Classifications

• • 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
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
• • 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
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
  • B01J13/18—In situ polymerisation with all reactants being present in the same phase
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/02—Inorganic compounds
• • 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
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/25—Silicon; 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
  • A61K8/34—Alcohols
  • A61K8/342—Alcohols having more than seven atoms in an unbroken chain
• • 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
  • A61K8/37—Esters of carboxylic acids
• • 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
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/416—Quaternary ammonium compounds
• • 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
  • A61K9/10—Dispersions; Emulsions
• • 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
  • A61K9/10—Dispersions; Emulsions
  • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
  • A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
• • 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
  • A61K9/501—Inorganic compounds
• • 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
  • A61K9/5073—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 having two or more different coatings optionally including drug-containing subcoatings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q13/00—Formulations or additives for perfume preparations
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
• • 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

Definitions

• the present invention relates to microcapsules and a method for producing microcapsules.
• microcapsules containing fragrances and bioactive agent substances have been developed and used in a wide range of business fields such as cosmetics, pharmaceuticals, general household products, and printing.
• aminoplast resins such as melamine resin and polyurea / urethane resin have been used as shells constituting microcapsules.
• microcapsules are inevitably discharged into the environment and have contributed to a substance of concern called microplastics in recent years. Therefore, it is desired to develop microcapsules having high environmental friendliness as an alternative to aminoplast resin.
• silica microcapsules having a shell containing silica as a constituent component are attracting attention as a material that can be expected to be environmentally friendly.
• Silica capsules are generally obtained by a method of forming silica on the surface of an emulsified drop by a sol-gel reaction.
• the shell of the silica capsule is also very thin and brittle. Therefore, a part of the contained component may be eluted to the external environment due to the disintegration of the shell and the diffusion of the contained component of the silica capsule through the micropores existing in the shell. Therefore, various silica capsules using a sol-gel reaction have been studied so far.
• Patent Document 1 describes a method for producing microcapsules having a core substance containing an active ingredient such as a sunscreen, and describes an oily phase composed of a water-insoluble precursor and a core substance. Described is a method for producing microcapsules, which comprises a step of producing an oil-in-water emulsion by emulsifying under appropriate shearing force and temperature conditions in an aqueous phase consisting of an aqueous solution having a predetermined pH.
• Patent Document 2 describes a core made of a functional oil such as a fragrance and a core for the purpose of providing a method for producing microcapsules capable of holding a functional oil as an active ingredient such as a fragrance for a long time.
• a method for producing microcapsules having a first shell encapsulating a core and a second shell encapsulating the first shell, an organic phase containing a functional oil agent and a tetraalkoxysilane is emulsified in an aqueous phase containing a surfactant.
• the first-step sol-gel reaction is carried out in the same state as above, and then the second-step sol-gel reaction is carried out by adding tetraarcossisisilane and maintaining a lower pH than the first-step sol-gel reaction. It is described that a silica capsule with high shell density can be obtained.
• the present invention is a microcapsule having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell.
• the organic compound relates to a microcapsule containing the following component (A) and component (B1).
• amide compounds having an alkyl group of several 8 or more (however, excluding component (A))
• Patent Documents 1 and 2 do not provide the desired silica capsules that suppress the leakage of core components depending on the contained oil, and may not be able to retain functional oils such as fragrances for a long period of time. did.
• microcapsules are also required to have excellent stability at the distribution stage because the microcapsules do not easily disintegrate.
• the physical strength of the microcapsules also depends on the particle size of the microcapsules, and from the viewpoint of increasing the physical strength of the microcapsules, it is possible to obtain microcapsules with a smaller particle size. Is also required.
• the present invention relates to microcapsules and a method for producing microcapsules, which can retain functional oils such as fragrances contained therein for a long period of time and have excellent controllability of particle size.
• the present inventors can reduce the particle size of microcapsules by containing a functional oil agent and a component having a specific hydrocarbon group and a polar group inside a shell containing an inorganic substance as a constituent component. It has also been found that the retention of the functional oil is improved.
• a method for producing microcapsules which comprises a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell.
• Component (A) Functional oil component (B1): Higher aliphatic alcohol having 6 or more carbon atoms, higher fatty acid having 6 or more carbon atoms, monoalkyl glyceryl ether having an alkyl group having 6 or more carbon atoms, and 8 or more carbon atoms.
• Functional oil component (B1) Higher aliphatic alcohol having 6 or more carbon atoms, higher fatty acid having 6 or more carbon atoms, monoalkyl glyceryl ether having an alkyl group having 6 or more carbon atoms, and 8 or more carbon atoms.
• microcapsule and a method for producing microcapsules which can retain a functional oil such as a fragrance contained therein for a long period of time and have excellent controllability of particle size.
• microcapsules of the present invention are microcapsules having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell, and the organic compound is the following component (A) and.
• the long-term retention of the component (A) contained in the microcapsules is also referred to as "long-term retention”.
• the "sol-gel reaction” means a reaction in which a shell precursor is hydrolyzed and polycondensed to form an inorganic substance which is a constituent of the shell through a sol and a gel state.
• the "shell precursor” means a substance that can form a shell of microcapsules.
• a sol-gel reaction for example, in a silica capsule, tetraalkoxysilane is hydrolyzed as a shell precursor, a silanol compound produces a siloxane oligomer by a dehydration condensation reaction and a dealcohol condensation reaction, and the dehydration condensation reaction further proceeds.
• a reaction in which silica is formed by the reaction can be mentioned.
• the organic compound contained in the core is a higher aliphatic alcohol having 6 or more carbon atoms, a higher fatty acid having 6 or more carbon atoms, and a higher carbon number of carbon atoms as the component (B1) in addition to the functional oil agent as the component (A). Further includes one or more selected from a monoalkyl glyceryl ether having 6 or more alkyl groups and an amide compound having an alkyl group having 8 or more carbon atoms.
• the component (B1) has a long-chain aliphatic hydrocarbon group and a polar group, and is highly hydrophobic. Therefore, when the oil phase component of the oil-water mixture used for preparing the emulsion to be subjected to the sol-gel reaction during the production of microcapsules contains the component (B1), the polar group of the component (B1) is at the interface with the aqueous phase. It is considered to have a function of orienting and forming an emulsified droplet that serves as a template for microcapsules in a stable and fine manner. Then, the component (B1) is closely oriented at the interface with the aqueous phase, so that the shell itself has a strong structure. As a result, it is presumed that microcapsules having a dense and strong shell can be obtained, leakage of functional oil is suppressed, long-term retention is improved, and controllability of the particle size of silica capsules is further improved.
• the organic compound contained in the core of the microcapsules of the present invention contains a functional oil as a component (A).
• the "functional oil agent" in the component (A) is an oil agent that exhibits a useful effect for the use or purpose depending on the use or purpose.
• the component (A) is preferably a fragrance, a fragrance precursor, a moisturizing agent, an antioxidant, an antibacterial agent, a fertilizer, a fiber, a surface modifier such as skin, and a hair, a cooling sensation agent, a dye, a pigment, a silicone, and the like.
• One or more selected from oil-soluble polymers more preferably one or more selected from fragrances, fragrance precursors, moisturizers, antioxidants, antibacterial agents, fertilizers, and surface modifiers, still more preferably fragrances.
• One or more selected from fragrance precursors, moisturizers, and antioxidants more preferably one or more selected from fragrances, fragrance precursors and moisturizers, and even more preferably selected from fragrances and fragrance precursors.
• one kind may be used alone or two or more kinds may be used.
• the fragrance precursor examples include a compound that releases a fragrance component in response to water, a compound that releases a fragrance component in response to light, and the like.
• the compound that releases the fragrance component in response to water examples include a siliceous ester compound having an alkoxy component derived from fragrance alcohol, a fatty acid ester compound having an alkoxy component derived from fragrance alcohol, a carbonyl component derived from fragrance aldehyde or a fragrance ketone, and an alcohol.
• Examples thereof include a hemiaminoal compound or a hydrazone compound obtained by the reaction.
• Examples of the compound that releases the fragrance component in response to light include a 2-nitrobenzyl ether compound having an alkoxy component derived from a fragrance alcohol, an ⁇ -ketoester compound having a carbonyl component derived from a fragrance aldehyde or a fragrance ketone, and an alkoxy derived from a fragrance alcohol.
• Examples thereof include coumarin acid ester compounds having components.
• These perfume precursors may be used, for example, as a polymer such as a reaction product of a part of carboxy group of polyacrylic acid and a perfume alcohol.
• the component (A) preferably has appropriate hydrophobicity from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsules.
• the cLogP value which is the calculated value of the common logarithm "LogP" of the partition coefficient P (n-octanol / water) between n-octanol and water, is used. Can be done.
• the cLogP value is LogP (cLogP) calculated by the method described in A.Leo Comprehensive Medicinal Chemistry, Vol.4 C.Hansch, PGSammens, JB Taylor and CARamsden, Eds., P.295, Pergamon Press, 1990. It is a value calculated by the program CLOGP v4.01.
• the cLogP value of the component (A) is obtained by multiplying the cLogP value of each component by the volume ratio of each component and summing them. Can be done.
• the cLogP value of the component (A) is preferably 1 or more, more preferably 2 or more, still more preferably, from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. Is 3 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.
• the organic compound contained in the core of the microcapsule of the present invention has a carbon number as a component (B1) from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsule.
• a component (B1) from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsule.
• the component (B1) excludes the component (A).
• the component (B1) one type may be used alone or two or more types may be used.
• the molecular weight of the component (B1) is preferably 500 or less, more preferably 450 or less, still more preferably 450 or less, from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. It is 400 or less, more preferably 350 or less, and preferably 150 or more.
• the carbon number of the higher aliphatic alcohol is preferably 8 or more, more preferably 10 or more, and further, from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. It is preferably 12 or more, more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.
• the higher aliphatic alcohol is preferably a linear or branched higher aliphatic alcohol, and more preferably a linear higher aliphatic primary alcohol. From the viewpoint of ease of handling, the higher aliphatic alcohol is preferably in a solid state (for example, having a melting point of 30 ° C.
• the melting point of the higher aliphatic alcohol is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, still more preferably 40 ° C. or higher, still more preferably 45 ° C. or higher.
• Examples of the higher aliphatic primary alcohol include 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and oleyl alcohol.
• the carbon number of the higher fatty acid is preferably 8 or more, more preferably 10 or more, still more preferably 10 or more, from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. It is 12 or more, more preferably 14 or more, still more preferably 16 or more, and preferably 26 or less, more preferably 22 or less, still more preferably 20 or less.
• Examples of the higher fatty acid include 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linolenic acid, linolenic acid, lanolinic acid, isostearic acid and the like. Among them, branched-chain saturated fatty acids are preferable, and isostearic acid is more preferable.
• the carbon number of the alkyl group of the monoalkyl glyceryl ether is preferably 10 or more, more preferably 12 from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules.
• the above is more preferably 14 or more, still more preferably 16 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 22 or less.
• Examples of the monoalkyl glyceryl ether include mono2-ethylhexyl glyceryl ether, monodecyl glyceryl ether, monolauryl glyceryl ether, monomyristyl glyceryl ether, monocetyl glyceryl ether, monostearyl glyceryl ether, monobehenyl glyceryl ether and the like. .. Among them, one or more selected from monocetyl glyceryl ether, monostearyl glyceryl ether, and monobehenyl glyceryl ether are preferable, and monostearyl glyceryl ether is more preferable.
• the monoalkyl glyceryl ether is usually an ⁇ form.
• the alkyl group of the amide compound preferably has 10 or more carbon atoms, more preferably 12 or more, still more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less. ..
• an amide compound having an alkyl group derived from a saturated or unsaturated fatty acid is preferable. Specific examples thereof include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, and oleic acid amide.
• the component (B1) is preferably one or more selected from higher fatty acids having 6 or more carbon atoms and higher aliphatic alcohols having 6 or more carbon atoms from the viewpoint of improving the controllability of the particle size of the microcapsules. Yes, more preferably a higher fatty acid having 6 or more carbon atoms.
• the component (B1) is preferably one selected from an alkyl glyceryl ether having an alkyl group having 8 or more carbon atoms and a higher fatty acid having 6 or more carbon atoms from the viewpoint of improving the long-term retention of the functional oil.
• the above is more preferable, and it is an alkyl glyceryl ether having an alkyl group having 8 or more carbon atoms.
• the content ratio of the component (B1) to the component (A) in the microcapsules of the present invention is preferable from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. Is 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably. Is 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less.
• the content ratio of the component (B1) to the component (A) is the content ratio when the component (A) in the microcapsules is 100% by mass.
• the organic compound contained in the core of the microcapsules of the present invention further contains the following component (B2) from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsules. It is preferable to include it.
• Component (B2) One or more selected from fatty acid esters having 6 or more carbon atoms and higher alkanes having 6 or more carbon atoms, and the component (B2) excludes the component (A).
• the cLogP value of the component (B2) is preferably 4 or more, more preferably 5 or more, still more preferably, from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. Is 6 or more, more preferably 7 or more, and preferably 10 or less, more preferably 9 or less.
• the total carbon number of the fatty acid ester is 6 or more, preferably 10 or more, more preferably 10 or more, from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsules. It is 14 or more, more preferably 18 or more, and preferably 50 or less.
• the fatty acid esters are fatty acid monoesters of fatty acids and monovalent alcohols, fatty acid diesters of fatty acids and divalent alcohols, dicarboxylic acid diesters of dicarboxylic acids and monovalent alcohols, and tricarboxylic acid triesters of tricarboxylic acids and monovalent alcohols.
• fatty acid monoesters are preferable from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules.
• the fatty acid monoester is preferably composed of a fatty acid having 8 or more and 22 or less carbon atoms and a monohydric alcohol having 1 or more and 24 or less carbon atoms.
• fatty acids constituting the fatty acid monoester examples include 2-ethylhexanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitreic acid, margaderic acid, stearic acid, oleic acid, linoleic acid, erucic acid, and arachidic acid.
• saturated or unsaturated fatty acids having 8 or more and 22 or less carbon atoms such as behenic acid.
• Examples of the monohydric alcohol constituting the fatty acid monoester include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, isopentyl alcohol, neopentyl alcohol, hexanol, and heptanol.
• fatty acid monoester examples include cetyl 2-ethylhexanoate, butyl stearate, isopropyl myristate, hexadecyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, hexadecyl palmitate, 2-ethylhexyl stearate and the like. .. Of these, isopropyl palmitate is preferable.
• the carbon number of the higher alkane is preferably 6 or more and 32 or less, and more preferably 10 or more and 32 or less.
• Examples of the higher alkanes include linear or branched linear or branched chains having 6 or more and 32 or less carbon atoms such as decane, undecane, dodecane, isododecane, tridecane, tetradecane, hexadecane, octadecane, icosan, docosan, squalane, and squalane. Higher alkanes can be mentioned.
• the component (B2) is preferably a fatty acid ester having a total carbon number of 6 or more from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsules.
• the content ratio of the component (B2) to the component (A) in the microcapsules of the present invention is preferable from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. Is 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.7% by mass or more, and preferably 10% by mass or less. It is more preferably 7% by mass or less, further preferably 5% by mass or less, still more preferably 4% by mass or less, still more preferably 3% by mass or less.
• the content ratio of the component (B2) to the component (A) is the content ratio when the component (A) in the microcapsules is 100% by mass.
• the shell of the microcapsules of the present invention contains an inorganic substance as a constituent.
• the inorganic substance is preferably a metal oxide containing a metal element or a metalloid element, and more preferably an inorganic polymer formed by a sol-gel reaction using a metal alkoxide [M (OR) x] as a shell precursor.
• M is a metal or a metalloid element
• R is a hydrocarbon group.
• the metal or metalloid element constituting the metal alkoxide include silicon, aluminum, titanium, zirconium, zinc and the like.
• the inorganic substance is preferably one or more metal alkoxides selected from silicon, aluminum, and titanium from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsules. It is an inorganic polymer formed by a sol-gel reaction using a shell precursor, and more preferably an alkoxysilane polymer.
• the alkoxysilane is preferably tetraalkoxysilane from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules.
• the tetraalkoxysilane preferably has an alkoxy group having 1 or more and 4 or less carbon atoms, and is more preferably selected from tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane. It is one or more, more preferably one or more selected from tetramethoxysilane and tetraethoxysilane, and even more preferably tetraethoxysilane.
• an oil-water mixture containing an oil phase component containing the following components (A), component (B1) and component (C) and an aqueous phase component is emulsified and subjected to a sol-gel reaction. It is obtained by a production method including a step of forming microcapsules (hereinafter, also referred to as "step I").
• the component (A) and the component (B1) are as described above. Since the component (B1) has a long-chain aliphatic hydrocarbon group and a polar group, it functions as an emulsifying aid during emulsification of an oil-water mixture, and the formation of stable and fine emulsified droplets can proceed rapidly. It is thought that it can be done. Therefore, it is possible to suppress the destruction of the shell due to long-term application of mechanical force, it is possible to provide an appropriate shell forming site as a template for microcapsules, improve the long-term retention of organic compounds, and further, the microcapsules. It is considered to improve the controllability of the particle size.
• the oil phase component of the oil-water mixture preferably further contains the above-mentioned component (B2) from the viewpoint of improving the long-term retention of the functional oil and the controllability of the particle size of the microcapsules.
• the component (B2) is considered to function as a particle size stabilizer that stabilizes the particle size of the emulsified droplet that serves as a template for microcapsules.
• the component (B2) contributes to the suppression of destabilization of the emulsified droplet due to Ostwald aging in which a relatively hydrophilic component as an oil phase component in the emulsified droplet diffuses into the aqueous phase which is a continuous phase, and the emulsified droplet is aged.
• the grain size of the emulsified droplet that serves as a template for the microcapsules can be stabilized by suppressing the coarsening in the water. Therefore, by using the component (B2) in combination with the component (B1), an appropriate shell forming site can be provided as a template for microcapsules, the long-term retention of the organic compound is improved, and the particle size of the microcapsules is further improved. It is thought that the controllability of the From this point of view, the logP value of the component (B2) is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 7 or more, and preferably 10 or less, as described above. More preferably, it is 9 or less.
• the component (B1) may have a function as a particle size stabilizer for stabilizing the particle size of the emulsified droplet as a template for microcapsules, in addition to the function as an emulsification aid.
• the component (B1) is preferably one or more selected from higher fatty acids having 6 or more carbon atoms and higher fatty alcohols having 6 or more carbon atoms, and more preferably 6 or more carbon atoms. It is a higher fatty acid.
• the cLogP value of the component (B1) is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 10 or less from the viewpoint of improving the long-term retention of the functional oil. , More preferably 9 or less.
• the cLogP value of the component (B1) is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 7 or more, from the viewpoint of improving the controllability of the particle size of the microcapsules. And it is preferably 10 or less, more preferably 9 or less.
• the amount of the component (B2) used in the production method of the present invention is preferably 20% by mass with respect to the total amount of the oil-water mixture from the viewpoint of not inhibiting the movement of the shell precursor to the oil-water interface in the system and the formation of the shell. % Or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and preferably 0.05% by mass or less. As mentioned above, it is more preferably 0.1% by mass or more, still more preferably 0.15% by mass or more.
• the amount of the component (B2) is an amount when the total amount of the oil-water mixture is 100% by mass.
• the oil phase component of the oil-water mixture contains a shell precursor as the component (C).
• the component (C) is a substance that can form a shell of microcapsules, and is preferably a metal alkoxide [M (OR) x].
• M and R are the same as described above.
• the metal or metalloid element constituting the metal alkoxide include silicon, aluminum, titanium, zirconium, zinc and the like.
• the component (C) is one or more metals preferably selected from silicon, aluminum, and titanium from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules. It is an alkoxide, more preferably an alkoxysilane.
• the alkoxysilane is preferably tetraalkoxysilane from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules.
• the tetraalkoxysilane preferably has an alkoxy group having 1 or more and 4 or less carbon atoms, and is more preferably selected from tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane. It is one or more, more preferably one or more selected from tetramethoxysilane and tetraethoxysilane, and even more preferably tetraethoxysilane.
• the amount of the component (C) used in the production method of the present invention is preferably 10% by mass with respect to the amount of the component (A) from the viewpoint of forming a shell surrounding the oil phase emulsified droplet containing the functional oil agent. % Or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and from the viewpoint of suppressing the residue of the shell precursor inside the oil phase droplets and efficiently promoting the conversion to the shell. It is preferably 100% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, still more preferably 30% by mass or less.
• the amount of the component (C) is an amount when the amount of the component (A) is 100% by mass.
• the aqueous phase component of the oil-water mixture preferably contains a cationic surfactant from the viewpoint of improving the long-term retention of the functional oil and improving the controllability of the particle size of the microcapsules.
• the cationic surfactant include an alkylamine salt and an alkyl quaternary ammonium salt.
• the alkyl group of the alkylamine salt and the alkyl quaternary ammonium salt preferably has 6 or more carbon atoms, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, still more preferably 14 or more. , And more preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.
• alkylamine salt examples include alkylamine acetates such as laurylamine acetate and stearylamine acetate.
• alkyl quaternary ammonium salt examples include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylbenzyldimethylammonium salt and the like.
• alkyltrimethylammonium salt examples include alkyltrimethylammonium chlorides such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride and stearyltrimethylammonium chloride; alkyltrimethylammonium bromides such as lauryltrimethylammonium bromide, cetyltrimethylammonium bromide and stearyltrimethylammonium bromide.
• alkyltrimethylammonium salt include dialkyldimethylammonium chloride such as distearyldimethylammonium chloride; and dialkyldimethylammonium bromide such as distearyldimethylammonium bromide.
• alkylbenzyldimethylammonium salt examples include alkylbenzyldimethylammonium chloride and alkylbenzyldimethylammonium bromide.
• the cationic surfactant may be used alone or in combination of two or more.
• the cationic surfactant is preferably a quaternary ammonium salt, more preferably an alkyltrimethylammonium salt having an alkyl group having 6 or more and 22 or less carbon atoms, and further preferably a lauryltrimethylammonium chloride.
• a quaternary ammonium salt more preferably an alkyltrimethylammonium salt having an alkyl group having 6 or more and 22 or less carbon atoms, and further preferably a lauryltrimethylammonium chloride.
• Stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride and more preferably cetyltrimethylammonium chloride.
• the amount of the cationic surfactant used in the production method of the present invention is preferably 0.1% by mass or more, more preferably 0.2, based on the amount of the component (A) from the viewpoint of obtaining a stable emulsion. It is by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less.
• the aqueous phase component of the oil-water mixture contains a cationic surfactant
• the component (B1) is used in combination with the cationic surfactant to improve the ability of the system to reduce the dynamic interface tension. Therefore, it is considered that the formation of stable and fine emulsified droplets can proceed rapidly.
• the molecular weight of the component (B1) is preferably 500 or less, more preferably 450 or less, still more preferably 400 or less, still more preferably 350 or less, as described above. be.
• the amount of the oil phase component with respect to the total amount of the oil-water mixture is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and a stable emulsion. From the viewpoint of obtaining the above, it is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.
• the mixing order of each component of the oil-water mixture is not particularly limited.
• the component (B1), the component (A), the component (B2), and the component (C) may be mixed if necessary, and the aqueous phase component and the oil phase component prepared in advance are mixed. You may.
• the component of the oil-water mixture is a solid, it may be heated at the time of mixing.
• the oil-water mixture is preferably prepared by a method including the following steps 1 to 3.
• Step 1 A step of preparing an aqueous phase component containing a cationic surfactant
• Step 2 A component (A), a component (B1), and if necessary, a component (B2) and a component (C) are mixed to prepare an oil phase.
• Step of preparing components Step 3: A step of adding the oil phase component obtained in step 2 to the aqueous phase component obtained in step 1 to obtain an oil-water mixture.
• the oil-water mixture is emulsified and then subjected to a sol-gel reaction.
• the stirring means used for emulsifying the oil-water mixture is not particularly limited, and a homogenizer having a shearing force, a high-pressure disperser, an ultrasonic disperser, or the like can be used.
• a homomixer "Disper” (trade name, manufactured by Primix Corporation), "Clairemix” (trade name, manufactured by M-Technique Co., Ltd.), “Cavitron” (trade name, manufactured by Ohira Yokinko Co., Ltd.), etc. are used. You can also do it.
• the temperature at the time of emulsification of the oil-water mixture is preferably 5 ° C.
• the median diameter D 50 of the emulsified droplet of the emulsified liquid obtained by emulsifying the oil-water mixture is preferably 0.1 ⁇ m from the viewpoint of reducing the specific surface area with respect to the external environment of the microcapsules and improving the long-term retention of the functional oil.
• the above is more preferably 0.2 ⁇ m or more, further preferably 0.3 ⁇ m or more, and from the viewpoint of improving the physical strength of the microcapsules and improving the long-term retention of the functional oil, and the particles of the microcapsules.
• the diameter is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, still more preferably 3 ⁇ m or less.
• the median diameter D 50 can be measured by the method described in Examples.
• the initial pH of the sol-gel reaction in step I is from the viewpoint of maintaining a balance between the hydrolysis reaction and the condensation reaction of the shell precursor, and from the viewpoint of suppressing the formation of a highly hydrophilic sol and promoting the progress of encapsulation. It is preferably 3.0 or more, more preferably 3.3 or more, still more preferably 3.5 or more, and suppresses the coexistence of shell formation and aggregation of emulsion droplets to obtain microcapsules having a dense shell. From the viewpoint, it is preferably 4.5 or less, more preferably 4.3 or less, still more preferably 4.1 or less.
• any acidic or alkaline pH adjustment is made depending on the acidity and alkaline strength of the oil phase component including the component (A) and the component (B1). It is preferable to add the agent to the emulsion.
• the pH of the emulsion is equal to or lower than a desired value, it is preferable to adjust the pH with an alkaline pH adjuster.
• the pH of the emulsion is equal to or higher than a desired value, it is preferable to adjust the pH with an acidic pH adjuster.
• the acidic pH adjuster examples include inorganic acids such as sulfuric acid, sulfite, hydrochloric acid and nitric acid; aromatic sulfonic acid compounds such as paratoluene sulfonic acid and benzene sulfonic acid, aliphatic sulfonic acid compounds of methane sulfonic acid and citric acid.
• Organic acid A liquid obtained by adding a cation exchange resin or the like to water, ethanol or the like.
• alkaline pH adjusters hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydrogen carbonates of alkali metals such as sodium hydrogen carbonate; ammonia; ammonium hydroxide; diethanolamine, triethanolamine, trishydroxymethyl Examples thereof include organic amines such as aminomethane. Above all, it is preferably one or more selected from sodium hydroxide and ammonium hydroxide.
• the pH adjuster one kind or two or more kinds can be used.
• the reaction temperature of the sol-gel reaction in step I can be any value as long as it is at least the melting point of water contained as a dispersion medium and below the boiling point, but the hydrolysis reaction and the condensation reaction in the sol-gel reaction can be selected. In order to control the balance and form a dense and strong shell, it is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 15 ° C. or higher, and preferably 60 ° C. or lower, more preferably 50 ° C. or higher. It is preferable to adjust the temperature to °C or less, more preferably 40 °C or less.
• the microcapsules obtained by step I are obtained as an aqueous dispersion containing microcapsules dispersed in water.
• the microcapsules can be used as they are as an aqueous dispersion, but depending on the use of the microcapsules, the microcapsules may be separated from the aqueous dispersion and used.
• the separation method a filtration method, a centrifugal separation method or the like can be adopted.
• the component (C) is further added to the aqueous dispersion containing the microcapsules obtained in the step I, and a sol-gel reaction is carried out to carry out the sol-gel reaction.
• a sol-gel reaction is carried out to carry out the sol-gel reaction.
• step II a step of forming a microcapsule having a shell for further encapsulating the capsule.
• the shell formed by step I is also referred to as a “first shell”
• the shell formed by step II is also referred to as a “second shell”.
• the temperature of the sol-gel reaction in step II may be the same as that in step I.
• the amount of the component (C) in the step II is preferably 3% by mass or more, more preferably 5% by mass or more, and further, from the viewpoint of improving the long-term retention of the functional oil with respect to the amount of the component (A). It is preferably 10% by mass or more, and is preferably 50% by mass or less, more preferably 30 from the viewpoint of suppressing the residue of the shell precursor inside the oil phase droplets and efficiently promoting the conversion to the shell. It is 0% by mass or less, more preferably 20% by mass or less.
• the median diameter D 50 of the microcapsules of the present invention varies depending on the type of shell, but in the case of silica capsules, for example, it is preferable from the viewpoint of improving the long-term retention of the functional oil and improving the dispersion stability of the silica capsules. Is 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 0.7 ⁇ m or more, and from the viewpoint of improving the physical strength of the silica capsule and improving the long-term retention of the functional oil agent, and.
• the particle size of the microcapsules is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less.
• the median diameter D 50 of the microcapsules can be measured by the method described in Examples.
• the microcapsules of the present invention can be used for various purposes, for example, cosmetics such as milky lotions, cosmetics, lotions, beauty essences, creams, gel preparations, hair treatment agents, quasi-drugs, and detergents. It can be suitably used for various applications such as softeners, fiber treatment agents such as anti-wrinkle sprays, sanitary products such as paper diapers, and fragrances.
• the microcapsules of the present invention can be blended and used in compositions such as detergent compositions, fiber treatment agent compositions, cosmetic compositions, air freshener compositions, and deodorant compositions.
• a detergent composition such as a powder detergent composition and a liquid detergent composition
• a fiber treatment agent composition such as a softener composition
• a fiber treatment agent composition is more preferable, and a softener is more preferable.
• the composition is more preferred.
• the present invention further discloses the following microcapsules and a method for producing microcapsules.
• the molecular weight of the component (B1) is preferably 500 or less, more preferably 450 or less, further preferably 400 or less, still more preferably 350 or less, and preferably 150 or more.
• the microcapsules described in. ⁇ 3> The component (B1) is preferably one or more selected from higher fatty acids having 6 or more carbon atoms and higher aliphatic alcohols having 6 or more carbon atoms, and more preferably higher fatty acids having 6 or more carbon atoms.
• the component (B1) is preferably one or more selected from an alkyl glyceryl ether having an alkyl group having 8 or more carbon atoms and a higher fatty acid having 6 or more carbon atoms, and more preferably 8 or more carbon atoms.
• the content ratio of the component (B1) to the component (A) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably.
• ⁇ 6> The microcapsule according to any one of ⁇ 1> to ⁇ 5>, wherein the organic compound further contains the following component (B2).
• the cLogP value of the component (B2) is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, still more preferably 7 or more, and preferably 10 or less, more preferably 9 or less.
• the content ratio of the component (B2) to the component (A) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably. 0.7% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 4% by mass or less, still more preferably 3% by mass.
• the component (A) is preferably a fragrance, a fragrance precursor, a moisturizing agent, an antioxidant, an antibacterial agent, a fertilizer, a fiber, a skin, a surface modifier such as hair, a cooling sensation agent, a dye, a pigment, and the like.
• One or more selected from silicone and oil-soluble polymers more preferably one or more selected from fragrances, fragrance precursors, moisturizers, antioxidants, antibacterial agents, fertilizers, and surface modifiers, even more preferably.
• One or more selected from fragrances, fragrance precursors, moisturizers, and antioxidants more preferably one or more selected from fragrances, fragrance precursors and moisturizers, even more preferably fragrances and fragrance precursors.
• the microcapsule according to any one of ⁇ 1> to ⁇ 9> which is one or more selected from the above.
• the cLogP value of the component (A) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.
• the inorganic substance is an inorganic polymer formed by a sol-gel reaction using one or more metal alkoxides preferably selected from silicon, aluminum, and titanium as shell precursors, and more preferably alkoxysilane.
• the median diameter D 50 of the microcapsules is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 0.7 ⁇ m or more, and preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
• the microcapsule according to any one of ⁇ 1> to ⁇ 12> which is more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less.
• a method for producing microcapsules which comprises a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell.
• component (B2) One or more selected from fatty acid esters having 6 or more carbon atoms and higher alkanes having 6 or more carbon atoms (however, excluding component (A)) ⁇ 16>
• the amount of the component (B2) is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, still more preferably 0.7% by mass, based on the total amount of the oil-water mixture.
• the component (C) is one or more metal alkoxides preferably selected from silicon, aluminum, and titanium, and more preferably alkoxysilane. How to make microcapsules. ⁇ 18>
• the amount of the component (C) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 20% by mass or more, based on the amount of the component (A).
• the median diameter D 50 of the emulsified droplet of the emulsion obtained by emulsifying the oil-water mixture is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more, and
• the organic compound contains the following component (A) and component (B1).
• the molecular weight of the component (B1) is 500 or less, Microcapsules in which the content ratio of the component (B1) to the component (A) is 0.01% by mass or more and 10% by mass or less.
• the cLogP value of the component (A) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.
• the organic compound contains the following component (A), component (B1), and component (B2).
• Component (B2) One or more selected from amide compounds having an alkyl group of (excluding component (A)) Component (B2): One or more selected from fatty acid esters having 6 or more carbon atoms and higher alkanes having 6 or more carbon atoms (however, excluding component (A))
• the content ratio of the component (B1) to the component (A) is 0.01% by mass or more and 10% by mass or less.
• Microcapsules in which the content ratio of the component (B2) to the component (A) is 0.01% by mass or more and 10% by mass or less.
• the molecular weight of the component (B1) is preferably 500 or less, more preferably 450 or less, still more preferably 400 or less, still more preferably 350 or less, and preferably 150 or more.
• the microcapsules described in. ⁇ 25> The cLogP value of the component (B2) is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 7 or more, and preferably 10 or less, more preferably 9 or less.
• the cLogP value of the component (A) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.
• Model fragrance> As the component (A) contained in the microcapsules, the model fragrance A1 (volume average cLogP value: 3.7, specific gravity: 0.97, oil-water interfacial tension: 17.0 mN / m) having the composition shown in Table 1 and Table 2 A model fragrance A2 (volume average cLogP value: 3.7, specific gravity: 0.97, oil-water interfacial tension: 16.3 mN / m) having the composition shown in the above was used. The volume average cLogP value of the model fragrance was calculated as the sum of the cLogP values of the fragrance components contained in the model fragrance multiplied by the volume ratio in the model fragrance.
• Example 1 Dilute 0.60 g of Coatamine 60 W (trade name, manufactured by Kao Corporation; cetyltrimethylammonium chloride (referred to as “CTAC” in Table 3 below), active ingredient 30% by mass) with 149.40 g of ion-exchanged water.
• the aqueous phase component was prepared.
• 38.4 g of model fragrance A1 as component (A) 10 g of tetraethoxysilane (hereinafter referred to as "TEOS") as component (C), and 1.2 g of cetyl as component (B1).
• An oil-water mixture was obtained by adding an oil phase component prepared by premixing alcohol and 0.4 g of isopropyl palmitate as the component (B2).
• the obtained oil-water mixture was emulsified at room temperature (about 25 ° C.) at a rotation speed of 8,500 rpm for 8 minutes using a homomixer (manufactured by HsiangTai, model: HM-310) to obtain an emulsified solution.
• the median diameter D 50 of the emulsified droplet at this time was 1.1 ⁇ m.
• the mixture was transferred to a separable flask equipped with a stirring blade, and the mixture was stirred at 200 rpm for 24 hours while keeping the liquid temperature at 30 ° C.
• An aqueous dispersion (1) containing a silica capsule having a core composed of the component (A), the component (B1) and the component (B2) and a shell composed of silica was obtained.
• the median diameter D 50 of the silica capsule of the aqueous dispersion (1) was 1.7 ⁇ m.
• Example 2 An aqueous phase component was prepared by diluting 0.60 g of coatamine 60 W (trade name, manufactured by Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass) with 149.40 g of ion-exchanged water.
• An oil phase component prepared by premixing 38.8 g of the model fragrance A2 as the component (A), 10 g of TEOS as the component (C), and 1.2 g of cetyl alcohol as the component (B1) with this aqueous phase component.
• an oil-water mixture was obtained.
• the obtained oil-water mixture was emulsified at room temperature (about 25 ° C.) for 8 minutes using the homomixer set at a rotation speed of 8,500 rpm to obtain an emulsified solution.
• the median diameter D 50 of the emulsified droplet at this time was 1.0 ⁇ m.
• the mixture was transferred to a separable flask equipped with a stirring blade, and the mixture was stirred at 200 rpm for 24 hours while keeping the liquid temperature at 30 ° C.
• An aqueous dispersion (2) containing a silica capsule having a core composed of the component (A) and the component (B1) and a shell composed of silica was obtained.
• the median diameter D 50 of the silica capsule of the aqueous dispersion (2) was 2.2 ⁇ m.
• aqueous phase component was prepared by diluting 0.60 g of coatamine 60 W (trade name, Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass) with 149.40 g of ion-exchanged water.
• An oil-water mixture was obtained by adding an oil-phase component prepared by mixing 40 g of model fragrance A1 as component (A) and 10 g of TEOS as component (C) to this aqueous phase component.
• the obtained oil-water mixture was emulsified at room temperature (about 25 ° C.) for 8 minutes using the homomixer set at a rotation speed of 8,500 rpm to obtain an emulsified solution.
• the median diameter D 50 of the emulsified droplet at this time was 2.0 ⁇ m.
• the mixture was transferred to a separable flask equipped with a stirring blade, and the mixture was stirred at 200 rpm for 24 hours while keeping the liquid temperature at 30 ° C. , An aqueous dispersion (C1) containing a silica capsule having a core composed of the component (A) and a shell composed of silica was obtained.
• the median diameter D 50 of the silica capsule of the aqueous dispersion (C1) was 2.6 ⁇ m.
• Example 3 An aqueous dispersion (1) containing silica capsules was obtained in the same manner as in Step I of Example 1. (Step II) Next, 4.5 g of TEOS was added to 150 g of the aqueous dispersion (1) over 7 hours using a dropping pump "Atlas syringe pump" (trade name: Syrris), and then the liquid temperature was 30. By stirring for 24 hours while keeping the temperature at ° C. and cooling to room temperature, a second shell encapsulating the silica capsule is formed, and the component (A), the component (B1) and the component (B2) are made of amorphous silica. An aqueous dispersion (3) containing an encapsulated silica capsule was obtained. The median diameter D 50 of the silica capsule of the aqueous dispersion (3) was 1.9 ⁇ m.
• Example 4 An aqueous dispersion (2) containing silica capsules was obtained in the same manner as in Step I of Example 2. (Step II) Next, 4.5 g of TEOS was added to 150 g of the aqueous dispersion (2) over 7 hours using the dropping pump, and then the mixture was stirred for 24 hours while maintaining the liquid temperature at 30 ° C. to room temperature. By cooling, a second shell enclosing the silica capsule was formed, and an aqueous dispersion (4) containing a silica capsule in which the component (A) and the component (B1) were encapsulated in amorphous silica was obtained. .. The median diameter D 50 of the silica capsule of the aqueous dispersion (4) was 2.2 ⁇ m.
• Example 5 An aqueous phase component was prepared by diluting 0.60 g of coatamine 60 W (trade name, Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass) with 149.40 g of ion-exchanged water. An oil phase component prepared by premixing this aqueous phase component with 38.8 g of model fragrance A2 as component (A), 10 g of TEOS as component (C), and 1.2 g of isostearic acid as component (B1). was added to obtain an oil-water mixture.
• coatamine 60 W trade name, Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass
• An oil phase component prepared by premixing this aqueous phase component with 38.8 g of model fragrance A2 as component (A), 10 g of TEOS as component (C), and 1.2 g of isostearic acid as component (B1). was added to obtain an oil-water mixture.
• the obtained oil-water mixture was emulsified at room temperature (about 25 ° C.) for 15 minutes using the homomixer set at a rotation speed of 8,000 rpm to obtain an emulsified solution.
• the median diameter D 50 of the emulsified droplet was 0.7 ⁇ m.
• the mixture was transferred to a separable flask equipped with a stirring blade, and the mixture was stirred at 200 rpm for 24 hours while keeping the liquid temperature at 30 ° C.
• aqueous dispersion (5') containing a silica capsule having a core composed of the component (A) and the component (B1) and a first shell composed of silica was obtained.
• Step II Next, 5.5 g of TEOS was added to the aqueous dispersion (5') over 7 hours using the dropping pump, and the mixture was further stirred for 17 hours and cooled to room temperature to cool the silica to room temperature. A second shell was formed to enclose the capsule, and an aqueous dispersion (5) containing a silica capsule in which the component (A) and the component (B1) were encapsulated in amorphous silica was obtained.
• the median diameter D 50 of the silica capsule of the aqueous dispersion (5) was 0.9 ⁇ m.
• Example 6 An aqueous phase component was prepared by diluting 0.61 g of coatamine 60 W (trade name, Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass) with 149.11 g of ion-exchanged water. An oil phase component prepared by premixing this aqueous phase component with 38.9 g of model fragrance A2 as component (A), 10 g of TEOS as component (C), and 1.2 g of bacillus alcohol as component (B1). was added to obtain an oil-water mixture.
• coatamine 60 W trade name, Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass
• An oil phase component prepared by premixing this aqueous phase component with 38.9 g of model fragrance A2 as component (A), 10 g of TEOS as component (C), and 1.2 g of bacillus alcohol as component (B1). was added to obtain an oil-water mixture.
• the obtained oil-water mixture was emulsified at room temperature (about 25 ° C.) for 8 minutes using the homomixer set at a rotation speed of 8,500 rpm to obtain an emulsified solution.
• the median diameter D 50 of the emulsified droplet was 0.7 ⁇ m.
• the mixture was transferred to a separable flask equipped with a stirring blade, and the mixture was stirred at 200 rpm for 24 hours while keeping the liquid temperature at 30 ° C.
• aqueous dispersion (6') containing a silica capsule having a core composed of the component (A) and the component (B1) and a first shell composed of silica was obtained.
• Step II Next, 0.71 g of TEOS was added to 25.36 g of the aqueous dispersion (6') over 10 seconds with the dropping pump, and then the mixture was stirred for 20 hours while keeping the liquid temperature at 30 ° C. to room temperature. By cooling to, a second shell enclosing the silica capsule is formed, and an aqueous dispersion (6) containing a silica capsule in which the component (A) and the component (B1) are encapsulated in amorphous silica is obtained.
• rice field The median diameter D 50 of the silica capsule of the aqueous dispersion (6) was 1.5 ⁇ m.
• aqueous phase component was prepared by diluting 0.60 g of coatamine 60 W (trade name, Kao Corporation; cetyltrimethylammonium chloride, active ingredient 30% by mass) with 149.41 g of ion-exchanged water.
• An oil phase prepared by premixing 38.80 g of model fragrance A1 as component (A), 10 g of TEOS as component (C), and 1.2 g of isopropyl palmitate as component (B2) with this aqueous phase component. The components were added to obtain an oil-water mixture.
• the obtained oil-water mixture was emulsified at room temperature (about 25 ° C.) for 8 minutes using the homomixer set at a rotation speed of 8,500 rpm to obtain an emulsified solution.
• the median diameter D 50 of the emulsified droplet at this time was 1.9 ⁇ m.
• the mixture was transferred to a separable flask equipped with a stirring blade, and the mixture was stirred at 200 rpm for 24 hours while keeping the liquid temperature at 30 ° C.
• aqueous dispersion (C2') containing a silica capsule having a core composed of the component (A) and the component (B2) and a first shell composed of silica was obtained.
• Step II' Next, the aqueous dispersion (C2') was stirred with respect to 190.00 g while maintaining the liquid temperature at 30 ° C., and 5.7 g of TEOS was added over 7 hours using the dropping pump, and then further. By stirring for 17 hours and cooling to room temperature, a second shell encapsulating the silica capsule is formed, and water dispersion containing the silica capsule in which the component (A) and the component (B2) are encapsulated in amorphous silica is contained. A body (C2) was obtained. The median diameter D 50 of the silica capsule of the aqueous dispersion (C2) was 1.4 ⁇ m.
• Example 3 the amount of cetyl alcohol as the component (B1) or the amount of isopropyl palmitate as the component (B2) was changed to the amount shown in Table 3, and the rotation speed and emulsification treatment time of the homomixer used for emulsifying the oil-water mixture were changed.
• aqueous dispersions (7) to (9) and (C3) containing silica capsules were obtained, respectively.
• Table 3 shows the median diameter D 50 of the emulsified droplet and the median diameter D 50 of the silica capsule.
• Example 7 From the comparison between Example 7 and Comparative Example 3 in Table 3, it can be seen that the median diameter D 50 of the obtained silica capsule becomes smaller depending on the amount of the component (B1) added. From Examples 3, 8 and 9 in Table 3, it can be seen that as the amount of the component (B2) added increases, the median diameter D 50 of the obtained silica capsule becomes smaller. From this, according to the present invention, by adjusting the amount of the component (B1) or the component (B2), microcapsules having a smaller particle size can be obtained, and the particle size of the microcapsules can be controlled. Therefore, it is useful for designing the composition of microcapsules according to the application. Further, since the microcapsules having a smaller particle size are considered to improve the physical strength, it is considered that the microcapsules are suppressed from collapsing at the distribution stage and the like, and the storage stability is also improved.
• the silica capsule is immersed in 2 mL of methanol containing dodecane at a concentration of 20 ⁇ g / mL as an internal standard, and the ultrasonic irradiation device is used.
• the ultrasonic irradiation device was irradiated with ultrasonic waves for 60 minutes under the conditions of an output of 180 W and an oscillation frequency of 42 kHz to elute the fragrance in the silica capsule.
• Perfume retention rate (%) ⁇ (GC peak area ratio ⁇ to internal standard of each perfume component contained in the silica capsule after storage) ⁇ (amount of methanol solution used for extraction) / (silica capsule used for evaluation) Amount of aqueous dispersion containing) ⁇ / ⁇ (GC peak area ratio ⁇ to internal standard of each fragrance component contained in the aqueous dispersion containing silica capsules before storage) ⁇ (amount of methanol solution used for extraction) / ( Amount of aqueous dispersion containing silica capsules used for evaluation) ⁇ x 100
• microcapsule and a method for producing microcapsules which can retain a functional oil such as a fragrance contained therein for a long period of time and have excellent controllability of particle size. Further, according to the present invention, the controllability of the particle size is excellent, the physical strength of the silica capsule having a small particle size is improved, and the stability at the distribution stage of the microcapsules is also excellent.
• the microcapsules are also useful in designing the compounding composition of the above, and the microcapsules are suitably used for various products containing functional oils such as fragrances.

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• 2020
  • 2020-12-28 US US18/259,227 patent/US12594534B2/en active Active
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