JP2018035082A - Emulsion composition for producing foam agent, form agent, method for improving foamability, foamability improving agent, and make-up method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide novel emulsion compositions for producing foam agents capable of producing foam without using surfactant, to provide foam agents, to provide methods for improving foamability, to provide foamability improving agents, and to provide make-up methods.SOLUTION: An emulsion composition for producing a foam agent comprises an oil phase, an aqueous phase, a closed endoplasmic reticulum formed of an amphipathic substance which forms a closed endoplasmic reticulum spontaneously, or a particle of a polycondensation polymer having a hydroxyl group, and a thickener. The foam agent comprises an undiluted solution consisting of the emulsion composition, and a propellant. A method for improving foamability is characterized by further incorporating a thickener into the emulsion composition for producing a foam agent which comprises an oil phase, an aqueous phase, a closed endoplasmic reticulum formed of an amphipathic substance which forms a closed endoplasmic reticulum spontaneously, or a particle of a polycondensation polymer having a hydroxyl group.SELECTED DRAWING: None

Description

  The present invention relates to an emulsified composition for foam preparation, a foam agent, a method for improving foam-forming ability, a foam-forming ability improving agent, and a cosmetic method.

  Foaming agents are used in various applications such as skin cosmetics, hair cosmetics, and cleaning products. Conventionally, an emulsion composition using a surfactant has been used as the stock solution. For example, Patent Document 1 discloses an emulsified composition with a predetermined amphoteric surfactant, and an aerosol-type cosmetic foam containing the emulsified composition and a propellant.

JP 2002-193767 A

  However, although the surfactant is excellent in the ability to form foam, for example, when used as a cosmetic, there are problems such as stickiness and strong irritation. Further, when the foam agent is used as an industrial cleaner or the like, there is a problem in that the surfactant remains on the cleaning surface, and it becomes easily cloudy.

  On the other hand, as an emulsification technique to replace the above surfactant, so-called three-phase emulsification using particles of a closed vesicle or a polycondensation polymer having a hydroxyl group formed by an amphiphile that spontaneously forms a closed vesicle The law is known. The present inventors have found that the above-mentioned problems caused by the surfactant can be solved in the foam agent using the emulsion composition by the three-phase emulsification method. However, the three-phase emulsification method has room for improvement in use as a foaming agent.

  Therefore, there is a need for a foaming agent that can form sufficient foam regardless of the surfactant.

  The present invention has been made in view of the above circumstances, and is a novel foam preparation-emulsifying composition capable of forming good foam without using a surfactant, a foam agent, and a method for improving foam-forming ability. An object of the present invention is to provide a foam-forming ability improver and a cosmetic method.

  The present inventors have found that good foam can be formed by adding a thickener to an emulsified composition obtained by three-phase emulsification, and have completed the present invention. More specifically, the present invention provides the following.

  (1) For forming a foam agent comprising an oil phase, an aqueous phase, particles of a polycondensation polymer having closed vesicles or hydroxyl groups formed by amphiphiles that spontaneously form closed vesicles, and a thickener. Emulsified composition.

  (2) The emulsion composition according to (1), which is an O / W emulsion.

  (3) The emulsion composition according to (1) or (2), wherein the thickener includes a polysaccharide having a network structure formed by hydrogen bonding.

  (4) The emulsion composition according to (3), wherein the polysaccharide is a thickening polysaccharide.

  (5) The emulsion composition according to (3) or (4), wherein the polysaccharide comprises one or more selected from the group consisting of starch, starch derivatives, and alginic acids.

  (6) The said thickener is an emulsion composition in any one of (1) to (5) whose viscosity in 20 degreeC of 1 mass% aqueous solution is 100 mPa * s or more and 100000 mPa * s or less.

(7) The average particle diameter of the closed vesicle formed of an amphiphile that spontaneously forms a closed vesicle is 8 nm or more and 800 nm or less,
The emulsion composition according to any one of (1) to (6), wherein the polycondensation polymer particles have an average particle size of 8 nm to 800 nm.

  (8) The emulsion composition according to any one of (1) to (7), wherein the oil phase contains one or more oils selected from the group consisting of ester oils, hydrocarbon oils, silicone oils, and vegetable oils. .

  (9) A foaming agent comprising a stock solution comprising the emulsion composition according to any one of (1) to (8) and a propellant.

  (10) The foam according to (9), which is applied to a human body or an animal.

  (11) In an emulsified composition for producing a foam agent, comprising an oil phase, an aqueous phase, and particles of a polycondensation polymer having a closed vesicle or a hydroxyl group formed by an amphiphile that spontaneously forms a closed vesicle Furthermore, the method of improving foam forming power by containing a thickener.

  (12) Preparation of foam agent comprising particles of a polycondensation polymer having a closed endoplasmic reticulum or a hydroxyl group formed of an oil phase, an aqueous phase, and an amphiphile that spontaneously forms a closed endoplasmic reticulum, comprising a thickener. A foam-forming agent for emulsifying compositions.

  (13) A cosmetic method comprising a step of applying the foam according to (9) or (10) to a human body or an animal.

  According to the present invention, there are provided a novel foam preparation emulsifying composition capable of forming good foam without using a surfactant, a foam agent, a method for improving foam-forming ability, a foam-forming ability improving agent, and a cosmetic method. Can be provided.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to this.

<Emulsified composition>
The emulsified composition of the present invention comprises an oil phase, an aqueous phase, particles of a polycondensation polymer having closed vesicles or hydroxyl groups formed by amphiphiles that spontaneously form closed vesicles, and a thickener. It is an emulsified composition for producing a foam agent (hereinafter sometimes referred to as “emulsified composition” in the present specification). In a foam prepared using the emulsion composition as a stock solution, good foam can be formed without using a surfactant. “Improving foam-forming ability” means that the fineness of foam, foam retention time, foam retention, and the like are improved.

  The emulsified composition of the present invention is an emulsified composition by a so-called three-phase emulsification method using closed vesicles formed of amphiphiles that spontaneously form closed vesicles or polycondensation polymer particles having a hydroxyl group. It is. As described above, the emulsion composition by the three-phase emulsification method is insufficient for use as a foaming agent. In the three-phase emulsification method, particles of a closed vesicle or a polycondensation polymer having a hydroxyl group formed by an amphiphile that spontaneously forms a closed vesicle are interposed at an oil-water interface, and the van der It can emulsify by adhering to the oil phase by the Waals force. Three-phase emulsification is different from emulsification with a surfactant that lowers the interfacial tension by hydrophilic groups and hydrophobic groups. The present inventors added a thickener to the emulsion composition by the three-phase emulsification method, so that even in the emulsion composition by the three-phase emulsification method, which was insufficient for use as a foaming agent, good foam was obtained. It was found that it can be formed. Therefore, compared to the emulsion composition with a surfactant, when used as a cosmetic, it can suppress stickiness, irritation, etc., and when used as a cleaning product, it is difficult for the surfactant to remain on the cleaning surface. , White turbidity can be suppressed.

  It is estimated that the reason why the emulsified composition of the present invention can form a good foam by including a thickener is as follows.

  The general generation mechanism of the aerosol foam is that when the propellant dissolved in the oil phase of the emulsified composition is ejected under atmospheric pressure, the propellant is vaporized to generate bubbles (from the aerosol packaging technique). Adjacent bubbles-bubbles are in the liquid phase, and the bubble-liquid interface is present with surfactant molecules with the hydrophobic groups facing the bubbles (gas phase) and the hydrophilic groups facing the liquid phase. Yes. When the propellant vaporizes, the oil phase volume of the emulsified composition increases abruptly, but in the case of an emulsified composition with a surfactant, surfactant molecules present in the aqueous phase immediately move to the bubble-liquid phase interface. By doing so, bubbles can be maintained. On the other hand, in the case of an emulsified composition of three-phase emulsification, there are three-phase emulsified particles at the bubble-liquid interface, but the magnitude of the oil phase volume increase rate of the emulsified composition when the propellant vaporizes Therefore, the movement of the three-phase emulsified particles does not catch up and it is difficult to maintain the bubbles, but according to the present invention, it can be assumed that the bubbles can be sufficiently maintained by the thickener.

  The form of the emulsion composition of the present invention is not particularly limited, and may be an O / W type emulsion structure or a W / O type emulsion structure. In particular, an O / W type emulsion structure is preferable because foam forming power of the foam agent is excellent.

(Thickener)
As described above, the thickener in the present invention can improve the foam forming power in the emulsion composition of the present invention. The type of thickener in the present invention is capable of improving the foam-forming ability of the foam agent. Specifically, polysaccharides, proteins (milk-derived protein, egg-derived protein, wheat protein, soybean-derived protein) , Gelatin, etc.), synthetic polymers (vinyl, vinylidene, polyacryl, polyamide, polyether, polyglycol, polyvinyl alcohol, polyalkylene oxide, and combinations thereof). Among these, it is preferable to use a polysaccharide because the foam-forming ability of the foam agent is particularly excellent. These thickeners may be used alone or in combination of two or more. However, for the purpose of preventing allergies, it is preferable not to include a thickener (eg, protein) that becomes an allergen.

  Types of polysaccharides include, for example, starch, starch derivatives, dextrin, alginic acids, agar, guar gum, locust bean gum, tara gum, fenugreek gum, tamarind gum, glucomannan, pectin, xanthan gum, gellan gum, κ carrageenan, ι carrageenan, λ Carrageenan, far cerulean, cassia gum, curdlan, queen seed, gum arabic, succino glucan, glycosaminoglycan, cellulosic polymer (methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, etc.) Etc. A polysaccharide may be used individually by 1 type and may use 2 or more types together. In the present invention, the polysaccharide used as a thickener has a network structure formed by hydrogen bonding.

  The polysaccharide in the present invention preferably contains at least one selected from the group consisting of starch, starch derivatives, and alginic acids because foam forming ability of foaming agent is particularly excellent. Although it does not specifically limit as starch, Natural starch, such as tapioca starch, rice starch, potato starch potato starch, sweet potato starch, wheat starch, sago starch, corn starch, potato starch, waste flour, can be used. Among these, it is preferable to use tapioca starch because foam forming ability of the foam agent is particularly excellent. Examples of starch derivatives include, but are not limited to, metal salts of alkenyl succinate starch (starch sodium octenyl succinate, starch aluminum octenyl succinate, etc.), alkyl starch (methyl starch, ethyl starch, etc.), carboxyalkyl starch (carboxymethyl starch, etc.) Carboxyethyl starch, etc.), hydroxyalkyl starch (hydroxyethyl starch, hydroxypropyl starch, etc.), metal salt of hydroxyalkyl phosphate (such as sodium hydroxypropyl phosphate), acetyl starch, aminoacetyl starch, allyl starch, etc. It can be illustrated. Among these, it is preferable to use a metal salt of alkenyl succinate (particularly starch sodium octenyl succinate) because foam forming ability of foaming agent is particularly excellent. Alginic acids are not particularly limited, and examples thereof include sodium alginate, potassium alginate, alginates (such as propylene glycol alginate), and the like. Is preferably used.

  Since the polysaccharide in the present invention has a higher viscosity of the aqueous solution, the foam forming ability of the foaming agent is superior. Among the above, thickening polysaccharides (for example, starch, starch derivatives, alginic acids, agar, guar gum, Locust bean gum, tara gum, fenugreek gum, tamarind gum, glucomannan, xanthan gum, gellan gum, gum arabic, etc.) are preferably used. From the same viewpoint, the thickener such as polysaccharides preferably has a viscosity of 1% by weight aqueous solution at 20 ° C. of preferably 100 mPa · s or more, and the viscosity of 1% by weight aqueous solution at 20 ° C. of 500 mPa · s or more. The viscosity at 20 ° C. of the 1% by mass aqueous solution is more preferably 1000 mPa · s or more. Moreover, the upper limit of the viscosity at 20 ° C. of the 1% by weight aqueous solution of the thickener is not particularly limited. However, when the viscosity is too high, the viscosity of the composition becomes too high and the feeling of use of the foaming agent decreases. If the viscosity is too high, vaporization of the propellant is suppressed, and after being sprayed from an aerosol can, foaming is delayed a little (slow foaming) and vaporization is accelerated when pressure is applied with heat, fingers, etc. The phenomenon of foaming with sound (cracking) occurs, and it is not suitable for use as a foaming agent. From this, the viscosity at 20 ° C. of the 1% by weight aqueous solution of the thickener is preferably 100000 mPa · s or less, more preferably 80000 mPa · s or less, and further preferably 60000 mPa · s or less. . The viscosity at 20 ° C. is measured with a B-type viscometer.

  The weight average molecular weight of the polysaccharide in the present invention may be, for example, 500 to 1,000,000. The weight average molecular weight is measured by size exclusion chromatography.

  The content of the thickener in the present invention is not particularly limited, and may be, for example, 0.01 to 3.0% by mass relative to the mass of the entire composition. Since the foam forming power of the agent is excellent, it is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, and further preferably 0.50% by mass or more. On the other hand, when the content of the thickener is too large, the viscosity becomes too high and the feeling of use of the foaming agent is reduced. From this, the content of the thickener in the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, and further preferably 1% by mass or less.

(Oil phase)
The oil contained in the oil phase in the present invention is not particularly limited, and examples thereof include ester oil, hydrocarbon oil, silicone oil, fats and oils (vegetable oil, animal oil, fish oil, etc.), higher alcohol, higher fatty acid, sterol and the like. . Oil may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to use one or more kinds of oils selected from the group consisting of ester oils, hydrocarbon oils, silicone oils, and vegetable oils because foam forming ability of the foaming agent is excellent.

  Examples of ester oils include, but are not limited to, ethyl hexyl methoxycinnamate, cetyl ethyl hexanoate, diisostearyl malate, isopropyl myristate, ethyl hexyl palmitate, octyl palmitate, octyl isopalmitate, isononyl isononanoate, isotridecyl isononanoate , Methyl heptyl laurate, hexyl laurate, glyceryl tri (caprylate / caprate), triethylhexanoin, neopentyl recall dicaprate, cetyl octoate, isocetyl stearate, isopropyl isostearate, isodecyl oleate, tri-2-ethyl Examples include glyceryl hexanoate, pentaerythritol tetra-2-ethylhexanoate, 2-ethylhexyl succinate, diethyl sebacate and the like. Among these, it is preferable to use ethylhexyl methoxycinnamate and cetyl ethylhexanoate because the foaming ability of the foaming agent is excellent.

  The hydrocarbon oil is not particularly limited, and examples thereof include liquid paraffin, squalane, squalene, ceresin, paraffin, petroleum jelly, liquid isoparaffin, microcrystalline wax, polybutene, and olefin oligomer. Of these, squalane is preferably used because of its excellent foam forming ability. These may be used alone or in combination of two or more.

  The silicone oil is not particularly limited, but dimethyl silicone (for example, methylpolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, highly polymerized methylpolysiloxane, etc.), methylphenylsilicone, cyclic dimethylsilicone (for example, octamethylcyclotetrasiloxane). , Decamethylcyclopentasiloxane, methylcyclopolysiloxane, cyclopentasiloxane, etc.), methyl hydrogen silicone, alcohol-modified silicone (eg stearoxymethyl polysiloxane, cetoxymethyl polysiloxane, etc.), alkyl-modified silicone, amino-modified silicone, etc. Is mentioned. Of these, cyclic dimethylsilicone is preferred, and cyclopentasiloxane is particularly preferred because of its excellent foam forming ability. These may be used alone or in combination of two or more.

  Examples of oils and fats include vegetable oils and animal oils. Vegetable oils include rice bran oil, olive oil, jojoba oil, almond oil, camellia oil, corn oil, mink oil, avocado oil, sasanqua oil, castor oil, saflower oil, sunflower oil, rapeseed oil, sesame oil, soybean oil, and permanent oil. Asa seed oil, flaxseed oil, peanut oil, cacao butter, grape seed oil, cottonseed oil, palm oil, palm oil, coconut oil, pistachio seed oil, hazelnut oil, macadamia nut oil, rosehip oil and the like. Among these, it is preferable to use rice bran oil, olive oil, jojoba oil, almond oil or the like because foam forming ability of the foaming agent is excellent. Examples of animal oils include beef tallow, lard, milk fat, sheep oil, horse oil, mink oil, emyu-oil, hydrogenated oil, egg yolk fat oil and the like. These may be used alone or in combination of two or more.

  The higher alcohol is not particularly limited, and examples thereof include isostearyl alcohol, octyldodecanol, oleyl alcohol, lauryl alcohol, myristyl alcohol, cetanol, stearyl alcohol, and behenyl alcohol. These may be used alone or in combination of two or more.

  The higher fatty acid is not particularly limited, and examples thereof include isostearic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, sorbic acid, and linoleic acid. These may be used alone or in combination of two or more.

  The sterol is not particularly limited, and examples thereof include cholesterol and phytosterol. These may be used alone or in combination of two or more.

  Moreover, you may use the oil used as a ultraviolet absorber as the oil contained in the oil phase in this invention. Examples of oils used as ultraviolet absorbers include 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester, paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, 2-Ethylhexyl paradimethylaminobenzoate, ethyl 4- [N, N-di (2-hydroxypropyl) amino] benzoate, ethylene glycol salicylate, 2-ethylhexyl salicylate, homomenthyl salicylate, 2-ethoxyethyl paramethoxycinnamate , 2-methoxyhexyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, dihydroxydimethoxybenzophenone, sodium dihydroxydimethoxydibenzophenone disulfonate, Hydroxybenzophenone, tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid, sodium hydroxymethoxybenzophenone sulfonate, ferulic acid, menthyl anthranilate, dimethicodiethylbenzalmalonate, terephthalylidene dicamphorsulfone Acid, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, 4-tert-butyl-4'-methoxy-dibenzoylmethane, 2,2-methylenebis (6- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) and the like.

  The oil content relative to the mass of the entire emulsion composition in the present invention is not particularly limited, and can be appropriately selected according to the form and purpose of the emulsion composition. However, if the amount of oil is excessive, the foam agent tends to hardly form foam, but according to the emulsion composition of the present invention, foam may be formed even if the amount of oil is large. Furthermore, even when the amount of oil is large when applied to the human body or animal, it is difficult to stick. In this respect, it is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, further preferably 10.0% by mass or more, and 20% by mass or more. Even more preferred is 28% by weight or more. However, since it is difficult to form bubbles when it is too much, for example, it is preferably 90% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, It is still more preferable that it is mass% or less, and it is most preferable that it is 35 mass% or less. In particular, when the emulsion composition of the present invention has an O / W type emulsion structure, the oil content is preferably within the above range.

(Water phase)
The closed vesicle or polycondensation polymer particles in the present invention are extremely excellent in emulsification performance. For this reason, the amount of water in the emulsified composition can be widely selected from the range of 0.1 to 95% by mass, and can be appropriately set according to the form of the emulsified composition and the amount of the oil phase. For example, it is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 50 to 70% by mass. In particular, when the emulsion composition of the present invention has an O / W type emulsion structure, the water content is preferably within the above range.

(Closed endoplasmic reticulum or polycondensation polymer particles)
The closed endoplasmic reticulum in the present invention is formed by an amphipathic substance that spontaneously forms a closed endoplasmic reticulum. Examples of amphiphilic substances that form closed endoplasmic reticulum include polyoxyethylene hydrogenated castor oil derivatives represented by the following general formula 1 or dialkylammonium derivatives, trialkylammonium derivatives, tetraalkyls represented by the general formula 2 A halogen salt derivative of an ammonium derivative, dialkenyl ammonium derivative, trialkenyl ammonium derivative, or tetraalkenyl ammonium derivative may be employed.

General formula 1

  In the formula, E, which is the average added mole number of ethylene oxide, is 3 to 100. If E is excessive, the type of good solvent that dissolves the amphiphilic substance is limited, and thus the degree of freedom in producing hydrophilic nanoparticles is narrowed. From this, the upper limit of E is preferably 50, more preferably 40. The lower limit of E is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and most preferably 30 or more because foam forming ability of the foaming agent is improved.

General formula 2

In the formula, R 1 and R 2 are each independently an alkyl group or alkenyl group having 8 to 22 carbon atoms, R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is F, Cl, Br, I or CH ₃ COO.

  Alternatively, phospholipids, phospholipid derivatives, and the like may be employed. As the phospholipid, among the structures represented by the following general formula 3, DLPC (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 12, DMPC (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-choline), DPPC with a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3-phospho-rac-1-choline) Can be adopted.

General formula 3

In addition, among the structures represented by the following general formula 4, DLPG (1,2-Diilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH ₄ salt of carbon chain length 12 and carbon DMPG chain length 14 (1,2-dimyristoyl-sn- glycero-3-phospho-rac-1-glycerol) Na salt or NH ₄ salt, DPPG (1,2-Dipalmitoyl-sn -glycero carbon chain length 16 Na salt or NH ₄ salt of -3-phospho-rac-1-glycerol) may be employed.

Formula 4

  As phospholipids and phospholipid derivatives, lecithin (natural lecithin, hydrogenated lecithin, etc.) can be used.

  As the amphiphilic substance, foam forming ability of the foaming agent is improved, so that derivatives of polyoxyethylene hydrogenated castor oil (“HCO-10”, “HCO-30”, “HCO-50” manufactured by Nikko Chemicals Co., Ltd.) are used. ”,“ HCO-100 ”, etc.), dilauroyl glutamate lysine Na, and lecithin are preferably used.

  The polycondensation polymer having a hydroxyl group is not particularly limited, and may be either a natural polymer or a synthetic polymer, and may be appropriately selected depending on the application. However, natural polymers are preferable from the viewpoint of safety and generally inexpensive, and sugar polymers described below are more preferable from the viewpoint of excellent emulsifying function. In addition, while the particle | grain includes both the thing which the polycondensation polymer was made into the single particle, or the thing with which the single particle connected, on the other hand, the aggregate (it has a network structure) before making into a single particle is not included. The above-mentioned “polysaccharides” are not particles, but form a network structure by hydrogen bonding, so they are clearly different from “polycondensation polymer particles” that have a so-called three-phase emulsifying ability. It is. Whether or not the polycondensation polymer is made into particles can be confirmed by observation with an electron microscope or a particle size distribution meter. The polycondensation polymer having a hydroxyl group may be used alone or in combination of two or more.

  The sugar polymer is a polymer having a glucoside structure such as cellulose and starch. For example, those produced by microorganisms with some sugars among monosaccharides such as ribose, xylose, rhamnose, fucose, glucose, mannose, glucuronic acid, gluconic acid, xanthan gum, gum arabic, guar gum, caraya gum, carrageenan , Pectin, fucoidan, quinseed gum, tranto gum, locust bean gum, galactomannan, curdlan, gellan gum, fucogel, casein, gelatin, starch, collagen, white jellyfish polysaccharide, natural polymers, methylcellulose, ethylcellulose, methylhydroxypropylcellulose , Carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, Allo carboxymethyl hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, propylene glycol alginate, cellulose crystals, starch-acrylic acid sodium graft polymers include semi-synthetic polymers such as hydrophobic hydroxypropyl methylcellulose. In addition to the sugar polymer, synthetic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, polyacrylate, and polyethylene oxide can be used. These may be used alone or in combination of two or more.

  The sugar polymer is preferably hydroxyethylcellulose, stearoxyhydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylcellulose, guar gum, or a salt thereof. In particular, the use of hydroxyethylcellulose can improve the foam-forming ability of the foam agent. preferable.

  The closed endoplasmic reticulum or polycondensation polymer particles in the present invention may have an average particle size of about 8 nm to 2000 nm, for example, but the smaller the particle size, the better the foam retention of the foam agent. From this, the average particle size is preferably 8 nm or more and 800 nm or less, and more preferably 8 nm or more and 500 nm or less. Since these preparation methods are conventionally known as methods for preparing particles having three-phase emulsification ability as disclosed in Japanese Patent No. 3855203, etc., the description thereof is omitted. Whether or not the particles can be emulsified in three phases can be determined by performing light scattering measurement on the hydrophilic nanoparticle dispersion used for emulsification and having an average particle diameter of, for example, 8 to 400 nm. Furthermore, about the prepared emulsion, it can judge by performing atomic microscope (AFM) observation and confirming that the emulsifier particle has adhered to the oil-droplet surface.

  The amount of the closed vesicle or the polycondensation polymer particles may be appropriately set according to the amount of the oil phase, and is not particularly limited, but may be 0.0001 to 5% by mass in total. Thereby, the foam formation power of a foaming agent improves. Unlike conventional surfactants, closed endoplasmic reticulum or polycondensation polymer particles have excellent emulsifying properties, and therefore 5% by mass or less (specifically, 4% by mass or less, 3% by mass or less, 2% by mass or less, The emulsified state can be maintained even with a small amount of 1.0% by mass or less and 0.75% by mass or less. In addition, all the said amounts are solid content. Moreover, since the foam agent can form foam even if the amount of the closed vesicles or polycondensation polymer particles is larger, the foaming agent can form a foam, so that the amount is 0.10% by mass or more based on the total mass of the emulsified composition. Is preferably 0.30% by mass or more, more preferably 0.50% by mass or more, and most preferably 0.70% by mass or more.

  The average particle size of the inner phase of the emulsion composition in the present invention is not particularly limited, and may be, for example, 0.001 μm or more, but the emulsion composition in the present invention is based on three-phase emulsification, Compared with conventional emulsification using a surfactant, the average particle size can be in a wide range. For example, when the emulsion composition of the present invention has an O / W emulsion structure, the average particle size of the oil phase that is the internal phase may be appropriately set according to the purpose and application. When used for the purpose of foam formation, the average particle size of the inner phase is preferably 500 μm or less, more preferably 250 μm or less, and even more preferably 100 μm or less. The average particle size of the inner phase is measured with a dense system particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

  The emulsified composition of the present invention may or may not contain a fragrance, a pH adjuster, a preservative, a colorant, an antioxidant, a surfactant and other emulsifiers in addition to the components other than those described above. Good. However, from the viewpoint of suppressing stickiness, irritation and the like, the content of the surfactant in the emulsion composition is preferably small, for example, 10% by mass or less (5% by mass with respect to the total mass of the emulsion composition). Hereinafter, it is preferably 1% by mass or less, 0.1% by mass or less, 0.05% by mass or less, 0.01% by mass or less, and the like, and more preferably the emulsion composition does not contain a surfactant.

  It is known that foams in foams can be formed by using a protein such as egg white, but there is a concern that the protein may act as an allergen when applied to the human body using the protein. However, the present invention can form sufficient bubbles without using protein such as egg white. From this viewpoint, the emulsified composition of the present invention is suitable for use as an emulsion for preparing a foam containing no protein.

  The emulsified composition is prepared by mixing a dispersion containing closed vesicles or polycondensation polymer particles with an oil component to prepare a composition of an O / W type or W / O type emulsion. It can be prepared by preparing an aqueous solution of the agent and mixing them. The water-soluble optional component may be added before emulsification, may be added before mixing, or may be added after mixing.

<Foaming agent>
The foam agent in the present invention includes a stock solution composed of the above-mentioned emulsion composition and a propellant. That is, the foam agent in the present invention is used in the form of an aerosol. As described above, the foam agent in the present invention can form bubbles without using a surfactant.

(Propellant)
Although it does not specifically limit as a propellant, Compressed gas, liquefied gas, or these mixed gas can be used. Since the liquefied gas is more easily dissolved in the emulsified composition and as a result, bubbles are easily formed, it is preferable to use the liquefied gas as the propellant.

  The liquefied gas is not particularly limited, and examples thereof include butane, propane, dimethyl ether, fluorocarbon, and liquefied petroleum gas. These may be used alone or in combination of two or more.

  The content of the liquefied gas is not particularly limited, and is appropriately determined in consideration of the solubility of the liquefied gas in the stock solution in the range of 0.5 to 60% by mass with respect to the total mass of the liquefied gas and the stock solution. May be. When the amount of the liquefied gas is increased, the ability to form bubbles can be improved. Therefore, the content of the liquefied gas is preferably 1.0% by mass or more with respect to the total mass of the liquefied gas and the stock solution. 2.0% by mass or more, more preferably 3.0% by mass or more, and most preferably 5.0% by mass or more.

  As the pressure when using the liquefied gas, a pressure at a temperature of 20 ° C., for example, 0.2 to 1.0 MPa can be used, but the higher the pressure, the better the ability to form bubbles. , 0.25 MPa or more, more preferably 0.3 MPa or more.

The compressed gas is not particularly limited, for example, may be used _{N 2, CO 2, N 2} O or the like, or can be a mixture of a plurality of gas such as air. When these compressed gases are used, it is difficult to form bubbles. However, since the foam agent of the present invention is excellent in foam forming ability as described above, it is possible to form bubbles even if compressed gas is used.

  Although the pressure of compressed gas is not specifically limited, For example, as prescribed | regulated by the high pressure gas safety law, it is less than 1 MPa at 35 degreeC and less than 1 MPa (for example, 0.1-0.91 MPa) at normal temperature. be able to. A higher pressure improves the ability to form bubbles, and is preferably 0.3 MPa or more, and more preferably 0.5 MPa or more.

(Method for producing foam agent)
The foam agent in the present invention can be produced according to a conventional method. For example, it can carry out by adding the stock solution which consists of the prepared emulsion composition to a container, and filling this with a propellant.

  The container filled with the foam agent is not particularly limited, and a container that can be used as a container of a conventionally known foam agent can be used. For example, a material such as metal, resin, or glass can be used. Moreover, you may equip a container with what is equipped with the container of the conventional well-known foam agent, such as a valve | bulb, an actuator, and a cap as needed.

(Use)
The use of the foam agent of the present invention is not particularly limited. For example, it is used for human body products (cosmetics, quasi-drugs, pharmaceutical products, etc.), animal products (pet products, etc.), industrial products (cleaning products, etc.), etc. Can do. Since the foam agent of the present invention can form foam without using a surfactant and can suppress stickiness and irritation, it is preferably used for applications (such as cosmetics) applied to the human body or animals. From another viewpoint, when used as an industrial cleaning product, the foam of the present invention is suitable for use as an industrial cleaning product because it hardly remains on the cleaning surface and does not easily become cloudy.

<Method for improving foam-forming ability>
The present invention relates to an emulsified composition for foam preparation comprising an oil phase, an aqueous phase, and particles of a polycondensation polymer having a closed vesicle or a hydroxyl group formed by an amphiphile that spontaneously forms a closed vesicle. Furthermore, the method of improving a foam formation power by including a thickener is included.

  As the emulsion composition for forming a foam agent, the same one as in the above-described emulsion composition of the present invention can be used. As the thickener, those similar to the thickener in the above-described emulsion composition of the present invention can be used.

<Foam forming power improver>
The present invention relates to a foam agent comprising particles of a polycondensation polymer having a closed endoplasmic reticulum or a hydroxyl group formed of an oil phase, an aqueous phase, and an amphiphile that spontaneously forms a closed endoplasmic reticulum, comprising a thickener. The foam-forming ability improving agent in the emulsified composition for preparation is included.

  The “foam forming ability improver” means an application for improving the fineness of foam, the retention time of foam, the retention capacity of foam, and the like.

<Makeup method>
This invention includes the cosmetic method which has the process of applying the said foam agent to a human body or an animal. According to the cosmetic method of the present invention, foam can be formed without using a surfactant or protein in the foam, so that when applied to the human body or animal, stickiness and irritation can be suppressed, and allergy due to protein can be prevented. It can be avoided. When applying to a human body or an animal, for example, it can be performed by attaching to the skin surface or hair of the human body or animal.

  As the foam agent, the same foam agent as that of the present invention described above can be used.

<Examples 1-5, Comparative Examples 1 and 2>
(Preparation of foam agent)
First, as shown in Table 1 described later, an aqueous polysaccharide solution was prepared using the amount of starch octenyl succinate Na, which is a polysaccharide, as a thickener. On the other hand, a closed vesicle dispersion of dilauroylglutamate ricin Na was prepared, and squalane and water were added to this dispersion and stirred to prepare a three-phase emulsion composition of an O / W emulsion. The aqueous polysaccharide solution and the three-phase emulsion composition were mixed and water was added to prepare a stock solution of foaming agents according to Examples 1-5. On the other hand, without using an aqueous polysaccharide solution of starch octenyl succinate Na, a stock solution of a foam agent consisting only of a three-phase emulsion composition of an O / W type emulsion was prepared so as to have the formulation shown in Table 1, and this was compared with Comparative Example. A foam stock solution according to No. 1 was used. Moreover, the stock solution of the foam agent which consists only of starch octenyl succinate Na and water was prepared so that it might become the prescription of Table 1, and this was made into the stock solution of the foam agent which concerns on the comparative example 2.

  The prepared stock solutions according to Examples 1 to 5 and Comparative Examples 1 and 2 were accommodated in a pressure-resistant glass bottle, and then L-0.29 (mixed gas of butane and propane, 20 as a liquefied gas with respect to the stock solution) The foaming agent according to Examples 1 to 5 and Comparative Examples 1 and 2 was prepared. The amount of each component added was such that the final mass ratio was as shown in Table 1 described later.

(Evaluation 1)
For the foams according to Examples 1 to 5 and Comparative Examples 1 and 2, after filling the propellant, the foam forming ability was visually observed, the fineness of the foam, the foam retention time, the foam retention power and The overall evaluation as a foam agent was evaluated in consideration of the whole.

The fineness of the foam was determined as follows.
X: Bubbles could not be formed so much and there was no fine texture.
Δ: Bubbles were slightly fine.
◯: Bubbles were fine.
A: Bubbles were very fine.

The foam retention time was determined as follows.
X: Bubble formation time was very short.
Δ: Bubble retention time was slightly short.
◯: The bubble retention time was long.
A: The foam retention time was very long.

The foam retention strength was determined as follows.
X: The foam retention force was very weak.
Δ: The foam holding power was slightly weak.
◯: The foam retention was strong.
(Double-circle): The foam retention power was very strong.

The overall evaluation was based on the following criteria.
X: Foam could not be formed so much, and the overall balance of the fineness of the foam, the foam retention time, and the foam retention was insufficient.
(Triangle | delta): Although foam can be formed, the whole balance of the fineness of a foam, the retention time of a foam, and the retention power of a foam was a little inadequate.
◯: Bubbles could be formed, and the overall balance of the fine texture of the foam, the foam retention time, and the foam retention was good.
A: Bubbles could be formed, and the overall balance of the fine texture of the foam, the retention time of the foam, and the retention of the foam was very good.

  Table 1 shows the formulations and evaluation results of the foams according to Examples 1 to 5 and Comparative Examples 1 and 2. Each numerical value in Table 1 indicates “mass%” of each component.

  As shown in Table 1, in Comparative Example 1 that does not contain the polysaccharide octenyl succinate starch Na as a thickener and Comparative Example 2 that does not contain the closed endoplasmic reticulum, the fineness of the foam, the retention time of the foam, While the evaluation of the holding power was low, in Examples 1 to 5, the overall evaluation of the fineness of the foam, the holding time of the foam, and the holding power of the foam were good. Thereby, it turned out that a favorable foam can be formed by adding a polysaccharide to a three-phase emulsion composition.

<Examples 6 to 16>
(Preparation of foam agent)
First, as shown in Table 2 described later, the foam agent according to Examples 6 to 12 was prepared in the same manner as in Example 4 except that the amount of the propellant (L-0.29) was changed. Prepared. The type of liquefied gas as a propellant is L-0.49 (mixed gas of butane and propane, pressure at 20 ° C .: 0.49 MPa), L-0.39 (mixed gas of butane and propane, at 20 ° C.) The pressure is 0.39 MPa) or L-0.69 (mixed gas of butane and propane, pressure at 20 ° C .: 0.69 MPa). As shown in 3, foaming agents according to Examples 13, 15, and 16 were prepared. But in this case changing the propellant from L-0.29 is liquefied gas to CO ₂ is compressed gas, the same procedure as in Example 4, as shown in Table 3 to be described later, form according to Example 14 An agent was prepared.

(Evaluation 2)
About the foam agent which concerns on Examples 6-16, evaluation of the fineness of foam, the retention time of foam, and the foam retention force and comprehensive evaluation were performed on the same criteria as “Evaluation 1”. Tables 2 and 3 show the formulations and evaluation results of the foams according to Examples 6 to 14. The item of CO ₂ of Example 14 in Table 3 indicates the pressure (MPa) at 25 ° C. of the compressed gas.

  As shown in Tables 2 and 3, it was shown that the larger the amount of L-0.29, the higher the overall evaluation of the foam. This is because the thickener is dissolved in the aqueous phase, and the foam generated during the vaporization of the aqueous phase is affected by the thickener, so that the larger amount of L-0.29 is the momentum during the vaporization of the aqueous phase. This is presumably because the foam forming ability was increased, and as a result, the overall evaluation of the foam was improved. Moreover, it was shown that Example 13, 15, 16 has higher foam comprehensive evaluation than Example 9 using L-0.29. This is because the pressure of L-0.49 is higher than that of L-0.29, and the higher the amount of L-0.29, the stronger the moment of vaporization of the aqueous phase. It is estimated that it became higher and as a result, the overall evaluation of the foam was good. In addition, it was shown that the example using the liquefied gas tends to have a longer bubble retention time than the example 14 using the compressed gas. This is presumed to be due to the fact that the amount of the compressed gas dissolved in the emulsified composition is small, so that the momentum during vaporization of the aqueous phase tends to be lower than that of the liquefied gas.

<Examples 17 and 18>
(Preparation of foam agent)
First, the foam agent according to Examples 17 and 18 was the same as Example 4 except that the type of thickener was changed to tapioca starch or Na alginate as shown in Table 4 described later. Was prepared.

(Evaluation 3)
About the foam agent which concerns on Examples 17 and 18, the fineness of foam, the retention time of foam, evaluation of foam retention, and comprehensive evaluation were performed on the same criteria as “Evaluation 1”. Table 4 shows the formulation and evaluation results of the foams according to Examples 4, 17, and 18 described above.

  As shown in Table 4, in all of octenyl succinate starch Na, tapioca starch, and alginic acids, the overall evaluation of foam was high. In particular, it was found that the overall evaluation of bubbles when Na alginate was used was excellent.

<Examples 19 to 22>
(Preparation of foam agent)
First, in Example 4, the three-phase emulsified particles used for emulsification are HCO-10 (polyoxyethylene hydrogenated castor oil derivative), HCO-30 (polyoxyethylene hydrogenated castor oil derivative), and recinol (hydrogenated lecithin). ), Or the point except having changed to hydroxyethyl cellulose, the foam agent which concerns on Examples 19-22 was prepared in the same procedure as shown in Table 5 mentioned later.

(Evaluation 4)
About the foam agent which concerns on Examples 19-22, evaluation of the fineness of foam, the retention time of foam, evaluation of foam retention, and comprehensive evaluation were performed on the same criteria as “Evaluation 1”. Table 4 shows the formulation and evaluation results of the foams according to Example 4 and Examples 19 to 22 described above.

  As shown in Table 5, it was shown that good foams could be formed in all of the foam agents according to Examples 19-22. Thereby, even if HCO-10 (polyoxyethylene hydrogenated castor oil), HCO-30 (polyoxyethylene hydrogenated castor oil), resinol (hydrogenated lecithin), or hydroxyethyl cellulose is used as the three-phase emulsified particles, good foam is produced. It was found that it can be formed.

  Moreover, the average particle diameter of HCO-10 was 500 nm, and the average particle diameter of HCO-30 was 20 nm. The reason why the evaluation of Example 20 was higher than that of Example 19 is presumed to be that the average particle diameter is small in this way, and it is easy to follow the generation of bubbles and to easily form bubbles.

<Examples 23 to 27>
(Preparation of foam agent)
Except that the type of oil used in the oil phase was changed to ethylhexyl methoxycinnamate, cyclopentasiloxane, or cetyl ethylhexanoate, the same procedure as in Example 4 was performed as shown in Table 6 described later. Foams according to Examples 23 to 25 were prepared.

  Except that the oil used in the oil phase was changed to a mixture of rice bran oil, olive oil, jojoba oil, and almond oil, the same procedure as in Example 4 above, as shown in Table 7 described later, in Example 26, Such a foam was prepared. As shown in Table 7 described later, a foam agent according to Example 27 was prepared in the same procedure as in Example 26 except that the amount of each component was changed.

(Evaluation 5)
About the foam agent which concerns on Examples 23-27, evaluation of the fineness of foam, the retention time of foam, evaluation of foam retention, and comprehensive evaluation were performed on the same criteria as “Evaluation 1”. Tables 6 and 7 show the formulations and evaluation results of the foams according to Example 4 and Examples 23 to 27 described above.

  As shown in Tables 6 and 7, not only hydrocarbon oils such as squalane, but also ester oils such as ethylhexyl methoxycinnamate and cetyl ethylhexanoate, silicone oils such as cyclopentasiloxane, rice bran oil, olive oil, jojoba It was shown that good foams could be formed even in vegetable oils such as oil and almond. In particular, it was found that the overall evaluation of foam was high when vegetable oil was used. Further, it was found that even when the total amount of oil was increased to about 30% by mass as in Example 27, good bubbles could be formed.

Claims (13)

  An emulsified composition for producing a foam agent, comprising an oil phase, an aqueous phase, particles of a closed vesicle formed by an amphiphilic substance that spontaneously forms a closed vesicle or a polycondensation polymer having a hydroxyl group, and a thickener. .   The emulsified composition according to claim 1, which is an O / W emulsion.   The emulsified composition according to claim 1 or 2, wherein the thickener includes a polysaccharide having a network structure formed by hydrogen bonding.   The emulsified composition according to claim 3, wherein the polysaccharide is a thickening polysaccharide.   The emulsified composition according to claim 3 or 4, wherein the polysaccharide comprises one or more selected from the group consisting of starch, starch derivatives and alginic acids.   The said thickener is an emulsion composition in any one of Claim 1 to 5 whose viscosity in 20 degreeC of 1 mass% aqueous solution is 100 mPa * s or more and 100000 mPa * s or less. An average particle diameter of the closed vesicle formed of an amphiphile that spontaneously forms a closed vesicle is 8 nm or more and 800 nm or less;
The emulsified composition according to any one of claims 1 to 6, wherein the average particle diameter of the polycondensation polymer particles is 8 nm or more and 800 nm or less.   The emulsified composition according to any one of claims 1 to 7, wherein the oil phase comprises one or more oils selected from the group consisting of ester oils, hydrocarbon oils, silicone oils and vegetable oils.   The foam agent containing the undiluted | stock solution which consists of an emulsion composition in any one of Claim 1 to 8, and a propellant.   The foam agent according to claim 9, which is applied to a human body or an animal.   In the emulsified composition for producing a foam agent comprising an oil phase, an aqueous phase, and particles of a polycondensation polymer having closed vesicles or hydroxyl groups formed by amphiphiles that spontaneously form closed vesicles, A method for improving foam-forming ability by containing a thickener.   An emulsified composition for producing a foam agent comprising particles of a polycondensation polymer having a closed vesicle or a hydroxyl group formed of an oil phase, an aqueous phase, and an amphiphile that spontaneously forms a closed vesicle comprising a thickener. Foam-forming ability improver for products.   The cosmetic method which has the process of applying the foam agent of Claim 9 or 10 to a human body or an animal.