Patent Application
20110274731
This application claims the priority of Japanese Patent Application No. 2009-5531 filed on Jan. 14, 2009, which is incorporated herein by reference.
The present invention relates to a production method of a fine O/W emulsion external preparation. In particular, it relates to a simple and economical production method and to improvement in stability of a fine O/W emulsion external preparation.
In the past, in order to maintain the emulsion stability of skin external preparations such as cosmetics, quasi-drugs, and pharmaceuticals, O/W emulsion compositions with the use of an α-gel, which is formed from a higher aliphatic alcohol and a polyoxyethylene-type nonionic surfactant, have been used and known especially for use as external preparations. As the preparation method of such an O/W emulsion external preparation, the following method has been used: a moisturizer and a hydrophilic polyoxyethylene-type nonionic surfactant are dissolved in water and heated to about 70° C. to prepare a water phase; an oil component and a higher alcohol, as essential components, were homogeneously mixed at about 70° C. to prepare an oil phase; the oil phase is emulsified by stirring with a homogenizer into the water phase; and the emulsion is rapidly cooled with a cooling machine such as an Onlator to about 35° C. (for example, refer to Non-patent Literature 1).
However, the thus far investigated method comprising emulsification at 70° C. followed by cooling has issues in that not only the method is energetically wasteful but also a large amount of water is used during washing after the use of a cooling machine such as an Onlator. In addition, it is difficult to prepare an emulsion having the particle size of 1 μm or less. In recent years, a low-energy emulsification technology has been sought-after because of increased environmental awareness.
Accordingly, the development of an O/W emulsion external preparation that can be economically and easily produced without using a conventional cooling apparatus such as an Onlator, and has long-term stability and smaller particle sizes, has been awaited.
The present invention was made in view of the above-described situation of the conventional art. The problems to be solved are to provide a simple and economical production method of a fine O/W emulsion external preparation and to provide a fine O/W emulsion external preparation excellent in stability.
In view of the above-described problems, the present inventors have diligently repeated studies. As a result, the present inventors have found that a fine O/W emulsion external preparation having the emulsion particle size of 50 to 500 nm with excellent stability can be produced without using a cooling apparatus such as an Onlator. This was achieved by mixing with stirring a specific composition at 70 to 80° C. to prepare a W/O emulsion and then by adding water or an aqueous formulation at 10 to 35° C. to the W/O emulsion while mixing with stirring to invert the W/O emulsion into a fine O/W emulsion. Furthermore, the present inventors have found that the obtained fine O/W emulsion can provide a light and fresh feeling during application but a moist and rich texture after application, though these properties could not be achieved by the conventional preparation method with the use of the Onlator, thus leading to completion of the present invention.
That is, the production method of a fine O/W emulsion external preparation of the present invention is a production method of a fine O/W emulsion external preparation having the emulsion particle size of 50 to 500 nm comprising the steps of:
mixing with stirring, at 70 to 80° C.,
adding, while mixing with stirring, (F) water or an aqueous formulation at 10 to 35° C. into the W/O emulsion to invert the W/O emulsion to a fine O/W emulsion.
In the production method of a fine O/W emulsion external preparation, it is preferable that the HLB of (A) the hydrophilic nonionic surfactant is 8 or higher.
In any of the production methods of a fine O/W emulsion external preparation, it is preferable that the mass ratio of (A) the hydrophilic nonionic surfactant and (B) the linear higher alcohol having 16 or more carbon atoms is 3:7 to 7:3.
In any of the production methods of a fine O/W emulsion external preparation, it is preferable that (C) the oil component is 1 to 40 mass % in the W/O emulsion.
In any of the production methods of a fine O/W emulsion external preparation, it is preferable that (D) the aqueous solvent is 5 mass % or higher in the W/O emulsion.
In any of the production methods of a fine O/W emulsion external preparation, it is preferable that (D) the aqueous solvent has three or less hydroxyl groups in the molecule.
In any of the production methods of a fine O/W emulsion external preparation, it is preferable that (D) the aqueous solvent is one or more selected from the group consisting of polypropylene glycol polyethylene glycol copolymer or its dimethyl ether, polyethylene glycol or its alkyl ethers, dipropylene glycol, isoprene glycol, and propylene glycol.
According to the production method of a fine O/W emulsion external preparation of the present invention, the emulsion can be easily produced with low-energy without using a cooling machine such as an Onlator; thus it is very economical. In addition, the fine O/W emulsion external preparation, produced by the production method of the present invention, is essentially obtained by emulsification only with a nonionic surfactant whose irritation to the human body is relatively small; thus, it is very safe to the human body. Furthermore, the particle size of the fine O/W emulsion external preparation, produced by the production method of the present invention, is very small ranging 50 to 500 nm; nevertheless, the stability is excellent, in addition, when compared with the O/W emulsion produced with the use of a cooling machine such as an Onlator, the present external preparation, regardless of the identical formulation, provides light and fresh feeling but also provides a rich feeling.
Hereinafter, the constitution of the present invention will be described in detail.
The fine O/W emulsion external preparation of the present invention is prepared by the emulsification method comprising the steps of:
mixing with stifling, at 70 to 80° C.,
adding, while mixing with stirring, (F) water or an aqueous formulation at 10 to 35° C. into the W/O emulsion to invert the W/O emulsion to a fine O/W emulsion,
wherein the emulsion particle size of the fine O/W emulsion is 50 to 500 nm.
In the present invention, the “fine O/W emulsion” is an emulsion system consisting of two liquid phases (in which the oil phase is emulsified in the water phase) for a water-surfactant-oil system. It is a thermodynamically unstable composition in which the emulsion particles are very fine to the extent that the emulsion is translucent or faint blue-white color.
(A) a hydrophilic nonionic surfactant used in the present invention is not limited in particular; however, it is the hydrophilic nonionic surfactant which can be soluble in the aqueous solvent by micellar dissolution. In particular, the hydrophilic nonionic surfactant having the HLB of 8 or higher is preferable. If the HLB of (A) the hydrophilic nonionic surfactant is smaller than 8, the preferable formation of the fine O/W emulsion may not be achieved.
Examples of (A) a hydrophilic nonionic surfactant used in the present invention include polyoxyethylene glycerol fatty acid esters, polyoxyethylene methylpolysiloxane copolymer, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, maltitol hydroxy aliphatic alkyl ethers, alkylated polysaccharides, alkyl glucosides, sucrose fatty acid esters, and polyoxyethylene hydrogenated castor oil. Preferable examples thereof include polyoxyethylene-added nonionic surfactants. Two or more hydrophilic nonionic surfactants can be used.
As (B) a linear higher alcohol having 16 or more carbon atoms used in the present invention, those normally usable in the external preparations such as cosmetics and pharmaceuticals may be appropriately used, and two or more can be used in combination. Preferable examples thereof include saturated or unsaturated linear higher alcohols having 16 to 24 carbon atoms, such as cetyl alcohol, stearyl alcohol, behenyl alcohol, and batyl alcohol.
The mass ratio of (A) the hydrophilic nonionic surfactant and (B) the linear higher alcohol having 16 or more carbon atoms used in the present invention is not limited in particular; however, it is preferable that the ratio in the W/O emulsion is 7 to 7:3. If the ratio deviates from this range, a stable fine O/W emulsion may not be formed.
The amount of (A) the hydrophilic nonionic surfactant and (B) the linear higher alcohol having 16 or more carbon atoms is not limited in particular; however, it is preferable that the sum of (A) the hydrophilic nonionic surfactant and (B) the linear higher alcohol having 16 or more carbon atoms in the W/O emulsion is 0.5 to 10 parts by mass with respect to the 10 parts by mass of (C) the oil component. If the amount is less than 0.5 parts by mass, the amount of surfactant and higher alcohol is too small, whereby a fine O/W emulsion with high stability may not be obtained. If the amount exceeds 10 parts by mass, the amount of surfactant and higher alcohol is too much, whereby the usability tends to be undesirable.
(C) the oil component used in the present invention is not limited in particular and the oil components normally usable in the external preparations such as cosmetics and pharmaceuticals can be appropriately used. Examples thereof include silicone oils, hydrocarbon oils, ester oils, liquid fats, solid fats, waxes, higher fatty acids and higher alcohols (excluding the above-described (B)). Two or more of these may also be used in combination.
Examples of silicone oils include: linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; silicone resins having three-dimensional network structure; silicone rubber; and various modified polysiloxanes such as amino-modified polysiloxanes, pnlyether-modified polysiloxanes, alkyl-modified polysiloxanes, and fluorine-modified polysiloxanes.
Examples of hydrocarbon oils include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
Examples of synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, acetylated lanolin, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid esters, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythrityl tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceryl tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, di-2-hexyldecyl adipate, diisopropyl sebacate, di-2-ethylhexyl succinate, and triethyl citrate.
Examples of liquid fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, china paulownia oil, Japanese paulownia oil, jojoba oil, germ oil, and triglycerin.
Examples of solid fats include cacao butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, mutton tallow, hydrogenated beef tallow, palm kernel nil, lard beef bone fat, Japan wax kernel nil, hydrogenated oil, neat's-foot oil, Japan wax, and hydrogenated castor oil.
Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, spermaceti wax, montan wax, rice bran wax, lanolin, kapok wax, acetylated lanolin, lanolin oil, sugar cane wax, lanolin fatty acid isopropyl ester, hexyl laurate, hydrogenated lanolin, jojoba wax, lanolin wax, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA).
Examples of higher alcohols include: linear alcohols such as lauryl alcohol, and myristyl alcohol; and branched-chain alcohols such as 2-decyltetradecynol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, and octyldodecanol.
The concentration of (C) the oil component used in the present invention is not limited in particular; however, it is preferable that the concentration is 1 to 40 mass % with respect to the total amount of the W/O emulsion. If the concentration exceeds 40 mass %, it is difficult to obtain a W/O emulsion with high stability.
(D) the aqueous solvent used in the present invention means a substance that is liquid at room temperature and miscible with water. In addition, it is necessary that , the aqueous solvent is immiscible with (C) the oil component and the critical micelle concentration (c.m.c.) of (A) the hydrophilic nonionic surfactant in the aqueous solvent is higher than that in water. Such (D) an aqueous solvent can lower the melting point of α-gel that is formed of (A) a hydrophilic nonionic surfactant and (B) a higher alcohol. Thus, when the W/O emulsion is prepared at 70 to 80° C. together with (D) an aqueous solvent and then (F) water or an aqueous formulation at 10 to 35° C. was added and mixed to the W/O emulsion, a fine stable O/W emulsion can easily be obtained without gelation. When such (D) an aqueous solvent is not used, when (D) an aqueous solvent is with (C) an oil component, or when the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant in the aqueous solvent is lower than that in water, a stable fine O/W emulsion cannot be obtained even if all other conditions are met.
(D) the aqueous solvent is not limited in particular if it is as those described above, and it is appropriately selected for use from publicly known aqueous solvents in accordance with the kinds of (C) an oil component and (A) a hydrophilic nonionic surfactant.
For an aqueous solvent, whether the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant in the aqueous solvent is higher than that in water is determined by comparing the two critical micelle concentrations (c.m.c.) after measuring the critical micelle concentration (c.m.c.) of (A) the hydrophilic nonionic surfactant under the two conditions, namely in the aqueous solvent and in water. In many cases of aqueous solvents, however, it is very difficult to measure the critical micelle concentration (c.m.c.) of a hydrophilic nonionic surfactant in an aqueous solvent alone. In such cases, an aqueous solvent-water solution is prepared by adding a suitable amount of an aqueous solvent into water, the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant is measured under the two conditions, namely in the aqueous solvent-water solution and in water (alone), and then both results may be compared. If the value of the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant in the aqueous solvent-water solution is higher than the value of the critical micelle concentration (c.m.c.) in water, it can be determined that the aqueous solvent provides a higher critical micelle concentration (c.m.c.) of (A) the hydrophilic nonionic surfactant therein than that in water.
More specifically, an aqueous solvent is dissolved in water to be 10% to prepare an aqueous solvent-water solution, and when the value of the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant in the 10% aqueous solvent-water solution is higher than the value of the critical micelle concentration (c.m.c.) in water by 30% or more, it can be determined that the aqueous solvent provides a higher critical micelle concentration (c.m.c.) of (A) the hydrophilic nonionic surfactant therein than that in water.
For example, when (A) the hydrophilic nonionic surfactant is POE(5) dodecyl ether, the critical micelle concentration (c.m.c.) in 10% POE(17) POP(4) dimethyl ether-water solution is 1.2×10−4 mol/L at 25° C., which is 84% higher than the critical micelle concentration in water, 6.5×10−5 mol/L. Thus, it can be said that POE(17) POP(4) dimethyl ether is an aqueous solvent that provides a higher critical micelle concentration (c.m.c.) of (A) the hydrophilic nonionic surfactant therein than that in water.
Furthermore, it is preferable that (D) an aqueous solvent used in the present invention provides a higher critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant therein. Specifically, it is preferable that the value of the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant in 10% aqueous solvent-water solution is higher than the value of the critical micelle concentration (c.m.c.) in water by 50% or more.
Specific examples of (D) an aqueous solvent used in the present invention include aqueous solvents having three or less hydroxyl groups in the molecule. More specific examples include poly-(C2-C4)alkylene glycol copolymer or its (C1-C5)alkyl ethers such as polypropylene glycol (1 to 20 mol) polyethylene glycol (5 to 30 mol) copolymer or its (C1 to C5)alkyl ethers and polyethylene glycol (1 to 50 mol) or its (C1-C5)alkyl ethers, polyoxy-(C2-C4)alkylene (2 to 30 mol) di-(C1-C5)alkylcarboxylates, 1,3-butylene glycol, dipropylene glycol, isoprene glycol, 1,2-pentane glycol, 1,2-hexane glycol, 2-methyl-1,3-propanol, ethyl carbitol, 1,2-butylene glycol, and glycerin. From these, (D) an aqueous solvent can be appropriately selected for use in accordance with the kinds of (C) an oil component and (A) a hydrophilic nonionic surfactant. Furthermore, as (D) an aqueous solvent of the present invention, two or more of these can be used in combination.
Examples of preferable aqueous solvents include polypropylene glycol (1 to 20 mol) polyethylene glycol (5 to 30 mol) copolymer or its dimethyl ether, polyethylene glycol (5 to 30 mol) or its (C1 to C2)alkyl ethers, dipropylene glycol, isoprene glycol, and propylene glycol.
On the other hand, a water-soluble substance having four or more hydroxyl groups in the molecule normally becomes a solid at room temperature, and often cannot be used as (D) an aqueous solvent of the present invention.
The amount of (D) an aqueous solvent used in the present invention is not limited in particular; however, it is preferably 5 mass % or more with respect to the intermediate W/O emulsion. If the amount is less than 5 mass %, the preparation of a stable fine O/W emulsion tends to be difficult.
With respect to the combination of (C) an oil component and (D) an aqueous solvent used in the present invention, it is necessary that (D) an aqueous solvent is immiscible with (C) an oil component. Examples of such combinations are as follows:
When (C) the oil component is dimethylpolysiloxane, (D) the aqueous solvent is polypropylene glycol polyethylene glycol copolymer or its dimethyl ether, polyethylene glycol or its ethyl ether, 1,3-butylene glycol, dipropylene glycol, isoprene glycol, etc.
When (C) the oil component is cyclodimethicone (pentamer), (D) the aqueous solvent is polypropylene glycol polyethylene glycol copolymer or its dimethyl ether, polyethylene glycol or its ethyl ether, etc.
When (C) the oil component is methylphenylpolysiloxane, (D) the aqueous solvent is polypropylene glycol polyethylene glycol copolymer or its dimethyl ether, 1,3-butylene glycol, glycerin, etc.
When (C) the oil component is liquid paraffin, (D) the aqueous solvent is polypropylene glycol polyethylene glycol copolymer or its dimethyl ether, polyethylene glycol or its ethyl ether, 1,3-butylene glycol, dipropylene glycol, isoprene glycol, etc.
The amount of (E) water used in the present invention needs to be adjusted to 5 to 25 weight % with respect to the total amount of the intermediate W/O emulsion. If the amount is less than 5 weight %, the emulsion particle size of the final fine O/W emulsion is large. If the amount exceeds 25 weight %, the advantage of low-energy preparation is lost.
In addition, the increasing value of the critical micelle concentration (c.m.c.) of (A) a hydrophilic nonionic surfactant in (D) an aqueous solvent, the amount of (E) water necessary for the production of the intermediate W/O emulsion tends to be smaller.
The fine O/W emulsion external preparation of the present invention is obtained by preparing a W/O emulsion, at about 70 to 80° C., containing the above-described (A) to (E) as the essential components, and then adding (F) water or an aqueous formulation at 10 to 35° C. to the W/O emulsion.
(F) water or an aqueous formulation used in the present invention is not limited in particular so far as the main medium thereof is water or an aqueous solvent. In addition to water or an aqueous solvent, the components normally used in cosmetics, pharmaceuticals, etc. can be blended thereto in the quantity range that the stability is not affected.
The final amount of water in the fine O/W emulsion external preparation of the present invention is the sum of the amount of (E) water used for the formation of the W/O emulsion and the amount of water contained in (F) water or an aqueous formulation. The total amount of water used in the present invention is not limited in particular. Generally, the total amount of water is preferably 40 to 95 weight % with respect to the total amount of the fine O/W emulsion external preparation.
Furthermore, the temperature of (F) water or an aqueous formulation is preferably at 10 to 35° C. and more preferably at 15 to 35° C. If the temperature is less than 10° C., the emulsion particle size in the fine O/W emulsion external preparation is large, whereby the effect of the invention tends to be impaired. If the temperature exceeds 35° C., the stability immediately after the production of the fine O/W emulsion external preparation tends to be poor.
Hereinafter, the concept of the production method of a fine O/W emulsion external preparation of the present invention will be explained.
In the present invention, a W/O emulsion is obtained by mixing with stirring, at 70 to 80° C., (A) a hydrophilic nonionic surfactant, (B) a linear higher alcohol having 16 or more carbon atoms, (C) an oil component, (D) an aqueous solvent that is freely soluble in water and provides a higher critical micelle concentration (c.m.c.) of the hydrophilic nonionic surfactant in the aqueous solvent than that in water, and (E) water in the amount of 5 to 25 weight % of the total amount of (A) to (E).
When (F) water or an aqueous formulation at 10 to 35° C. is gradually added to the W/O emulsion with stirring, as shown by the direction of the arrow in
The particle size of the obtained fine O/W emulsion external preparation is very small ranging 50 to 500 nm. Nevertheless, the external preparation is stable in a wide temperature range for a long period.
If a W/O emulsion is prepared, by mixing with stirring, at a lower temperature than 70 to 80° C., the gelation takes place because the temperature is lower than the melting point of α-gel (temperature at the top of the gelation region in
In the W/O emulsion preparation process in the method of the present invention, a specific (D) aqueous solvent is blended in order to lower the melting point of the α-gel and decrease the viscosity. When such a specific (D) aqueous solvent is not blended, the gelation region is large and the melting point of α-gel is high, compared with when such a specific (D) aqueous solvent is blended. In such a case, when a hydrophobic W/O emulsion is prepared at a high temperature, 70 to 80° C., and (F) water or an aqueous formulation at 10 to 30° C. is added to the W/O emulsion, the gelation takes place during the passage through the gelation region: thus, even if more (F) water or an aqueous formulation is added afterwards, a stable fine O/W emulsion of the present invention cannot be obtained anymore.
In the conventional O/W emulsion production method, as shown in
On the other hand, in the case of the fine O/W emulsion external preparation obtained by the production method of the present invention, the use of a cooling machine such as an Onlator and the heating of a large amount of (F) water or an aqueous formulation are not necessary during emulsification: thus, the O/W emulsion can be easily produced with low energy. In addition, since the O/W emulsion is substantially obtained by emulsification only with a nonionic surfactant whose irritation to the human body is relatively small, it has excellent safety. Furthermore, the O/W emulsion provides a light and fresh but also rich feeling in use, compared with the O/W emulsion produced from the identical components with the use of a cooling machine such as an Onlator: thus it has excellent usability.
As mentioned above, in the production method of a fine O/W emulsion external preparation of the present invention, an excellent fine O/W emulsion external preparation can be obtained only by blending water or an aqueous formulation to a pre-produced W/O emulsion; thus the conventional production process can be drastically simplified.
The fine O/W emulsion external preparation of the present invention can be used as products that can be applied to the body parts such as the skin and hair such as skin cosmetics, hair cleanser, skin cleanser, and hair styling preparations.
Furthermore, in the fine O/W emulsion external preparation of the present invention, in addition to the above-described essential components, the components normally used in cosmetics, pharmaceuticals, etc. can be blended in the quantity range that the stability is not affected. Examples of such components include the following.
Oil components such as avocado oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, evening primrose oil, castor oil, sunflower oil, tea seed oil, rice bran oil, jojoba oil, cacao butter, coconut oil, squalene, beef tallow, Japan wax, beeswax, candelilla wax, carnauba wax, spermaceti wax, lanolin, liquid paraffin, polyoxyethylene (8 mol) oleyl alcohol ether, and glyceryl monooleate.
Higher alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cholesterol, and phytosterol.
Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, and linolenic acid.
Moisturizers such as polyethylene glycol and its alkyl ethers, glycerin, sorbitol, xylitol, maltitol, mucopolysaccharides, hyaluronic acid, chondroitin sulfate, and chitosan.
Thickeners such as methylcellulose, ethylcellulose, gum arabic, and polyvinyl alcohol.
Organic solvents such as ethanol and 1,3-butylene glycol.
Antioxidants such as butylhydroxytoluene, tocopherol, and phytic acid.
Antimicrobial preservative agents such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid ester (ethylparaben, butylparaben, etc.), and hexachlorophene.
Amino acids such as glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, and histidine; and their hydrochlorides.
Organic acids such as acyl sarcosinic acid (for example, sodium lauroyl sarcosinate), glutathione, citric acid, malic acid, tartaric acid, and lactic acid.
Vitamins including: vitamin A and its derivatives; vitamin Bs such as vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, and vitamin B15 and its derivatives; vitamin Cs such as ascorbic acid, ascorbyl phosphate (its salts), and ascorbyl dipalmitate; vitamin Es such as α-tocopherol, β-tocopherol, γ-tocopherol vitamin E acetate, and vitamin E nicotinate; vitamin Ds; vitamin H; pantothenic acid; and pantethine. Various agents such as nicotinic acid amide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizic acid (its salts), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucalyptol, thymol, inositol, saponins (saikosaponin, ginseng saponin, luffa cylindrica saponin, sapindus mukorossi saponin, etc.), pantothenyl ethyl ether, ethinylestradiol, tranexamic acid, cepharanthine, and placenta extract.
Natural extracts, obtained by extraction with a solvent such as organic solvents, alcohols, polyhydric alcohols, water and aqueous alcohols, from materials such as sorrel, Sophora flavescens Aiton, cow lily, orange, sage, thyme, yarrow, mallow, cnidium root, Swertia japonica, Angelica acutiloba, spruce, birch, field horsetail, Luffa cylindrica, horse chestnut, saxifrage, arnica, lily, mugwort, peony, aloe, gardenia, sawara cypress, etc.
Cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, and laurylamine oxide.
Sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, and gluconic acid.
In addition, powder components, anionic surfactants, amphoteric surfactants, water-soluble polymers, thickeners, film-forming agents, UV absorbers, whitening agents, perfumes, scrubbing materials, etc. may be appropriately blended so far as the stability is not impaired.
Hereinafter, the present invention will be explained in further detail by the examples of the fine O/W emulsion external preparations of the present invention. However, the present invention is not limited by these examples.
(1) A composition containing 5.5 mass % of polyoxyethylene (60 mol) glyceryl isostearate (manufactured by Nihon Emulsion Co., Ltd., EMALEX GWIS-160 (HLB19)) as (A) a hydrophilic nonionic surfactant, 4.5 mass % of deodorized cetanol (manufactured by Kokyu Alcohol Kogyo Co., Ltd.) as (B) a linear higher alcohol having 16 or more carbon atoms, 10 mass % of liquid paraffin (manufactured by Nippon Oil Corporation, liquid paraffin E) as (C) an oil component, 5 mass % of dipropylene glycol as (D) an aqueous solvent, and 5 mass % of (E) water was heated to 70° C. and mixed with stirring, to obtain W/O emulsion.
(2) Subsequently, (F) 70 mass % of water at 20° C. was gradually added to the W/O emulsion obtained in the above-described (1) while being stirred, thereby obtaining a faint blue-white fine O/W emulsion (Production Example 1-1).
When 20 mass % of water was added, the composition changed to a faint blue-white fine O/W emulsion.
A 400 times magnification micrograph of the fine O/W emulsion of Production Example 1-1 is shown on the left side in
(1) 5.5 mass % of polyoxyethylene (60 mol) glyceryl isostearate (manufactured by Nihon Emulsion Co., Ltd., EMALEX GWIS-160 (HLB19)) as (A) a hydrophilic nonionic surfactant, 5 mass % of dipropylene glycol as (D) an aqueous solvent, and 75 mass % of (E) water were heated to 70° C. and uniformly mixed.
(2) 4.5 mass % of deodorized cetanol (manufactured by Kokyu Alcohol Kogyo Co., Ltd.) as (B) a linear higher alcohol having 16 or more carbon atoms and 10 mass % of liquid paraffin (manufactured by Nippon Oil Corporation, liquid paraffin) as (C) an oil component were heated to 70° C. and uniformly mixed.
(3) The component (2) was added and emulsified into the component (1) at 70° C. while stirring with a homogenizer to prepare an O/W emulsion. The obtained O/W emulsion was passed through an Onlator to be cooled to 35° C., thereby finally obtaining an O/W emulsion.
A 400 times magnification micrograph of the O/W emulsion of the Comparative Example 1-1 is shown on the right side in
Except for the use of 5 mass % of polyoxyethylene (14 mol) polyoxypropylene (7 mol) copolymer dimethyl ether as (D) an aqueous solvent, a similar operation to that of Production Example 1-1 was carried out, to obtain a faint blue-white fine O/W emulsion (Production Example 1-2).
When 25 weight % of (E) water was added, the composition changed to a stable fine O/W emulsion.
A 400 times magnification micrograph of the fine O/W emulsion of the Production Example 1-2 is shown on the left side in
Except for the use of 5 mass % of polyoxyethylene (14 mol) polyoxypropylene (7 mol) copolymer dimethyl ether as (D) an aqueous solvent, a similar operation to that of Comparative Example 1-1 was carried out.
A 400 times magnification micrograph of the O/W emulsion of the Comparative Example 1-2 is shown on the right side in
The evaluation results of the emulsion particles and stability for the n/W emulsions of the above-described Production Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2 are summarized, with each blending composition, in the following Table 1. Here, the evaluation items are as follows, and the amounts in the following table are expressed by mass %.
For the O/W emulsion compositions formed in the Production Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2, the particle sizes and micrographs were shown.
The O/W emulsions formed in the Production Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2 were stored at 50° C. for 1 month and then the stability was evaluated.
O: The O/W emulsion was not separated.
X: The O/W emulsion was separated.
As seen from the above Table 1 and
Subsequently, in order to investigate the preferable temperature of (F) water or an aqueous formulation, which is added in the step of inversion to a fine O/W emulsion, the present inventors have investigated the stability of each emulsion by appropriately varying the temperature of (F) water, using the same formulation as that of Production Example 1-1 in the Table 1.
As shown in the above Table 2, the temperature of (F) ion-exchanged water was appropriately varied in the production method of the present invention using the same blending formulation as the Production Example 1-1, to investigate the emulsion stability.
As a result, it was to be found that when the temperature of the added (F) ion-exchanged water was 10 to 35° C., and in particular when the temperature was 15 to 35° C. (Production Examples 2-2 to 2-7), the emulsion particles were fine and excellent stability was provided.
On the other hand, when the temperature of (F) ion-exchanged water was 5° C. (Production Example 2-1), an emulsion with large particle sizes was formed; thus the desired fine O/W emulsion could not be obtained. When the temperature was 40° C., the stability was also poor (Production Example 2-8).
The micrographs for the O/W emulsions formed in the Production Examples 2-2 to 2-7 are shown in
Subsequently, the present inventors have investigated the mechanism of stability improvement of the O/W emulsion composition due to the combination of (A) a hydrophilic nonionic surfactant and (B) a linear higher alcohol having 16 or more carbon atoms. The production method was according to the Production Example 1-1.
As shown in the above Table 3, the total amount of (A) a hydrophilic nonionic surfactant and (B) a higher alcohol was set to be 10 mass % in Test Examples 3-1 to 3-12, but the blending ratio was changed, to investigate the stability of each emulsion.
As a result, when the blending ratio of (A) a hydrophilic nonionic surfactant and (B) a higher alcohol was 3:7 to 7:3 (Test Examples 3-3 to 3-10), the emulsion stability was excellent compared with when each component was used alone (Test Examples 3-1 and 3-12) or the blending ratio was 2:8 or 8:2 (Test Examples 3-2 and 3-11).
The micrographs of the O/W emulsion compositions formed in the Test Examples 3-4 to 3-8 were shown in
Subsequently, the present inventors have investigated the preferable (D) aqueous solvent used for the preparation of a stable O/W emulsion. The production method was according to the Production Example 1-1.
As shown in the above Table 4, when polypropylene glycol (7 mol) polyethylene glycol (14 mol) copolymer, polyethylene glycol, dipropylene glycol (molecular weight: 1000), isoprene glycol, or propylene glycol, which is an aqueous solvent having three or less hydroxyl groups in the water molecule and providing a higher c.m.c. of (A) a hydrophilic nonionic surfactant therein than the c.m.c. in water, was used (Test Examples 4-1 to 4-5), an O/W emulsion having fine emulsion particles and high stability could be obtained.
On the other hand, when erythritol (Test Example 4-6) or maltitol (Test Example 4-7), which has four or more hydroxyl groups in the molecule, was used, the composition became a hard gel during the step of the O/W emulsion preparation, and the desired fine O/W emulsion external preparation could not be obtained.
Furthermore, the present inventors have investigated the blending percentage of (E) water for the preparation of a fine O/W emulsion with excellent in stability. The production method was according to the Production Example 1-1.
As shown in the above Table 5, the preferable blending percentage of (E) water for the preparation of the fine O/W emulsion of the present invention was investigated.
As a result, when the amount of (E) water was 1 to 4 mass %, the particle size was large and the stability had a tendency to be poorer (Test Examples 5-1 to 5-4). However, when the amount of (E) water was 5 to 25 mass %, the particle size of the fine O/W emulsion was very small and the stability was excellent (Test Examples 5-5 to 5-7). When the amount of (E) water was higher than 25 mass %, however, it has been clear to be found that the efficiency of emulsification turned out to be poor, and the advantage of low-energy preparation was lost because the volume to be heated became large (Test Example 5-8).
The micrographs of the O/W emulsions formed in the Test Examples 5-1 to 5-5 were shown in
Hereinafter, the present invention will be further explained with reference to examples. However, the present invention is not limited by these examples. The quantities in the following formulation are expressed in mass %.
Components (1) to (7) were heated to 75° C. and stirred to obtain a W/O emulsion. Aqueous components (8) to (13) were mixed at 25° C. and gradually added to the W/O emulsion while being stirred with a homogenizer, to obtain an essence. The emulsion particle size of the obtained essence was finer than that of the essence, of the identical formulation, obtained by separately heating the oil phase and the water phase at 75° C., emulsifying them, and then cooling the emulsion with an Onlator. The obtained essence was stable and provided a light and fresh but also rich feeling in use.
Components (1) to (8) were heated to 75° C. and stirred to obtain a W/O emulsion. Aqueous components (9) to (13) were mixed at 30° C. and gradually added to the W/O emulsion while being stirred with a homogenizer, to obtain a cream. The emulsion particle size of the obtained cream was finer than that of the cream, of the identical formulation, obtained by separately heating the oil phase and the water phase at 75° C., emulsifying them, and then cooling the emulsion with an Onlator. The obtained cream was stable and provided a light and fresh but also rich feeling in use.
Components (1) to (7) were heated to 70° C. and stirred to obtain a W/O emulsion. Aqueous components (8) to (9) were mixed at 25° C. and gradually added to the W/O emulsion while being stirred with a homogenizer, to obtain a cleansing lotion. The emulsion particle size of the obtained cleansing lotion was finer than that of the cream, of the identical formulation, obtained by separately heating the oil phase and the water phase at 70° C., emulsifying them, and then cooling the emulsion with an Onlator. The obtained cream was stable and provided good spreadability in use.
Components (1) to (13) were heated to 75° C. and stirred to obtain a W/O emulsion. Aqueous components (14) to (20) were mixed at 20° C. and gradually added to the W/O emulsion while being stirred with a homogenizer, to obtain a milky lotion. The emulsion particle size of the obtained cream was finer than that of the milky lotion, of the identical formulation, obtained by separately heating the oil phase and the water phase at 75° C., emulsifying them, and then cooling the emulsion with an Onlator. The obtained milky lotion was stable and provided good spreadability and rich feeling in use.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2009-005531 | Jan 2009 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2010/050341 | 1/14/2010 | WO | 00 | 7/12/2011 |
