type nonionic surfactant having an HLB of 5 to 10 in (A) is polyoxyethylene (2) cetyl ether.

3. 3. The water-in-oil emulsion composition according to claim 1, wherein the nonionic surfactant having an HLB of 11 to 14 in (A) is polyglyceryl-4 lauryl ether.

4. The (poly)glycerin fatty acid ester in (B) is polyglyceryl-10 pentastearate, The sorbitan fatty acid ester in (B) is sorbitan tristearate, 4. The water-in-oil emulsion composition according to claim 1, wherein the polyoxyalkylene alkyl ether in (B) is polyoxyethylene (2) stearyl ether.

5. 5. The water-in-oil emulsion composition according to claim 1, wherein the content of the (A) ether-type nonionic surfactant having an HLB of 5 to 10 or the nonionic surfactant having an HLB of 11 to 14 is 0.01 to 10% by mass based on the total mass of the composition.

6. 6. The water-in-oil emulsion composition according to claim 1, wherein the nonionic surfactant (B) having an HLB of 1 to 4.5 is present in an amount of 0.01 to 10% by mass based on the total mass of the composition.

7. 7. The water-in-oil emulsion composition according to claim 1, wherein the content of the oil agent (C) is 1 to 50% by mass based on the total mass of the composition.

8. 8. The water-in-oil emulsion composition according to claim 1, wherein the content of the (E) organically modified clay mineral is 1 to 20% by mass based on the total mass of the composition.

9. The water-in-oil emulsion composition according to any one of claims 1 to 8, wherein the water-in-oil emulsion composition is a skin topical agent.

10. The water-in-oil emulsion composition according to claim 9, wherein the topical skin preparation is a cosmetic.

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