Patent Application
20190029932
This application claims the priority of Japanese Patent Application No. 2016-013168 filed on Jan. 27, 2016, which is incorporated herein by reference.
The present invention relates to a ripple-phase-containing composition, an α-gel forming composition, and an external skin care composition and an α-gel composition using the same, particularly to an α-gel composition substantially (practically) formed only by polyoxyethylene surfactants.
α-Gel-containing external skin care preparations, which use α-gel formed by a higher aliphatic alcohol or a higher fatty acid and a hydrophilic surfactant, have been long used for the purpose of maintaining the emulsion stability of external skin care preparations such as cosmetics, quasi-drugs, and pharmaceutical products. Such α-gel has a high viscosity and stabilizes an external skin care preparation but has problems of causing a slimy feel during application and easily depositing crystals of a higher alcohol or a higher fatty acid over time in terms of stability (e.g., see Non-Patent Literature 1).
Additionally, the increase in the viscosity over time commonly occurs and accordingly use of a double-chain cationic surfactant as a viscosity increase inhibitor has been investigated but sufficiently good stability has not yet been achieved (e.g., see Non-Patent Literature 2).
Further, oil components and moisturizers have been blended into external skin care preparations such as cosmetics, quasi-drugs, and pharmaceutical products, for the purpose of preventing rough skin caused by the dry outdoor air. These oil components and moisturizers play a role of sebum which is lost when washed and impart to external skin care preparations with a function as an emollient agent to keep the skin soft and a moisturizing function replacing NMF (natural moisturizing factor). However, these oil components and moisturizers have a drawback of easily causing oiliness and stickiness when blended in a large amount. Particularly, when the α-gel formed by higher aliphatic alcohols or higher fatty acids and a hydrophilic surfactant was blended together for the purpose of maintaining the emulsion stability, a large amount of an aqueous phase is oriented between lamellar layers of the α-gel formed in water (e.g., see Reference Literature 3) and thus the evaporation does not easily occur, making the stickiness during application not disappear easily.
Furthermore, a water-in-oil (W/O) type external skin care preparation provides a high skin protection effect due to the occlusion effect of the oil component (e.g., see Reference Literature 4), however, the α-gel composition has never been blended into water-in-oil (W/O) type external skin care preparations so far because it is basically formed in an aqueous phase.
The present invention was made in view of the prior art, and an object thereof is to provide a ripple-phase-containing composition, an α-gel forming composition, and a composition for external skin care use using the same and an α-gel composition using the same which are refreshing during application, have a high skin-moisturizing effect after application, and have a high-stability with no crystal deposition or viscosity increase over time.
Another object is to provide a water-in-oil (W/O) external skin care preparation and an oil-in-water (O/W) external skin care preparation formulating the α-gel forming composition, which are not sticky but refreshing the skin during application even when a large amount of oil components and moisturizers are present and provide a high-emollient effect and a moisturizing effect on the skin once an applied coat is dried.
The present inventors conducted extensive studies to solve the above objects and as a result, found that a composition for external skin care use and an α-gel composition using a totally novel α-gel forming composition consisting only of polyoxyethylene surfactants without containing higher alcohols and higher fatty acids have a high skin moisturizing effect and do not have a problem of the over-time stability such as crystal deposition and a viscosity increase over time, whereby the present invention was accomplished.
More specifically, the ripple-phase-containing composition of the present invention comprises: polyoxyethylene dialkyl ester and/or polyoxyethylene dialkyl ether represented by the following formula (I), and polyoxyethylene alkyl ester and/or polyoxyethylene alkyl ether represented by the following formula (II):
wherein in the formula (I), R1 and R2 each represent a straight-chain aliphatic acid residue or a straight-chain aliphatic alcohol residue having 16 to 24 carbon atoms, and n represents an integer of 4 to 15, and in the formula (II), R represents a straight-chain aliphatic acid residue or a straight-chain aliphatic alcohol residue having 16 to 24 carbon atoms, and n represents an integer of 8 to 30.
The ripple-phase-containing composition comprises polyoxyethylene dialkyl ester and/or polyoxyethylene dialkyl ether is preferably 15 to 45% by mass based on a total amount of the polyoxyethylene surfactants.
In addition, the ripple-phase-containing composition comprises water, wherein a content of water is preferably 20 to 70% by mass in the ripple-phase-containing composition.
The α-gel forming composition according to the present invention comprises the above ripple-phase-containing composition and in addition, polyoxyethylene sterol ether represented by the following formula (III):
wherein in the formula (III), R3 represents a cholesterol and/or phytosterol residue, and n represents an integer of 5 to 30.
In the α-gel forming composition, polyoxyethylene dialkyl ester and/or polyoxyethylene dialkyl ether is preferably 15 to 50% by mass, polyoxyethylene alkyl ester and/or polyoxyethylene alkyl ether is preferably 5 to 80% by mass, and polyoxyethylene sterol ether is preferably 80% by mass or less, based on the total amount of the polyoxyethylene surfactants.
The α-gel forming composition comprises water.
The water content in the above forming composition α-gel is preferably 15 to 50% by mass in the α-gel forming composition.
The external skin care composition, according to the present invention, comprises the α-gel forming composition.
The water-in-oil external skin care composition according to the present invention comprises the external skin care composition.
In the water-in-oil external skin care composition preferably further comprises an aliphatic alcohol and/or a fatty acid.
The oil-in-water composition for external skin care use according to the present invention comprises the composition for external skin care use.
The α-gel composition according to the present invention comprises:
polyoxyethylene dialkyl ester and/or polyoxyethylene dialkyl ether represented by the following formula (I),
polyoxyethylene alkyl ester and/or polyoxyethylene alkyl ether represented by the following formula (II), and
polyoxyethylene sterol ether represented by the following formula (III):
wherein in the formula (I), R1 and R2 each represent a straight-chain aliphatic acid residue or a straight-chain aliphatic alcohol residue having 16 to 24 carbon atoms, and n represents an integer of 4 to 15,
wherein in the formula (II), R represents a straight-chain aliphatic acid residue or a straight-chain aliphatic alcohol residue having 16 to 24 carbon atoms, and n represents an integer of 8 to 30,
wherein in the formula (III), R3 represents a cholesterol and/or phytosterol residue, and n represents an integer of 5 to 30.
The ripple-phase-containing composition, the α-gel forming composition, and the α-gel composition using the same according to the present invention do not have a problem of the stability such as crystal deposition and a viscosity increase over time. And yet, the base of the composition is drying up during application and the water content is lesser to form the α-gel formed by polyoxyethylene surfactant having a similar structure, whereby these compositions are refreshing the skin during application and have a good skin moisturizing effect after application.
Additionally, the water-in-oil (W/O) external skin care preparation to which the α-gel forming composition has been blended is separated to a hydrophobic amphiphile component and a hydrophilic amphiphile component in a preparation having a high water content, wherein the hydrophobic amphiphile component is partitioned to an oil phase and the hydrophilic amphiphile component is partitioned to an aqueous phase respectively, and does not contribute to a viscosity increase as the conventional α-gels in which all components are in the aqueous phase. Consequently, the same amphiphile component can be prepared into an oil-in-water (O/W) type emulsification and a water-in-oil (W/O) type emulsification.
The hydrophobic amphiphile component and the hydrophilic amphiphile component become a single phase as water evaporates during application to finally form the α-gel. Thus, the preparation does not take in the aqueous component between the layers enabling a quick coat formation, thus leading to a refreshing feel when used.
Hereinafter, the constitution according to the present invention is described in detail.
The α-gel forming composition of the present invention comprises 2 phases of a ripple phase and a micellar phase in a region having a high-water-content, but instead, a single α-gel phase in a region having a low-water-content (
The polyoxyethylene dialkyl ester and/or ether of (I) used in the present invention preferably has a straight-chain aliphatic acid residue or a straight-chain aliphatic alcohol residue having 16 to 24 carbon atoms, and a polyoxyethylene chain is preferably 4 to 15 mol.
Examples of the commercial product include polyoxyethylene (4 mol) distearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex 200DIS), polyoxyethylene (6 mol) distearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex 300DIS), polyoxyethylene (8 mol) distearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex 400DIS), polyoxyethylene (12 mol) distearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex 600DIS), steareth-4 stearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex SWS-4), steareth-6 stearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex SWS-6), steareth-9 stearate (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex SWS-9), and polyoxyethylene (8 mol) dibehenyl ether. The binding form of the polyoxyethylene chain and the alkyl group may contain ester, ether, or both of them.
The polyoxyethylene alkyl ester and/or polyoxyethylene alkyl ether of (II) used in the present invention preferably has a straight-chain aliphatic acid residue or a straight-chain aliphatic alcohol residue having 16 to 24 carbon atoms, and a polyoxyethylene chain is preferably 8 to 30 mol.
Examples of the commercial product include polyoxyethylene (5 mol) behenyl ether (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BB-5), polyoxyethylene (10 mol) behenyl ether (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BB-10), polyoxyethylene (20 mol) behenyl ether (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BB-20), polyoxyethylene (10 mol) stearyl ether (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex 610), and polyoxyethylene (7 mol) cetyl ether (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex 107).
The polyoxyethylene sterol ether of (III) used in the present invention preferably has, as the hydrophobic group, phytosterol, cholesterol, or ergosterol, and a polyoxyethylene chain is preferably 5 to 30 mol.
Examples of the commercial product include polyoxyethylene (5 mol) phytosterol (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BPS-5), polyoxyethylene (10 mol) phytosterol (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BPS-10), polyoxyethylene (20 mol) phytosterol (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BPS-20), polyoxyethylene (30 mol) phytosterol (e.g., manufactured by Nikko Chemicals, Co., Ltd., Nikkol BPS-30), and polyoxyethylene (10 mol) cholesterol (e.g., manufactured by Nihon Emulsion Co., Ltd., Emalex CS-10).
(Ripple-Phase-Containing Composition)
In the present invention, when the ripple-phase-containing composition changing to the α-gel is formed at a low water content only by the polyoxyethylene surfactants represented by (I) and (II), the polyoxyethylene dialkyl ester and/or ether of (I) is preferably 15 to 45% by mass based on the total amount of the polyoxyethylene surfactants, and the balance is preferably the polyoxyethylene alkyl ester and/or ether of (II). Further, the water content is preferably 20 to 70% by mass in the ripple-phase-containing composition.
(Ripple Phase)
The ripple phase refers to a phase having the hydrocarbon chain part being close to a crystalline state but the membrane is curved. In the present invention, the formation of the ripple phase was confirmed by the match of scattering peak positions actually measured and scattering peak positions obtained by determining an X-ray scattering pattern indicating peak assignments of each active component concentration and calculating mathematically from the ripple phase unit cell based on a literature (*Karen P. Shaw et al., Soft Matter, 2012, 8, 1070-1078 J. Stamatoff et al., Biophys. J., 38, 217-226 (1982)), and freeze fracture TEM (FF-TEM) (
(α-Gel Phase)
The α-gel is an aggregate formed by a higher aliphatic alcohol and a hydrophilic surfactant in water, and means α-gel taking the α-structure (by Shoji Fukushima, “sechiru arukoru no butsuri kagaku” (“physical chemistry of cetyl alcohol” in English”), published by Fragrance Journal).
(Phase Behavior by Changes in Amount of Water)
The (I) to (III) components were then selected to confirm the phase behavior by changes in the amount of water. Polyoxyethylene (6 mol) distearate (manufactured by Nihon Emulsion Co., Ltd., Emalex 300DIS) was selected as (I) polyoxyethylene dialkyl ester and/or ether.
Further, polyoxyethylene (10 mol) behenyl ether (manufactured by Nikko Chemicals, Co., Ltd., Nikkol BB-10) was selected as (II) polyoxyethylene alkyl ester and/or polyoxyethylene alkyl ether.
Furthermore, (10 mol) phytosterol (manufactured by Nikko Chemicals, Co., Ltd., Nikkol BPS-10) was selected as (III) polyoxyethylene sterol ether polyoxyethylene.
When the selected components (I) to (III) are mixed in the ratio of (I):(II):(III)=1.5:6:2.5, the micellar phase and the ripple phase change to the α-gel phase along with decreasing of the water content and relatively increasing of the concentration of the active components (
For example, when the concentration of such active components is 10 to 20% by mass, the phase of the composition is 2-phases including the micellar phase of (III) component, and the ripple phase of (I) component and (II) component. The micellar phase was confirmed by phosphotungstic acid stain, and the ripple phase was confirmed from the X-ray scattering pattern described above.
Further, when the concentration of the active component is around 40% by mass, the phase is mostly the ripple phase.
And when the concentration of the active component is 60% by mass, (I) component, (11) component, and (III) component form α-phase. The α-phase was confirmed by the appearance of scattering peaks suggesting the α-gel (
Thus, (I) and (II) form the ripple phase due to a high-water-content in a product and during storage over time. And (III) forms the microemulsion (micelles) phase.
However, when the base components are drying upon and after application and when water is lower, (I) component, (II) component, and (III) component form the α-gel.
In other words, the state of the phase thereof is optional by adjusting a water content depending on the usage and purpose.
That is, the hydrophobic part of the present α-gel composition produced when a water content is high is not mixed with the hydrophilic part as a single phase but emulsified in the hydrophobic part as dissolved in the oil phase, enabling the W/O emulsification. Further, water volatilizes also in the water-in-oil (W/O) type external skin care preparation composition.
At this time, the present α-gel composition which has been separately present in the hydrophobic part and the hydrophilic part is mixed to be a single phase and form a α-gel applied coat. Thus, in the α-gel composition of the present invention, the multiphase changes occur as a water content changes which has never occurred in the conventional α-gel, due to which the water-in-oil (W/O) type external skin care preparation can be prepared. Further, when the hydrophilic part and the hydrophobic part are mixed, an oil-water interfacial tension comes to an extremely low state and thereby the composition seemingly provides good skin compatibility and a refreshing feel when used.
Additionally, in the present invention, a plurality of surfactants can be added to the essential components as needed for the purpose of adjusting the usability. Further, the α-gel of the present invention does not form a mixed micelle of the hydrophilic part and the hydrophobic part in the formulation having a lot of water, and thus the substantially same amphiphile component can be prepared into an O/W emulsification with the hydrophilic part, in addition to the W/O emulsification.
Further, in the external skin care preparation composition, any amounts of the ripple-phase-containing composition, the α-gel forming composition, and the α-gel composition using the same can be blended, but generally the total of each nonionic surfactant in the external skin care preparation is preferably 0.1% to 20%.
(Three-Component System Phase Equilibrium Diagram)
The ripple-phase-containing composition according to the present invention can be obtained by melting (1) polyoxyethylene dialkyl ester and/or ether and (II) polyoxyethylene alkyl ester and/or ether at 70 to 80° C., adding a proportion of 40 to 90% by weight of ion exchange water at 70 to 80° C., stirring and subsequently cooling.
Further, the α-gel forming composition according to the present invention can be obtained by further adding (III) polyoxyethylene sterol ether to (I) polyoxyethylene dialkyl ester and/or ether and (II) polyoxyethylene alkyl ester and/or ether, subsequently melting at 70 to 80° C., adding a proportion of 40 to 90% by weight of ion exchange water at 70 to 80° C., stirring and subsequently cooling.
As a specific example of the α-gel composition, polyoxyethylene (6 mol) distearate (manufactured by Nihon Emulsion Co., Ltd., Emalex 300DIS) was selected as (I) component. Further, polyoxyethylene (10 mol) behenyl ether (manufactured by Nikko Chemicals, Co., Ltd., Nikkol BB-10) was selected as (II) component. Additionally, polyoxyethylene (10 mol) phytosterol (manufactured by Nikko Chemicals, Co., Ltd., Nikkol BPS-10) was selected as (III) component.
A mixture of the selected (I) to (III) components were formed into a single phase at 70 to 80° C. Subsequently, ion exchange water heated to the same temperature was added in a proportion of 50% by weight, and cooled to room temperature (25° C.) to thereby obtain an α-gel composition having a surfactant active component of 50% by weight. A three-component system phase equilibrium diagram is shown in
The shaded area in
In the present invention, nonionic surfactants alone can construct the α-gel forming composition, but a higher aliphatic alcohol having 16 or more carbon atoms can also be added as needed for the purpose of adjusting the usability. Example of the higher aliphatic alcohol having 16 or more carbon atoms include cetyl alcohol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, and batyl alcohol. Further, the ratio of the polyoxyethylene dialkyl ester and/or ether to the polyoxyethylene alkyl ester and/or polyoxyethylene alkyl ether used in the present invention is preferably (7:3 to 1:9). A ratio outside this range deposits crystals, hence not suitable for the formulation. Additionally, the amount of polyoxyethylene sterol ether to the above mixture is preferably 0 to 80 wt %, and an amount more than this fails to form the α-gel even when a water content reduces during and after application.
The oil component used in the external skin care preparation of the present invention is not particularly limited, and, for example, a liquid oil and fat, a solid oil and fat, a wax, a hydrocarbon oil, a higher fatty acid, a synthetic ester oil, or a silicone oil can be suitably blended, and further some higher alcohols can also be dissolved in these oils and emulsified. The content in the α-gel-containing external skin care preparation of interest is not particularly limited, and 0.05 to 50% by mass is preferable. A content of 0.05% by mass or less results in a poor effect as the external skin care preparation, whereas a content exceeding 50% by mass causes an undesirable feel when used.
Examples of liquid fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, par chic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cotton seed oil, perilla oil, soybean oil, groundnut oil, brown real oil, torreya oil, rice bran oil, Chinese wood oil, jojoba oil, germ oil, and triglycerol.
Examples of solid fats include cacao butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef fat, mutton suet, hydrogenated beef fat, palm kernel oil, lard, beef bones fat, Japan wax kernel oil, hardened oil, hoof oil, Japan wax, and hydrogenated castor oil.
Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, insect wax, spermaceti, montan wax, bran wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether and cetyl palmitate.
Examples of hydrocarbon oils include liquid paraffin, ozocerite, squalene, pristane, paraffin, ceresin, squalane, vaseline, and microcrystalline wax.
Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA).
Examples of the synthetic ester oil include cetyl octanoate, myristyl myristate, glyceryl tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, dioctyl succinate, and tripropylene glycol dineopentanoate.
Examples of the silicone oil include chain polysiloxanes (e.g., dimethyl polysiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane); cyclic polysiloxanes (e.g., octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane), silicone resins having a three-dimensional network, silicone rubbers, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane), and acrylic silicones.
The α-gel-containing external skin care preparation of the present invention can be used, for example, in skin cosmetics, hair cleansers, skin cleansers, and hair styling products applicable to the body such as skins and hair.
The α-gel-containing external skin care preparation of the present invention can further contain, in addition to the essential components described above, components typically used in cosmetics and pharmaceutical products at a content in a range which does not affect the stability. Examples of such a component include powder components, amphoteric surfactants, ionic surfactants, nonionic surfactants, moisturizers, thickeners, coating agent, UV absorbers, sequestering agents, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, and fragrances.
Examples of powder components include inorganic powder (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metallic soap (for example, zinc myristate, calcium palimitate, and aluminum stearate), and boron nitride); organic powder (for example, polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder, polystyrene powder, styrene-acrylic acid copolymer resin powder, benzoguanamine resin powder, poly(tetrafluroethylene) powder, and cellulose powder); inorganic white family pigment (for example, zinc oxide); inorganic red family pigment (for example, iron titanate); inorganic purple family pigment (for example, mango violet, cobalt violet); inorganic green family pigment (for example, chrome oxide, chrome hydroxide, cobalt titanate); inorganic blue family pigment (for example, ultramarine, iron blue); pearl pigment (for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, argentine); metal powder pigment (for example, aluminum powder, and copper powder); organic pigment such as zirconium, barium, or aluminum lake (for example, organic pigment such as Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404, or Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, and Blue No. 1); natural pigment (for example, chlorophyll, and β-carotene).
Examples of ampholytic surfactants include imidazoline base ampholytic surfactant (for example, sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy)-2-sodium salt; and betaine base surfactant (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethyl aminoacetate betaine, alkyl betaine, amidobetaine, and sulfobetaine). Example of ionic surfactants include N-acyl methyl sodium, N-acyl glutamic acid salt, alkyl sulfate, polyoxyethylene alkyl sulfate, fatty acid soap, alkyl quaternary ammonium salt and di alkyl quaternary ammonium salt
Examples of lipophilic nonionic surfactants include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2 ethylhexylate, and diglycerol sorbitan tetra-2 ethylhexylate); glyceryl polyglyceryl fatty acids (for example, glyceryl monocotton oil fatty acid, glyceryl monoerucate, glyceryl sesquioleate, glyceryl monostearate, glyceryl α, α′-oleate pyroglutamate, and glyceryl monostearate malate); propylene glycol fatty acid esters (for example, propylene glycol monostearate); hydrogenated castor oil derivative; and glyceryl alkyl ether.
Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, and POE-sorbitan tetraoleate); POE-sorbit fatty acid esters (for example, POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit pentaoleate, and POE-sorbit monostearate), POE-glyceryl fatty acid esters (for example, POE-glyceryl monostearate; POE-glyceryl monoisostearate, and POE-glyceryl triisostearate); POE-fatty acid esters (for example, POE-distearate, POE-monodioleate, and ethyleneglycol distearate); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, and POE-cholestanol ether); pluronic types (for example, Pluronic), POE/POP-alkyl ethers (for example, POE/POP-cetyl ether, POE/POP-2-decyltetradecyl ether, POE/POP-monobutyl ether, POE/POP-hydrogenated lanoline, and POE/POP glycerin ether); tetra POE/tetra POP-ethylenediamine condensation products (for example, Tetronic); POE-castor oil hydrogenated castor oil derivatives (for example, POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamate monoisostearate diester, and POE-hydrogenated oil maleate); POE-beeswax/lanoline derivatives (for example, POE-sorbitol beeswax); alkanolamides (for example, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, and fatty acid isopropanolamide); POE-propyleneglycol fatty acid esters; POE-alkyl amines; POE-fatty acid amides; sucrose fatty acid esters; alkylethoxydimethylamine oxide; and trioleyl phosphoric acid.
Examples of natural water-soluble polymers include plant-based polymer (for example, gum Arabic, gum tragacanth, galactan, guar gum, locust bean gum, gum karaya, carrageenan, pectine, agar, quince seed (cydonia oblonga), algae colloid (brown algae extract), starch (rice, corn, potato, and wheat), and glicyrrhizic acid), microorganisms based polymer (for example, xanthan gum, dextran, succinoglycan, and pullulan), animal-based polymer (for example, collagen, casein, and albumin, gelatine).
Examples of semisynthetic water-soluble polymers include starch-based polymer (for example, carboxymethyl starch, and methylhydroxypropyl starch), cellulosic polymer (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, cellulose sodium sulfate, hydroxypropylcellulose, carboxymethylcellulose, sodium calboxymethyl cellulose, micrclrystalline cellulose, and cellulose powder), alginic acid base polymer (for example, sodium alginate, and propylene glycol ester alginate) and sodium pectate.
Examples of synthetic water-soluble polymers include vinyl base polymer (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, and carboxyvinylpolymer); polyoxyethylene base polymer (for example, polyethylene glycol 20,000, 40,000, and 60,000); Poly (dimethyldiallylammonium halide) type cationic polymer (for example, Merquat100 Merck U.S.A Co. ltd); Copolymerizable type cationic polymers of dimethyldiallylammonium halide and acrylamide (for example Merquat550 Merck U.S.A Co. ltd,); acrylic polymer (for example, sodium polyacrylate, polyethylacrylate, and polyacrylamide); polyethyleneimine; cationpolymer and magnesium aluminum silicate.
Examples of ultraviolet light absorbers include benzoic acid family ultraviolet light absorbers (for example, p-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerine ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, and N,N-dimethyl PABA ethyl ester); anthranilic acid family ultraviolet light absorbers (for example, homomenthyl N-acetylanthranilate); salicylic acid family ultraviolet light absorbers (for example, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate); cinnamic acid family ultraviolet light absorbers (for example, octyl cinnamate, ethyl 4-isopropylcinnamate, methyl 2,5-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, methyl 2,4-diisopropylcinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), 2-ethoxyethyl p-methoxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyl-diparamethoxy cinnamate); benzophenone family ultraviolet light absorbers (for example, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, and 4-hydroxy-3-carboxybenzophenone); 3-(4′-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor; 2-phenyl-5-methylbenzoxazol; 2,2′-hydroxy-5-methylphenylbenzotriazol; 2-(2′-hydroxy-5′-t-octylphenyl) benzotriazol, 2-(2′-hydroxy-5′-methylphenylbenzotriazol; dibenzalazine; dianisoylmethane; 4-methoxy-4′-t-butyldibenzoylmethane; and 5-(3,3-dimethyl-2-norbornylidene)-3-pentane-2-one.
Example of sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid and ethylenediamine hydroxyethyl triacetate trisodium.
Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of the vitamin include vitamins A, B1, B2, B6, C, E, and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisol, and gallic acid esters.
Examples of anti-oxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexamethaphosphate, phytic acid, and ethylene diamine tetra-acetic acid.
Examples of other blendable components include antiseptic agent (ethylparaben, butylparaben, etc.); lightening agent (for example, placental extract, saxifrage extract, and arbutin); blood circulation promotion agent (for example, nicotine acid, nicotine acid benzyl, tocopherol nicotinate, nicotine acid β-butoxy ester, minoxidil, or their analogs, vitamine E type, γ-oryzanol, alkoxycarbonylpyridine N-oxide, capronium chloride, acetylcholine and their derivatives); various extract (for example, ginger, oat, Japanese coptis, lithospermum, birch, loquat, carrot, aloe, mallow, iris, grape, sponge gourd, lily, saffron, cnidium rhizome, ginger, hypericum, restharrow, garlic, red pepper, citrus unshiu, Japanese angelica, Japanese tree peoney, and seaweed); activator agent (for example, pantothenyl ethyl ether, nicotinamide, biotin, pantothenic acid, royal jelly, and cholesterol derivative); and antiseborrheric agent (for example, pyridoxine, and thianthl).
Further, fragrances, scrubbing agents, and the like can suitably be blended in a range which does not affect the stability.
Hereinafter, the present invention is described in further detail in reference with Examples, but not limited thereto. The content is all shown in % by mass, unless specifically stated otherwise.
First of all, absence of the α-gel of the present invention in a formulation having a high-water-content is described in reference with test results. Assuming the situation where water volatilizes and dries, each of the compositions shown in Table 1 was prepared respectively at 75° C. using a common α-gel consisting of stearoyl N-sodium methyltaurate and behenyl alcohol and a α-gel preparation containing polyoxyethylene (10 mol) phytosterol (tradename: Nikkol BPS-10): polyoxyethylene (6 mol) distearate (tradename: Emalex 300DI-S): polyoxyethylene (10 mol) behenyl ether (tradename: Nikkol BB-10) (6:2:2).
In the compositions of Table 1, compositions in the table entry described as α-gel component are shown in Table 2. Both have the same contents of the total α-gel active component.
Further,
(Feel of O/W Emulsion Containing the α-Gel Forming Composition when Used)
An O/W emulsion containing the α-gel forming composition of Example 1 containing the polyoxyethylene surfactants based α-gel forming composition according to the present invention (polyoxyethylene (6 mol) distearate, polyoxyethylene (10 mol) behenyl ether, and polyoxyethylene (10 mol) phytosterol) and an emulsion containing the α-gel of Comparative Example 1 using a common higher alcohol based α-gel (behenyl alcohol, stearyl alcohol, and sodium N-stearoyl methyltaurate) were respectively prepared by a routine method. The amounts of components constituting the α-gels were the same, and other components and the amounts of components were identical.
For the use test, proper doses of Example 1 and Comparative Example 1 were respectively applied to half each of the face by 6 trained panelists and feels of use of Example 1 compared to Comparative Example 1 were evaluated on 5 scales for each evaluation entry. Evaluation score 0 was the feel of use equivalent to that of Comparative Example 1.
2H2O
(Results)
Results are shown in
(Viscosity Stability Test)
Further, the O/W emulsion containing the α-gel forming composition of Example 1 and the external skin care preparation containing the α-gel of Comparative Example 1 were respectively compared for the viscosity stability.
(Comparison on the Viscosity Stability)
The samples of Example 1 and Comparative Example 1 were stored each at 0 to 50° C., the viscosity over time was retained at 30° C. for 30 minutes or longer, and subsequently measured using a B type viscometer (rotor No. 2 or No. 3, 6 rpm, 1 minute). The measured
As is evident in Table 5, the emulsion of Example 1 was revealed to have maintained constant viscosity compared to Comparative Example 1. This is because in Comparative Example 1 the higher aliphatic alcohol, which is the constituting component of the α-gel causing the viscosity, is dissolved in the oil phase and sodium N-stearoyl methyltaurate is dissolved in the aqueous phase wherein the higher aliphatic alcohol present in the oil phase flows out into the aqueous phase and gradually mixes with sodium N-stearoyl methyltaurate to thereby increase the viscosity, whereas the α-gel forming composition of the present invention is constituted with the nonionic surfactants all having similar solubilities.
(Feel of W/O Emulsion Containing the α-Gel Forming Composition when Used)
A W/O cream containing the ca-gel forming composition of Example 1 containing polyoxyethylene (6 mol) distearate, polyoxyethylene (10 mol) behenyl ether, polyoxyethylene (10 mol) phytosterol, and polyoxyethylene (10 mol) behenyl ether, and other 3 different kinds of W/O creams were respectively prepared by a routine method.
For the use test, sensory evaluations were carried out when each of the W/O creams was applied by 10 trained panelists and average values obtained by evaluating on 5 scale scores are shown in the table.
As is evident in Table 6, the W/O cream containing the α-gel forming composition of the present invention was revealed to have been sensed having a less sticky feel and quick skin compatibility compared to the W/O creams obtained by other emulsification methods.
(Moisturizing (Occlusion) Effect Test)
Further, the skin moisturizing effects of the W/O creams of Example 1 and Comparative Examples 1 to 3 were evaluated as the occlusion effect. More specifically, each formulation was homogeneously applied to a filter paper in a rate of 5 mg/cm2 and allowed to stand for 1 day. In a thermo-hygrostat (23° C., relative humidity=45%), 5 mL of water was placed in a 25 mL vial, immediately the filter paper was inserted and fixed with the cap of the vial, and an amount of water evaporated was measured successively. The amount of water evaporated per hour (attenuation wt %) was defined as water evaporation rate constant (%/hour). Thus, the smaller a water evaporation rate constant (%/hour) is, the higher the ability to retain water is.
As is evident in Table 7, the W/O cream containing the α-gel forming composition of the present invention (Example Formulation 1) was revealed to have a higher occlusion effect compared to the W/O creams obtained by other emulsification methods (Comparative Examples 1 to 3).
Hereinafter, the present invention is further described in reference with Examples, but is not limited thereto.
(Production Method)
The emulsification was carried out by a routine method to obtain the above emulsion. The obtained emulsion was not slimy but refreshing when used and had good viscosity stability.
(Production Method)
The emulsification was carried out by a routine method to obtain the above serum. The obtained serum was not slimy but refreshing when used and had good viscosity stability.
(Production Method)
The emulsification was carried out by a routine method to obtain the above emulsion. The obtained emulsion was not slimy but refreshing when used and had good viscosity stability.
(Production Method)
The emulsification was carried out by a routine method to obtain the above sun block cream. The obtained sun block cream was not slimy but refreshing when used, and had good viscosity stability.
(Production Method)
The emulsification was carried out by a routine method to obtain the cream. The obtained cream was not slimy but refreshing when used, and had good viscosity stability.
(Production Method)
The emulsification was carried out by a routine method to obtain the sun block cream. The obtained sun block cream was not sticky but refreshing when used, and had good stability.
(Production Method)
The emulsification was carried out by a routine method to obtain the cream. The obtained cream was not sticky but refreshing when used, and had good stability.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-013168 | Jan 2016 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2017/003070 | 1/27/2017 | WO | 00 |
