Water-in-oil emulsion composition
The oil-in-water emulsion composition, utilizing amphiphilic solid particles and a specific polysaccharide, addresses the challenge of maintaining stability and freshness in cosmetics, especially at high temperatures, without using surfactants.
Patent Information
- Application Number
- JP2023150896
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-09-19
- Publication Date
- 2025-04-01
AI Technical Summary
Existing cosmetic emulsions face challenges in maintaining stability over time, especially at high temperatures, and often compromise on feel and freshness due to the use of surfactants or heat-sensitive ingredients.
An oil-in-water emulsion composition that uses amphiphilic solid particles and a specific type of polysaccharide with aldohexose or acidic sugars in the main chain and deoxysaccharides in the side chain, which stabilizes the emulsion without relying on surfactants or high temperatures.
The composition achieves long-term stability and freshness, preventing creaming and sedimentation, while maintaining a non-sticky, fresh feel, even at high temperatures.
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Abstract
Description
[Technical field]
[0001] The present invention relates to an oil-in-water emulsion composition which is surfactant-free and contains an aqueous component, an oily component, amphiphilic solid particles, and a polysaccharide, and which has excellent stability over time without impairing the feel when used, and to a method for producing the same. [Background technology]
[0002] Cosmetics are required to have a wide variety of functional effects depending on the type of cosmetic, and therefore contain a wide variety of ingredients. For example, functional oily bases or functional granules that have functions such as cleansing, water retention, scrubbing effect, emollient effect, and protective effect on the skin surface, and functions to improve the spreadability, smoothness, gloss, adhesion, etc. of cosmetics contain ingredients such as organic solvents, organic pigments, inorganic pigments, oils, moisturizers, astringents, whitening agents, UV protection agents, antioxidants, and fragrances. When these functional oily bases or functional granules are used in cosmetics, many types of surfactants are selected and used according to the required HLB of the functional oily base and the surface properties of the functional granules to perform emulsification and dispersion (Non-Patent Documents 1 to 4).
[0003] Thus, surfactants are generally used, but depending on the type of surfactant, there are problems such as stickiness, deterioration of the feeling of use due to a specific odor, and makeup coming off due to moisture such as sweat. In addition, in order to obtain a stable emulsion, the type of surfactant that can be used is limited depending on the type of oil. On the other hand, as an emulsification method that overcomes the above-mentioned problems, there is a known technology for a cosmetic in an oil-in-water emulsion state that is well compatible with the skin, which does not use a surfactant, but is produced by blending two or more types of specific polysaccharides and specific higher alcohols in an emulsification method for oily components, emulsifying them at 70°C or higher, and then cooling them to 40°C while stirring (Patent Documents 1 to 3).
[0004] However, this method involves heating at 70°C or higher during emulsification, which leads to the deterioration of heat-sensitive ingredients. For example, vitamins are active ingredients in cosmetics, but heat-sensitive ingredients such as p-aminobenzoic acid, thiamine, calcium pantothenate, and ascorbyl tetrahexyldecanoate, a vitamin C derivative, are prone to decomposition or oxidative deterioration.
[0005] In addition, Pickering emulsification, which uses solid particles as an emulsifier, is known as an emulsification method that does not use a surfactant at room temperature. Formulations in which amphiphilic solid particles are adsorbed to the interface to form an emulsion have been conventionally known as Pickering emulsions, and their use in cosmetics has also been proposed. For example, titanium dioxide, zinc oxide, etc. have been proposed as the solid particles, and it has been proposed to use solid particles whose surfaces have been hydrophobized to prepare Pickering emulsions (Patent Document 4). In addition, there is a report that it has been found that by blending spherical polylactic acid powder as solid particles, it has excellent emulsion stability, and is fresh and refreshing to use without stickiness or squeaking or powderiness (Patent Document 5). The emulsion obtained by Pickering emulsification is characterized by having a high stability of the oil-in-water emulsion state compared to when a surfactant is used, and is less likely to separate after emulsification. However, even with Pickering emulsification, cosmetic preparations may have poor emulsification properties or post-emulsification stability due to the influence of the oil type and cosmetic ingredients. In order to improve emulsion stability, a technique is known in which an acrylic acid polymer is added to improve the dispersion state of powder adsorbed to the emulsion interface, thereby preparing a Pickering emulsion with fine emulsion particle size and excellent stability (Patent Document 6). However, even if the emulsion particle stability was obtained, the stability against settling and creaming of the emulsion particles over time was insufficient.
[0006] In order to stabilize the oil-in-water emulsified state of cosmetic emulsion preparations, it is necessary to prevent the settling and creaming of emulsion particles over time. In general, in order to provide stability to the system against changes over time, it is necessary to incorporate a water-soluble polymer into the aqueous phase component. As a known method, there is a method of preventing separation of emulsion particles by imparting an appropriate viscosity to the emulsion preparation, and water-soluble polymers such as starch derivatives, cellulose derivatives, carbopol, and xanthan gum have been proposed as thickeners. However, cosmetics are required to maintain a stable emulsified dispersion state for a long time over a wide temperature range. The viscosity of starch derivatives, cellulose derivatives, carbopol, etc. is temperature dependent, so at a high temperature of 50°C, the viscosity decreases and creaming occurs. As a water-soluble polymer, it has been proposed to incorporate xanthan gum because its viscosity is not significantly affected by pH, salt, etc. (Patent Document 7). However, xanthan gum is sticky and easily removed from the container onto the hands or fingers, which is problematic for cosmetics that require a less sticky feel.
[0007] [Non-Patent Document 1] "Emulsion Science" Edited by P. Sherman, Academic Press Inc. (1969) [Non-Patent Document 2] "Microemulsions-Theory and Practice-Edited by Leon M.price,Academic Press lnc.(1977) [Non-Patent Document 3] "Technology of Emulsification and Solubilization" by Tsuji Komo, Kogaku Tosho Publishing (1976) [Non-Patent Document 4] "Development Technology of Functional Surfactants" CMC Publishing (1998) [Patent Document 1] Patent No. 4947267 [Patent Document 2] Patent No. 5051987 [Patent Document 3] Patent No. 5633951 [Patent Document 4] Special Publication No. 2001-518111 [Patent Document 5] Patent No. 2656226 [Patent Document 6] Patent No. 7237463 [Patent Document 7] JP 2013-129626 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]
[0008] The present invention provides an oil-in-water emulsion composition formed by Pickering emulsification from water, an oily component, and amphiphilic solid particles, which composition inhibits changes over time in the oil-in-water emulsion state at high temperatures without impairing the feel when used, and a method for producing the same. [Means for solving the problem]
[0009] The present inventors have conducted extensive research into the stability over time of oil-in-water emulsion compositions produced by Pickering emulsification, particularly the stability at high temperatures. As a result, they have found that in a two-phase system of an oily component and an aqueous component, containing amphiphilic solid particles (A) and a polysaccharide (B) having at least one type of aldohexose or acidic sugar in its main chain and having a deoxy sugar in its side chain, is effective in suppressing changes in emulsion stability over time at room temperature and at high temperatures, and have completed the present invention.
[0010] The invention of claim 1 is an oil-in-water emulsion composition characterized by comprising amphiphilic solid particles (A) and a polysaccharide (B) having at least one type of aldohexose or acidic sugar in its main chain and having a deoxy sugar in its side chain, in a two-phase system of an oily component and an aqueous component.
[0011] The amphiphilic solid particles (A) described in claim 1 have both hydrophilic and lipophilic properties. Examples of the inorganic solid particle component of the amphiphilic solid particle (A) include acrylic resin-coated aluminum powder, aluminum powder, epoxy-treated aluminum, bismuth oxychloride, carbon black, kaolin, calamine, ultramarine, ultramarine violet, ultramarine pink, aluminum silicate, calcium silicate, strontium silicate, barium silicate, magnesium silicate, magnesium silicate, konjo, silica, aluminum stearate, zeolite, ceramic powder, sericite, talc, metal tungstate, titanium-titanium dioxide sintered product, aluminum stearate-treated titanium dioxide, dimethylpolysiloxane-treated titanium dioxide, silica-treated titanium dioxide, cobalt titanate, permiculite, higilite, pyroferrite clay, calcium palmitate, hydroxyapatite, hectorite, red iron oxide, bentonite, mica, magnesium, manganese violet, zinc myristate, montmorillonite, calcium phosphate, logite, Magnesium oxide treated with sodium phosphate, mica, yellow iron oxide, yellow ochre, gold colloid, phlogopite, gold leaf, sericite, red mica, synthetic aluminum silicate, synthetic mica, biotite, black titanium oxide, black iron oxide, aluminum oxide, aluminum cobalt oxide, chromium oxide, zirconium oxide, cerium oxide, titanium oxide sol, magnesium oxide, zinc oxide, iron oxide-titanium dioxide sintered product, calcined calcium sulfate (calcined gypsum), chromium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, natural Aluminum silicate, copper powder, titanium dioxide, muscovite, fluorapatite, anhydrous silicic acid, anhydrous aluminum silicate, magnesium stearate-treated silica, silica silylate, silica silylate, barium sulfate, aluminum lake, copper powder, cobalt violet, zirconium, iron titanate, barium um lake, fish scale foil, ultramarine, Prussian blue, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, titanium dioxide-coated mica, colored titanium dioxide-coated mica.
[0012] Examples of the organic solid particle component of the amphiphilic solid particles (A) include acylamino acids such as caproyl lysine, lauroyl lysine, lauroyl lysine-treated Saccharomyces culture, metal soaps (fatty acid salts) such as magnesium stearate, aluminum stearate, and calcium stearate, (meth)acrylic acid ester-based resin powders containing (meth)acrylic acid or a salt thereof, polyamide resin powders (nylon powders), polyethylene powders, polymethyl methacrylate powders, polystyrene powders, styrene-acrylic acid copolymer resin powders, porous cellulose powders, porous nylon powders, polyethylene powders, tetrafluoroethylene powders, crosslinked polystyrene powders, silicone-based resin powders, crosslinked silicone powders, network-type methylpolysiloxane powders, benzoguanamine resin powders, polytetrafluoroethylene powders, kapok fiber fine powders, cellulose powders, cellulose acetate powders, crystalline cellulose, cellulose treated with magnesium stearate, silk powders, wool powders, starch, and rice starch treated with magnesium stearate.
[0013] From the viewpoint of emulsion stability, it is preferable to include at least one selected from the group consisting of lauroyl lysine, bentonite, caproyl lysine, magnesium stearate, aluminum stearate, calcium stearate, cellulose powder, crystalline cellulose, cellulose acetate powder, rice starch treated with magnesium stearate, cellulose treated with magnesium stearate, silica treated with magnesium stearate, lauroyl lysine-treated Saccharomyces culture, silica silylate, titanium dioxide treated with aluminum stearate, titanium dioxide treated with dimethylpolysiloxane, and titanium dioxide treated with silica.
[0014] The particle size of the amphiphilic solid particles (A) is not particularly specified, but when a powder with a large particle size is used, large emulsion particles are formed, and when a powder with a small particle size is used, small emulsion particles are formed. When the appearance of the oil-in-water emulsion composition is characterized by visible large particles, the particle size is preferably 0.1 to 5 mm. On the other hand, from the viewpoints of ease of handling when blending into the oil-in-water emulsion composition and emulsion stability, the particle size is preferably 0.1 to 20 μm, and more preferably 1 to 10 μm.
[0015] The amount of the amphiphilic solid particles (A) is preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass, based on the total amount of the components. If the amount is less than 0.1% by mass, emulsification may not proceed sufficiently, whereas if it exceeds 20% by mass, emulsion stability and compatibility with the skin tend to decrease.
[0016] The oily component described in claim 1 is not particularly limited, but examples of oily agents include hydrocarbons, vegetable oils, synthetic esters, and silicone oils.
[0017] Examples of hydrocarbons include liquid paraffin (mineral oil), heavy liquid isoparaffin, light liquid isoparaffin, α-olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, etc. Examples of plant-derived oils include coconut oil, palm oil, palm kernel oil, safflower oil, olive oil, castor oil, avocado oil, sesame oil, tea oil, evening primrose oil, wheat germ oil, macadamia nut oil, hazelnut oil, kukui nut oil, rosehip oil, meadowfoam oil, persic oil, tea tree oil, peppermint oil, corn oil, rapeseed oil, sunflower oil, wheat germ oil, linseed oil, cottonseed oil, soybean oil, peanut oil, rice bran oil, cacao butter, shea butter, hydrogenated coconut oil, hydrogenated castor oil, jojoba oil, hydrogenated jojoba oil, etc. Synthetic esters include octyldodecyl myristate, hexyldecyl myristate, octyldodecyl isostearate, cetyl palmitate, octyldodecyl palmitate, cetyl octanoate, hexyldecyl octanoate, isotridecyl isononanoate, isononyl isononanoate, octyl isononanoate, isotridecyl isononanoate, isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neodecanoate, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, octyldodecyl lanolinate, dicaprylyl carbonate, hexyldecyl dimethyloctanoate, octyldodecyl erucate, ethyl oleate, and avocado oil fat. Ethyl myristate, isopropyl palmitate, octyl palmitate, isopropyl isostearate, isopropyl lanolate, methylheptyl laurate, methylheptyl myristate, methylheptyl palmitate, methylheptyl isostearate, diethyl sebacate, diisopropyl sebacate, dioctyl sebacate, diisopropyl adipate, dibutyloctyl sebacate, diisobutyl adipate, dioctyl succinate, triethyl citrate, cetyl lactate, hydrogenated castor oil monoisostearate, γ-erucalactone, diisostearyl malate, glyceryl trioctanoate, glyceryl trioleate, glyceryl triisostearate, glyceryl diisostearate,Caprylic / capric triglyceride, glyceryl tri-2-ethylhexanoate, caprylic / capric / myristic / stearic triglyceride, hydrogenated rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), trimethylolpropane trioctanoate, trimethylolpropane triisostearate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, 2-butyl-2-ethyl-1,3-propanediol dioctanoate, propylene glycol dioleate, pentaerythrityl tetraoctanoate, hydrogenated rosin pentaerythrityl, ditrimethylolpropane triethylhexanoate, Ditrimethylolpropane (isostearate / sebacic acid), pentaerythrityl triethylhexanoate, dipentaerythrityl (hydroxystearic acid / stearic acid / rosin acid), diglyceryl diisostearate, polyglyceryl tetraisostearate, polyglyceryl-10 nonaisostearate, polyglyceryl-8 deca(erucic acid / isostearic acid / ricinoleic acid), diglyceryl oligoester (hexyldecanoic acid / sebacic acid), glycol distearate (ethylene glycol distearate), 3-methyl-1,5-pentanediol dineopentanoate, 2,4-diethyl-1,5-pentanediol dineopentanoate, etc.
[0018] Examples of silicone oils include dimethicone (dimethylpolysiloxane), highly polymerized dimethicone (highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic dimethylsiloxane, decamethylcyclopentasiloxane), phenyl trimethicone, diphenyl dimethicone, phenyl dimethicone, (aminoethyl aminopropyl methicone / dimethicone) copolymer, dimethiconol, dimethiconol crosspolymer, silicone resin, silicone rubber, amino-modified silicones such as aminopropyl dimethicone and amodimethicone, cation-modified silicones, polyether-modified silicones such as dimethicone copolyol, Examples include polyglycerin-modified silicone, sugar-modified silicone, carboxylic acid-modified silicone, phosphate-modified silicone, sulfate-modified silicone, alkyl-modified silicone, fatty acid-modified silicone, alkyl ether-modified silicone, amino acid-modified silicone, peptide-modified silicone, fluorine-modified silicone, cation-modified and polyether-modified silicone, amino-modified and polyether-modified silicone, alkyl-modified and polyether-modified silicone, amidoalkyl-modified silicone, aminoglycol-modified silicone, aminophenyl-modified silicone, polysiloxane-oxyalkylene copolymer, etc. These may be used alone or in combination. Among them, from the viewpoint of emulsion stability, it is preferable to include at least one of squalane, jojoba oil, olive oil, meadowfoam oil, glyceryl tri-2-ethylhexanoate, glyceryl tri(capryl-caprate), and mineral oil. The amount of oily agent to be blended varies depending on the type of oily agent and is selected appropriately, but the oily component is 0.5-40% by mass relative to the total amount of blended components. If it is less than 0.5%, the emollient feeling of the oil-in-water emulsion composition is inferior, and if it is more than 40%, the freshness may be impaired.
[0019] The emulsion composition of the present invention is a Pickering emulsion, which is an oil-in-water type emulsion, in which amphiphilic solid particles are wrapped around the oil droplets and dispersed in the aqueous component. In this case, it is extremely rare and unrealistic that the specific gravity of the oil droplet particles is exactly the same as that of the aqueous component. In particular, the specific gravity of the aqueous component changes depending on the temperature. Due to this specific gravity difference, the oil component floats or sinks, causing a separation state called creaming. In order to prevent creaming, a hydrophilic polymer is generally blended to give viscosity to the continuous phase and prevent separation. This method is the same for emulsification using a surfactant, but in the case of emulsification using a surfactant, the surface of the oil droplets is covered with hydrophilic groups, so that they are fixed by hydrogen bonds with the hydrophilic polymers spreading in the continuous phase, and the emulsion state is stabilized.
[0020] Pickering emulsion refers to an emulsion stabilized by solid particles adsorbed to the liquid-liquid interface between the oily component and water or aqueous component. Therefore, solid particles are adsorbed to the liquid-liquid interface when the oily component and the water or hydrophilic component have appropriate wettability. The adsorption energy F at this time is F=π×particle diameter of solid particle×particle diameter of solid particle×interfacial tension of oil-water interface×(1-cos contact angle of solid to interface). Therefore, when the adsorption energy is maximum, which is the most stable Pickering emulsion, the contact angle to the solid interface is 90°, and the contact angle of 90° is when the wettability of the solid particles to the oily component and aqueous component is equal. Therefore, the most stable state of Pickering emulsion is when the solid particles covering the surface have equal affinity to both the oily component and the aqueous component, so electrostatic repulsion occurs with the hydrophilic polymer spreading in the continuous layer, and the polymer inhibits adsorption to the solid surface. As a result, the coalescence prevention effect of the adsorbed polymer due to steric inhibition is weakened, resulting in poor emulsion stability. To prevent this, a method is generally adopted in which a large amount of hydrophilic polymer is blended to increase the viscosity of the continuous phase, thereby improving stability. However, an increase in the polymer concentration causes the oil-in-water emulsion composition to lose its freshness and become sticky.
[0021] The polysaccharide (B) according to claim 1 has at least one kind of aldohexose or acidic sugar in the main chain and has deoxy sugar in the side chain. The main chain has at least one kind of aldohexose or acidic sugar, and deoxy sugar is sandwiched at a certain interval. The methyl group contained in the deoxy sugar is hydrophobic and generates hydrophobic-hydrophilic repulsion against the aldohexose and acidic sugar. Due to this action, the polysaccharide does not self-crystallize and is in a spread state. In addition, all carbons of the aldohexose or acidic sugar in the main chain have HO and H groups, and are bonded to the aqueous component, which is the continuous phase, by hydrogen bonds to maintain a stable state. And by having deoxy sugar in the side chain, the hydrophobic methyl group is in a state of protruding outward due to hydrophobic-hydrophilic repulsion. Since the methyl group does not have hydrogen bonds, no electrostatic repulsion occurs with the solid particles, and the oil droplets can approach the solid surface to the extent that van der Waals forces are generated, and are fixed by van der Waals forces, covered by the solid particles, and stabilized, resulting in a stable emulsion system. This makes it possible to prevent creaming in the Pickering emulsion system without depending on the viscosity of the continuous phase, and to obtain a fresh, non-sticky oil-in-water emulsion composition that is low in viscosity and does not depend on the feel of the polymer. Specific examples of polysaccharides include Alcaligenes-producing polysaccharides whose main chain is composed of glucose, glucuronic acid, and rhamnose and whose side chains have fucose, which is a deoxy sugar; diutan gum (manufactured by CP Kelco) whose main chain has a repeating structure of glucose-glucuronic acid-glucose-rhamnose and whose side chains have rhamnose-rhamnose; and welan gum (manufactured by CP Kelco) whose main chain has a repeating structure of glucose-glucuronic acid-glucose-rhamnose and whose side chains have rhamnose.
[0022] The invention of claim 2 is an oil-in-water emulsion composition, characterized in that the polysaccharide (B) contains at least a polysaccharide represented by the following general formula (1): TIFF2025043550000001.tif44116
[0023] The polysaccharide of the present invention has a repeating structure of the unit shown in general formula (1). The main chain is composed of glucose and glucuronic acid, with glucuronic acid sandwiched between glucose, and the deoxy sugar rhamnose is also sandwiched between glucose, forming a repeating structure of the unit. This causes ion dissociation, and the highly polar carboxyl group and the non-polar methyl group are regularly present at a moderate interval, making the polysaccharide less likely to self-crystallize, which is an ideal arrangement of the constituent monosaccharides. In addition, the presence of the deoxy sugar fucose in the side chain gives the polysaccharide a shape that can be bonded to solid particles by van der Waals forces, which is an ideal arrangement for Pickering emulsification. An example of a polysaccharide of general formula (1) is Alcaligenes-producing polysaccharide (trade name "Alcasealan", manufactured by Hakuto Co., Ltd.).
[0024] The invention of claim 3 is the oil-in-water emulsion composition according to claim 1 or 2, characterized in that the (A) solid particles comprise at least one selected from the group consisting of lauroyl lysine, bentonite, caproyl lysine, magnesium stearate, aluminum stearate, calcium stearate, cellulose powder, crystalline cellulose, cellulose acetate powder, rice starch treated with magnesium stearate, cellulose treated with magnesium stearate, silica treated with magnesium stearate, lauroyl lysine-treated Saccharomyces culture, silica silylate, titanium dioxide treated with aluminum stearate, titanium dioxide treated with dimethylpolysiloxane, and titanium dioxide treated with silica.
[0025] The invention of claim 4 relates to the oil-in-water emulsion composition according to claim 1 or 2, characterized in that the (B) polysaccharide is contained in an amount of 0.02 to 0.5% by mass based on the total amount of the blended components.
[0026] The blending amount of the polysaccharide is preferably 0.02 to 0.5% by mass, more preferably 0.04 to 0.1%. If it is less than 0.02%, sufficient creaming prevention effect cannot be obtained, and if it is more than 0.5%, stickiness occurs, which impairs the feel even as an oil-in-water emulsion composition.
[0027] The invention of claim 5 relates to a method for producing an oil-in-water emulsion composition, comprising the steps of dissolving the polysaccharide (B) to prepare an aqueous phase, and mixing the solid particles (A) with an oil component to prepare an oil phase, and adding the prepared oil phase to the aqueous phase to emulsify the composition.
[0028] The oil-in-water emulsion composition of the present invention is characterized by carrying out an emulsification step at room temperature. Specifically, a polysaccharide having deoxy sugars in its side chain is stirred and dissolved in water and / or a hydrophilic solvent at room temperature to 80°C in an amount equivalent to 0.02% to 0.5% by mass relative to the total amount of the blended components of the oil-in-water emulsion composition using a homomixer or the like to produce an aqueous polysaccharide solution. The dissolution temperature can be changed at any time depending on the type of polysaccharide and the dissolution time, but differences in dissolution temperature do not impair the present invention. Next, a solid powder having amphiphilicity is added to the oil component, and stirring and mixing are carried out using a disperser. There is no specific method for the dispersion method, but it is necessary that the solid powder is sufficiently uniformly dispersed. Next, the polysaccharide is dissolved in this oil phase, and gradually added to the aqueous phase stirred and mixed with a disperser at room temperature, and emulsified by stirring to obtain the oil-in-water emulsion composition of the present invention. The stirring method is not particularly limited, but propeller stirring and agitator can be used.
[0029] When blending an oil-based component that is sensitive to heat, the amphipathic solid powder is added first, and then the oil-based component is added. When blending an aqueous component that is sensitive to heat, the aqueous component is added during the emulsification step, and thus an oil-in-water emulsion composition can be obtained without decomposition of both components due to heat.
[0030] The oil-in-water emulsion composition of the present invention is available in various types depending on the purpose of use, and therefore, if necessary, components such as purified water, hot spring water, deep sea water, coloring agents (pigments), aqueous polymers, moisturizing agents, astringents, whitening agents, UV protection agents, anti-inflammatory (anti-inflammatory) agents, skin (cell) activators, bactericides (including some preservative components), percutaneous absorption promoters, cooling agents, antioxidants, fragrances, organic solvents, sequestering agents and preservatives, anti-fading agents, buffers, etc., which are components that are blended into medicines, quasi-drugs, cosmetics, etc., may be arbitrarily added. The present invention does not limit the blending of these various additives within the scope that does not interfere with the intended effect.
[0031] Examples of water-soluble polymers include plant-based polymers such as tamarind, gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, algae colloid, fucoidan, trant gum, locust bean gum, and galactomannan; microbial polymers such as xanthan gum, curdlan, gellan gum, fucogel, dextran, succinoglucan, and pullulan; animal polymers such as chitosan, casein, albumin, and gelatin; starch-based polymers such as starch, carboxymethyl starch, and methylhydroxypropyl starch; cellulose-based polymers such as methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, and cellulose powder; alginic acid-based polymers such as sodium alginate and propylene glycol alginate; and vinyl-based polymers such as polyvinyl methyl ether, carboxyvinyl polymer, and alkyl-modified carboxyvinyl polymer. Polyoxyethylene-polyoxypropylene copolymer-based polymers of polyoxyethylene-based polymers. Acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide. Inorganic water-soluble polymers such as polyethyleneimine, cationic polymers, bentonite, laponite, and hectorite. Film-forming agents such as polyvinyl alcohol and polyvinylpyrrolidone are also included. The amount of the water-soluble polymer varies depending on the type of water-soluble polymer and cannot be uniformly determined, but is usually 0.01 to 1.0% by mass of the total amount of the oil-in-water emulsion composition.
[0032] Coloring agents include organic synthetic dyes such as azo dyes, Yellow No. 5, Red No. 505, etc., xanthene dyes, such as Red No. 213, Red No. 230, etc., quinoline dyes, such as Yellow No. 204, triphenylmethene dyes, such as Blue No. 1, anthraquinone dyes, such as Green No. 201, indigo dyes, lake pigments, such as Red No. 202, Red No. 208, Red No. 228, Red No. 226, Blue No. 404, etc., and natural dyes, such as carotene, carthamine, and cochineal.
[0033] Moisturizing agents include alkaline simple hot spring water, deep sea water, mucopolysaccharides such as hyaluronic acid, chondroitin sulfate, dermatan sulfate, heparan sulfate, heparin, and keratan sulfate, or their salts, proteins such as collagen, elastin, and keratin, or their derivatives and their salts, phospholipids, glycolipids, ceramides, mucin, honey, erythritol, maltose, maltitol, xylitol, xylose, pentaerythritol, fructose, dextrin, and their derivatives derived from soybeans and eggs, sugars such as mannitol, sorbitol, inositol, trehalose, and glucose, and urea. Asparagine, aspartic acid, alanine, arginine, isoleucine, ornithine, glutamine, glycine, glutamic acid and their derivatives and their salts, cysteine, cystine, citrulline, threonine, serine, tyrosine, tryptophan, theanine, valine, histidine, hydroxylysine, hydroxyproline, pyrrolidone carboxylic acid and its salts, amino acids such as proline, phenylalanine, methionine, lysine and their derivatives or their salts, and D-panthenol.Further examples of plant extracts include avocado extract, almond oil, carob extract, rice extract, strawberry extract, fennel extract, marshal extract, coptis jasmine extract, olive oil, white lamb extract, cacao butter, oat extract, ivy extract, kumazasa extract, gardenia extract, grapefruit extract, geranium extract, gentiana extract, burdock extract, sedge extract, sesame extract, cactus extract, soapwort extract, ginger extract, rehmannia extract, shea butter extract, meadowsweet extract, cnidium rhizome extract, mallow extract, thyme extract, camellia extract, corn extract, and tocca extract. The moisturizing ingredients include citrus extract, tormentilla extract, dokudami extract, bahama extract, lupin extract, hamamelis extract, mint extract, green peppermint extract, peppermint extract, parsley extract, rose extract, sunflower extract, cypress extract, loofah extract, prune extract, butcher's broom extract, borage oil, peony extract, jojoba oil, linden extract, hop extract, pine extract, horse chestnut extract, macadamia nut oil, quince extract, purple extract, meadowhoo oil, melissa extract, cornflower extract, lily extract, yuzu extract, lime extract, lavender extract, gentian extract, burnet extract and apple extract. The moisturizing ingredients include yeast metabolites, yeast extract, rice fermentation extract, rice bran fermentation extract, Euglena extract, lactic acid fermentation product of raw milk and skimmed milk powder, trehalose or its derivatives, etc. These moisturizing ingredients can be used alone or in combination of two or more kinds. The blending amount varies depending on the type of moisturizing component and cannot be determined uniformly, but is usually 0.1 to 10% by mass of the total amount of the oil-in-water emulsion composition.
[0034] Examples of the astringent include zinc sulfophenol, sodium sulfophenol, and plant extracts, such as arnica, hawthorn, cinchona, salvia, linden, ginseng, juniper, rosemary, hypericum, ginkgo, melissa, ononis, horse chestnut, swertia japonica, garlic, chamomile, thyme, peppermint, nettle, chili pepper, ginger, hops, horse chestnut, lavender, mustard, cassia, pine, cnidium, elderberry, mountain water parsley, peony, Japanese bayberry, dokudami, watercress, chickweed, calendula, and gubijin. Examples of plant extracts include soybean, gentian, grape, litchi, bitter orange, yuzu, calamus, summer citrus, witch hazel, merry lotus, fennel, Japanese pepper, peony, eucalyptus, mugwort, Japanese laurel, rice, sophora flavescens, ginger, clove, walnut leaves, Scutellaria root, sage, hops, rosemary, Polygonum polyhedrinum, Coptis chinensis, Phellodendron bark, Scutellaria baicalensis, Chinese yarrow, Citrus unshiu peel, ginseng, Toushin, propolis, Taxusia, tannin, birch tar, royal jelly, and yeast extract. One or more of these astringents can be used in combination. The amount of the astringent varies depending on the type of astringent and cannot be uniformly determined, but is usually 0.001 to 5% by weight, preferably 0.01 to 3% by weight, of the total amount of the oil-in-water emulsion composition.
[0035] Examples of skin whitening agents include tyrosinase inhibitors, endothelin antagonists, α-MSH inhibitors, glabridin, glabrene, liquiritin, isoliquiritin, ellagic acid and its salts and derivatives, kojic acid and its salts and derivatives, arbutin and its salts and derivatives, cysteine and its salts and derivatives, glutathione and its salts and derivatives, resorcin and its salts and derivatives, rucinol, neoagarobiose, and agarose oligosaccharide. Examples of plant extracts include asparagus extract, althea extract, ibuki toranoo extract, inchinko extract, pea extract, radish extract, Chinese laurel extract, Scutellaria root extract, Ononis extract, seaweed extract, fire thorn extract, licorice extract, raspberry extract, solanum root extract, brown sugar extract, keiske tu extract, gokahi extract, wheat germ extract, saishin extract, hawthorn extract, sunflower extract, peony extract, white lily extract, sappanha extract, soybean extract, placenta extract, taranoki extract, tea extract, angelica extract, molasses extract, multiflora rose extract, white juniper extract, grape seed extract, beech extract, flordemanita extract, hop extract, mikaika extract, mokka extract, saxifrage extract, coix seed extract, monk fruit extract, and the like. One or more of these whitening agents (ingredients) can be used in combination. The amount of the whitening agent to be added varies depending on the type of whitening agent (ingredient) and cannot be determined uniformly, but is usually 0.01 to 10% by weight. When using a plant extract as is, the amount is calculated as the dry solid content.
[0036] UV protection agents include organic compound-based UV absorbers and inorganic compound-based UV scattering agents, and examples of UV absorbers include para-aminobenzoic acid-based UV absorbers, cinnamic acid-based UV absorbers, salicylic acid-based UV absorbers, and benzophenone-based UV absorbers. UV absorbers of para-aminobenzoic acid-based UV absorbers include para-aminobenzoic acid, glyceryl para-aminobenzoate, ethyl dihydropropyl para-aminobenzoate, amyl para-dimethyl para-aminobenzoate, octyl para-methyl para-aminobenzoate, ethyl para-aminobenzoate, and isobutyl para-aminobenzoate. Cinnamic acid-based UV absorbers include isopropyl para-methoxycinnamate, diisopropyl cinnamate, octyl methoxycinnamate, mono-di-para-methoxycinnamate, and glyceryl 2-ethylhexanoate. Salicylic acid-based UV absorbers include homomenthyl salicylate, octyl salicylate, phenyl salicylate, triethanolamine salicylate, amyl salicylate, benzyl salicylate, p-tert-butylphenyl salicylate, ethylene glycol salicylate, salicylic acid, etc. Benzophenone-based UV absorbers include dihydroxybenzophenone, tetrahydroxybenzophenone, oxybenzone, oxybenzone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, dihydroxydimethoxybenzophenone, 2-hydroxychlorobenzophenone, dioxybenzone, sodium dihydroxydimethoxybenzophenone disulfonate, 2-hydroxy-4-methoxy-4'-methylbenzophenone, octabenzone, etc. Others include urocanic acid, ethyl urocanate, 4-tert-4'-methoxydibenzoylmethane, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, anthranilic acid, etc. Inorganic compounds used as ultraviolet scattering agents include titanium oxide, zinc oxide, cerium oxide, zirconium oxide, iron oxide, etc. The amount of ultraviolet protection agent to be added varies depending on the type of ultraviolet absorber and cannot be uniformly determined, but is usually 0.01 to 1% by weight based on the total amount of the oil-in-water emulsion composition.
[0037] Anti-inflammatory (anti-phlogistic) agents include zinc oxide, sulfur and its derivatives, glycyrrhizinic acid, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate and other glycyrrhizinic acid and its derivatives and their salts, β-glycyrrhetinic acid, stearyl glycyrrhetinate, disodium 3-succinyloxyglycyrrhetinate and other glycyrrhetinic acid and its derivatives and their salts, tranexamic acid, chondroitin sulfate, mefenamic acid, phenylbutazone, indomethacin, ibuprofen, ketoprofen, allantoin, guaiazulene and its derivatives and their salts, various extracts of microorganisms, animals and plants, etc.
[0038] Skin (cell) activators include deoxyribonucleic acid and its salts; adenylic acid derivatives such as adenosine triphosphate and adenosine monophosphate and their salts; ribonucleic acid and its salts, cyclic AMP, cyclic GMP, flavin adenine nucleotide, guanine, adenine, cytosine, thymine, xanthine and their derivatives; caffeine, theophylline and its salts; retinol and retinol derivatives such as retinol palmitate and retinol acetate; retinal derivatives such as retinal and dehydroretinal; carotenoids such as carotene and vitamin A; thiamine and thiamine salts such as thiamine hydrochloride and thiamine sulfate; riboflavin salts such as riboflavin and riboflavin acetate; pyridoxine and pyridoxine salts such as pyridoxine hydrochloride and pyridoxine dioctanoate. These include flavin adenine nucleotide, cyanocobalamin, folic acids, nicotinic acid and nicotinamide, nicotinic acid derivatives such as benzyl nicotinate, vitamin B group such as choline, vitamins such as p-aminobenzoic acid and calcium pantothenate, gamma-linolenic acid and its derivatives, eicosapentaenoic acid and its derivatives, estradiol and its derivatives and their salts, organic acids such as glycolic acid, succinic acid, lactic acid, salicylic acid and their derivatives and their salts.
[0039] Bactericides include benzoic acid, sodium benzoate, carbolic acid, sorbic acid, potassium sorbate, paraoxybenzoic acid esters, parachlormetacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizers, zinc bis(2-pyridylthio-1-oxide), phenoxyethanol, thianthol, isopropylmethylphenol, ethylhexylglycerin, and the like.
[0040] Antioxidants include carotenoids such as α-carotene, β-carotene, γ-carotene, cryptoxanthin, astaxanthin, and fucoxanthin, and derivatives thereof; B vitamins such as pyridoxine, pyridoxal, pyridoxal-5-phosphate, and pyridoxamine, and derivatives thereof, and salts thereof; C vitamins such as ascorbic acid, sodium ascorbate, ascorbyl stearate, ascorbyl palmitate, ascorbyl dipalmitate, P-aminobenzoic acid, thiamine, calcium pantothenate, ascorbyl tetrahexyldecanoate, and magnesium ascorbyl phosphate, and derivatives thereof, and salts thereof; and D vitamins such as ergocalciferol, cholecalciferol, and 1,25-dihydroxy-cholecalciferol, and derivatives thereof, and salts thereof. Vitamin E, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol, δ-tocotrienol, tocopherol acetate, tocopherol nicotinate, and derivatives and salts thereof. Trolox, its derivatives and salts thereof. Dihydroxytoluene, butylhydroxytoluene, butylhydroxyanisole, dibutylhydroxytoluene, α-lipoic acid, dehydrolipoic acid, glutathione, its derivatives and salts thereof. Erythorbic acid, such as uric acid, erythorbic acid, sodium erythorbate, its derivatives and salts thereof. Gallic acid, such as gallic acid, propyl gallate, its derivatives and salts thereof. Rutin, such as rutin and α-glycosyl-rutin, its derivatives and salts thereof. Tryptophan, its derivatives and salts thereof. Histidine, its derivatives and salts thereof. Cysteine derivatives and their salts, such as N-acetylcysteine, N-acetylhomocysteine, N-octanoylcysteine, and N-acetylcysteine methyl ester. Cystine derivatives and their salts, such as N,N'-diacetylcystine dimethyl ester, N,N'-dioctanoylcystine dimethyl ester, and N,N'-dioctanoylhomocystine dimethyl ester. Carnosine and its derivatives and their salts. Homocarnosine and its derivatives and their salts. Anserine and its derivatives and their salts. Carcinine and its derivatives and their salts.Dipeptide or tripeptide derivatives containing histidine and / or tryptophan and / or histamine and their salts. Flavonoids such as flavanone, flavone, anthocyanin, anthocyanidin, flavonol, quercetin, quercitrin, myricetin, fisetin, hamamelitannin, catechin, epicatechin, gallocatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate. Tannic acid, caffeic acid, ferulic acid, and protocatechuic acid. Chalcone, oryzanol, carnosol, sesamol, sesamin, sesamolin, zingerone, curcumin, tetrahydrocurcumin, clovamide, deoxyclovamide, shogaol, capsaicin, vanillylamide, ellagic acid, bromphenol, flavogracin, melanoidin, riboflavin, riboflavin butyrate, flavin mononucleotide, flavin adenine nucleotide, ubiquinone, ubiquinol, mannitol, bilirubin, cholesterol, ebselen, selenomethionine, ceruloplasmin, transferrin, lactoferrin, albumin, superoxide dismutase, catalase, glutathione peroxidase, metallothionein, O-phosphono-pyridoxylidene rhodamine, derivatives thereof and salts thereof, and N-(4-pyridoxylmethylene) amino acids, derivatives thereof and salts thereof, etc. The amount of these antioxidants (ingredients) to be added varies depending on the type of antioxidant (ingredients) and cannot be uniformly determined, but is usually 0.01 to 10% by weight. When using plant extracts as is, the amount is calculated as the dry solid content.
[0041] Fragrances include natural and synthetic fragrances. Representative examples of natural fragrances include plant-based fragrances such as rose oil, jasmine oil, neroli oil, lavender oil, tuberose oil, ylang-ylang oil, clary sage oil, clove oil, peppermint oil, geranium oil, patchouli oil, sandalwood oil, cinnamon oil, coriander oil, nutmeg oil, pine oil, vanilla oil, Peru balsam oil, banana oil, apple oil, fennel oil, tonka bean oil, pepper oil, lemon oil, orange oil, bergamot oil, opoponax oil, vetiver oil, orris oil, oakmoss oil, anise oil, and bois rose oil; and animal-based fragrances such as musk oil, civet oil, castoreum oil, and ambergris oil.
[0042] Specific examples of synthetic fragrances include hydrocarbons such as limonene and β-caryophylline, alcohols such as cis-3-hexenol, linalool, farnesol, β-phenylethyl alcohol, geraniol, citronellol, terpineol, menthol, santalol, bacdanol, and brahmanol, aldehydes such as lilanol, lilial, 2,6-nonadienal, citral, and α-hexylcinnamic aldehyde, β-ionone, l-carvone, cyclopentadecanone, damascone, methyl ionone, iron, isoe super, and acetophenone. Ketones such as tylcedrene and muscone, esters such as benzyl acetate, methyl dihydrojasmonate, methyl jasmonate, linalyl acetate, and benzyl benzoate, lactones such as γ-undecalactone, jasmine lactone, cyclopentadecanolide, and ethylene brassylate, oxides such as galacsolid, ambroxan, and rose oxide, phenols such as eugenol, nitrogen-containing compounds such as indole, acetals such as phenylacetaldehyde dimethyl acetal, and Schiff bases such as aurantiol, etc. In general, fragrances are rarely used alone, but are used as blended fragrances by combining multiple types depending on the purpose.
[0043] Examples of the organic solvent include ethanol, acetone, ethyl acetate, butyl acetate, 1,3-butylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, butanol, and propanol.
[0044] Examples of the sequestering agents and preservatives include hydroxyethanediphosphonates, phenacetin, EDTA and its salts, parabens, and stannates. Examples of the polymer compounds include poly(dimethylallylammonium halide)-type cationic polymers, polyethylene glycol, epichlorohydrin, propyleneamine, and tallowylamine condensation products obtained from beef tallow fatty acid. Examples of the cationic polymers include cationic polymers that are condensation products of cocoylamine obtained from polyethylene glycol, epichlorohydrin, propyleneamine, and coconut fatty acid, vinylpyrrolidone, dimethylaminomethacrylate copolymer-type cationic polymers, and quaternary nitrogen-containing cellulose ether-type cationic polymers. EXAMPLES
[0045] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these.
[0046] (Polysaccharides and water-soluble polymers) A-1 Polysaccharides Alcaligenes-produced polysaccharides (trade name "Alcasealan" manufactured by Hakuto Co., Ltd.) A-2 Polysaccharides Diutan gum [Product name "Kelcrete 200" manufactured by CP Kelco] A-3 Polysaccharides Xanthan gum (Product name: "Xanthan gum" manufactured by CP Kelco) A-4 Semi-synthetic polymer Carboxymethylcellulose [Product name "CMC" manufactured by Daicel Chemical Industries, Ltd.] A-5 Synthetic polymer Polyvinyl alcohol [Product name "PVAB-17" manufactured by Denki Kagaku Kogyo Co., Ltd.] A-6 Synthetic polymer Acrylic acid polymer [Product name "Hiviswako 104" manufactured by Wako Pure Chemical Industries, Ltd.] A-7 Synthetic polymer: Acrylic acid-methacrylic acid ester copolymer [Product name: PEMULEN TR-1, manufactured by BF Goodrich] A-8 Synthetic polymer Acrylic acid-acrylic acid ester copolymer [Product name "Carbopol" manufactured by BF Goodrich]
[0047] (Amphophilic solid particles) B-1 Titanium oxide (aluminum hydroxide, stearic acid-coated titanium oxide) [Product name "MT-01" manufactured by Teika Co., Ltd.] B-2 Bentonite (Product name: "Kunipia G4" manufactured by Kunimine Industries Co., Ltd.) B-3 Silica (Product name "Soliemer", manufactured by Sanyo Chemical Industries, Ltd.) B-4 Cellulose acetate particles (product name "BELLOCEA" manufactured by Daicel Corporation) B-5 Cellulose particles (product name "BiNFi-s" manufactured by Sugino Machine Co., Ltd.) B-6 Lauroyl Lysine [Product name "Amihope LL" manufactured by Ajinomoto Co., Inc.] B-7 Caproyl Lysine [Product name: "Amihope OL" manufactured by Ajinomoto Co., Inc.] B-8 Crystalline cellulose (product name "Naturecel 750" manufactured by Micro Powders, Inc.) B-9 Magnesium stearate (product name "Magnesium Stearate-S", NOF Corporation) B-10 Aluminum stearate (product name: Aluminum stearate 600 vegetable oil, manufactured by NOF Corp.) B-11 Calcium stearate (product name "Calcium stearate plant extract" manufactured by NOF Corp.) B-12 Magnesium stearate treated rice starch [Product name: "MST treated MAKIGREEN RICE S" manufactured by Daito Kasei Kogyo Co., Ltd.] B-13 Magnesium stearate-treated cellulose (product name "MST-treated MST-CELLULOBEAD" manufactured by Daito Kasei Kogyo Co., Ltd.) B-14 Magnesium stearate treated silica (Product name: "ST Powder G-MG ST" by Suzuki Oil Industries) B-15 Lauroyl lysine-treated Saccharomyces culture (trade name "Granpowder BBP-700" manufactured by Grant Industries, Inc.)
[0048] (Oily ingredients) C-1 Squalane (Product name: Kuraray Squalane N, manufactured by Kuraray Co., Ltd.) C-2 Jojoba Oil (Product name: Jojoba Oil, manufactured by B&O Research Institute) C-3 Olive oil (Product name: "Cropure OL" manufactured by Croda Japan Co., Ltd.) C-4 Meadowfoam oil (Product name: "KuroPure MDF" manufactured by Croda Japan Co., Ltd.) C-5 Glyceryl tri-2-ethylhexanoate [Product name: NIKKOL Trifat S-308, manufactured by Nikko Chemicals Co., Ltd.] C-6 Caprylic / Capric Triglyceride (Product Name: ODO, manufactured by Nisshin Oillio Group, Ltd.) C-7 Mineral Oil (Product name: "Mineral Oil" manufactured by B&O Research Institute)
[0049] <Compatibility test between oily ingredients and amphiphilic solid particles> 10g of water and 10g of oily components C-1 to C-7 were added to a 20ml vial to make a mixture. Next, amphiphilic solid particles B-1 to B-15 and oily components C-1 to C-7 were added in a 1:2 (weight ratio) ratio, and the mixture was kneaded in a mortar to make a paste. 0.53g of this paste was added to the mixture of water and oily components, shaken by hand for 1 minute, and left to stand for 30 minutes, and the emulsified state was evaluated. The results are shown in Table 1.
[0050] <Method for evaluating emulsion state> ×1: A combination that is incompatible with both oil-based ingredients and water (Figure 1) ×2: A combination that has affinity for oily ingredients but not for water (Figure 2) ×3: A combination that is incompatible with oily ingredients but compatible with water (Figure 3) 〇: A combination that is compatible with both oil-based ingredients and water (Figure 4)
[0051] [Table 1]
[0052] When amphiphilic solid particles B-1 to B-15 were combined with oily components C-1 to C-7, it was shown that there was an optimal combination. Furthermore, tri-2-ethylhexanoic acid glyceryl of oily component C-5 showed good emulsification with all amphiphilic solid particles, and was therefore shown to be the optimal oily component for Pickering emulsification. Furthermore, amphiphilic solid particles B-6 lauroyl lysine and B-7 caproyl lysine showed good emulsification with all oily components, and were therefore shown to be the optimal solid particles for Pickering emulsification. From this, it was suggested that the hydrophilic polymer could be evaluated with less influence of oily components and amphiphilic solid particles by using a combination of tri-2-ethylhexanoic acid glyceryl of C-5 and lauroyl lysine of B-6, and therefore the evaluation was centered on this combination.
[0053] <Evaluation of polysaccharides and water-soluble polymers> The oil-in-water emulsion compositions of Examples 1 to 19 were prepared by the following method. Add 38 g of oil components C-1 to C-7 to a 100 ml beaker, then add 2 g of amphiphilic solid particles B-1 to B-15. Next, mix with a disperser at 300 rpm for 3 minutes to make oil phase A. In a 200 ml beaker, add 136.16 g of water, then add 6 g of glycerin, 6 g of pentylene glycol, 1.8 g of phenoxyethanol, and 4 g of butylene glycol. Then, while stirring at 8,000 rpm with an IKA homomixer (T-25), gradually add 0.04 g of polysaccharide A-1 or A-2. After addition, heat to 80°C and maintain for 5 minutes. After stirring and mixing, cool to 30°C with water, then add 3Na citrate. 2 Add 2 g of a 6.6% aqueous solution of water and 4 g of a 0.32% aqueous solution of anhydrous citric acid, mix and stir to make aqueous phase B. The oil phase (A) was added to 160 g of the aqueous phase (B) and emulsified by propeller stirring at 300 rpm for 1 minute to prepare the Example. When the amount of A-1 or A-2 added was changed, the amount of water added was changed so that the total amount of the aqueous phase (B) was 160 g. The formulations of the examples are shown in Tables 2 and 3.
[0054] [Table 2]
[0055] [Table 3]
[0056] The oil-in-water emulsion compositions of Comparative Examples 1 to 12 were prepared by the following method. A-1 or A-2 was replaced with A-3 to A-5, and the amount of water to be mixed was changed so that the total amount of water phase B was 160g. 40g of oil phase A was added thereto, and emulsified by propeller stirring at 300 rpm for 1 minute. When A-6 to A-8 were mixed, 133g of water was mixed when preparing water phase B, 40g of oil phase A was added thereto, and emulsified by propeller stirring at 300 rpm for 1 minute. Then, the mixture was neutralized to pH 7 with 0.1N sulfuric acid water, and water was added so that the total amount of water phase B was 160g. The composition of the comparative example is shown in Table 4.
[0057] [Table 4]
[0058] <Stability test over time> The oil-in-water emulsion compositions of Examples 1 to 15 and Comparative Examples 1 to 12 were placed in No. 8 standard glass bottles (transparent wide-mouthed) at 80 ml each, and the conditions after storage for one month at 30° C. and 50° C. were observed to evaluate the stability over time. The results are shown in Table 5.
[0059] <Method for evaluating stability over time> 〇: Maintains emulsion state ×: Creaming
[0060] [Table 5]
[0061] In Examples 1 to 19, in which the polysaccharides of the present invention, A-1 Alcasealan and A-2 Diutan gum, were used, the emulsified state was maintained and stable at both 30°C and 50°C when the blending amount of the polysaccharide was 0.02 to 0.5% by mass. On the other hand, in Comparative Examples 1 to 6, in which water-soluble polymers outside the present invention, A-3 to A-8, were used, creaming occurred at a blending amount of 0.05% by mass. Then, as in Comparative Example 7, the blending amount of A-3 xanthan gum was increased, and the emulsification was maintained at both 30°C and 50°C. On the other hand, as in Comparative Examples 8 to 12, when the blending amounts of A-4 to A-8 were increased, the emulsification was maintained at 30°C, but separation occurred at the high temperature of 50°C.
[0062] <Sensory test (evaluation of usability)> The oil-in-water emulsion compositions of Examples 1 to 19 and Comparative Examples 1 to 12 were prepared and allowed to stand for one day. A total of 10 panelists were selected, two from each age group ranging from their 20s to their 60s, and each panelist took an appropriate amount on their fingers, then applied it to the backs of both hands and spread it, and a sensory evaluation of "stickiness" was performed. The evaluation criteria were as follows. The results are shown in Table 6.
[0063] <Evaluation criteria> ○: 8 or more out of 10 people rated it as not sticky △: 3 to 7 out of 10 people rated it as not sticky ×: Less than 2 out of 10 people rated it as not sticky
[0064] [Table 6]
[0065] In the case of using the polysaccharides of the present invention A-1 Alcasealan and A-2 Diutan gum as in Examples 1 to 19, many people did not feel sticky even when they were mixed up to 0.5% by mass. On the other hand, in the case of using the xanthan gum of A-3, the carboxymethyl cellulose of A-4, the polyvinyl alcohol of A-5, the acrylic acid polymer of A-6, the acrylic acid-methacrylic acid ester copolymer of A-7, and the acrylic acid-acrylic acid ester copolymer of A-8 as in Comparative Examples 1 to 6, some people did not feel sticky at a mixing amount of 0.05% by mass, but as in Comparative Examples 7 to 12, when the mixing amount of the water-soluble polymer was increased to 0.5 to 1% by mass, most people felt sticky, which was not suitable as an oil-in-water emulsion composition. [Brief description of the drawings]
[0066] [Figure 1] This is a photograph showing a combination that is incompatible with both oily components and water. [Diagram 2] This is a photograph showing a combination that has affinity for oily components but not for water. [Diagram 3] This is a photograph showing a combination that is incompatible with oily components but is compatible with water. [Figure 4] This is a photograph showing a combination that is compatible with both oil-based components and water.
Claims
1. An oil-in-water emulsion composition, characterized in that it comprises amphiphilic solid particles (A) and a polysaccharide (B) having at least one type of aldohexose or acidic sugar in its main chain and having a deoxy sugar in its side chain, in a two-phase system of an oily component and an aqueous component.
2. 1. An oil-in-water emulsion composition, wherein the polysaccharide (B) contains at least a polysaccharide represented by the following general formula (1):
3. 3. The oil-in-water emulsion composition according to claim 1 or 2, wherein the solid particles (A) comprise at least one selected from the group consisting of lauroyl lysine, bentonite, caproyl lysine, magnesium stearate, aluminum stearate, calcium stearate, cellulose powder, crystalline cellulose, cellulose acetate powder, rice starch treated with magnesium stearate, cellulose treated with magnesium stearate, silica treated with magnesium stearate, lauroyl lysine-treated Saccharomyces culture, silica silylate, aluminum stearate-treated titanium dioxide, dimethylpolysiloxane-treated titanium dioxide, and silica-treated titanium dioxide.
4. 3. The oil-in-water emulsion composition according to claim 1, wherein the polysaccharide (B) is contained in an amount of 0.02 to 0.5% by mass based on the total amount of the blended components.
5. A method for producing an oil-in-water emulsion composition, comprising the steps of dissolving the polysaccharide (B) in an aqueous component to prepare an aqueous phase, and mixing the solid particles (A) with an oil component to prepare an oil phase, and adding the prepared oil phase to the aqueous phase to emulsify.