WO2017090998A1 - Bi-continuous phase emulsion composition containing amphiphilic anisotropic powder - Google Patents

Bi-continuous phase emulsion composition containing amphiphilic anisotropic powder Download PDF

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WO2017090998A1
WO2017090998A1 PCT/KR2016/013606 KR2016013606W WO2017090998A1 WO 2017090998 A1 WO2017090998 A1 WO 2017090998A1 KR 2016013606 W KR2016013606 W KR 2016013606W WO 2017090998 A1 WO2017090998 A1 WO 2017090998A1
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anisotropic powder
group
polymer spheroid
composition
polymer
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PCT/KR2016/013606
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French (fr)
Korean (ko)
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김영선
남진
피봉수
진유진
안순애
강병영
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(주)아모레퍼시픽
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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
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular 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
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • 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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • 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

Definitions

  • the present specification relates to a dual continuous phase emulsion composition comprising an amphiphilic anisotropic powder and a method for producing the same.
  • oil-in-water (O / W) or water-in-oil (W / O) emulsion formulations are formed depending on the HLB (Hydrophile-Lipophile Balance) value of the surfactant.
  • HLB Hydrophile Balance
  • Bi-Continuous Emulsion is a formulation in which two phases coexist without distinction between internal and external phases.
  • 2 is a structural diagram schematically showing an oil-in-water type, a water-in-oil type, and a dual continuous emulsion formulation.
  • Dual continuous emulsion formulations also called “soft solids”, are emulsion formulations in which particles are wetted in a continuous phase, causing spinodal separation to stabilize. According to these structural characteristics it is also called BIJEL (Bicontinuous Interfacially Jammed Emulsion Gel).
  • Dual-phase emulsion formulations have been applied in various fields such as catalysts, separation processes, cellular engineering, fuel cells, solar cells, barrier materials, sensors, etc. due to the unique formulation properties.
  • Forming a dual continuous emulsion formulation using a conventional surfactant can be implemented only in a very limited composition ratio of the system (water, oil, surfactant), and has been difficult to stabilize due to the fluidity of the emulsion surfactant.
  • the application possibilities are expanded.
  • One such application is a pickling emulsion that can form stabilized large emulsified particles using fine spherical particles.
  • the contact angle ⁇ is different between the aqueous phase and the oil phase.
  • O / W emulsified particles are formed at a contact angle of 90 ° or more, and W / O emulsified particles are formed at 90 ° or less.
  • the problem to be solved by the present invention is to provide a double continuous emulsion composition excellent in emulsion stability.
  • the problem to be solved by the present invention is to provide a dual continuous emulsion composition capable of simultaneously imparting the characteristics of each of the water phase and the oil phase.
  • the problem to be solved by the present invention is to provide a dual continuous emulsion composition in which the formulation remains stable at various temperature ranges.
  • the problem to be solved by the present invention is to provide a double continuous emulsion composition excellent in stability over time.
  • the problem to be solved by the present invention is to provide an emulsified composition of a gel formulation characterized by no flow.
  • a bi-continuous emulsion composition comprising amphiphilic anisotropic powder, nonpolar oil and water,
  • a hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid A hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid
  • the first polymer spheroid and the second polymer spheroid are combined at least partially in a structure that penetrates the relative polymer spheroid,
  • the first polymer spheroid has a core-shell structure, and the shell provides an emulsified composition.
  • the present invention can provide a dual continuous emulsion composition having excellent emulsion stability.
  • the present invention can provide a dual continuous emulsion composition capable of simultaneously imparting the characteristics of each of the aqueous and oil phases.
  • the present invention may provide a dual continuous emulsion composition in which the formulation remains stable at various temperature ranges.
  • the present invention can provide a dual continuous emulsion composition having excellent stability over time.
  • the present invention may provide an emulsified composition of a characteristic gel formulation with no flow.
  • FIG. 1 is a schematic diagram of forming an amphipathic anisotropic powder according to an embodiment of the present invention.
  • Figure 2 is a diagram illustrating the oil-in-water (O / W), water-in-oil (W / O) and double continuous phase (BCE) emulsion formulation.
  • FIG. 3 is a photograph showing the results of experiments confirming the formation of a dual continuous emulsion formulation using the dyeability of water-soluble and fat-soluble dyes.
  • Figure 4 is a graph showing the change in formulation and the change in conductivity characteristics according to the oil content of the formulation of Examples and Comparative Examples.
  • Figure 5 is a photograph confirming the gel (gel) formation and stability of the dual-phase emulsion (BCE) formulation.
  • (meth) acryl may mean acryl and / or methacryl.
  • the particle size of the amphipathic anisotropic powder herein is a measure of the maximum length, which is the longest length of the powder particles.
  • the particle size range of the amphipathic anisotropic powder herein means that at least 95% of the amphipathic anisotropic powder present in the composition falls within this range.
  • a bi-continuous emlusion composition including amphipathic anisotropic powder is provided.
  • the interface film formed by the general molecular-level surfactant forms a dynamic emulsification state, while the thickness of the emulsified interface film formed by the amphiphilic anisotropic powder increases to several hundred nm, and is firm through strong bonding between the powders.
  • An interface film is formed.
  • the composition according to the present embodiment may include an amphiphilic anisotropic powder to maintain a dense and stable continuous phase interface, and form a stable dual continuous emulsion formulation.
  • the dual continuous emulsion composition may include an amphiphilic anisotropic powder and a nonpolar oil.
  • the non-polar oil may comprise 40% to 65% by weight, for example 56% to 60% by weight relative to the total weight of the composition.
  • the nonpolar oil is, for example, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight or more, based on the total weight of the amphipathic anisotropic powder, the nonpolar oil, and water.
  • the amphiphilic anisotropic powder is at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, at least 3.0 wt%, or at least 3.5 wt%, and at least 8.0 wt%, based on the total weight of the composition.
  • It may be up to%, 7.5 wt%, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, 5.0 wt% or less, 4.5 wt% or less, or 4.0 wt% or less, for example, 1 wt% to 8 wt%, for example, 2 wt% to 4 wt%. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time. As the amphiphilic anisotropic powder content increases, a more dense interface may be formed, thereby improving formulation stability.
  • the water may comprise 22% to 59% by weight, for example 36% to 44% by weight relative to the total weight of the composition. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
  • the amphiphilic anisotropic powder and the nonpolar oil may be 1:15 to 30, for example, 1:25 in the weight ratio of the amphiphilic anisotropic powder to the nonpolar oil. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
  • amphipathic anisotropic powder and water may be, for example, 1: 2 to 20, 1: 4 to 15, or 1: 5 by a weight ratio of amphiphilic anisotropic powder to water. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
  • amphipathic anisotropic powder, nonpolar oil and water may be 1: 15-30: 4-15 in the weight ratio of amphiphilic anisotropic powder: nonpolar oil: water. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
  • nonpolar oil for example, a nonpolar hydrocarbon oil may be used, and for example, hexane, octane, decane, dodecane, tetradecane, hexadecane, mineral oil, liquid paraffin, isohexadecane, isododecane, Ozokerite, hydrogenated poly (C6-14 olefin), hydrogenated polydecene, squalane, squalene, paraffin, isoparaffin, ceresin, petrolatum, dimethicone, decamethylcyclopentasiloxane, hydrogenated polyisobutene Can be used, but is not limited thereto.
  • the water may be distilled water, deionized water or the like.
  • the amphiphilic anisotropic powder comprises a hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid, wherein the first polymer spheroid and the second polymer spheroid are at least partially counterpart polymer spheroids.
  • the shell may include a functional group.
  • the spheroid is a body composed of a polymer, and may be, for example, a sphere, globoid or oval shape, and based on the longest length in the cross section of the body, It can have a long axis length of units or nano units.
  • the core of the first polymer spheroid and the second polymer spheroid may include a vinyl polymer
  • the shell of the first polymer spheroid may include a copolymer of a vinyl monomer and a monomer containing a functional group
  • the vinyl polymer may be a vinyl aromatic polymer, for example, may be polystyrene.
  • the vinyl monomer may be vinyl aromatic. In one example, the vinyl monomer may be substituted or unsubstituted styrene.
  • the functional group may be a siloxane.
  • the monomer containing a functional group may be a siloxane-containing (meth) acrylate, specifically, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, vinyl Triethoxysilane, vinyltrimethoxysilane or mixtures thereof.
  • the shell of the first polymer spheroid may be further introduced with a hydrophilic functional group.
  • the hydrophilic functional group may be a negatively charged or positively charged functional group or polyethylene glycol (PEG) series, carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydride It may be at least one selected from the group consisting of a hydroxyl group.
  • PEG polyethylene glycol
  • the shell of the first polymer spheroid may be further introduced with a functional group containing a sugar.
  • the sugar-containing functional group is N- ⁇ N- (3-triethoxysilylpropyl) aminoethyl ⁇ gluconamide, N- (3-triethoxysilylpropyl) gluconamide and N- ⁇ N It may be derived from one or more selected from the group consisting of-(3-triethoxysilylpropyl) aminoethyl ⁇ -oligo-hyaluronamide.
  • the amphipathic anisotropic powder may have a symmetrical shape, an asymmetrical snowman shape or an asymmetrical inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are combined.
  • the snowman shape means that the first and second polymer spheroids having different sizes are bonded to each other.
  • the amphipathic anisotropic powder may have a particle size of 100 to 2500 nm. In another aspect, the amphipathic anisotropic powder may have a particle size of 100 to 1500 nm, 100 to 500 nm, or 200 to 300 nm.
  • the amphiphilic anisotropic powder has a particle size of 100 nm or more, 200 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1000 nm Or more, 1100 nm or more, 1200 nm or more, 1300 nm or more, 1400 nm or more, or 1500 nm or more, 2500 nm or less, 2400 nm or less, 2300 nm or less, 2200 nm or less, 2100 nm or less, 2000 nm or less, 1900 nm 1800 nm or less, 1700 nm or less, 1600 nm or less, 1500 nm or less, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or
  • the amphipathic anisotropic powder is prepared by polymerizing a first monomer to prepare a core of a first polymer spheroid, and coating a core of the first polymer spheroid to the first polymer sp of the core-shell structure It may be prepared to prepare the Lloyd, and reacting the first polymer spheroid and the first monomer of the core-shell structure to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.
  • the core of the first polymer spheroid may be penetrated through the shell of the first polymer spheroid, and then powdered to form a second polymer spheroid.
  • the amphiphilic anisotropic powder may be prepared by (1) stirring a first monomer and a polymerization initiator to prepare a core of a first polymer spheroid; (2) stirring the core of the prepared first polymer spheroid with a monomer containing a first monomer, a polymerization initiator, and a functional group to prepare a coated core-shell structured first polymer spheroid; (3) stirring the first polymer spheroid of the core-shell structure prepared above with the second monomer and the polymerization initiator to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.
  • the stirring may be rotary stirring.
  • Rotational agitation is preferred because uniform mechanical mixing is required along with chemical modification to produce uniform particles.
  • the rotary stirring may be rotary stirring in a cylindrical rotary reactor, but the rotary stirring method is not limited thereto.
  • the size and location of the baffles in the cylindrical rotary reactor and the degree of spacing with the impeller greatly affect the uniformity of the particles produced. It is desirable to minimize the blade gap between the inner wing and the impeller to equalize the convective flow and its strength, and to supply the powder reaction liquid below the wing length and maintain the impeller rotation speed at a high speed. It may be rotated at a highway of 200 rpm or more, and the ratio of the length of the diameter and the height of the reactor may be 1 to 3: 1 to 5, more specifically, 10 to 30 cm in diameter and 10 to 50 cm in height. The reactor size can vary in proportion to the reaction capacity. In addition, the material of the cylindrical rotary reactor may be a ceramic, glass, and the like, the temperature of the stirring is preferably 50 to 90 °C.
  • the simple rotary method enables the production of uniform particles and is a low energy method that requires less energy, and has a characteristic of enabling mass production by maximizing reaction efficiency.
  • the tumbling method in which the reactor itself rotates in the related art requires high energy and rotates the reactor at a predetermined angle, thus requiring high energy and restricting the size of the reactor. Due to the limitations of the reactor size, the amount produced is also limited to small amounts of about several hundred mg to several g, making it unsuitable for mass production.
  • the first monomer and the second monomer may be the same or different, specifically, may be a vinyl monomer.
  • the first monomer added in step (2) is the same as the first monomer used in step (1), the polymerization initiator used in each step may be the same or different.
  • the vinyl monomer may be vinyl aromatic. In one example, the vinyl monomer may be substituted or unsubstituted styrene.
  • the polymerization initiator may be a radical polymerization initiator, specifically, may be a peroxide-based, azo-based or a mixture thereof. Moreover, ammonium persulfate, sodium persulfate, potassium persulfate can also be used.
  • the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 1000: 1. In another aspect, the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 750: 1, or 100 to 500: 1, or 100 to 250: 1.
  • a stabilizer may be added together with the first monomer and the polymerization initiator to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 5.
  • the powder size and shape are determined according to the size adjustment of the first polymer spheroid in the initial stage (1), and the first polymer spheroid size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator and the stabilizer.
  • the weight ratio of the said range there exists an effect which can raise the uniformity of anisotropic powder.
  • the stabilizer may be an ionic vinyl monomer, specifically sodium 4-vinylbenzenesulfonate may be used. Stabilizers prevent swelling of the resulting particles and impart positive or negative charges to the surface of the powder to electrostatically prevent mutual coalescence (bonding) during particle generation.
  • the weight ratio of the first monomer, the polymerization initiator, and the stabilizer is 110 to 130: 1: 1 to 5, specifically 115 to 125: 1: 1 to 2-4 It can be prepared from 1 polymer spheroid.
  • the weight ratio of the first monomer, the polymerization initiator and the stabilizer is 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 3 It can be prepared from the first polymeric spheroid.
  • the amphiphilic anisotropic powder has a size of 1100 to 2500 nm
  • the first polymer having a weight ratio of the first monomer, the polymerization initiator, and the stabilizer is 110 to 130: 1: 0, specifically 115 to 125: 1: 0 It can be prepared from spheroids.
  • amphipathic anisotropic powder of the asymmetrical snowman shape has a weight ratio of the first monomer, the polymerization initiator, and the stabilizer of 100 to 140: 1: 8 to 12, specifically 110 to 130: 1: 9 to 11 It can be prepared from polymeric spheroids.
  • amphipathic anisotropic powder of the asymmetric inverse snowman shape is made of a weight ratio of the first monomer, the polymerization initiator, and the stabilizing agent is 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 1 to 2-4 It can be prepared from 1 polymer spheroid.
  • the monomer containing a functional group in the step (2) may be a siloxane-containing (meth) acrylate, specifically, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl Methacrylate, vinyltriethoxysilane, vinyltrimethoxysilane or mixtures thereof.
  • the monomer containing the first monomer, the polymerization initiator and the functional group in the step (2) may be mixed in a weight ratio of 80 to 98: 0.2 to 1.0: 1 to 20.
  • the first monomer, the polymerization initiator and the monomer containing a functional group may be mixed in a weight ratio of 160 to 200: 1: 6 to 40.
  • the degree of coating can be adjusted according to the weight ratio, and the shape of the amphipathic anisotropic powder is subsequently determined according to the degree of coating, and when reacting with the weight ratio, the coating thickness increases to about 10-30%, specifically 20%, relative to the initial thickness.
  • the coating is too thick so that powdering does not proceed or is too thin so that the powdering proceeds well without the problem of powdering in multiple directions. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
  • a part of the core of the first polymer spheroid protrudes through the shell from one direction of the first polymer spheroid of the core-shell structure, and the protrusion grows by the polymer of the second monomer to form an anisotropic powder. It can form the form of.
  • the second monomer and the polymerization initiator may be mixed in a weight ratio of 150 to 250: 1.
  • the second monomer and the polymerization initiator are 160 to 250: 1, or 170 to 250: 1, or 180 to 250: 1, or 190 to 250: 1, or 200 to 250: 1, or 210 to 250 It can be mixed in a weight ratio of: 1, or 220 to 250: 1, or 230 to 250: 1, or 240 to 250: 1.
  • the second monomer, the polymerization initiator and the stabilizer may be added together with the second monomer and the polymerization initiator to mix the second monomer, the polymerization initiator and the stabilizer in a weight ratio of 150 to 250: 1: 1: 0.001 to 5.
  • the specific kind of stabilizer is as above-mentioned.
  • the second monomer content in the step (3) may be mixed to 40 to 300 parts by weight when the weight of the first polymer spheroid of the core-shell structure is 100 parts by weight.
  • an asymmetric snowman type powder is obtained, and 100 to 150 parts by weight, or 110 to 150 parts by weight.
  • parts by weight a symmetrical powder is obtained, and in the case of 150 to 300 parts by weight, or in the case of 160 to 300 parts by weight, an asymmetric inverse snowman type powder is obtained.
  • by mixing in the weight ratio of the said range there exists an effect which can raise the uniformity of anisotropic powder.
  • (4) when preparing the amphipathic anisotropic powder according to an embodiment of the present invention, after the step (3), (4) may further include introducing a hydrophilic functional group into the prepared anisotropic powder. have.
  • the hydrophilic functional group in step (4) is not limited thereto, but may be introduced using a silane coupling agent and a reaction regulator.
  • the silane coupling agent is (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) propyl] ethylenedi Ammonium chloride, (N-succinyl-3-aminopropyl) trimethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea and 3-[(trimethoxysilyl) propyloxy] -1,2 It may be one or more selected from the group consisting of propanediol, specifically N- [3- (trimethoxysilyl) propyl] ethylenediamine.
  • the silane coupling agent may be mixed in an amount of 35 to 65 parts by weight, for example 40 to 60 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (3). Hydrophilization can be suitably made within the said range.
  • reaction modifier may be ammonium hydroxide.
  • reaction regulator may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example 90 parts by weight to 110 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (3). Hydrophilization can be suitably made within the said range.
  • the functional group containing sugar in step (4) is not limited thereto, but may be introduced using a sugar-containing silane coupling agent and a reaction regulator.
  • the sugar-containing silane coupling agent is N- ⁇ N- (3-triethoxysilylpropyl) aminoethyl ⁇ gluconamide, N- (3-triethoxysilylpropyl) gluconamide And N- ⁇ N- (3-triethoxysilylpropyl) aminoethyl ⁇ -oligo-hyaluronamide.
  • the reaction modifier may be ammonium hydroxide.
  • the reaction regulator may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example 90 parts by weight to 110 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (3).
  • Introduction of the functional group containing a sugar in the said range can be made suitably.
  • Amphiphilic anisotropic powder according to the above method does not use a crosslinking agent, there is no entanglement in production, the yield is high and uniform, and it is easy to mass-produce compared to the tumbling method using a simple stirring method.
  • the composition according to this embodiment may be a composition having a dual continuous emulsion formulation. Since the formulation is a formulation in which the oil phase and the water phase cross each other and are present in succession, the formulation may have a unique effect of simultaneously giving the characteristics of the oil phase component and the characteristics of the aqueous phase component.
  • the composition according to the present embodiment may have a hardness of 7 to 60 (mN). It is possible to provide a feeling unique to the double continuous phase while being stable within the above range.
  • composition according to the present embodiment may form a gel formulation with no flow due to the characteristics of the dual continuous emulsion formulation.
  • composition according to the present embodiment may exhibit emulsion stability over time in a wide temperature range, and the temperature may be, for example, -15 ° C to 60 ° C.
  • composition according to the embodiments of the present invention has a unique stem structure that supports the interface of the continuous phase, utilizing these properties to make cosmetics, catalysts, separation processes, cellular engineering, fuel cells, solar cells, barrier materials, sensors It can be used in various fields such as.
  • composition when used in a cosmetic composition, it is possible to provide a cleansing cosmetic that simultaneously imparts cleaning power of oil and freshness of water.
  • Cosmetic compositions according to embodiments of the present invention may be formulated containing a cosmetically or dermatologically acceptable medium or base. It is any formulation suitable for topical application, in the form of suspensions, microemulsions, microcapsules, microgranules or ionic (liposomal) and nonionic vesicle dispersants or creams, skins, lotions, powders, ointments, sprays or concealers. It may be provided in the form of a stick. It may also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions can be prepared according to conventional methods in the art.
  • the cosmetic composition according to the embodiments of the present invention may be a powder, a fatty substance, an organic solvent, a dissolving agent, a thickening agent, a gelling agent, a softening agent, an antioxidant, a suspending agent, a stabilizer, a foaming agent, a fragrance, a surfactant.
  • ionic or nonionic emulsifiers fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics It may contain adjuvants conventionally used in the cosmetic or dermatological fields, such as any other ingredients used. Such adjuvants are introduced in amounts generally used in the cosmetic or dermatological arts.
  • the cosmetic composition according to the embodiments of the present invention may further contain a skin absorption promoting substance to increase the skin improving effect.
  • the component used by the following preparation example is as follows.
  • KPS Potassium persulfate (initiator)
  • SVBS Sodium vinyl benzene sulfonate (stabilizer)
  • AIBN Azobisisobutyronitrile (polymerization initiator)
  • Formulation Example 1 (Unit: weight%) Formulation Example 1 (O / W) Formulation Example 2 (W / O) Formulation Example 3 (BCE) Anisotropic powder solution (8% by weight of anisotropic powder content in aqueous solution) 30 30 30 30 Deionized water 40 0 10 Squalane 30 70 60
  • Formulation Example 1 which is an O / W formulation, mixes well with water but does not mix with oil, and when water-soluble dye is dropped, blue of TPP blue is uniformly mixed with the composition, whereas it is not mixed with fat-soluble dye and thus Nile red. You can see that the red color and the formulation is separated.
  • Formulation Example 2 of the W / O formulation is mixed with oil but not mixed with water, so that when the water-soluble dye is dropped, the composition and the dye are not mixed, and when the fat-soluble dye is dropped, the dye is evenly mixed in the formulation.
  • Amphiphilic anisotropic powder An aqueous solution in which the amphiphilic anisotropic powder prepared in Preparation Example 3 was dissolved in deionized water at 20% by weight based on the total weight of the aqueous solution.
  • Ion regulator E.D.T.A.-2NA, Neode
  • Example 1 Example 2
  • Example 3 Example 4 ASP aqueous solution 2.5 5 7.5 10 20 (ASP content) (0.5) (One) (1.5) (2)
  • Deionized water 37.45 34.95 32.45 29.95 19.95
  • Example 5 Example 6
  • Example 7 Comparative Example 2 Comparative Example 3 ASP aqueous solution 20 20 20 - (ASP content) (4) (4) (4) (4) (4) - Surfactants - - - - 4 Deionized water Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Ion regulator 0.05 0.05 0.05 0.05 0.05 0.05 Nonpolar oil 56 58 60 64 60
  • compositions of Examples 1 to 7 stably form a dual continuous emulsion formulation, have high hardness, and do not cause problems such as oil bleeding or formulation separation for about 4 weeks in a temperature range of -5 to 60 ° C., at the time of initial preparation.
  • Comparative Example 1 in which the amphiphilic anisotropic powder content is less than 1% by weight, the dual continuous phase formulation is not formed, and in Comparative Example 2 in which the nonpolar oil exceeds 60% by weight, the dual continuous phase formulation is W / O formulations were produced, and hardness cannot be determined due to the nature of the formulation.
  • O / W formulation was produced by using a general surfactant, and it was impossible to measure hardness due to the flowable formulation. It can be seen that low.
  • an emulsion formulation was prepared in the same composition as in Example 5, and electrical conductivity evaluation was performed to confirm the formation of a double continuous phase.
  • Figure 4 shows the conductivity value according to the non-polar oil content.
  • the electrical conductivity did not change with time, but in the range of 40 wt% to 60 wt% of the non-polar oil content, the electrical conductivity was measured irregularly, and it was confirmed that the bicontinuous phase formulation was formed.
  • composition of Examples 3 to 6 was placed in a beaker, turned over so that the inlet faced the bottom, and maintained at -15 to 60 ° C for 180 days.
  • compositions of Examples 3-6 maintained stability over time in the entire temperature range to maintain a stable formulation without flowing.
  • FIG. 5 shows the composition appearance photograph and hardness at 30 ° C. after the preparation of the composition of Example 4 and the following day and after 180 days.
  • the composition can be confirmed to form a gel formulation with no flow to maintain a stable formulation without flowing down even after 180 days without changing the hardness.

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Abstract

The present specification describes a bi-continuous emulsion composition, wherein the bi-continuous emulsion composition contains an amphiphilic anisotropic powder, a non-polar oil, and water, the amphiphilic anisotropic powder comprising a first polymer spheroid having hydrophilicity and a second polymer spheroid having hydrophobicity; the first polymer spheroid and the second polymer spheroid are bound in a structure of at least partially penetrating the counterpart polymer spheroid; and the first polymer spheroid has a core-shell structure, the shell comprising a functional group.

Description

양친매성 이방성 분체를 포함하는 이중 연속상 유화 조성물Dual continuous phase emulsion composition comprising amphipathic anisotropic powder
본 명세서는 양친매성 이방성 분체를 포함하는 이중 연속상 유화 조성물 및 그 제조방법에 관한다.The present specification relates to a dual continuous phase emulsion composition comprising an amphiphilic anisotropic powder and a method for producing the same.
계면활성제를 사용하는 유화시스템에서는 계면활성제의 HLB (Hydrophile-Lipophile Balance)값에 따라 수중유형(O/W) 또는 유중수형(W/O) 유화 제형을 형성한다. 즉, 수상과 유상을 혼합하여 유화하여 내상과 외상이 구분되는 경시적으로 안정한 유화 시스템을 형성하는 것이다.In emulsifying systems using surfactants, oil-in-water (O / W) or water-in-oil (W / O) emulsion formulations are formed depending on the HLB (Hydrophile-Lipophile Balance) value of the surfactant. In other words, by mixing and emulsifying the water phase and oil phase to form a stable emulsion system over time to distinguish the inner and outer phase.
이중연속상 유화 제형(Bi-Continuous Emulsion, BCE)은 내외상의 구분 없이 두 가지의 상이 공존하는 제형으로, 유상과 수상이 상호 교차되어 연속적으로 존재하는 제형이다. 도 2에 수중유형, 유중수형 및 이중연속상 유화 제형을 모식적으로 나타낸 구조도를 나타낸다. 이중연속상 유화 제형은 “Soft solid”라고도 불리며, 연속상에 입자가 웨팅(wetting)되어 스피노달 분리(Spinodal Decomposition)를 일으켜 안정화되는 유화 제형이다. 이러한 구조적 특성에 따라 BIJEL(Bicontinuous Interfacially Jammed Emulsion Gel)라고 부르기도 한다. 이중연속상 유화 제형은 독특한 제형의 성질로 인하여 촉매, 분리 공정, 세포 공학, 연료 전지, 태양열 전지, 장벽 물질, 센서 등의 다양한 분야에서 적용되고 있다.Bi-Continuous Emulsion (BCE) is a formulation in which two phases coexist without distinction between internal and external phases. 2 is a structural diagram schematically showing an oil-in-water type, a water-in-oil type, and a dual continuous emulsion formulation. Dual continuous emulsion formulations, also called “soft solids”, are emulsion formulations in which particles are wetted in a continuous phase, causing spinodal separation to stabilize. According to these structural characteristics it is also called BIJEL (Bicontinuous Interfacially Jammed Emulsion Gel). Dual-phase emulsion formulations have been applied in various fields such as catalysts, separation processes, cellular engineering, fuel cells, solar cells, barrier materials, sensors, etc. due to the unique formulation properties.
종래의 계면활성제를 사용하여 이중연속상 유화 제형을 형성하는 것은 지극히 제한적인 삼성분계(물, 오일, 계면활성제)의 조성비에서만 구현이 가능하며, 유화 계면막의 유동성 때문에 안정화가 어려운 문제가 있어 왔다.Forming a dual continuous emulsion formulation using a conventional surfactant can be implemented only in a very limited composition ratio of the system (water, oil, surfactant), and has been difficult to stabilize due to the fluidity of the emulsion surfactant.
고분자로 이루어진 구형 미세 입자는 그 제조방법에 따라서 사이즈와 형태가 조절됨에 따라 응용 가능성이 확대되고 있다. 그 응용 예들 중에 하나로 미세 구형 입자를 이용하여 안정화된 거대 유화 입자를 형성할 수 있는 피커링 에멀젼이 있다. 구형 입자의 친수성/소수성 정도에 따라서 수상과 유상 사이에 접촉각(θ)이 차이가 나고 접촉각 90° 이상에서는 O/W 유화 입자를 형성하고 90° 이하에서는 W/O 유화 입자를 형성한다. As the spherical fine particles made of a polymer are controlled in size and shape according to the production method, the application possibilities are expanded. One such application is a pickling emulsion that can form stabilized large emulsified particles using fine spherical particles. Depending on the degree of hydrophilicity / hydrophobicity of the spherical particles, the contact angle θ is different between the aqueous phase and the oil phase. O / W emulsified particles are formed at a contact angle of 90 ° or more, and W / O emulsified particles are formed at 90 ° or less.
미세 구형 입자에 친수성과 소수성을 동시에 가지는 양친매성을 부여함으로써 새로운 이방성 분체를 제조하려는 시도가 있어 왔다. 그 예로 야누스 구형입자를 들 수 있다. 하지만 이러한 구형의 형태학적 제한 때문에 화학적인 이방성에는 한계가 있다. 즉, 형태학적으로는 이방성일지라도 전체적으로 소수성이거나 친수성이어서 화학적 이방성에 한계가 있었다. Attempts have been made to produce new anisotropic powders by imparting amphiphilic properties having both hydrophilicity and hydrophobicity to the fine spherical particles. An example is Janus spherical particles. However, these spherical morphological limitations limit chemical anisotropy. That is, although morphologically anisotropic, it is hydrophobic or hydrophilic as a whole, so that there is a limit to chemical anisotropy.
이에 기하학적인 형태 조절과 함께 화학적인 이방성을 부여함으로써 계면활성력을 가지는 이방성 분체의 제조가 시도되어 왔으나, 양친매성 이방성 분체의 그 응용가능성이 크다는 장점에도 불구하고 현재까지는 그 대량 생산이 가능한 제조방법이 구체적으로 개발되지 못하였고, 산업적으로 균일하게 대량 생산하기 어렵다는 문제점이 있어 실질적인 산업적인 응용이 이루어지지 않았다.This has been attempted to produce anisotropic powders having an interfacial activity by providing chemical anisotropy with geometrical shape control, but the production method that can be mass-produced so far despite the advantage that the amphipathic anisotropic powders have great applicability This has not been specifically developed, there is a problem that it is difficult to mass-produce industrially uniformly, and practical industrial applications have not been achieved.
일 관점에서, 본 발명이 해결하고자 하는 과제는 유화 안정성이 우수한 이중연속상 유화 조성물을 제공하는 것이다.In one aspect, the problem to be solved by the present invention is to provide a double continuous emulsion composition excellent in emulsion stability.
다른 관점에서, 본 발명이 해결하고자 하는 과제는 수상과 오일상 각각의 특성을 동시에 부여할 수 있는 이중연속상 유화 조성물을 제공하는 것이다.In another aspect, the problem to be solved by the present invention is to provide a dual continuous emulsion composition capable of simultaneously imparting the characteristics of each of the water phase and the oil phase.
또 다른 관점에서, 본 발명이 해결하고자 하는 과제는 다양한 온도 범위에서 제형이 안정하게 유지되는 이중연속상 유화 조성물을 제공하는 것이다.In another aspect, the problem to be solved by the present invention is to provide a dual continuous emulsion composition in which the formulation remains stable at various temperature ranges.
또 다른 관점에서, 본 발명이 해결하고자 하는 과제는 경시 안정성이 우수한 이중연속상 유화 조성물을 제공하는 것이다.In another aspect, the problem to be solved by the present invention is to provide a double continuous emulsion composition excellent in stability over time.
또 다른 관점에서, 본 발명이 해결하고자 하는 과제는 흐름성이 없는 특징적인 겔(gel) 제형의 유화 조성물을 제공하는 것이다.In another aspect, the problem to be solved by the present invention is to provide an emulsified composition of a gel formulation characterized by no flow.
양친매성 이방성 분체, 비극성 오일 및 물을 포함하는 이중연속상 유화(Bi-continuous emulsion) 조성물이고,A bi-continuous emulsion composition comprising amphiphilic anisotropic powder, nonpolar oil and water,
상기 양친매성 이방성 분체는,The amphipathic anisotropic powder,
친수성인 제1고분자 스페로이드 및 소수성인 제2고분자 스페로이드를 포함하고,A hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid,
상기 제1고분자 스페로이드 및 제2고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하고,The first polymer spheroid and the second polymer spheroid are combined at least partially in a structure that penetrates the relative polymer spheroid,
상기 제1고분자 스페로이드는 코어-쉘 구조를 갖고, 상기 쉘은 관능기를 포함하는, 유화 조성물을 제공한다.The first polymer spheroid has a core-shell structure, and the shell provides an emulsified composition.
일 관점에서, 본 발명은 유화 안정성이 우수한 이중연속상 유화 조성물을 제공할 수 있다.In one aspect, the present invention can provide a dual continuous emulsion composition having excellent emulsion stability.
다른 관점에서, 본 발명은 수상과 오일상 각각의 특성을 동시에 부여할 수 있는 이중연속상 유화 조성물을 제공할 수 있다.In another aspect, the present invention can provide a dual continuous emulsion composition capable of simultaneously imparting the characteristics of each of the aqueous and oil phases.
또 다른 관점에서, 본 발명은 다양한 온도 범위에서 제형이 안정하게 유지되는 이중연속상 유화 조성물을 제공할 수 있다.In another aspect, the present invention may provide a dual continuous emulsion composition in which the formulation remains stable at various temperature ranges.
또 다른 관점에서, 본 발명은 경시 안정성이 우수한 이중연속상 유화 조성물을 제공할 수 있다.In another aspect, the present invention can provide a dual continuous emulsion composition having excellent stability over time.
또 다른 관점에서, 본 발명은 흐름성이 없는 특징적인 겔(gel) 제형의 유화 조성물을 제공할 수 있다.In another aspect, the present invention may provide an emulsified composition of a characteristic gel formulation with no flow.
도 1은 본 발명의 일 실시예에 따른 양친매성 이방성 분체를 형성하는 모식도이다.1 is a schematic diagram of forming an amphipathic anisotropic powder according to an embodiment of the present invention.
도 2는 수중유형(O/W), 유중수형(W/O) 및 이중연속상(BCE) 유화 제형을 도식화하여 나타낸 그림이다.Figure 2 is a diagram illustrating the oil-in-water (O / W), water-in-oil (W / O) and double continuous phase (BCE) emulsion formulation.
도 3은 수용성 및 지용성 염료의 염착성을 이용하여 이중연속상 유화 제형 형성 여부를 확인한 실험 결과를 나타낸 사진이다.3 is a photograph showing the results of experiments confirming the formation of a dual continuous emulsion formulation using the dyeability of water-soluble and fat-soluble dyes.
도 4는 실시예 및 비교예 제형의 오일함량에 따른 제형 변화와 전기전도도 특성 변화를 나타낸 그래프이다.Figure 4 is a graph showing the change in formulation and the change in conductivity characteristics according to the oil content of the formulation of Examples and Comparative Examples.
도 5는 이중연속상 유화(BCE) 제형의 겔(gel) 형성 및 안정도를 확인한 사진이다.Figure 5 is a photograph confirming the gel (gel) formation and stability of the dual-phase emulsion (BCE) formulation.
이하, 첨부한 도면들을 참조하여, 본 출원의 실시예들을 보다 상세하게 설명하고자 한다. 그러나 본 출원에 개시된 기술은 여기서 설명되는 실시예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. 단지, 여기서 소개되는 실시예들은 개시된 내용이 철저하고 완전해질 수 있도록 그리고 당업자에게 본 출원의 사상이 충분히 전달될 수 있도록 하기 위해 제공되는 것이다. 도면에서 각 구성요소를 명확하게 표현하기 위하여 구성요소의 폭이나 두께 등의 크기를 다소 확대하여 나타내었다. 또한, 설명의 편의를 위하여 구성요소의 일부만을 도시하기도 하였으나, 당업자라면 구성요소의 나머지 부분에 대하여도 용이하게 파악할 수 있을 것이다. 또한, 해당 분야에서 통상의 지식을 가진 자라면 본 출원의 기술적 사상을 벗어나지 않는 범위 내에서 본 출원의 사상을 다양한 다른 형태로 구현할 수 있을 것이다.Hereinafter, with reference to the accompanying drawings, it will be described embodiments of the present application in more detail. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. It is merely to be understood that the embodiments introduced herein are provided so that the disclosure can be made thorough and complete, and that the spirit of the present application can be fully conveyed to those skilled in the art. In order to clearly express each component in the drawings, the size, such as the width or thickness of the component, is shown to be somewhat enlarged. In addition, although only a part of the components are shown for convenience of description, those skilled in the art will be able to easily understand the rest of the components. In addition, one of ordinary skill in the art may implement the spirit of the present application in various other forms without departing from the technical spirit of the present application.
본 명세서에서 “치환된”은 별도의 정의가 없는 한, 본 발명의 작용기 중 하나 이상의 수소 원자가 할로겐 (F, Cl, Br 또는 I), 히드록시기, 니트로기, 이미노기(=NH, =NR, R은 탄소수 1-10의 알킬기이다), 아미디노기, 히드라진 또는 히드라존기, 카르복시기, 치환 또는 비치환된 탄소수 1-20의 알킬기, 치환 또는 비치환된 탄소수 3-30의 헤테로아릴기, 치환 또는 비치환된 탄소수 2-30의 헤테로시클로알킬기로 치환되는 것을 의미할 수 있다.As used herein, unless otherwise defined, "substituted" means that one or more hydrogen atoms of the functional groups of the present invention are halogen (F, Cl, Br or I), hydroxy, nitro, imino (= NH, = NR, R Is an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted It may mean substituted with a heterocycloalkyl group having 2 to 30 ring carbon atoms.
본 명세서에서 본 명세서에서 "(메트)아크릴"은 아크릴(acryl) 및/또는 메타크릴(methacryl)을 의미할 수 있다.As used herein, "(meth) acryl" may mean acryl and / or methacryl.
본 명세서에서 양친매성 이방성 분체의 입자 크기는 분체 입자의 가장 긴 길이인 최장경(maximum length)을 측정한 것이다. 본 명세서에서 양친매성 이방성 분체의 입자 크기 범위는 조성물 내에 존재하는 양친매성 이방성 분체의 95% 이상이 상기 범위 내에 속함을 의미한다.The particle size of the amphipathic anisotropic powder herein is a measure of the maximum length, which is the longest length of the powder particles. The particle size range of the amphipathic anisotropic powder herein means that at least 95% of the amphipathic anisotropic powder present in the composition falls within this range.
본 발명 일 실시예에 따르면, 양친매성 이방성 분체를 포함하는 이중연속상 유화(Bi-continuous emlusion) 조성물을 제공한다. 본 실시예에 따르면 일반적인 분자 수준의 계면활성제에 의하여 형성되는 계면막이 동적 유화 상태를 이루는 반면 상기 양친매성 이방성 분체에 의하여 형성되는 유화 계면막의 두께가 수백 nm로 증가하며, 분체 간의 강한 결합을 통하여 견고한 계면막을 형성하게 된다. 이에 따라 본 실시예에 따른 조성물은 양친매성 이방성 분체를 포함하여 조밀하고 안정한 연속상 계면을 유지하고, 안정적인 이중연속상 유화 제형을 형성할 수 있다.According to an embodiment of the present invention, a bi-continuous emlusion composition including amphipathic anisotropic powder is provided. According to this embodiment, the interface film formed by the general molecular-level surfactant forms a dynamic emulsification state, while the thickness of the emulsified interface film formed by the amphiphilic anisotropic powder increases to several hundred nm, and is firm through strong bonding between the powders. An interface film is formed. Accordingly, the composition according to the present embodiment may include an amphiphilic anisotropic powder to maintain a dense and stable continuous phase interface, and form a stable dual continuous emulsion formulation.
본 실시예에서, 상기 이중연속상 유화 조성물은 양친매성 이방성 분체 및 비극성 오일을 포함할 수 있다.In this embodiment, the dual continuous emulsion composition may include an amphiphilic anisotropic powder and a nonpolar oil.
상기 비극성 오일은 조성물 총 중량에 대하여 40중량% 내지 65중량%, 예를 들어 56 중량% 내지 60중량%로 포함할 수 있다. 상기 비극성 오일은 양친매성 이방성 분체, 비극성 오일 및 물의 합계 중량에 대하여 예를 들어, 40중량% 이상, 41 중량% 이상, 42 중량% 이상, 43 중량% 이상, 44 중량% 이상, 45 중량% 이상, 46 중량% 이상, 47 중량% 이상, 48 중량% 이상, 49 중량% 이상, 50 중량% 이상, 51 중량% 이상, 52 중량% 이상, 53 중량% 이상, 54 중량% 이상, 55 중량% 이상 또는 56 중량% 이상이고, 60 중량% 이하, 59 중량% 이하, 58 중량% 이하, 또는 57 중량% 이하로 포함될 수 있다. 상기 범위 내에서 안정적인 이중연속상 유화 제형을 형성할 수 있으며, 경시적으로 안정한 제형을 유지할 수 있다.The non-polar oil may comprise 40% to 65% by weight, for example 56% to 60% by weight relative to the total weight of the composition. The nonpolar oil is, for example, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight or more, based on the total weight of the amphipathic anisotropic powder, the nonpolar oil, and water. , At least 46 wt%, at least 47 wt%, at least 48 wt%, at least 49 wt%, at least 50 wt%, at least 51 wt%, at least 52 wt%, at least 53 wt%, at least 54 wt%, at least 55 wt% Or 56 wt% or more, 60 wt% or less, 59 wt% or less, 58 wt% or less, or 57 wt% or less. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
본 실시예에서, 상기 양친매성 이방성 분체는 조성물 총 중량에 대하여 1.0 중량% 이상, 1.5 중량% 이상, 2.0 중량% 이상, 2.5 중량% 이상, 3.0 중량% 이상, 또는 3.5 중량% 이상이고, 8.0 중량% 이하, 7.5 중량% 이하, 7.0 중량% 이하, 6.5 중량% 이하, 6.0 중량% 이하, 5.5 중량% 이하, 5.0 중량% 이하, 4.5 중량% 이하, 또는 4.0 중량% 이하일 수 있으며, 예를 들어, 1 중량% 내지 8중량%, 예를 들어 2 중량% 내지 4 중량%로 포함할 수 있다. 상기 범위 내에서 안정적인 이중연속상 유화 제형을 형성할 수 있으며, 경시적으로 안정한 제형을 유지할 수 있다. 양친매성 이방성 분체 함량이 높아질수록 보다 조밀한 계면을 형성하여 제형 안정성이 우수할 수 있다.In this embodiment, the amphiphilic anisotropic powder is at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, at least 3.0 wt%, or at least 3.5 wt%, and at least 8.0 wt%, based on the total weight of the composition. It may be up to%, 7.5 wt%, 7.0 wt% or less, 6.5 wt% or less, 6.0 wt% or less, 5.5 wt% or less, 5.0 wt% or less, 4.5 wt% or less, or 4.0 wt% or less, for example, 1 wt% to 8 wt%, for example, 2 wt% to 4 wt%. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time. As the amphiphilic anisotropic powder content increases, a more dense interface may be formed, thereby improving formulation stability.
본 실시예에서, 상기 물은 조성물 총 중량에 대하여 22 중량% 내지 59 중량%, 예를 들어 36 중량% 내지 44 중량%로 포함할 수 있다. 상기 범위 내에서 안정적인 이중연속상 유화 제형을 형성할 수 있으며, 경시적으로 안정한 제형을 유지할 수 있다.In this embodiment, the water may comprise 22% to 59% by weight, for example 36% to 44% by weight relative to the total weight of the composition. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
본 실시예에서 상기 양친매성 이방성 분체와 비극성 오일은 양친매성 이방성 분체 : 비극성 오일의 중량비로 1 : 15~30예를 들어 1:25일 수 있다. 상기 범위 내에서 안정적인 이중연속상 유화 제형을 형성할 수 있으며, 경시적으로 안정한 제형을 유지할 수 있다.In the present embodiment, the amphiphilic anisotropic powder and the nonpolar oil may be 1:15 to 30, for example, 1:25 in the weight ratio of the amphiphilic anisotropic powder to the nonpolar oil. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
본 실시예에서 상기 양친매성 이방성 분체와 물은 양친매성 이방성 분체 : 물의 중량비로 예를 들어 1 : 2~20, 1 :4~15, 또는 1:5일 수 있다. 상기 범위 내에서 안정적인 이중연속상 유화 제형을 형성할 수 있으며, 경시적으로 안정한 제형을 유지할 수 있다.In this embodiment, the amphipathic anisotropic powder and water may be, for example, 1: 2 to 20, 1: 4 to 15, or 1: 5 by a weight ratio of amphiphilic anisotropic powder to water. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
본 실시예에서, 상기 양친매성 이방성 분체, 비극성 오일 및 물은 양친매성 이방성 분체 : 비극성 오일 : 물의 중량비로 1: 15~30 : 4~15일 수 있다. 상기 범위 내에서 안정적인 이중연속상 유화 제형을 형성할 수 있으며, 경시적으로 안정한 제형을 유지할 수 있다.In the present embodiment, the amphipathic anisotropic powder, nonpolar oil and water may be 1: 15-30: 4-15 in the weight ratio of amphiphilic anisotropic powder: nonpolar oil: water. It is possible to form a stable dual-phase emulsion formulation within the above range, it is possible to maintain a stable formulation over time.
상기 비극성 오일은, 예를 들어 비극성 탄화수소계 오일을 사용할 수 있으며, 예를 들어, 헥산, 옥탄, 데칸, 도데칸, 테트라데칸, 헥사데칸, 미네랄 오일, 유동 파라핀, 이소헥사데칸, 이소도데칸, 오조케라이트, 하이드로제네이티드폴리(C6-14올레핀), 하이드로제네이티드폴리데센, 스쿠알란, 스쿠알렌, 파라핀, 이소파라핀, 세레신, 바셀린, 디메치콘, 데카메칠사이클로펜타실록산, 하이드로제네이티드폴리이소부텐등을 사용할 수 있으나 이에 제한되지 않는다.As the nonpolar oil, for example, a nonpolar hydrocarbon oil may be used, and for example, hexane, octane, decane, dodecane, tetradecane, hexadecane, mineral oil, liquid paraffin, isohexadecane, isododecane, Ozokerite, hydrogenated poly (C6-14 olefin), hydrogenated polydecene, squalane, squalene, paraffin, isoparaffin, ceresin, petrolatum, dimethicone, decamethylcyclopentasiloxane, hydrogenated polyisobutene Can be used, but is not limited thereto.
상기 물은 증류수, 탈이온수 등을 사용할 수 있다.The water may be distilled water, deionized water or the like.
본 실시예에서, 상기 양친매성 이방성 분체는 친수성인 제1고분자 스페로이드 및 소수성인 제2고분자 스페로이드를 포함하고, 상기 제1고분자 스페로이드 및 제2고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하고, 상기 제1고분자 스페로이드는 코어-쉘 구조를 갖고, 상기 쉘은 관능기를 포함할 수 있다.In this embodiment, the amphiphilic anisotropic powder comprises a hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid, wherein the first polymer spheroid and the second polymer spheroid are at least partially counterpart polymer spheroids. Combined into a structure that penetrates, the first polymer spheroid has a core-shell structure, the shell may include a functional group.
본 실시예에서 스페로이드는 고분자로 구성된 하나의 몸체로서, 예를 들어 구형체(sphere), 구상체(globoid) 또는 타원형체(oval shape)일 수 있으며, 몸체 단면에서 가장 긴 길이를 기준으로 마이크로 단위 또는 나노 단위의 장축 길이를 가질 수 있다.In this embodiment, the spheroid is a body composed of a polymer, and may be, for example, a sphere, globoid or oval shape, and based on the longest length in the cross section of the body, It can have a long axis length of units or nano units.
일예에서, 상기 제1 고분자 스페로이드의 코어와 제2 고분자 스페로이드는 비닐 고분자를 포함하며, 상기 제1 고분자 스페로이드의 쉘은 비닐 모노머와 관능기를 함유하는 모노머의 공중합체를 포함할 수 있다.In one example, the core of the first polymer spheroid and the second polymer spheroid may include a vinyl polymer, and the shell of the first polymer spheroid may include a copolymer of a vinyl monomer and a monomer containing a functional group.
일예에서, 상기 비닐 고분자는 비닐 방향족계 고분자일 수 있으며, 일례로, 폴리스티렌일 수 있다.In one embodiment, the vinyl polymer may be a vinyl aromatic polymer, for example, may be polystyrene.
일예에서, 상기 비닐 모노머는 비닐 방향족계일 수 있다. 일례로, 상기 비닐 모노머는 치환 또는 비치환된 스티렌일 수 있다.In one example, the vinyl monomer may be vinyl aromatic. In one example, the vinyl monomer may be substituted or unsubstituted styrene.
일예에서, 상기 관능기는 실록산일 수 있다.In one embodiment, the functional group may be a siloxane.
일예에서, 상기 관능기를 함유하는 모노머는 실록산 함유 (메트)아크릴레이트일 수 있으며, 구체적으로, 3-(트리메톡시실릴)프로필 아크릴레이트, 3-(트리메톡시실릴)프로필 메타크릴레이트, 비닐트리에톡시실란, 비닐트리메톡시실란 또는 이들의 혼합물일 수 있다.In one embodiment, the monomer containing a functional group may be a siloxane-containing (meth) acrylate, specifically, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, vinyl Triethoxysilane, vinyltrimethoxysilane or mixtures thereof.
일예에서, 상기 제1 고분자 스페로이드의 쉘은 친수성 관능기가 추가적으로 도입될 수 있다.In one embodiment, the shell of the first polymer spheroid may be further introduced with a hydrophilic functional group.
일예에서, 상기 친수성 관능기는 음전하 또는 양전하를 가진 관능기 또는 PEG(Polyethylene glycol) 계열일 수 있으며, 카르복실산기, 설폰기, 포스페이트기, 아미노기, 알콕시기, 에스테르기, 아세테이트기, 폴리에틸렌글리콜기 및 하이드록실기로 이루어진 군에서 선택되는 1 이상일 수 있다.In one embodiment, the hydrophilic functional group may be a negatively charged or positively charged functional group or polyethylene glycol (PEG) series, carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydride It may be at least one selected from the group consisting of a hydroxyl group.
일예에서, 상기 제1고분자스페로이드의 쉘은 당을 함유하는 관능기가 추가적으로 도입될 수 있다.In one embodiment, the shell of the first polymer spheroid may be further introduced with a functional group containing a sugar.
일예에서, 상기 당을 함유하는 관능기는 N-{N-(3-트리에톡시실릴프로필)아미노에틸}글루콘아미드, N-(3-트리에톡시실릴프로필)글루콘아미드 및 N-{N-(3-트리에톡시실릴프로필)아미노에틸}-올리고-히아루론아미드로 이루어진 군에서 선택되는 1종 이상으로부터 유래된 것일 수 있다.In one embodiment, the sugar-containing functional group is N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) gluconamide and N- {N It may be derived from one or more selected from the group consisting of-(3-triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide.
일예에서, 상기 양친매성 이방성 분체는 제1 고분자 스페로이드 및 제2 고분자 스페로이드가 결합된 결합부를 기준으로 대칭 형상, 비대칭 스노우맨(snowman) 형상 또는 비대칭 역스노우맨 형상을 가질 수 있다. 상기 스노우맨 형상은 결합되는 서로 크기가 상이한 제1 및 제2 고분자 스페로이드가 결합된 것을 의미한다.In one embodiment, the amphipathic anisotropic powder may have a symmetrical shape, an asymmetrical snowman shape or an asymmetrical inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are combined. The snowman shape means that the first and second polymer spheroids having different sizes are bonded to each other.
일예에서, 상기 양친매성 이방성 분체는 입자 크기가 100 내지 2500 nm일 수 있다. 다른 측면에서, 상기 양친매성 이방성 분체는 입자 크기가 100 내지 1500 nm, 100 내지 500 nm, 또는 200 내지 300 nm일 수 있다. 구체적으로, 상기 양친매성 이방성 분체는 입자 크기가 100 nm 이상, 200 nm 이상, 300 nm 이상, 400 nm 이상, 500 nm 이상, 600 nm 이상, 700 nm 이상, 800 nm 이상, 900 nm 이상, 1000 nm 이상, 1100 nm 이상, 1200 nm 이상, 1300 nm 이상, 1400 nm 이상 또는 1500 nm 이상일 수 있으며, 2500 nm 이하, 2400 nm 이하, 2300 nm 이하, 2200 nm 이하, 2100 nm 이하, 2000 nm 이하, 1900 nm 이하, 1800 nm 이하, 1700 nm 이하, 1600 nm 이하, 1500 nm 이하, 1400 nm 이하, 1300 nm 이하, 1200 nm 이하, 1100 nm 이하, 1000 nm 이하, 900 nm 이하, 800 nm 이하, 700 nm 이하, 600 nm 이하, 500 nm 이하, 400 nm 이하, 300 nm 이하 또는 200 nm 이하일 수 있다.In one embodiment, the amphipathic anisotropic powder may have a particle size of 100 to 2500 nm. In another aspect, the amphipathic anisotropic powder may have a particle size of 100 to 1500 nm, 100 to 500 nm, or 200 to 300 nm. Specifically, the amphiphilic anisotropic powder has a particle size of 100 nm or more, 200 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1000 nm Or more, 1100 nm or more, 1200 nm or more, 1300 nm or more, 1400 nm or more, or 1500 nm or more, 2500 nm or less, 2400 nm or less, 2300 nm or less, 2200 nm or less, 2100 nm or less, 2000 nm or less, 1900 nm 1800 nm or less, 1700 nm or less, 1600 nm or less, 1500 nm or less, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, or 200 nm or less.
본 발명 일 실시예에서, 상기 양친매성 이방성 분체는 제1모노머를 중합하여 제1고분자 스페로이드의 코어를 제조하고, 상기 제1고분자 스페로이드의 코어를 코팅하여 코어-쉘 구조의 제1고분자 스페로이드를 제조하고, 상기 코어-쉘 구조의 제1고분자 스페로이드와 제1모노머를 반응시켜 제2고분자 스페로이드가 형성된 양친매성 이방성 분체를 제조하는 것을 포함하여 제조될 수 있다.In one embodiment of the present invention, the amphipathic anisotropic powder is prepared by polymerizing a first monomer to prepare a core of a first polymer spheroid, and coating a core of the first polymer spheroid to the first polymer sp of the core-shell structure It may be prepared to prepare the Lloyd, and reacting the first polymer spheroid and the first monomer of the core-shell structure to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.
도 1은 본 발명의 일 실시예에 따른 양친매성 이방성 분체의 형성 원리를 나타낸 모식도이다. 상기 제조 방법에 의하여 제1 고분자 스페로이드의 코어가 제1고분자 스페로이드의 쉘을 뚫고 외부로 성장하여 분체화되어 제2고분자 스페로이드를 형성할 수 있다.1 is a schematic diagram showing the principle of formation of amphipathic anisotropic powder according to an embodiment of the present invention. According to the manufacturing method, the core of the first polymer spheroid may be penetrated through the shell of the first polymer spheroid, and then powdered to form a second polymer spheroid.
일예에서, 상기 양친매성 이방성 분체는 (1) 제1 모노머 및 중합 개시제를 교반하여 제1 고분자 스페로이드의 코어를 제조하는 단계; (2) 상기 제조된 제1 고분자 스페로이드의 코어를, 제1 모노머, 중합 개시제 및 관능기를 함유하는 모노머와 교반하여 코팅된 코어-쉘 구조의 제1 고분자 스페로이드를 제조하는 단계; (3) 상기 제조된 코어-쉘 구조의 제1 고분자 스페로이드를, 제2 모노머 및 중합 개시제와 교반하여 제2 고분자 스페로이드가 형성된 양친매성 이방성 분체를 제조하는 단계를 포함할 수 있다.In one embodiment, the amphiphilic anisotropic powder may be prepared by (1) stirring a first monomer and a polymerization initiator to prepare a core of a first polymer spheroid; (2) stirring the core of the prepared first polymer spheroid with a monomer containing a first monomer, a polymerization initiator, and a functional group to prepare a coated core-shell structured first polymer spheroid; (3) stirring the first polymer spheroid of the core-shell structure prepared above with the second monomer and the polymerization initiator to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.
상기 (1), (2) 및 (3)단계에서 교반은 회전 교반일 수 있다. 균일한 입자 생성을 위하여 화학적인 개질과 더불어 균일한 기계적 혼합이 필요하기 때문에 회전 교반하는 것이 바람직하다. 상기 회전 교반은 원통형 회전 반응기에서 회전 교반할 수 있으나, 회전 교반 방법을 이에 한정하는 것은 아니다. In the steps (1), (2) and (3), the stirring may be rotary stirring. Rotational agitation is preferred because uniform mechanical mixing is required along with chemical modification to produce uniform particles. The rotary stirring may be rotary stirring in a cylindrical rotary reactor, but the rotary stirring method is not limited thereto.
이때, 반응기 내부 디자인은 분체 형성에 큰 영향을 미친다. 원통형 회전 반응기 내 날개(baffles)의 크기와 위치, 및 임펠러(impeller)와의 간격 정도는 생성되는 입자의 균일성에 큰 영향을 미친다. 내부 날개와 임펠러의 블레이드(blade) 간격을 최소화하여 대류 흐름과 그 세기를 균일화하고, 분체 반응액은 날개 길이 이하로 투입되며 임펠러 회전속도는 고속을 유지하는 것이 바람직하다. 200 rpm 이상의 고속도로 회전될 수 있고, 반응기의 지름과 높이의 길이 비율은 1 내지 3 : 1 내지 5, 더욱 구체적으로 지름 10 내지 30 cm 및 높이 10 내지 50 cm일 수 있다. 반응기 크기는 반응 용량에 비례하여 변화가 가능하다. 또한, 원통형 회전 반응기의 재질은 세라믹, 유리 등일 수 있고, 교반시 온도는 50 내지 90 ℃인 것이 바람직하다.At this time, the design inside the reactor has a great influence on the powder formation. The size and location of the baffles in the cylindrical rotary reactor and the degree of spacing with the impeller greatly affect the uniformity of the particles produced. It is desirable to minimize the blade gap between the inner wing and the impeller to equalize the convective flow and its strength, and to supply the powder reaction liquid below the wing length and maintain the impeller rotation speed at a high speed. It may be rotated at a highway of 200 rpm or more, and the ratio of the length of the diameter and the height of the reactor may be 1 to 3: 1 to 5, more specifically, 10 to 30 cm in diameter and 10 to 50 cm in height. The reactor size can vary in proportion to the reaction capacity. In addition, the material of the cylindrical rotary reactor may be a ceramic, glass, and the like, the temperature of the stirring is preferably 50 to 90 ℃.
원통형 회전 반응기에서 단순 회전법은 균일한 입자의 생성을 가능하게 하고 에너지가 적게 소요되는 저에너지 방법이면서 반응 효율이 극대화되어 대량 생산을 가능하게 하는 특징이 있다. 종래 사용되었던 반응기 자체가 회전하는 텀블링 방식은 반응기 전체를 일정한 각도로 기울여서 고속으로 회전시켜야 하므로 고에너지가 필요하고 반응기의 크기가 제한적이었다. 반응기 크기의 한계 때문에 생성되는 양 또한 약 수백 mg 내지 수 g 정도의 소량으로 제한적이어서 대량 생산에 부적합하였다.In the cylindrical rotary reactor, the simple rotary method enables the production of uniform particles and is a low energy method that requires less energy, and has a characteristic of enabling mass production by maximizing reaction efficiency. The tumbling method in which the reactor itself rotates in the related art requires high energy and rotates the reactor at a predetermined angle, thus requiring high energy and restricting the size of the reactor. Due to the limitations of the reactor size, the amount produced is also limited to small amounts of about several hundred mg to several g, making it unsuitable for mass production.
일예에서, 상기 제1 모노머와 제2 모노머는 동일 또는 상이할 수 있으며, 구체적으로 비닐 모노머일 수 있다. 또한, 상기 (2)단계에서 첨가되는 제1 모노머는 상기 (1)단계에서 사용된 제1 모노머와 동일하며, 각 단계에서 사용되는 중합 개시제는 동일 또는 상이할 수 있다.In one embodiment, the first monomer and the second monomer may be the same or different, specifically, may be a vinyl monomer. In addition, the first monomer added in step (2) is the same as the first monomer used in step (1), the polymerization initiator used in each step may be the same or different.
일예에서, 상기 비닐 모노머는 비닐 방향족계일 수 있다. 일례로, 상기 비닐 모노머는 치환되거나 또는 비치환된 스티렌일 수 있다.In one example, the vinyl monomer may be vinyl aromatic. In one example, the vinyl monomer may be substituted or unsubstituted styrene.
일예에서, 상기 중합 개시제는 라디칼 중합 개시제일 수 있으며, 구체적으로, 퍼옥사이드계, 아조계 또는 이들의 혼합물일 수 있다. 또한, 과황산암모늄, 과황산나트륨, 과황산칼륨도 사용 가능하다.In one example, the polymerization initiator may be a radical polymerization initiator, specifically, may be a peroxide-based, azo-based or a mixture thereof. Moreover, ammonium persulfate, sodium persulfate, potassium persulfate can also be used.
일예에서, 상기 (1)단계에서 제1 모노머 및 중합 개시제는 100 내지 1000 : 1의 중량비로 혼합할 수 있다. 다른 측면에서, 상기 제1 모노머 및 중합 개시제는 100 내지 750 : 1, 또는 100 내지 500 : 1, 또는 100 내지 250 : 1의 중량비로 혼합할 수 있다.In one example, in step (1), the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 1000: 1. In another aspect, the first monomer and the polymerization initiator may be mixed in a weight ratio of 100 to 750: 1, or 100 to 500: 1, or 100 to 250: 1.
다른 측면에서, 상기 (1)단계에서 제1 모노머, 중합 개시제와 함께 안정화제를 첨가하여 제1 모노머, 중합 개시제 및 안정화제를 100 내지 1000 : 1 : 0.001 내지 5의 중량비로 혼합할 수 있다. 분체 사이즈 및 형태는 초기 (1)단계의 제1 고분자 스페로이드 사이즈 조절에 따라 결정되고, 제1 고분자 스페로이드 사이즈는 제1 모노머, 중합 개시제 및 안정화제의 중량비에 따라 조절될 수 있다. 또한, 상기 범위의 중량비로 혼합함으로써, 이방성 분체의 균일도를 높일 수 있는 효과가 있다.In another aspect, in the step (1), a stabilizer may be added together with the first monomer and the polymerization initiator to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 5. The powder size and shape are determined according to the size adjustment of the first polymer spheroid in the initial stage (1), and the first polymer spheroid size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator and the stabilizer. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
일예에서, 상기 안정화제는 이온성 비닐 모노머일 수 있으며, 구체적으로 소듐 4-비닐벤젠설포네이트를 이용할 수 있다. 안정화제는 생성되는 입자의 팽윤을 막아주고 분체 표면에 양 또는 음 전하를 부여함으로써 입자 생성 중에 상호 합일(결합)을 정전기적으로 방지한다.In one example, the stabilizer may be an ionic vinyl monomer, specifically sodium 4-vinylbenzenesulfonate may be used. Stabilizers prevent swelling of the resulting particles and impart positive or negative charges to the surface of the powder to electrostatically prevent mutual coalescence (bonding) during particle generation.
양친매성 이방성 분체가 200 내지 250 nm의 크기를 가질 경우, 제 1모노머, 중합 개시제 및 안정화제의 중량비가 110 내지 130 : 1 : 1 내지 5, 구체적으로 115 내지 125 : 1 : 2 내지 4인 제1 고분자 스페로이드로부터 제조될 수 있다. When the amphiphilic anisotropic powder has a size of 200 to 250 nm, the weight ratio of the first monomer, the polymerization initiator, and the stabilizer is 110 to 130: 1: 1 to 5, specifically 115 to 125: 1: 1 to 2-4 It can be prepared from 1 polymer spheroid.
또한, 양친매성 이방성 분체가 400 내지 450 nm의 크기를 가질 경우, 제 1모노머, 중합 개시제 및 안정화제의 중량비가 225 내지 240 : 1 : 1 내지 3, 구체적으로 230 내지 235 : 1 : 1 내지 3인 제1 고분자 스페로이드로부터 제조될 수 있다. In addition, when the amphiphilic anisotropic powder has a size of 400 to 450 nm, the weight ratio of the first monomer, the polymerization initiator and the stabilizer is 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 3 It can be prepared from the first polymeric spheroid.
또한, 양친매성 이방성 분체가 1100 내지 2500 nm의 크기를 가질 경우, 제 1모노머, 중합 개시제 및 안정화제의 중량비가 110 내지 130 : 1 : 0, 구체적으로 115 내지 125 : 1 : 0인 제1 고분자 스페로이드로부터 제조될 수 있다. In addition, when the amphiphilic anisotropic powder has a size of 1100 to 2500 nm, the first polymer having a weight ratio of the first monomer, the polymerization initiator, and the stabilizer is 110 to 130: 1: 0, specifically 115 to 125: 1: 0 It can be prepared from spheroids.
또한, 비대칭 스노우맨 형상의 양친매성 이방성 분체는 제1 모노머, 중합 개시제 및 안정화제의 중량비가 100 내지 140 : 1 : 8 내지 12, 구체적으로 110 내지 130 : 1 : 9 내지 11 로 제조된 제1 고분자 스페로이드로부터 제조될 수 있다. In addition, the amphipathic anisotropic powder of the asymmetrical snowman shape has a weight ratio of the first monomer, the polymerization initiator, and the stabilizer of 100 to 140: 1: 8 to 12, specifically 110 to 130: 1: 9 to 11 It can be prepared from polymeric spheroids.
또한, 비대칭 역스노우맨 형상의 양친매성 이방성 분체는 제1 모노머, 중합 개시제 및 안정화제의 중량비가 100 내지 140 : 1 : 1 내지 5, 구체적으로 110 내지 130 : 1 : 2 내지 4로 제조된 제1 고분자 스페로이드로부터 제조될 수 있다.In addition, the amphipathic anisotropic powder of the asymmetric inverse snowman shape is made of a weight ratio of the first monomer, the polymerization initiator, and the stabilizing agent is 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 1 to 2-4 It can be prepared from 1 polymer spheroid.
일예에서, 상기 (2)단계에서 관능기를 함유하는 모노머는 실록산 함유 (메트)아크릴레이트일 수 있으며, 구체적으로, 3-(트리메톡시실릴)프로필 아크릴레이트, 3-(트리메톡시실릴)프로필 메타크릴레이트, 비닐트리에톡시실란, 비닐트리메톡시실란 또는 이들의 혼합물일 수 있다.In one embodiment, the monomer containing a functional group in the step (2) may be a siloxane-containing (meth) acrylate, specifically, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl Methacrylate, vinyltriethoxysilane, vinyltrimethoxysilane or mixtures thereof.
일예에서, 상기 (2)단계에서 제1 모노머, 중합 개시제 및 관능기를 함유하는 모노머는 80 내지 98 : 0.2 내지 1.0 : 1 내지 20의 중량비로 혼합할 수 있다. 다른 측면에서, 상기 제1 모노머, 중합 개시제 및 관능기를 함유하는 모노머는 160 내지 200 : 1 : 6 내지 40 중량비로 혼합할 수 있다. 중량비에 따라 코팅 정도를 조절할 수 있고 코팅 정도에 따라서 이후 양친매성 이방성 분체의 형상이 결정되며, 상기 중량비로 반응시킬 경우 처음 두께 대비 약 10 내지 30%, 구체적으로 20% 내외로 코팅 두께가 증가하게 되며, 코팅이 너무 두꺼워 분체화가 진행되지 않거나 너무 얇아 다방향으로 분체화되는 문제 없이 분체화가 잘 진행하게 된다. 또한, 상기 범위의 중량비로 혼합함으로써, 이방성 분체의 균일도를 높일 수 있는 효과가 있다.In one example, the monomer containing the first monomer, the polymerization initiator and the functional group in the step (2) may be mixed in a weight ratio of 80 to 98: 0.2 to 1.0: 1 to 20. In another aspect, the first monomer, the polymerization initiator and the monomer containing a functional group may be mixed in a weight ratio of 160 to 200: 1: 6 to 40. The degree of coating can be adjusted according to the weight ratio, and the shape of the amphipathic anisotropic powder is subsequently determined according to the degree of coating, and when reacting with the weight ratio, the coating thickness increases to about 10-30%, specifically 20%, relative to the initial thickness. The coating is too thick so that powdering does not proceed or is too thin so that the powdering proceeds well without the problem of powdering in multiple directions. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
상기 (3)단계에 의하여, 코어-쉘 구조의 제1고분자 스페로이드의 일방향으로부터 제1고분자 스페로이드의 코어의 일부가 쉘을 투과하여 돌출되면서 돌출부가 제2모노머의 중합체에 의해 성장하여 이방성 분체의 형태를 형성할 수 있다.By the step (3), a part of the core of the first polymer spheroid protrudes through the shell from one direction of the first polymer spheroid of the core-shell structure, and the protrusion grows by the polymer of the second monomer to form an anisotropic powder. It can form the form of.
일예에서, 상기 (3)단계에서 제2 모노머 및 중합 개시제는 150 내지 250 : 1의 중량비로 혼합할 수 있다. 다른 측면에서, 상기 제2 모노머 및 중합 개시제는 160 내지 250 : 1, 또는 170 내지 250 : 1, 또는 180 내지 250 : 1, 또는 190 내지 250 : 1, 또는 200 내지 250 : 1, 또는 210 내지 250 : 1, 또는 220 내지 250 : 1, 또는 230 내지 250 : 1, 또는 240 내지 250 : 1의 중량비로 혼합할 수 있다.In one example, in the step (3), the second monomer and the polymerization initiator may be mixed in a weight ratio of 150 to 250: 1. In another aspect, the second monomer and the polymerization initiator are 160 to 250: 1, or 170 to 250: 1, or 180 to 250: 1, or 190 to 250: 1, or 200 to 250: 1, or 210 to 250 It can be mixed in a weight ratio of: 1, or 220 to 250: 1, or 230 to 250: 1, or 240 to 250: 1.
다른 측면에서, 상기 (3)단계에서 제2 모노머, 중합 개시제와 함께 안정화제를 첨가하여 제2 모노머, 중합 개시제 및 안정화제를 150 내지 250 : 1 : 0.001 내지 5의 중량비로 혼합할 수 있다. 안정화제의 구체적인 종류는 상술한 바와 같다. 상기 범위의 중량비로 혼합함으로써, 이방성 분체의 균일도를 높일 수 있는 효과가 있다.In another aspect, in step (3), the second monomer, the polymerization initiator and the stabilizer may be added together with the second monomer and the polymerization initiator to mix the second monomer, the polymerization initiator and the stabilizer in a weight ratio of 150 to 250: 1: 1: 0.001 to 5. The specific kind of stabilizer is as above-mentioned. By mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
일예에서, 상기 (3)단계에서 제2 모노머 함량은 코어-쉘 구조의 제1 고분자 스페로이드 중량이 100 중량부일 때 40 내지 300 중량부로 혼합할 수 있다. 구체적으로, 제2 모노머 함량이 코어-쉘 구조의 제1 고분자 스페로이드 중량이 100 중량부일 때 40 내지 100 중량부일 경우 비대칭 스노우맨 타입의 분체가 얻어지고, 100 내지 150 중량부, 또는 110 내지 150 중량부일 경우 대칭 형상의 분체가 얻어지고, 150 내지 300 중량부, 또는 160 내지 300 중량부일 경우 비대칭 역스노우맨 타입의 분체가 얻어진다. 또한, 상기 범위의 중량비로 혼합함으로써, 이방성 분체의 균일도를 높일 수 있는 효과가 있다.In one example, the second monomer content in the step (3) may be mixed to 40 to 300 parts by weight when the weight of the first polymer spheroid of the core-shell structure is 100 parts by weight. Specifically, when the second monomer content is 40 to 100 parts by weight when the weight of the first polymer spheroid of the core-shell structure is 100 parts by weight, an asymmetric snowman type powder is obtained, and 100 to 150 parts by weight, or 110 to 150 parts by weight. In the case of parts by weight, a symmetrical powder is obtained, and in the case of 150 to 300 parts by weight, or in the case of 160 to 300 parts by weight, an asymmetric inverse snowman type powder is obtained. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
본 발명 다른 실시예에서, 본 발명 일실시예에 따른 양친매성 이방성 분체를 제조할 때에, 상기 (3) 단계 이후에 (4) 상기 제조된 이방성 분체에 친수성 관능기를 도입하는 단계를 더 포함할 수 있다.In another embodiment of the present invention, when preparing the amphipathic anisotropic powder according to an embodiment of the present invention, after the step (3), (4) may further include introducing a hydrophilic functional group into the prepared anisotropic powder. have.
일예에서, 상기 (4)단계에서 친수성 관능기는 이에 제한하는 것은 아니나, 실란 커플링제와 반응 조절제를 이용하여 도입할 수 있다.In one example, the hydrophilic functional group in step (4) is not limited thereto, but may be introduced using a silane coupling agent and a reaction regulator.
일예에서, 상기 실란 커플링제는 (3-아미노프로필)트리메톡시실란, N-[3-(트리메톡시실릴)프로필]에틸렌디아민, N-[3-(트리메톡시실릴)프로필]에틸렌디암모늄 클로라이드, (N-숙시닐-3-아미노프로필)트리메톡시실란, 1-[3-(트리메톡시실릴)프로필]우레아 및 3-[(트리메톡시실릴)프로필옥시]-1,2-프로판디올로 이루어진 군에서 선택되는 1 이상일 수 있으며, 구체적으로 N-[3-(트리메톡시실릴)프로필]에틸렌디아민일 수 있다.In one embodiment, the silane coupling agent is (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) propyl] ethylenedi Ammonium chloride, (N-succinyl-3-aminopropyl) trimethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea and 3-[(trimethoxysilyl) propyloxy] -1,2 It may be one or more selected from the group consisting of propanediol, specifically N- [3- (trimethoxysilyl) propyl] ethylenediamine.
일예에서, 상기 실란 커플링제는 상기 (3)단계에서 제조된 이방성 분체 100중량부에 대하여 35중량부 내지 65중량부, 예를 들어 40중량부 내지 60중량부로 혼합할 수 있다. 상기 범위 내에서 친수화가 적절하게 이루어질 수 있다.In one example, the silane coupling agent may be mixed in an amount of 35 to 65 parts by weight, for example 40 to 60 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (3). Hydrophilization can be suitably made within the said range.
일예에서, 상기 반응 조절제는 암모늄 하이드록사이드일 수 있다.In one embodiment, the reaction modifier may be ammonium hydroxide.
일예에서, 상기 반응 조절제는 상기 (3)단계에서 제조된 이방성 분체 100중량부에 대하여 85중량부 내지 115중량부, 예를 들어 90중량부 내지 110중량부로 혼합할 수 있다. 상기 범위 내에서 친수화가 적절하게 이루어질 수 있다.In one example, the reaction regulator may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example 90 parts by weight to 110 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (3). Hydrophilization can be suitably made within the said range.
본 발명 또 다른 실시예에서, 본 발명 일실시예에 따른 양친매성 이방성 분체를 제조할 때에, 상기 (3) 단계 이후에 (4) 상기 제조된 이방성 분체에 당을 함유하는 관능기를 도입하는 단계를 더 포함할 수 있다.In another embodiment of the present invention, when preparing the amphipathic anisotropic powder according to an embodiment of the present invention, after the step (3), (4) introducing a functional group containing a sugar into the prepared anisotropic powder It may further include.
상기 (4)단계에서 당을 포함하는 관능기는 이에 제한하는 것은 아니나, 당 함유 실란커플링제와 반응 조절제를 이용하여 도입할 수 있다.The functional group containing sugar in step (4) is not limited thereto, but may be introduced using a sugar-containing silane coupling agent and a reaction regulator.
예시적인 일 구현예에 따르면, 상기 당 함유 실란커플링제는 N-{N-(3-트리에톡시실릴프로필)아미노에틸}글루콘아미드, N-(3-트리에톡시실릴프로필)글루콘아미드 및 N-{N-(3-트리에톡시실릴프로필)아미노에틸}-올리고-히아루론아미드로 이루어진 군에서 선택되는 1종 이상일 수 있다.According to one exemplary embodiment, the sugar-containing silane coupling agent is N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) gluconamide And N- {N- (3-triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide.
예시적인 일 구현예에 따르면, 상기 반응 조절제는 암모늄 하이드록사이드일 수 있다.According to one exemplary embodiment, the reaction modifier may be ammonium hydroxide.
일예에서, 상기 반응 조절제는 상기 (3)단계에서 제조된 이방성 분체 100중량부에 대하여 85중량부 내지 115중량부, 예를 들어 90중량부 내지 110중량부로 혼합할 수 있다. 상기 범위 내에서 당을 함유하는 관능기의 도입이 적절하게 이루어질 수 있다.In one example, the reaction regulator may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example 90 parts by weight to 110 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (3). Introduction of the functional group containing a sugar in the said range can be made suitably.
상기 방법에 따른 양친매성 이방성 분체의 제조는 가교제를 사용하지 않아 제조상 엉김이 없어 수율이 높고 균일하며, 단순 교반 방법을 이용하여 텀블링 방법에 비해 대량 생산이 용이하다. 특히, 300 nm 이하 크기의 나노 사이즈를 수십 g 내지 수십 kg 단위로 대량 생산할 수 있는 이점이 있다.Amphiphilic anisotropic powder according to the above method does not use a crosslinking agent, there is no entanglement in production, the yield is high and uniform, and it is easy to mass-produce compared to the tumbling method using a simple stirring method. In particular, there is an advantage that can be mass-produced in the size of several tens g to several tens of kg nano size of 300 nm or less.
본 실시예에 따른 조성물은 이중연속상 유화 제형을 갖는 조성물일 수 있다. 상기 제형은 유상과 수상이 상호 교차되어 연속적으로 존재하는 제형이므로 유상 성분의 특징과 수상 성분의 특징을 동시에 부여하는 독특한 효과를 나타낼 수 있다. The composition according to this embodiment may be a composition having a dual continuous emulsion formulation. Since the formulation is a formulation in which the oil phase and the water phase cross each other and are present in succession, the formulation may have a unique effect of simultaneously giving the characteristics of the oil phase component and the characteristics of the aqueous phase component.
본 실시예에 따른 조성물은 경도가 7 내지 60(mN)일 수 있다. 상기 범위 내에서 안정하면서 이중연속상 특유의 사용감을 제공할 수 있다.The composition according to the present embodiment may have a hardness of 7 to 60 (mN). It is possible to provide a feeling unique to the double continuous phase while being stable within the above range.
본 실시예에 따른 조성물은 이중연속상 유화 제형의 특징상 흐름성 없는 겔(gel) 제형을 형성할 수 있다.The composition according to the present embodiment may form a gel formulation with no flow due to the characteristics of the dual continuous emulsion formulation.
본 실시예에 따른 조성물은 넓은 온도 범위에서 경시 유화 안정성을 나타낼 수 있으며, 상기 온도는 예를 들어 -15℃ 내지 60℃ 일 수 있다.The composition according to the present embodiment may exhibit emulsion stability over time in a wide temperature range, and the temperature may be, for example, -15 ° C to 60 ° C.
본 발명 실시예들에 따른 조성물은 연속적인 상의 계면을 지탱하는 독특한 줄기(stem) 구조를 가져, 이러한 특성을 이용하여 화장료, 촉매, 분리 공정, 세포 공학, 연료 전지, 태양열 전지, 장벽 물질, 센서 등의 다양한 분야에서 사용될 수 있다.The composition according to the embodiments of the present invention has a unique stem structure that supports the interface of the continuous phase, utilizing these properties to make cosmetics, catalysts, separation processes, cellular engineering, fuel cells, solar cells, barrier materials, sensors It can be used in various fields such as.
예를 들어 상기 조성물을 화장료 조성물에 사용할 경우, 오일의 세정력과 물의 산뜻함을 동시에 부여하는 클렌징용 화장료를 제공할 수 있다.For example, when the composition is used in a cosmetic composition, it is possible to provide a cleansing cosmetic that simultaneously imparts cleaning power of oil and freshness of water.
본 발명의 실시예들에 따른 화장료 조성물은 화장품학 또는 피부과학적으로 허용가능한 매질 또는 기제를 함유하여 제형화될 수 있다. 이는 국소적용에 적합한 모든 제형으로서, 현탁액, 마이크로에멀젼, 마이크로캡슐, 미세과립구 또는 이온형(리포좀) 및 비이온형의 소낭 분산제의 형태로, 또는 크림, 스킨, 로션, 파우더, 연고, 스프레이 또는 콘실 스틱의 형태로 제공될 수 있다. 또한 포말(foam)의 형태로 또는 압축된 추진제를 더 함유한 에어로졸 조성물의 형태로도 사용될 수 있다. 이들 조성물은 당해 분야의 통상적인 방법에 따라 제조될 수 있다.Cosmetic compositions according to embodiments of the present invention may be formulated containing a cosmetically or dermatologically acceptable medium or base. It is any formulation suitable for topical application, in the form of suspensions, microemulsions, microcapsules, microgranules or ionic (liposomal) and nonionic vesicle dispersants or creams, skins, lotions, powders, ointments, sprays or concealers. It may be provided in the form of a stick. It may also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions can be prepared according to conventional methods in the art.
또한, 본 발명의 실시예들에 따른 화장료 조성물은 분체, 지방 물질, 유기용매, 용해제, 농축제, 겔화제, 연화제, 항산화제, 현탁화제, 안정화제, 발포제(foaming agent), 방향제, 계면활성제, 물, 이온형 또는 비이온형 유화제, 충전제, 금속이온봉쇄제, 킬레이트화제, 보존제, 비타민, 차단제, 습윤화제, 필수 오일, 염료, 안료, 친수성 또는 친유성 활성제, 지질 소낭 또는 화장품에 통상적으로 사용되는 임의의 다른 성분과 같은 화장품학 또는 피부과학 분야에서 통상적으로 사용되는 보조제를 함유할 수 있다. 상기 보조제는 화장품학 또는 피부과학 분야에서 일반적으로 사용되는 양으로 도입된다. 본 발명의 실시예들에 따른 화장료 조성물은 피부 개선 효과를 증가시키기 위하여 피부 흡수 촉진 물질을 더 함유할 수 있다. In addition, the cosmetic composition according to the embodiments of the present invention may be a powder, a fatty substance, an organic solvent, a dissolving agent, a thickening agent, a gelling agent, a softening agent, an antioxidant, a suspending agent, a stabilizer, a foaming agent, a fragrance, a surfactant. Commonly used in water, ionic or nonionic emulsifiers, fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics It may contain adjuvants conventionally used in the cosmetic or dermatological fields, such as any other ingredients used. Such adjuvants are introduced in amounts generally used in the cosmetic or dermatological arts. The cosmetic composition according to the embodiments of the present invention may further contain a skin absorption promoting substance to increase the skin improving effect.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples.
[제조예 1~4][Manufacture example 1-4]
하기 표 1의 조성에 따라 제조예 1~4를 제조하였다. 구체적인 방법은 아래에 분술한다According to the composition of Table 1, Preparation Examples 1 to 4 were prepared. Specific methods are described below.
하기 제조예에서 사용한 성분은 아래와 같다.The component used by the following preparation example is as follows.
PS(1L 진탕형 반응조)PS (1L shake reactor) CSCS DBDB
WaterWater 300300 PSPS 300300 CSCS 240240
MeOHMeOH 4040 WaterWater 250250 WaterWater 350350
StyreneStyrene 5050 TMSPA TMSPA 66 AIBNAIBN 0.20.2
KPSKPS 0.50.5 StyreneStyrene 5050 Styrene Styrene 4040
SVBSSVBS 1.01.0 AIBNAIBN 0.20.2 SVBSSVBS 0.350.35
MeOH: Methanol 공용매(cosolvent)MeOH: Methanol cosolvent
KPS: Potassium persulfate (개시제)KPS: Potassium persulfate (initiator)
SVBS: Sodium vinyl benzene sulfonate (안정화제)SVBS: Sodium vinyl benzene sulfonate (stabilizer)
PS: Polystyrene (고분자비드)PS: Polystyrene
CS: 코어-쉘 구조의 코팅된 제1고분자 스페로이드CS: coated first polymer spheroid of core-shell structure
DB: 양친매서 이방성 분체 DB: anisotropic powder
TMSPA: Trimethoxysilyl propylacrylate (관능기)TMSPA: Trimethoxysilyl propylacrylate (functional group)
AIBN : Azobisisobutyronitrile (중합 개시제)AIBN: Azobisisobutyronitrile (polymerization initiator)
제조예Production Example 1. 폴리스티렌(Polystyrene, PS) 제1 고분자  1.Polystyrene (PS) first polymer 스페로이드Spheroid 제조 Produce
수상에 모노머로서 스티렌(Styrene) 50g, 안정화제로서 소듐 4-비닐벤젠설포네이트(Sodium 4-vinylbenzenesulfonate) 1.0g, 중합 개시제로서 아조비스이소부티로니트릴(Azobisisobutyronitrile, AIBN) 0.5g을 혼합하여 75℃에서 8시간 동안 반응시켰다. 반응은 원통형 회전 반응기에서 교반하였으며, 원통형 회전 반응기는 지름 11cm, 높이 17cm, 유리재질이고, 200 rpm의 속도로 회전시켰다. 50 g of styrene as a monomer, 1.0 g of sodium 4-vinylbenzenesulfonate as a stabilizer, and 0.5 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were mixed in an aqueous phase to 75 ° C. The reaction was carried out for 8 hours. The reaction was stirred in a cylindrical rotary reactor, the cylindrical rotary reactor was 11 cm in diameter, 17 cm in height, glass, and was rotated at a speed of 200 rpm.
제조예 2. 코어-쉘(Core-Shell, CS) 구조의 코팅된 제1 고분자 스페로이드 제조 Preparation Example 2 Preparation of Coated First Polymer Spheroid of Core-Shell (CS) Structure
상기 얻어진 폴리스티렌(Polystyrene, PS) 제1 고분자 스페로이드 300g에, 모노머로서 스티렌(Styrene) 50g, TMSPA(3-(trimethoxysilyl) propylacrylate) 6g, 중합 개시제로서 아조비스이소부티로니트릴 0.2g(Azobisisobutyronitrile, AIBN)을 혼합하여 75℃에서 8시간 동안 반응시켰다. 반응은 원통형 회전 반응기에서 교반하였다.To 300 g of the polystyrene (PS) first polymer spheroid obtained above, 50 g of styrene as a monomer, 6 g of TMSPA (3- (trimethoxysilyl) propylacrylate), and 0.2 g of azobisisobutyronitrile as a polymerization initiator (Azobisisobutyronitrile, AIBN) ) Was mixed and reacted at 75 ° C. for 8 hours. The reaction was stirred in a cylindrical rotary reactor.
제조예Production Example 3.  3. 양친매성Amphipathic 이방성  Anisotropy 분체Powder (DB) 제조 (DB) manufacturing
상기 반응 결과 얻어진 폴리스티렌-코어쉘(PS-CS) 수분산 용액 240g에, 모노머로서 스티렌(Styrene) 40g, 안정화제로서 소듐 4-비닐벤젠설포네이트(Sodium 4-vinylbenzenesulfonate) 0.35g, 중합 개시제로서 아조비스이소부티로니트릴(Azobisisobutyronitrile, AIBN) 0.2g을 혼합하고 75℃로 가열하여 8시간 동안 반응을 진행하였다. 반응은 원통형 회전 반응기에서 교반하여 양친매성 이방성 분체를 제조하였다.To 240 g of polystyrene-coreshell (PS-CS) aqueous dispersion solution obtained as a result of the reaction, 40 g of styrene as a monomer, 0.35 g of sodium 4-vinylbenzenesulfonate as a stabilizer, and azo as a polymerization initiator 0.2 g of bisisobutyronitrile (Azobisisobutyronitrile, AIBN) was mixed and heated to 75 ° C. for 8 hours. The reaction was stirred in a cylindrical rotary reactor to prepare amphiphilic anisotropic powder.
제조예Production Example 4.  4. 친수화된Hydrophilized 양친매성Amphipathic 이방성  Anisotropy 분체Powder 제조 Produce
상기 얻어진 이방성 분체의 수분산 용액 600g에 실란 커플링제로서 N-[3-(트리메톡시실릴)프로필]에틸렌디아민(N-[3-(Trimethoxysilyl)propyl]ethylenediamine) 30g과 반응 조절제로서 암모늄 하이드록사이드(Ammmonium hydroxide) 60g을 혼합하여 25℃에서 24시간 동안 반응시켜 친수성 관능기를 도입하였다. 반응은 원통형 회전 반응기에서 교반하여 친수화된 양친매성 이방성 분체를 제조하였다.30 g of N- [3- (trimethoxysilyl) propyl] ethylenediamine (N- [3- (trimethoxysilyl) propyl] ethylenediamine) as a silane coupling agent in 600 g of the aqueous dispersion solution of the anisotropic powder thus obtained, and ammonium hydroxide as the reaction regulator. 60 g of ammonium hydroxide was mixed and reacted at 25 ° C. for 24 hours to introduce a hydrophilic functional group. The reaction was stirred in a cylindrical rotary reactor to produce hydrophilized amphiphilic anisotropic powder.
[ 시험예 1] 이중연속상 유화 여부 확인 [Test Example 1] Check upset emulsion yijungyeon
상기 제조예 3에 따른 이방성 분체, 탈이온수 및 스쿠알란(squalane)을 사용하여 하기 표 2에 따른 조성으로 비커에 담아 7500 rpm으로 3분간 호모믹싱하여 제형예 1~3의 3종의 조성물을 제조하였다. 또한 수용성 염료를 표 3의 조성에 따라 아지믹서로 3분간 혼합하여 제조하고, 지용성 염료를 표 3의 조성에 따라 70℃로 가온하면서 아지믹서로 3분간 혼합하여 제조하였다. Using the anisotropic powder, deionized water and squalane (squalane) according to Preparation Example 3 in the composition according to the following Table 2 in a beaker homomixed at 7500 rpm for 3 minutes to prepare three compositions of Formulation Examples 1-3. . In addition, the water-soluble dye was prepared by mixing for 3 minutes with an azimixer according to the composition of Table 3, the fat-soluble dye was prepared by mixing for 3 minutes with an azimixer while warming to 70 ℃ according to the composition of Table 3.
(단위: 중량%)(Unit: weight%) 제형예 1(O/W)Formulation Example 1 (O / W) 제형예 2(W/O)Formulation Example 2 (W / O) 제형예 3(BCE)Formulation Example 3 (BCE)
이방성 분체 수용액(수용액 중 이방성 분체 함량 8 중량%)Anisotropic powder solution (8% by weight of anisotropic powder content in aqueous solution) 3030 3030 3030
탈이온수 Deionized water 4040 00 1010
스쿠알란Squalane 3030 7070 6060
(단위: 중량%)(Unit: weight%) 수용성 염료Water soluble dyes 지용성 염료Fat-soluble dyes
탈이온수Deionized water 99.99999.999 00
TPP blueTPP blue 0.0010.001 00
스쿠알란 Squalane 00 99.99999.999
Nile redNile red 00 0.0010.001
상기 표 2에 따라 제조한 제형예 1~3 의 조성물을 유리판에 0.5g씩 올려놓고, 각 조성물에 상기 수용성 염료 및 지용성 염료를 각각 0.5㎖씩 떨어뜨리고 스패츌러로 섞어준 후 분산 상태를 육안으로 확인하였다. 분산 상태를 확인한 사진을 하기 도 3에 나타낸다.0.5 g of the compositions of Formulation Examples 1 to 3 prepared according to Table 2 were placed on a glass plate, and 0.5 ml of each of the water-soluble dyes and fat-soluble dyes was added to each composition, mixed with a spatula, and then dispersed in the naked eye. Confirmed. The photograph which confirmed the dispersion state is shown in FIG.
도 3의 결과에서, O/W 제형인 제형예 1은 물에는 잘 섞이지만 오일에는 섞이지 않아 수용성 염료를 떨어뜨린 경우 TPP blue의 파란색이 조성물에 균일하게 혼합되는 반면, 지용성 염료와 섞이지 않아 Nile red의 붉은색과 제형이 분리되는 것을 확인할 수 있다. W/O 제형인 제형예 2는 반대로 오일에 섞이지만 물에 섞이지 않아 수용성 염료를 떨어뜨린 경우 조성물과 염료가 섞이지 않고 분리되고, 지용성 염료를 떨어뜨린 경우 제형에 염료가 골고루 섞인 것을 확인할 수 있다. 반면, 이중연속상 유화 제형인 제형예 3의 경우 수용성 염료와 지용성 염료 양쪽에 모두 고르게 섞이는 것을 확인할 수 있다. 지용성 염료를 이용한 W/O의 경우에는 오일에는 잘 섞이지만 물에는 섞이지 않는 것을 확인하였다. 이러한 성질은 BCE가 유상과 수상이 혼재되어 있다는 것을 알려주며 2가지의 연속상 즉, Bi-continuous한 것을 나타내는 것이다.In the results of FIG. 3, Formulation Example 1, which is an O / W formulation, mixes well with water but does not mix with oil, and when water-soluble dye is dropped, blue of TPP blue is uniformly mixed with the composition, whereas it is not mixed with fat-soluble dye and thus Nile red. You can see that the red color and the formulation is separated. Formulation Example 2 of the W / O formulation, on the contrary, is mixed with oil but not mixed with water, so that when the water-soluble dye is dropped, the composition and the dye are not mixed, and when the fat-soluble dye is dropped, the dye is evenly mixed in the formulation. On the other hand, in the case of Formulation Example 3, which is a dual continuous emulsion formulation, it can be seen that both the water-soluble dye and the fat-soluble dye are mixed evenly. In the case of W / O using a fat-soluble dye, it was confirmed that the oil was mixed well but not the water. This property indicates that the BCE is a mixture of oil and water phases, indicating two continuous phases, Bi-continuous.
하기 실시예 및 비교예에서 사용한 성분은 구체적으로 아래와 같다.The components used in the following Examples and Comparative Examples are specifically as follows.
(a) 양친매성 이방성 분체 (ASP): 제조예 3에서 제조한 양친매성 이방성 분체를 탈이온수에 수용액 총 중량에 대해 20중량%로 용해시킨 수용액(A) Amphiphilic anisotropic powder (ASP): An aqueous solution in which the amphiphilic anisotropic powder prepared in Preparation Example 3 was dissolved in deionized water at 20% by weight based on the total weight of the aqueous solution.
(b) 비극성 오일: 스쿠알란 (Squalane, Neossance squalane, Amyris)(b) Nonpolar Oils: Squalane, Neossance squalane, Amyris
(c) 이온 조절제: EDTA (Ethylenediaminetetraacetic acid, E.D.T.A.-2NA, (주)네오드)(c) Ion regulator: EDTA (Ethylenediaminetetraacetic acid, E.D.T.A.-2NA, Neode)
(d) 계면활성제: 글리세릴스테아레이트/피이지-100 스테아레이트 (Glyceryl Stearate and PEG-100 Stearate, Arlacel 170-PA-(SG), Uniquema)(d) Surfactant: Glyceryl Stearate and PEG-100 Stearate, Arlacel 170-PA- (SG), Uniquema
[[ 실시예Example 1~4 및  1-4 and 비교예Comparative example 1] One]
하기 표 4의 조성에 따라 실시예 1~4 및 비교예 1의 유화 조성물을 제조하였다. 제조 방법은 조성에 따른 재료를 7500rpm에서 3분간 호모믹싱하여 제조하였다. To prepare an emulsion composition of Examples 1 to 4 and Comparative Example 1 according to the composition of Table 4. The manufacturing method was prepared by homomixing the material according to the composition at 7500 rpm for 3 minutes.
단위: 중량%Unit: weight% 비교예1Comparative Example 1 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4
ASP 수용액ASP aqueous solution 2.52.5 55 7.57.5 1010 2020
(ASP 함량)(ASP content) (0.5)(0.5) (1)(One) (1.5)(1.5) (2)(2) (4)(4)
탈이온수Deionized water 37.4537.45 34.9534.95 32.4532.45 29.9529.95 19.9519.95
이온조절제Ion regulator 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05
비극성 오일 Nonpolar oil 6060 6060 6060 6060 6060
[[ 실시예Example 5~7,  5 ~ 7, 비교예Comparative example 2~3] 2 ~ 3]
하기 표 5의 조성에 따라 실시예 5~7 및 비교예 2의 유화 조성물을 제조하였다. 제조 방법은 조성에 따른 재료를 7500rpm에서 3분간 호모믹싱하여 제조하였다.To the emulsion composition of Examples 5-7 and Comparative Example 2 according to the composition of Table 5. The manufacturing method was prepared by homomixing the material according to the composition at 7500 rpm for 3 minutes.
단위: 중량%Unit: weight% 실시예5Example 5 실시예6Example 6 실시예7Example 7 비교예 2Comparative Example 2 비교예 3Comparative Example 3
ASP 수용액ASP aqueous solution 2020 2020 2020 2020 --
(ASP 함량)(ASP content) (4)(4) (4)(4) (4)(4) (4)(4) --
계면활성제Surfactants -- -- -- -- 44
탈이온수Deionized water 잔량Remaining amount 잔량Remaining amount 잔량Remaining amount 잔량Remaining amount 잔량Remaining amount
이온조절제Ion regulator 0.050.05 0.050.05 0.050.05 0.050.05 0.050.05
비극성 오일Nonpolar oil 5656 5858 6060 6464 6060
[물성 평가][Property evaluation]
상기에서 제조한 실시예 1~7 및 비교예 1,2에 대하여 하기와 같이 물성평가를 하여 결과를 표 6 및 7에 나타내었다.In Examples 1 to 7 and Comparative Examples 1 and 2 prepared above, physical properties were evaluated as follows, and the results are shown in Tables 6 and 7.
(1) 제형 형성 여부: 이중연속상 유화 제형이 형성되었는지 여부를 상기 시험예 1과 동일한 방법으로 수용성 염료와 지용성 염료의 혼합 여부를 통하여 확인하였다. ○는 이중연속상 유화 제형이 형성된 것이고, △는 이중연속상 유화가 이루어졌으나 제조 후 상층부에 오일이 배어 나오는 것, X는 이중연속상이 형성되지 않고 물과 오일이 분리된 상태인 것을 나타낸다.(1) Formulation Formation: Whether the dual continuous emulsion formulation was formed was confirmed by mixing the water-soluble dye and the fat-soluble dye in the same manner as in Test Example 1. ○ indicates that the double continuous phase emulsion formulation is formed, and Δ indicates that the double continuous phase emulsification is made, but oil bleeds out in the upper layer after preparation, and X indicates that the water and oil are separated without the double continuous phase.
(2) 경도 (mN): 상기 실시예 및 비교예의 조성물을 30℃에서 Rheometer(compact-100II, Sun scientific co., LTD)를 사용하여 경도를 측정하였다.(2) Hardness (mN): The hardness of the compositions of Examples and Comparative Examples was measured using a Rheometer (compact-100II, Sun scientific co., LTD.) At 30 ° C.
(3) 온도 안정도: 상기 실시에 및 비교예의 조성물을 -15℃~60℃에서 4주간 보관하고, 초기에 제조한 상태와 면 상태가 동일한지 여부, 표면 오일 배어 나옴, 제형 무너짐이 있는지 여부를 외관 평가하여 실온 상태의 샘플과 비교하여 온도 안정도를 평가하였다. ○ 는 실온상태와 동일 △는 실온상태와 비교해 불안정성 확인 X는 제형 형태 유지 불가능을 나타낸다.(3) Temperature Stability: The compositions of the above Examples and Comparative Examples were stored at -15 ° C to 60 ° C for 4 weeks, and the state of the prepared state and the surface state were the same, whether the surface oil was soaked, and whether the formulation collapsed. Appearance evaluation evaluated the temperature stability compared with the sample of the room temperature state. ○ is the same as the room temperature △ is instability confirmed compared to the room temperature X indicates that the formulation form can not be maintained.
단위: 중량%Unit: weight% 비교예1Comparative Example 1 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4
제형 형성 여부Formulation Formation XX ○○ ○○ ○○ ○○
경도 (mN)Hardness (mN) X X 77 99 1717 2424
온도 안정도Temperature stability XX △△ △△ ○○ ○○
단위: 중량%Unit: weight% 실시예5Example 5 실시예6Example 6 실시예7Example 7 비교예 2Comparative Example 2 비교예 3Comparative Example 3
제형 형성 여부Formulation Formation ○○ ○○ ○○ X(WO 생성)X (WO generation) X(OW 생성)X (generate OW)
경도 (mN)Hardness (mN) 1717 2323 2727 XX XX
온도 안정도Temperature stability ○○ ○○ ○○ △ △ XX
실시예 1~7의 조성물은 안정하게 이중연속상 유화 제형을 형성하며, 경도가 높고, 온도 -5~60℃의 영역에서 약 4주간 오일 배어나옴이나 제형 분리 등의 문제가 발생하지 않고 초기 제조 시와 동일한 형태를 유지하는 반면, 양친매성 이방성 분체 함량이 1중량% 미만인 비교예 1의 경우 이중연속상 제형이 형성되지 않으며, 비극성 오일이 60중량%을 초과하는 비교예 2의 경우, 이중연속상 제형이 아닌 W/O 제형이 생성되었으며, 제형 특성상 경도를 측정할 수 없없다. 비교예 3의 경우 일반 계면활성제를 사용하여 O/W 제형이 생성되며, 흐름성 있는 제형으로 경도 측정이 불가능하였으며, 점증제 없이 오일이 고함량으로 함유된 제형으로 유화 제형 유지가 어렵고 안정도가 현저하게 낮은 것을 알 수 있다.The compositions of Examples 1 to 7 stably form a dual continuous emulsion formulation, have high hardness, and do not cause problems such as oil bleeding or formulation separation for about 4 weeks in a temperature range of -5 to 60 ° C., at the time of initial preparation. In Comparative Example 1, in which the amphiphilic anisotropic powder content is less than 1% by weight, the dual continuous phase formulation is not formed, and in Comparative Example 2 in which the nonpolar oil exceeds 60% by weight, the dual continuous phase formulation is W / O formulations were produced, and hardness cannot be determined due to the nature of the formulation. In case of Comparative Example 3, O / W formulation was produced by using a general surfactant, and it was impossible to measure hardness due to the flowable formulation. It can be seen that low.
[[ 시험예Test Example 2] 전기 전도도 평가 2] electrical conductivity evaluation
비극성 오일의 함량을 0~80중량%로 한 것을 제외하고는 상기 실시예 5와 동일 조성으로 유화 제형을 제조하고, 이중연속상 형성 여부를 확인하기 위하여 전기전도도 평가를 수행하였다. Except that the non-polar oil content of 0 to 80% by weight, an emulsion formulation was prepared in the same composition as in Example 5, and electrical conductivity evaluation was performed to confirm the formation of a double continuous phase.
수중유형 유화가 형성되는 경우 수상 부분이 높아져 전기전도도가 높게 측정되고, 유중수형 유화가 형성되는 경우 전기전도도가 낮게 측정되며, 이중연속상의 경우 수상과 유상이 연속상으로 존재하는 특성상 전기전도도값이 불규칙하게 측정된다.In the case of oil-in-water type emulsification, the water phase becomes high and the electrical conductivity is high.In the case of water-in-oil type emulsification, the electric conductivity is measured low. It is measured irregularly.
하기 도 4은 비극성 오일 함량에 따른 전기전도도 값을 나타낸다. 도 4에서는 시간에 따른 전기전도도 변화를 나타내지 않았으나, 비극성 오일 함량이 40중량% 내지 60중량% 범위에서는 전기전도도가 불규칙하게 측정되며, 이중연속상 제형이 형성되었음을 확인할 수 있다.Figure 4 shows the conductivity value according to the non-polar oil content. In FIG. 4, the electrical conductivity did not change with time, but in the range of 40 wt% to 60 wt% of the non-polar oil content, the electrical conductivity was measured irregularly, and it was confirmed that the bicontinuous phase formulation was formed.
[[ 시험예Test Example 3] 제형의 경시 안정도 평가 3] Evaluation of stability over time
상기 실시예 3~6의 조성물을 비이커에 담아 입구가 바닥을 향하도록 뒤집어 -15~60℃에서 180일간 유지하였다.The composition of Examples 3 to 6 was placed in a beaker, turned over so that the inlet faced the bottom, and maintained at -15 to 60 ° C for 180 days.
실시예 3~6의 조성물 모두 전 온도 범위에서 경시 안정도가 유지되어 흘러내지리 않고 안정적인 제형을 유지하였다.All of the compositions of Examples 3-6 maintained stability over time in the entire temperature range to maintain a stable formulation without flowing.
도 5는 실시예 4의 조성물을 제조한 후 30℃에서 유지하고 다음날 및 180일 경과시의 조성물 외관 사진 및 경도를 나타낸다. 조성물은 흐름성 없는 겔(gel) 제형을 형성하여 180일 경과 후에도 경도 변화 없이 흘러내리지 않고 안정적인 제형을 유지하는 것을 확인할 수 있다.FIG. 5 shows the composition appearance photograph and hardness at 30 ° C. after the preparation of the composition of Example 4 and the following day and after 180 days. The composition can be confirmed to form a gel formulation with no flow to maintain a stable formulation without flowing down even after 180 days without changing the hardness.

Claims (17)

  1. 양친매성 이방성 분체, 비극성 오일 및 물을 포함하는 이중연속상 유화(Bi-continuous emulsion) 조성물이고,A bi-continuous emulsion composition comprising amphiphilic anisotropic powder, nonpolar oil and water,
    상기 양친매성 이방성 분체는,The amphipathic anisotropic powder,
    친수성인 제1고분자 스페로이드 및 소수성인 제2고분자 스페로이드를 포함하고,A hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid,
    상기 제1고분자 스페로이드 및 제2고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하고,The first polymer spheroid and the second polymer spheroid are combined at least partially in a structure that penetrates the relative polymer spheroid,
    상기 제1고분자 스페로이드는 코어-쉘 구조를 갖고, 상기 쉘은 관능기를 포함하는, 유화 조성물.The first polymer spheroid has a core-shell structure, and the shell comprises a functional group.
  2. 제1항에 있어서,The method of claim 1,
    상기 조성물은 상기 양친매성 이방성 분체를 조성물 총 중량에 대하여 1중량% 내지 8중량%로 포함하는 조성물.The composition comprises 1% to 8% by weight of the amphipathic anisotropic powder relative to the total weight of the composition.
  3. 제1항에 있어서,The method of claim 1,
    상기 조성물은 상기 비극성 오일을 조성물 총 중량에 대하여 40중량% 내지 60중량%로 포함하는 조성물.The composition comprises 40% to 60% by weight of the non-polar oil relative to the total weight of the composition.
  4. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체와 비극성 오일은 양친매성 이방성 분체 : 비극성 오일의 중량비로 1 : 15~30로 포함되는 조성물.The amphipathic anisotropic powder and the non-polar oil are compositions comprising 1: 15 to 30 by weight ratio of the amphipathic anisotropic powder: non-polar oil.
  5. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체, 비극성 오일 및 물은 양친매성 이방성 분체:비극성 오일:물의 중량비로 1 : 4~15로 포함되는 조성물.The amphipathic anisotropic powder, non-polar oil and water is a composition comprising 1: 4 to 15 in the weight ratio of amphiphilic anisotropic powder: non-polar oil: water.
  6. 제1항에 있어서,The method of claim 1,
    상기 비극성 오일은 탄화수소계 오일인, 조성물.Wherein said nonpolar oil is a hydrocarbon-based oil.
  7. 제1항에 있어서,The method of claim 1,
    상기 관능기는 실록산인, 조성물.Wherein said functional group is a siloxane.
  8. 제1항에 있어서,The method of claim 1,
    상기 제1고분자 스페로이드의 코어와 제2고분자 스페로이드는 비닐 고분자를 포함하고,The core and the second polymer spheroid of the first polymer spheroid includes a vinyl polymer,
    상기 제1고분자 스페로이드의 쉘은 비닐 모노머; 및 관능기를 함유하는 모노머;의 공중합체를 포함하는, 조성물.The shell of the first polymer spheroid is a vinyl monomer; And a monomer containing a functional group.
  9. 제8항에 있어서,The method of claim 8,
    상기 비닐 고분자는 비닐 방향족계 고분자인, 조성물.The vinyl polymer is a vinyl aromatic polymer, composition.
  10. 제8항에 있어서,The method of claim 8,
    상기 비닐 모노머는 비닐 방향족계 모노머인, 조성물.Wherein said vinyl monomer is a vinyl aromatic monomer.
  11. 제8항에 있어서,The method of claim 8,
    상기 관능기를 함유하는 모노머는 실록산 함유 (메트)아크릴레이트인, 조성물.The monomer containing the said functional group is a siloxane containing (meth) acrylate.
  12. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체는 제1고분자 스페로이드 및 제2고분자 스페로이드가 결합된 결합부를 기준으로 대칭 형상, 비대칭 스노우맨(snowman) 형상 또는 비대칭 역스노우맨 형상을 갖는, 조성물.The amphipathic anisotropic powder has a symmetrical shape, an asymmetrical snowman shape or an asymmetrical inverse snowman shape based on the bonding portion of the first polymer spheroid and the second polymer spheroid.
  13. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체는 입자 크기가 100 내지 2500nm인, 조성물.The amphipathic anisotropic powder has a particle size of 100 to 2500 nm.
  14. 제1항에 있어서,The method of claim 1,
    상기 제1고분자 스페로이드의 쉘은 친수성 관능기가 추가적으로 도입된 것인, 조성물.The shell of the first polymer spheroid is that the hydrophilic functional group is further introduced.
  15. 제14항에 있어서,The method of claim 14,
    상기 친수성 관능기는 카르복실산기, 설폰기, 포스페이트기, 아미노기, 알콕시기, 에스테르기, 아세테이트기, 폴리에틸렌글리콜기 및 하이드록실기로 이루어진 군에서 선택되는 1 이상인, 조성물.Wherein said hydrophilic functional group is at least one selected from the group consisting of a carboxylic acid group, a sulfone group, a phosphate group, an amino group, an alkoxy group, an ester group, an acetate group, a polyethylene glycol group, and a hydroxyl group.
  16. 제1항에 있어서,The method of claim 1,
    상기 제1고분자 스페로이드의 쉘은 당을 함유하는 관능기가 추가적으로 도입된 것인, 조성물.The shell of the first polymer spheroid is a composition wherein a sugar-containing functional group is further introduced.
  17. 제16항에 있어서,The method of claim 16,
    상기 당을 함유하는 관능기는 N-{N-(3-트리에톡시실릴프로필)아미노에틸}글루콘아미드, N-(3-트리에톡시실릴프로필)글루콘아미드 및 N-{N-(3-트리에톡시실릴프로필)아미노에틸}-올리고-히아루론아미드로 이루어진 군에서 선택되는 1 이상으로부터 유래된 것인, 조성물.The sugar-containing functional groups are N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) gluconamide and N- {N- (3 -Triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide, wherein the composition is derived from one or more selected from the group consisting of.
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