WO2017090214A1 - カプセルの製造方法 - Google Patents
カプセルの製造方法 Download PDFInfo
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- WO2017090214A1 WO2017090214A1 PCT/JP2016/001051 JP2016001051W WO2017090214A1 WO 2017090214 A1 WO2017090214 A1 WO 2017090214A1 JP 2016001051 W JP2016001051 W JP 2016001051W WO 2017090214 A1 WO2017090214 A1 WO 2017090214A1
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- WIPO (PCT)
- Prior art keywords
- hydrophilic polymer
- capsule
- gelling agent
- added
- polymer gelling
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/733—Alginic acid; Salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/30—Encapsulation of particles, e.g. foodstuff additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/805—Corresponding aspects not provided for by any of codes A61K2800/81 - A61K2800/95
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poly(lactide-co-glycolide)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
Definitions
- the present invention relates to a capsule manufacturing method.
- capsules have been widely used in the fields of cosmetics, pharmaceuticals, foods, etc.
- the stability of the functional substance is improved. can do.
- an O / W emulsion is prepared by using an encapsulated oil droplet (oil phase) and an aqueous phase containing an encapsulating agent, and then prepared in the outer oil phase.
- a method has been proposed in which an O / W / O emulsion is prepared by dispersing and emulsifying and then the aqueous phase is solidified and encapsulated.
- an O / W emulsion at a temperature equal to or higher than the solidification temperature of the gelling agent from an inner oil phase and an aqueous phase in which agar or carrageenan, which is a hydrophilic polymer gelling agent, is heated and dissolved in advance.
- An O / W emulsion preparation step an O / W emulsion preparation step in which the O / W emulsion is dispersed and emulsified in the outer oil phase above the solidification temperature of the gelling agent, and the O / W / O emulsion is gelled.
- a method for producing a microcapsule comprising an encapsulation step of solidifying an aqueous phase by cooling to below the solidification temperature of the agent is disclosed. And it is described by such a method that the microcapsule which has a fine inclusion oil droplet, and is excellent in stability and the retention property of the inclusion oil droplet after application
- coating can be obtained (for example, patent document 1). reference).
- coenzyme Q10-containing emulsion is sprayed from the top of the cylindrical coagulation chamber using a two-fluid nozzle, and an aqueous calcium chloride solution is sprayed while mixing with air using a two-fluid nozzle, and then coenzyme Q10-containing emulsification is performed.
- a method is disclosed in which capsules are produced by gelling an object into a particulate state and recovering it as an aqueous suspension, and dehydrating and drying the recovered suspension by a conventional method (for example, see Patent Document 2). ).
- Patent Document 2 requires a special device such as a two-fluid nozzle as described above, so that the manufacturing process is complicated and the cost is increased.
- the present invention has been made in view of the above-described problems, and a capsule manufacturing method that can manufacture capsules that can be used in water-based products such as skin lotions by an inexpensive and simple method.
- the purpose is to provide.
- a method for producing a capsule of the present invention comprises an aqueous anionic hydrophilic polymer gelling agent solution containing at least one selected from the group consisting of carrageenan, agar, sodium alginate, and gellan gum, It is characterized by comprising at least a step of preparing a mixture by mixing an amphiphile compatible with oil and water, a step of adding a cation to the mixture, and a step of removing the amphiphile.
- a capsule that can be used for water-based products such as skin lotion can be provided by an inexpensive and simple method.
- a capsule having a particle size of 0.2 mm or more and a uniform particle size can be provided.
- FIG. 1 is a conceptual diagram showing a capsule of the present invention.
- the capsule 1 of the present invention is composed of an anionic hydrophilic polymer gelling agent 2 and encapsulated oil droplets 3 dispersed in the hydrophilic polymer gelling agent 2. .
- carrageenan can be preferably used as the hydrophilic polymer gelling agent 2.
- Carrageenan is a polysaccharide extracted from red algae and is used as the hydrophilic polymer gelling agent 2.
- this carrageenan for example, iota carrageenan that gels by reacting with calcium ions as counter ions is used.
- kappa carrageenan or lambda carrageenan may be used as the carrageenan.
- hydrophilic polymer gelling agent 2 agar, sodium alginate, gellan gum or the like may be used instead of the carrageenan.
- these can be used individually or in combination of 2 or more types.
- the concentration of the hydrophilic polymer gelling agent 2 with respect to the whole aqueous solution of the hydrophilic polymer gelling agent is preferably 0.2 to 5% by mass, and more preferably 0.5 to 4% by mass.
- the encapsulated oil droplets 3 are not particularly limited, and those generally used for cosmetics and the like can be blended within a range that does not impair the effects of the present invention. In the present invention, the encapsulated oil droplets can be omitted.
- Examples of the encapsulated oil droplets include hydrocarbons, fats and oils, waxes, and hardened oils, regardless of the origin, such as animal oil, vegetable oil, synthetic oil, and properties such as solid oil, semi-solid oil, and liquid oil. Ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, oily gelling agents and the like can be used.
- hydrocarbons such as ethylene / propylene copolymer, polyethylene wax, ceresin, paraffin wax, microcrystalline wax, hydrogenated microcrystalline wax, liquid paraffin, squalane, petrolatum, polybutene, olive oil, castor oil, jojoba oil , Oils such as macadamian nut oil, beeswax, carnauba wax, candelilla wax, waxes such as owl, triethylhexanoin, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, sesquiisostearic acid Sorbitan, octyldodecyl isostearate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, diocta Acid neopentyl glycol, cholesterol fatty acid ester
- a hydrophilic polymer gelling agent 2 such as carrageenan or agar is added to ion-exchanged water, and this ion-exchanged water is heated at a predetermined temperature (for example, 90 ° C.) to obtain a hydrophilic polymer gelling agent. 2 is dissolved to prepare an aqueous solution in which the hydrophilic polymer gelling agent 2 is dissolved.
- hydrophilic polymer gelling agent 2 in addition to the hydrophilic polymer gelling agent 2, commonly used components (humectants such as 1,3-butylene glycol and glycerin, preservatives such as methylparaben, white pearl powder, Coloring agents such as gold pearl powder, auxiliary components of grains such as poly- ⁇ -glutamic acid Na and hydroxyethyl cellulose, etc.) can be blended within a range not impairing the effects of the present invention.
- humectants such as 1,3-butylene glycol and glycerin, preservatives such as methylparaben, white pearl powder, Coloring agents such as gold pearl powder, auxiliary components of grains such as poly- ⁇ -glutamic acid Na and hydroxyethyl cellulose, etc.
- an amphiphilic substance is added to the above-described hydrophilic polymer gelling agent aqueous solution, and, for example, by stirring and mixing with a propeller stirrer, the hydrophilic polymer gelling agent aqueous solution and the amphiphilic substance are mixed. A mixture is obtained.
- the hydrophilic polymer gelling agent 2 is dispersed in a granular (capsule) state in the amphiphilic substance.
- an aqueous solution in which the hydrophilic polymer gelling agent 2 is dissolved is prepared by the above-described hydrophilic polymer gelling agent aqueous solution preparation step.
- an encapsulated fat is produced.
- PEG-60 hydrogenated castor oil which is a hydrophilic surfactant
- 1,3-butylene glycol which is a humectant
- ion-exchanged water is added, and after stirring and dissolving, the mixture is cooled to a predetermined temperature (for example, 30 ° C.) to obtain an aqueous phase.
- PEG-60 hydrogenated castor oil is added to 1,3-butylene glycol, and heated to a predetermined temperature (eg, 50 ° C.) for dissolution.
- a predetermined temperature eg, 50 ° C.
- glycerin as a moisturizing agent
- sorbitan sesquiisostearate as a hydrophilic surfactant
- oil for example, triethylhexanoin
- an O / W emulsion is obtained by adding the prepared encapsulated oil phase to an aqueous hydrophilic polymer gelling agent solution and stirring and mixing.
- an amphiphilic substance is added to the above-mentioned O / W emulsion, and, for example, the mixture is stirred and mixed with a propeller stirrer to obtain a mixture of the O / W emulsion and the amphiphilic substance.
- the hydrophilic polymer gelling agent 2 is dispersed in a granular (capsule) state in the amphiphilic substance.
- an O / W emulsion or an aqueous hydrophilic polymer gelling agent solution may be added to an amphiphilic substance and mixed by stirring.
- amphiphilic substance means “a substance compatible with oil and water”, for example, bisethoxydiglycol succinate, bisethoxydiglycol cyclohexane-1,4-dicarboxylate, dioctyl succinate.
- examples include ethoxyethyl, 1,2-hexanediol, hexylene glycol, PEG / PPG / polybutylene glycol-8 / 5/3 glycerin, and PPG-9 diglyceryl.
- polyoxyethylene (17) polyoxypropylene (4) dimethyl ether and polyoxyethylene (14) polyoxypropylene (7) dimethyl ether dimethyl ether such as polyoxyethylene (17) polyoxypropylene (4) dimethyl ether are used as amphiphilic substances. can do. In addition, these can be used individually or in combination of 2 or more types.
- the capsule 1 having a substantially spherical shape or a substantially elliptic shape it is preferable to use bisethoxydiglycol succinate or bisethoxydiglycol cyclohexane-1,4-dicarboxylate. Further, when the capsule 1 having a fiber shape is produced, it is preferable to use diethoxyethyl succinate, 1,2-hexanediol, or hexylene glycol as a dispersion solvent.
- the shape of the capsule 1 can be controlled by changing the amphiphilic substance to be used.
- the hydrophilic polymer gelling agent is dispersed in the amphiphilic substance, capsules having a particle diameter of 0.2 mm or more and a uniform particle diameter can be produced.
- the mixture of the O / W emulsion obtained in the above-mentioned amphiphile mixing step and the amphiphile is set at a predetermined temperature. After cooling to (for example, 45 ° C.), a cation (inorganic cation, organic cation) is added to the mixture. Then, the hydrophilic polymer gelling agent 2 of the anionic polymer and the cation react to form a reaction product of the hydrophilic polymer gelling agent 2 and the cation (hereinafter referred to as “cationic reactant”).
- the capsule shown in 1 can be obtained.
- the cation may be an inorganic cation or an organic cation that is electrically neutral with the anion portion of the hydrophilic polymer gelling agent.
- the inorganic cation for example, calcium ions or magnesium ions generated by dissolving calcium chloride dihydrate or magnesium sulfate in ion-exchanged water can be used.
- organic cation for example, a quaternary ammonium cation generated by dissolving benzalkonium chloride or cetrimonium chloride in ion-exchanged water can be used.
- the hydrophilic polymer gelling agent of the anionic polymer reacts with the cation, and the hydrophilic polymer gelling agent gels to form an outer film.
- the capsule shown in 1 is produced.
- the hydrophilic polymer gelling agent 2 (or O / W emulsion) is dispersed in the amphiphilic substance. Therefore, when the capsule 1 is used, the amphiphilic substance is formed on the surface of the capsule 1. Even in the case of remaining, since the amphiphilic substance is dissolved in water, it can be easily removed by filtration and washing with water. Therefore, it becomes possible to manufacture the capsule 1 that can be used for a water-based product such as lotion by an inexpensive and simple method.
- capsule 1 that is not easily crushed on the skin can be produced.
- agar and calcium ions are reacted, Capsule 1 that is easily crushed on the skin can be produced. Therefore, the ease of crushing of the capsule 1 can be designed freely, so that it is possible to provide both a capsule that is easily crushed on the skin and a capsule that is not easily crushed on the skin.
- a special apparatus is not required, and a simple apparatus (propeller stirrer) is used to make a hydrophilic polymer gelling agent (or O / W emulsion) and the amphiphilic substance need only be mixed and stirred, so that capsules can be produced by an inexpensive and simple method.
- Example 2 a hydrophilic polymer gelling aqueous solution was added to bisethoxydiglycol succinate, and the mixture was stirred and mixed using the above-described propeller stirrer, thereby forming a hydrophilic polymer gel. A mixture of an aqueous agent solution and an amphiphile was obtained.
- capsules were produced by removing the bisethoxydiglycol succinate used as the dispersion medium by filtration and washing with water.
- Example 8 to 14 and Comparative Example 4 ⁇ Method for producing capsule>
- the capsules of Examples 8 to 14 and Comparative Example 4 having the composition (mass%) shown in Table 2 were produced by the following production method.
- amphiphilic substances bisethoxydiglycol succinate, bisethoxydiglycol cyclohexane-1,4-dicarboxylate, diethoxyethyl succinate
- amphiphilic substances heated to 50 ° C. 1,2-hexanediol, PEG / PPG / polybutylene glycol-8 / 5/3 glycerin, PPG-9 diglyceryl
- a hydrophilic polymer gelling agent aqueous solution and using the propeller stirrer described above, By stirring and mixing at the speed shown in Table 2, a mixture of an aqueous hydrophilic polymer gelling agent solution and an amphiphilic substance was obtained.
- an aqueous solution of the hydrophilic polymer gelling agent prepared was added to an amphiphilic substance (bisethoxydiglycol succinate, diethoxyethyl succinate, 1,2-hexane) heated to 50 ° C. Diol, or PEG / PPG / polybutylene glycol-8 / 5/3 glycerin), and using the propeller stirrer described above, the mixture is stirred and mixed at the speed shown in Table 2. A mixture of an aqueous agent and an amphiphile was obtained.
- an amphiphilic substance bisethoxydiglycol succinate, diethoxyethyl succinate, 1,2-hexane
- hydrophilic polymer poly- ⁇ -glutamic acid Na, and hydroxyethyl cellulose is added to ion-exchanged water, heated to 90 ° C., stirred and dissolved, then cooled to 50 ° C., white pearl powder, Then, an aqueous solution containing the hydrophilic polymer gelling agents of Examples 16 to 21 was obtained by adding and stirring and dispersing the gold pearl powder.
- the encapsulated oil phase in Example 19 was produced by the following method. First, PEG-60 hydrogenated castor oil was added to 1,3-butylene glycol and dissolved by heating to 50 ° C. Next, ion-exchanged water was added, dissolved by stirring, and then cooled to 30 ° C. to obtain an aqueous phase. Then, triethylhexanoin and dimethylpolysiloxane were added to the aqueous phase, and the mixture was processed using a homomixer (emulsifier) to obtain an encapsulated oil phase that was an emulsified liquid phase.
- a homomixer emulsifier
- the encapsulated oil phase in Example 20 was produced by the following method. First, PEG-60 hydrogenated castor oil was added to 1,3-butylene glycol and dissolved by heating to 50 ° C. Next, glycerin, sorbitan sesquiisostearate, and triethylhexanoin were added and dissolved by stirring. And the inclusion oil phase which is an emulsified liquid phase was obtained by adding this mixed phase in ion-exchange water, stirring.
- capsules were produced by removing the bisethoxydiglycol succinate used as the dispersion medium by filtration and washing with water.
- an amphiphilic substance bisethoxydiglycol succinate, 1,2-hexanediol heated to 50 ° C. is added to the prepared hydrophilic polymer gelling aqueous solution, and the above-described propeller stirrer is used.
- the mixture of the hydrophilic polymer gelling agent and the amphiphilic substance was obtained by stirring and mixing at a speed of 500 rpm.
- Example 22 ion-exchanged water and sodium chloride (a substance having a salting-out effect) were added to the amphiphilic substance from the viewpoint of easy production of capsules having a fiber shape.
- capsules were produced by removing bisethoxydiglycol succinate, 1,2-hexanediol, and sodium chloride used as dispersion media by filtration and washing with water.
- ⁇ Residual dispersion medium> Using liquid chromatography (manufactured by Shimadzu Corporation, trade name: Prominence), the presence or absence of the residual dispersion medium (that is, the amphiphilic substance remaining on the surface of the capsule) was evaluated. Evaluation criteria When the concentration is less than 100 ppm: ⁇ Oil film or oil floating is observed when put in water, or when 100 ppm or more: ⁇
- an anionic hydrophilic polymer gelling agent at least one of carrageenan, agar, sodium alginate, and gellan gum
- an amphiphilic substance bisethoxydiglycol succinate, cyclohexane
- cations calcium ions, magnesium ions, or quaternary ammonium cations
- an anionic hydrophilic polymer gelling agent at least one of carrageenan, agar, sodium alginate, and gellan gum
- an amphiphilic substance bisethoxydiglycol succinate, and 1
- capsules having excellent stability and a fiber shape can be provided. I understand that I can do it.
- Comparative Example 3 in which no cation was added, although the capsule could be produced, it can be seen that the stability of the capsule was poor. Further, in Comparative Example 4 in which the amphiphilic substance of the present invention was not mixed, it was clearly found that oil remained and could be blended in the oil system and the W / O system but not in the water system. It was.
- the present invention is particularly useful for a method for producing capsules used in the fields of cosmetics, pharmaceuticals, foods and the like.
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Abstract
Description
本発明においては、親水性高分子ゲル化剤2として、カラギーナンが好適に使用できる。カラギーナンは、紅藻類から抽出される多糖類であり、親水性高分子ゲル化剤2として使用される。このカラギーナンとしては、例えば、カウンターイオンであるカルシウムイオンと反応することによりゲル化するイオタカラギーナンが使用される。
内包油滴3は、特に限定されず、一般的に化粧料等に使用されるものを、本発明の効果を損なわない範囲内で配合することができる。なお、本発明においては、この内包油滴は、省略することができる。
<親水性高分子ゲル化剤水溶液作製工程>
まず、カラギーナンや寒天等の親水性高分子ゲル化剤2を、イオン交換水に添加し、このイオン交換水を所定の温度(例えば、90℃)で加熱して、親水性高分子ゲル化剤2を溶解することにより、親水性高分子ゲル化剤2が溶解した水溶液を調製する。
次に、上述の親水性高分子ゲル化剤水溶液に、両親媒性物質を添加し、例えば、プロペラ攪拌機により攪拌して混合することにより、親水性高分子ゲル化剤水溶液と両親媒性物質の混合物を得る。
まず、上述の親水性高分子ゲル化剤水溶液作製工程により、親水性高分子ゲル化剤2が溶解した水溶液を調製する。
次に、内包油脂を作製する。例えば、保湿剤である1,3-ブチレングリコールに親水性界面活性剤であるPEG-60水添ヒマシ油を添加し、所定の温度(例えば、50℃)に加熱し溶解する。次に、イオン交換水を添加して、撹拌溶解後、所定の温度(例えば、30℃)まで冷却して水相を得る。そして、この水相へ油(例えば、トリエチルヘキサノイン、ジメチルポリシロキサン)を添加し、ホモミキサー(乳化機)を使用して処理を行い、乳化液相である内包油滴3を得る。
次に、作製した内包油相を親水性高分子ゲル化剤水溶液に添加し、攪拌して混合することにより、O/Wエマルジョンを得る。
次に、上述のO/Wエマルジョンに、両親媒性物質を添加し、例えば、プロペラ攪拌機により攪拌して混合することにより、O/Wエマルジョンと両親媒性物質の混合物を得る。
次に、上記両親媒性物質混合工程において得られたO/Wエマルジョンと両親媒性物質との混合物(または、親水性高分子ゲル化剤水溶液と両親媒性物質との混合物)を所定の温度(例えば、45℃)まで冷却した後、この混合物に、カチオン(無機カチオン、有機カチオン)を添加する。そうすると、アニオン性高分子の親水性高分子ゲル化剤2とカチオンとが反応し、親水性高分子ゲル化剤2とカチオンとの反応物(以下、「カチオン反応物」)が形成され、図1に示すカプセルを得ることができる。
また、本発明においては、親水性高分子ゲル化剤2(または、O/Wエマルジョン)を両親媒性物質に分散させるため、カプセル1を使用する際に、カプセル1の表面に両親媒性物質が残存している場合であっても、両親媒性物質は水に溶解するため、ろ過・水洗を行うことにより、簡単に除去することができる。従って、化粧水等の水系の製品に使用可能なカプセル1を安価かつ簡単な方法で製造することが可能になる。
<カプセルの製造方法>
表1に示す組成(質量%)を有する実施例1~7及び比較例1~3のカプセルを、下記の製造方法により製造した。
1,3―ブチレングリコールにメチルパラベンを添加し、50℃に加熱して溶解した後、グリセリンを添加し、撹拌して溶解した。次に、親水性高分子を添加し、湿潤させて、撹拌分散した。次に、親水性高分子の分散相をイオン交換水中に添加し、90℃に加熱して撹拌溶解した後、50℃まで冷却し、実施例1~7の親水性高分子ゲル化剤水溶液を得た。
次に、作製した親水性高分子ゲル化剤水溶液に、50℃に加熱した両親媒性物質であるコハク酸ビスエトキシジグリコールを添加し、プロペラ攪拌機(アズワン(株)製、商品名:STIRRER、P-1)を使用して、300rpmの速度で攪拌して混合することにより、親水性高分子ゲル化剤水溶液と両親媒性物質の混合物を得た。
次に、上記両親媒性物質混合工程において得られた親水性高分子ゲル化剤水溶液と両親媒性物質との混合物を45℃まで冷却した後、この混合物に、塩化カルシウム二水和物が溶解したイオン交換水を添加することにより、カプセル分散物を製造した。
次に、分散媒として用いたコハク酸ビスエトキシジグリコールをろ過・水洗して除去することにより、カプセルを製造した。
<カプセルの製造方法>
表2に示す組成(質量%)を有する実施例8~14及び比較例4のカプセルを、下記の製造方法により製造した。
1,3―ブチレングリコールにメチルパラベンを添加し、50℃に加熱して溶解した後、グリセリン、及びPPG-9ジグリセリルを添加し、撹拌して溶解した。次に、親水性高分子とヒドロキシエチルセルロースを添加し、湿潤させて、撹拌分散した。次に、親水性高分子とヒドロキシエチルセルロースの分散相をイオン交換水中に添加し、90℃に加熱して撹拌溶解した後、50℃まで冷却し、ゴールドパール粉末を添加して、攪拌分散することにより実施例9~15、比較例4の親水性高分子ゲル化剤を含む水溶液を得た。
次に、実施例9~11,13~14においては、50℃に加熱した両親媒性物質(コハク酸ビスエトキシジグリコール、シクロヘキサン-1,4-ジカルボン酸ビスエトキシジグリコール、コハク酸ジエトキシエチル、1,2-ヘキサンジオール、PEG/PPG/ポリブチレングリコール-8/5/3グリセリン、PPG-9ジグルセリル)に親水性高分子ゲル化剤水溶液を添加し、上述のプロペラ攪拌機を使用して、表2に示す速度で攪拌して混合することにより、親水性高分子ゲル化剤水溶液と両親媒性物質の混合物を得た。
次に、上記両親媒性物質混合工程において得られた親水性高分子ゲル化剤水溶液と両親媒性物質との混合物を45℃まで冷却した後、この混合物に、塩化カルシウム二水和物が溶解したイオン交換水を添加することにより、カプセル分散物を製造した。
次に、分散媒として用いたコハク酸ビスエトキシジグリコール、シクロヘキサン-1,4-ジカルボン酸ビスエトキシジグリコール、コハク酸ジエトキシエチル、1,2-ヘキサンジオール、PEG/PPG/ポリブチレングリコール-8/5/3グリセリン、PPG-9ジグルセリルをろ過・水洗して除去することにより、カプセルを製造した。
<カプセルの製造方法>
表3に示す組成(質量%)を有する実施例15~20のカプセルを、下記の製造方法により製造した。
1,3―ブチレングリコールにメチルパラベンを添加し、50℃に加熱して溶解した後、グリセリンを添加し、撹拌して溶解した。次に、親水性高分子、ポリ-γ-グルタミン酸Na、及びヒドロキシエチルセルロースを添加し、湿潤させて、撹拌分散した。次に、親水性高分子、ポリ-γ-グルタミン酸Na、及びヒドロキシエチルセルロースの分散相をイオン交換水中に添加し、90℃に加熱して撹拌溶解した後、50℃まで冷却し、ホワイトパール粉末、及びゴールドパール粉末を添加して、攪拌分散することにより実施例16~21の親水性高分子ゲル化剤を含む水溶液を得た。
実施例19における内包油相は次の方法により作製した。まず、1,3-ブチレングリコールにPEG-60水添ヒマシ油を添加し、50℃に加熱し溶解した。次に、イオン交換水を添加して、撹拌溶解後、30℃まで冷却して水相を得た。そして、この水相へトリエチルヘキサノイン、及びジメチルポリシロキサンを添加し、ホモミキサー(乳化機)を使用して処理を行い、乳化液相である内包油相を得た。
次に、作製した内包油相を親水性高分子ゲル化剤水溶液に添加し、攪拌して混合することにより、O/Wエマルジョンを得た。
次に、実施例15~18においては、作製した親水性高分子ゲル化剤水溶液に、50℃に加熱した両親媒性物質であるコハク酸ビスエトキシジグリコールを添加し、上述のプロペラ攪拌機を使用して、400rpmの速度で攪拌して混合することにより、親水性高分子ゲル化剤水溶液と両親媒性物質の混合物を得た。
次に、上記両親媒性物質混合工程において得られた親水性高分子ゲル化剤水溶液と両親媒性物質との混合物(実施例19~20においては、O/Wエマルジョンと両親媒性物質との混合物)を45℃まで冷却した後、この混合物に、塩化カルシウム二水和物、硫酸マグネシウム、塩化ベンザルコニウム、及びセトリモニウムクロリドの少なくとも1種が溶解したイオン交換水を添加することにより、カプセル分散物を製造した。
次に、分散媒として用いたコハク酸ビスエトキシジグリコールをろ過・水洗して除去することにより、カプセルを製造した。
<カプセルの製造方法>
表4に示す組成(質量%)を有する実施例21~24のカプセルを、下記の製造方法により製造した。
1,3―ブチレングリコールにメチルパラベンを添加し、50℃に加熱して溶解した後、グリセリンを添加し、撹拌して溶解した。次に、親水性高分子とポリビニルアルコールを添加し、湿潤させて、撹拌分散した。次に、親水性高分子とポリビニルアルコールの分散相をイオン交換水中に添加し、90℃に加熱して撹拌溶解した後、50℃まで冷却し、ゴールドパール粉末を添加して、攪拌分散することにより実施例21~24の親水性高分子ゲル化剤を含む水溶液を得た。
次に、作製した親水性高分子ゲル化剤水溶液に、50℃に加熱した両親媒性物質(コハク酸ビスエトキシジグリコール、1,2-ヘキサンジオール)を添加し、上述のプロペラ攪拌機を使用して、500rpmの速度で攪拌して混合することにより、親水性高分子ゲル化剤と両親媒性物質の混合物を得た。
次に、上記両親媒性物質混合工程において得られた親水性高分子ゲル化剤水溶液と両親媒性物質との混合物を45℃まで冷却した後、この混合物に、塩化カルシウム二水和物が溶解したイオン交換水を添加することにより、カプセル分散物を製造した。
次に、分散媒として用いたコハク酸ビスエトキシジグリコール、1,2-ヘキサンジオール、及び食塩をろ過・水洗して除去することにより、カプセルを製造した。
目視により、実施例、及び比較例の各カプセルの形状を評価した。
物差しを使用して、目視により、実施例、及び比較例の各カプセルの径を測定した。
作製したカプセルを、50℃の環境下でスクリュー管内に1ヶ月間、保存し、その後、カプセルの変形、破壊、凝集等の変化について、目視により確認した。
評価基準
カプセルの変形、破壊、凝集が全く認められないか僅かに認められる場合:○
カプセルの変形、破壊、凝集が少し認められるか明らかに認められる場合:×
液体クロマトグラフィー(島津製作所(株)製、商品名:Prominence)を使用して、残存分散媒(即ち、カプセルの表面に残存する両親媒性物質)の有無について評価した。
評価基準
濃度が100ppm未満の場合:○
水に入れた時に油膜または油浮きが認められる、又は100ppm以上の場合:×
2 アニオン性の親水性高分子ゲル化剤
3 内包油脂
Claims (5)
- カラギーナン、寒天、アルギン酸ナトリウム、及びジェランガムからなる群より選ばれる少なくとも1種を含むアニオン性の親水性高分子ゲル化剤水溶液と、油分及び水と相溶可能な両親媒性物質とを混合して混合物を作製する工程と、
前記混合物にカチオンを添加する工程と
前記両親媒性物質を除去する工程と
を少なくとも備えることを特徴とするカプセルの製造方法。 - 前記両親媒性物質が、コハク酸ビスエトキシジグリコール、シクロヘキサン-1,4-ジカルボン酸ビスエトキシジグリコール、コハク酸ジエトキシエチル、1,2-ヘキサンジオール、及びヘキシレングリコールからなる群から選ばれる少なくとも1種であることを特徴とする請求項1に記載のカプセルの製造方法。
- 前記カチオンが、カルシウムイオン、マグネシウムイオン及び第4級アンモニウムカチオンからなる群から選ばれる少なくとも1種であることを特徴とする請求項1または請求項2に記載のカプセルの製造方法。
- 前記混合物作製工程において、前記親水性高分子ゲル化剤水溶液に対して前記両親媒性物質を添加することを特徴とする請求項1~請求項3のいずれか1項に記載のカプセルの製造方法。
- 前記混合物作製工程において、前記両親媒性物質に対して前記親水性高分子ゲル化剤水溶液を添加することを特徴とする請求項1~請求項3のいずれか1項に記載のカプセルの製造方法。
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JP2021500351A (ja) * | 2017-10-19 | 2021-01-07 | フイルメニツヒ ソシエテ アノニムFirmenich Sa | ヒドロゲルビーズ |
JP7034248B1 (ja) | 2020-10-16 | 2022-03-11 | 広東丸美生物技術股▲フン▼有限公司 | 微細乳化マトリックス、その調製方法及び化粧品 |
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FR3122575A1 (fr) * | 2021-05-05 | 2022-11-11 | Gabrielle De La Goublaye De Nantois | Capsules molles cosmétiques |
CN116103811A (zh) * | 2022-12-22 | 2023-05-12 | 福建省天鑫高科新材料有限公司 | 一种石墨烯驱蚊面料及制备方法 |
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