JP2015127323A - Water-in-oil type emulsified composition retaining liquid crystal structure in aqueous phase, and cosmetic or external preparation for skin containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably and readily prepare a water-in-oil type emulsified composition having a liquid crystal structure in an aqueous phase which is difficult to prepare conventionally due to the mechanical and chemical instability of the liquid crystal structure in the aqueous phase, and to provide a cosmetic and external preparation for skin containing the same.SOLUTION: The above subject is solved by finding that when a liquid crystal structure is constructed in an aqueous phase by containing (a) β-branched monoalkyl phosphate ester, (b) one or more neutralizer selected from a basic amino acid, an organic base, and an inorganic base, and (c) water in the aqueous phase as an essential ingredient, and further the aqueous phase is emulsified and dispersed into oil, a water-in-oil type emulsified composition retaining the liquid crystal structure in the aqueous phase can be prepared stably and readily without receiving the effect of species of oil components or emulsifying agents.

Description

  The present invention relates to a water-in-oil emulsion composition in which a liquid crystal formed by a β-branched monoalkyl phosphate salt is held in an aqueous phase, and a cosmetic or skin external preparation containing the same.

  In the field of conventional cosmetics, an emulsion composition having a liquid crystal structure in the water phase part, which is the outer phase of the oil-in-water emulsion, and an oil-in-water emulsion technique in which liquid crystal is constructed on the emulsion film surface (Patent Documents 1 and 2) Many reports on the liquid crystal structure in oil-in-water emulsions are known. However, a water-in-oil composition in which an aqueous phase having a liquid crystal structure is emulsified or dispersed in an oil phase has not been reported yet. This is because the liquid crystal structure formed in the aqueous phase is weak to mechanical force when emulsified or dispersed, it collapses during preparation, and the structure changes due to the influence of other components when emulsified, especially This is because the influence when mixed with an oil agent is great, and the liquid crystal structure is collapsed. Furthermore, at 25-30 ° C. near room temperature in water, there are few ionic surfactants that build a stable liquid crystal structure without precipitating crystals, etc., and general ionic surfactants have strong hydrophilic groups, so Kraft Since the temperature is high, it is difficult to dissolve at 25-30 ° C. near room temperature. For this reason, it is difficult to remove higher-order structures such as liquid crystals in water, which hinders the preparation of a water-in-oil emulsion composition having a liquid crystal structure in the aqueous phase.

JP 2008-115612 A JP2010-280587A

  It is an object of the present invention to prepare a water-in-oil emulsion composition that retains a liquid crystal structure in an aqueous phase that has not been prepared so far, and to provide a cosmetic or an external preparation for skin containing the same. .

  In view of these circumstances, the present inventors have conducted extensive studies on the preparation of a stable water-in-oil emulsion composition while maintaining a liquid crystal structure in the aqueous phase, and cosmetics or skin external preparations containing the same. By constructing a liquid crystal structure with a β-branched monoalkyl phosphate ester and a specific neutralizing agent and water in the phase, and then mixing with the outer phase oil and surfactant and / or organically modified clay mineral, As a result, a water-in-oil emulsified composition having a liquid crystal structure in the aqueous phase, and a cosmetic or skin external preparation containing the same were obtained.

  That is, the present invention comprises (a) a β-branched monoalkyl phosphate ester and (b) one or more neutralizers selected from basic amino acids, organic bases, and inorganic bases, and (c A water-in-oil emulsion composition of a completely new dosage form characterized in that a liquid crystal structure is constructed in water by containing water as an essential component, and this is emulsified or dispersed in oil.

  The present invention relates to a novel water-in-oil prepared by using a β-branched monoalkyl phosphate ester and a specific neutralizing agent in a water-in-oil emulsion composition that retains a liquid crystal structure in water that could not be prepared conventionally. Type emulsified composition, and cosmetics or skin external preparations containing the same. The inventors focused on the fact that β-branched monoalkyl phosphate salts have a very low Kraft point and can construct a stable liquid crystal structure at 25-30 ° C. near room temperature. It was found that by using an alkyl phosphate ester salt, a water-in-oil emulsion composition can be prepared while maintaining a stable liquid crystal structure in water. Furthermore, the novel cosmetic and novel skin external preparation obtained by the present invention, unlike conventional preparations, can obtain a higher moisturizing effect than conventional water-in-oil emulsion compositions by retaining the liquid crystal structure in water. There is expected. In addition, in spite of being an ionic surfactant that has been difficult in the past, it is possible to construct a stable liquid crystal structure in the range of 25 to 30 ° C. near room temperature. Is very useful in the future development of cosmetics. For example, in addition to the moisturizing effect derived from the oil phase of the water-in-oil emulsion composition, it is expected that a further moisturizing effect can be obtained by retaining the liquid crystal structure in the aqueous phase. Furthermore, a more moist feel can be imparted to the preparation.

Hereinafter, the present invention will be described in detail.
The component (a) β-branched monoalkyl phosphate used in the present invention preferably has an alkyl group having 12 to 36 carbon atoms, more preferably 12 to 30 carbon atoms, and still more preferably 14 to 22 carbon atoms. Alkyl phosphate esters with different alkyl chain lengths can be easily synthesized. In general, phosphorylation of alcohol with phosphorous pentoxide and phosphorylation of alcohol with phosphoryl chloride (Oil Chemistry, Vol. 43 , No. 6, 1990, P250-258), Alkyl with chain length arbitrarily changed by direct phosphorylation of alcohol with phosphoric acid (Oil Chemistry, Vol. 43, No. 6, 1990, P259-266) It is possible to obtain phosphate esters. In the present invention, one or more of the β-branched monoalkyl phosphates thus obtained can be used in combination.

  Specific examples of the component (b) one or more neutralizers selected from the basic amino acids, organic bases and inorganic bases used in the present invention include bases such as arginine, lysine, histidine and tryptophan. Amino acids, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanol, aminomethylpropanediol, aminoethylpropanediol, organic bases such as trishydroxymethylaminomethane, and inorganic bases such as sodium hydroxide and potassium hydroxide. Can be mentioned. Of these, basic amino acids are preferable, and arginine is particularly preferable.

  Further, the oil phase, the emulsifier and other components for preparing the water-in-oil emulsion composition of the present invention are not particularly limited, and are the raw materials used when preparing a normal water-in-oil emulsion. Any can be used.

  The oily component used in the present invention does not affect the liquid crystal structure in the aqueous phase of the present invention depending on the composition and properties of the oil, and is particularly limited as long as it is normally used in cosmetics and the like. It is not a thing. Moreover, these components can also be used in combination. Specifically, hydrocarbons such as squalane and liquid paraffin, vegetable oils such as olive oil, macadamian nut oil, jojoba oil, animal oils such as beef tallow, glyceryl triisooctanoate, isopropyl myristate, cetyl isooctanoate, isooctyl palmitate, etc. Esters, dimethyl silicone, phenylmethyl silicone, cyclomethicone and other silicones, ultraviolet sorbents such as ethyl hexyl methoxide, octocrylene, ethyl hexyl salicylate, homosalate, and polysilicone-15. Solid oils, polar lipids, etc. can also be used in the same manner, specifically, higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, and polar lipids. Include ceramides, phospholipids, cholesterol and derivatives thereof, glycolipids, and the like.

  As for the emulsifier used in the present invention, there are surfactants, organically modified clay minerals, etc., but the type does not affect the liquid crystal structure in the aqueous phase of the present invention, and usually a water-in-oil emulsion composition. There is no particular limitation as long as it is used for things. Moreover, these components can also be used in combination. Specific examples of the surfactant include POE alkyl ethers, POE fatty acid esters, POE sorbite fatty acid esters, POE glycerin fatty acid esters, POE / POP alkyl ethers, polysorbates, sorbitan fatty acid esters, polyglycerin. Nonionic surfactants such as fatty acid esters, POE-modified silicones, sucrose fatty acid esters, and glycerin fatty acid esters. Anionic surfactants such as fatty acid soaps, sulfate esters, acylated amino acid salts, phosphate esters. There are quaternary ammonium salts and the like. The organically modified clay mineral is preferably a cation-modified clay mineral treated with a quaternary ammonium salt type cationic surfactant, such as dimethyl distearyl ammonium hectorite, dimethyl distearyl ammonium bentonite, and benzyl dimethyl stearyl ammonium hectorite. It is done. Examples of commercially available products include Benton 38VCG (dimethylstearylammonium hectorite) manufactured by Elementis Japan.

  In the water-in-oil emulsion composition having a liquid crystal structure in the aqueous phase of the present invention, the aqueous phase containing the components (a) to (c) is uniformly mixed at 60 ° C. or higher and stirred and cooled to room temperature. Next, it can prepare by adding the aqueous phase prepared previously gradually, stirring arbitrary oil phases.

  In addition, the cosmetic or skin external preparation of the present invention includes various components that are usually used in cosmetics or skin external preparations, such as active ingredients, moisturizing ingredients, antibacterial ingredients, and viscosity adjustments, as long as the effects of the present invention are not impaired. Agents, pigments, fragrances and the like can be blended.

  As active ingredients, ascorbic acid, magnesium ascorbate phosphate ester, ascorbyl palmitate, ascorbyl stearate, ascorbyl tetraisopalmitate, ascorbic acid glucoside, arbutin, ellagic acid, lucinol and other NMF components such as amino acids, Examples include water-soluble collagen, elastin, glycyrrhizic acid, glycyrrhetinic acid, anti-roughing agents such as ceramide, anti-aging agents such as retinol and vitamin A acid, various vitamins, and derivatives thereof.

  Examples of the moisturizing component include polyethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, sorbitol, xylitol, maltitol, chondroitin sulfate, hyaluronic acid, sodium pyrrolidone carboxylate and the like.

  The use of the cosmetic or external preparation for skin according to the present invention is not particularly limited, but it can be applied to various products such as emulsions, gels, creams and hair treatments.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Moreover, the mass% shown below is mass% with respect to the whole composition. In particular, for branched monoalkyl phosphate esters not described for purity, the monoalkyl purity indicates 90% or more.

Water-in-oil emulsion compositions having a liquid crystal structure in the water phase were prepared according to the formulations shown in Tables 1 and 2. The phase shown in Table B was heated and mixed, cooled to room temperature, and then the Phase B shown in Table A, which had been mixed in advance, was gradually mixed to complete the preparation.
(1) Confirmation of liquid crystal structure of water phase Confirmation of whether the water phase of the prepared water-in-oil emulsion composition has a liquid crystal structure was observed using a polarizing microscope. ○ that the optical anisotropy that means the existence of the liquid crystal structure was confirmed under a polarizing microscope, it can be confirmed from immediately after the preparation until 3 months, △ that is difficult to confirm after that, can not be confirmed immediately after the preparation Was marked with x.

Moisture cream (A) NIKKKOL Nikomulus WO 4.0 (mass%)
Dimethicone (6cs) 5.0
Cyclopentasiloxane 15.0
(B) Branched C18 phosphate ester 1.0
Branched C16 phosphate ester 1.5
Arginine 1.0
Glycerin 10.0
Preservative Suitable amount Purified water Remaining amount (C) Sodium hyaluronate (1% aqueous solution) 1.0
Purified water 5.0
Preparation method: B is heated, and after uniform dissolution, it is cooled to room temperature. Thereafter, B and C are mixed at room temperature. While stirring A, B + C is gradually added. The preparation is completed after uniform stirring.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.

Whitening Milk (A) NIKKKOL HEXAGLYN PR-15 3.0 (mass%)
Macadamia nut oil 10.0
Glyceryl tri-2-ethylhexanoate 15.0
Ascorbyl tetrahexyldecanoate 3.0
(B) Branched C20 phosphate ester 1.0
Branched C16 phosphate 0.5
Potassium hydroxide 0.2
Glycerin 8.0
Preservative Appropriate amount Purified water Remaining amount preparation method: B is heated, uniformly dissolved, and then cooled to room temperature. While A is being stirred, B is gradually added. The preparation is completed after uniform stirring.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.

Moisture gel (A) NIKKOL Nikomurus WO 4.0 (mass%)
Cyclopentasiloxane 10.0
(B) 1,3-butylene glycol 3.0
Glycerin 25.0
Branched C20 phosphate ester 3.0
Branched C14 phosphate ester 1.0
Triethanolamine 2.0
Preservative Suitable amount Purified water Remaining amount (C) Sodium hyaluronate (1% aqueous solution) 1.0
Purified water 5.0
Preparation method: B is heated, uniformly dissolved, and then cooled to room temperature. Thereafter, B and C are mixed at room temperature. While stirring A, B + C is gradually added. The preparation is completed after uniform stirring.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.

Hair Treatment (A) NIKKOL Nikomulus WO 3.0 (mass%)
Dimethicone (6cs) 15.0
Amodimethicone 0.5
Panthenol 0.5
(B) Branched C24 phosphate 2.0
Branched C18 phosphate 0.5
Glycerin 7.0
Arginine 1.0
Preservative Appropriate amount Purified water Remaining amount preparation method: B is heated, uniformly dissolved, and then cooled to room temperature. While A is being stirred, B is gradually added. The preparation is completed after uniform stirring.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.

Mascara (A) NIKKOL Nikomulus WO 3.0 (mass%)
NIKKOL Nikomulus WO-NS 3.0
Isododecane 13.0
Hydrogenated polyisobutene 10.0
Paraffin 7.5
Silica 1.0
Carnauba 3.5
Iron oxide 4.0
Talc 3.0
(B) Sodium chloride 1.0
1,3-butylene glycol 1.0
Branched C20 phosphate ester 2.0
Arginine 0.8
Preservative Appropriate amount Purified water Remaining amount preparation method: A and B are heated and dissolved uniformly. B is gradually added while A is being stirred. After uniform stirring, stirring and cooling to room temperature is completed.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.
* NIKKOL Nikomurusu WO-NS: Polyglyceryl 6 polyricinoleate, polyglyceryl-2 isostearate, disteardimonium hectorite

Sunscreen milk (A) cyclopentasiloxane 35.0 (mass%)
Ethylhexyl palmitate 3.0
PEG-9 polydimethylsiloxyethyl dimethicone 1.0
Dimethicone (6cs) 4.5
Titanium oxide 9.0
Zinc oxide 13.0
PEG-10 Dimethicone 4.5
(B) 1,3-butylene glycol 5.0
Sodium chloride 0.5
Branched C24 phosphate 3.2
Triethanolamine 1.5
Preservative Appropriate amount Purified water Remaining amount preparation method: A and B are heated and dissolved uniformly. B is gradually added while A is being stirred. After uniform stirring, stirring and cooling to room temperature is completed.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.

Lip Balm (A) Paraffin 8.00 (mass%)
Beeswah 8.00
Candelilla Row 6.00
Carnauba 5.00
Tri (caprylic / capric) glyceryl 35.00
Castor oil 13.00
NIKKOL Nico Wax LM 9.00
(B) Heptahydroxystearic acid polyglyceryl 10 2.00
Cetanol 3.50
(C) Branched C18 phosphate 0.80
Sodium hydroxide 0.15
Preservative Appropriate amount Purified water Remaining amount preparation method: A, B, and C are heated and dissolved uniformly. B is gradually added while A is being stirred. Thereafter, C is gradually added. After uniform stirring, stirring and cooling to room temperature is completed.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.
* NIKKOL Nico Wax LM: (hydroxystearic acid / stearic acid / eicosane diacid) polyglyceryl 10, dextrin palmitate

Ointment (A) NIKKKOL HEXAGLYN PR-15 2.00 (mass%)
Polyglyceryl oleate 2 0.50
(B) Sodium glutamate 1.00
Purified water 5.00
(C) Mineral oil 10.00
Triethylhexanoin 5.00
(D) Glycerin 8.00
Magnesium chloride 0.75
Branched C18 phosphate 2.50
Branched C16 phosphate 2.50
Arginine 1.00
Sodium hydroxide 0.75
Preservative Appropriate amount Purified water Remaining amount preparation method: Warm dissolve all phases individually. Add Phase B to Phase A with stirring. Add Phase A + B to Phase C with stirring and mix uniformly. Phase D is gradually added thereto, and after stirring and cooling to room temperature, the preparation is completed.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.

BB cream (A) NIKKOL Nikomurus WO 6.0 (mass%)
Cyclopentasiloxane 30.0
KSG-16 2.0
KSP-100 2.0
Titanium oxide 10.0
Iron oxide 2.0
Talc 5.0
(B) Glycerin 10.0
Magnesium sulfate 0.3
Branched C14 phosphate 0.7
Branched C12 phosphate 0.3
Arginine 0.6
Preservative Appropriate amount Purified water Remaining amount preparation method: A and B are heated and dissolved uniformly. B is gradually added while A is being stirred. After uniform stirring, stirring and cooling to room temperature is completed.
Liquid crystal structure confirmation: Optical anisotropy was confirmed in the water phase by a polarizing microscope.
* KSG-16: (dimethicone / vinyl dimethicone) cross polymer, dimethicone * KSP-100: (vinyl dimethicone / methicone silsesquioxane) cross polymer

  The water-in-oil emulsified composition having a liquid crystal structure in the aqueous phase of the present invention or the cosmetic or skin external preparation containing the same is liquid crystal in the water phase of a water-in-oil emulsified composition that has been difficult to prepare. It is possible to provide an unprecedented new cosmetic or external skin preparation that can stably maintain the structure.

Claims (5)

A water-in-oil emulsion composition having a liquid crystal structure in an aqueous phase, wherein the aqueous phase contains the following (a) to (c) as essential components.
(A) β-branched monoalkyl phosphate (b) one or more neutralizers selected from basic amino acids, organic bases and inorganic bases (c) water The water-in-oil emulsion composition having a liquid crystal structure in an aqueous phase according to claim 1, wherein the alkyl group of the component (a) has 12 to 36 carbon atoms. The water-in-oil emulsion composition having a liquid crystal structure in an aqueous phase according to claim 1 or 2, wherein the component (a) has a monoester content of 90% or more. A cosmetic comprising a water-in-oil emulsified composition having a liquid crystal structure retained in the water phase according to any one of claims 1 to 3. The skin external preparation characterized by including the water-in-oil type emulsion composition which hold | maintained the liquid crystal structure in the water phase of any one of Claims 1-3.