WO2019108008A1 - Emulsion composition comprising amphiphilic anisotropic powder and having improved stability - Google Patents

Emulsion composition comprising amphiphilic anisotropic powder and having improved stability Download PDF

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WO2019108008A1
WO2019108008A1 PCT/KR2018/015069 KR2018015069W WO2019108008A1 WO 2019108008 A1 WO2019108008 A1 WO 2019108008A1 KR 2018015069 W KR2018015069 W KR 2018015069W WO 2019108008 A1 WO2019108008 A1 WO 2019108008A1
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composition
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substance
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PCT/KR2018/015069
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French (fr)
Korean (ko)
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신지식
김선영
남진
박승한
서병휘
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(주)아모레퍼시픽
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Priority claimed from KR1020180151000A external-priority patent/KR102645441B1/en
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Priority to CN201880077914.4A priority Critical patent/CN111447911A/en
Publication of WO2019108008A1 publication Critical patent/WO2019108008A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin

Definitions

  • the present disclosure relates to emulsified compositions comprising a substance having a positive potential, an amphiphilic anisotropic powder, and a substance having a negative potential.
  • an aqueous emulsion is formed by mixing an aqueous phase with an aqueous phase according to the HLB (Hydrophile-Lipophile Balance) value of the surfactant to emulsify the internal phase and the external phase.
  • HLB Hydrophile Balance
  • the size and shape of the spherical fine particles made of the polymer are controlled according to the manufacturing method, and thus the application possibility is expanded.
  • One of its applications is Pickering emulsion which can form stabilized macroporous particles using micro spherical particles.
  • O / W emulsified particles are formed at a contact angle of 90 ° or more, and W / O emulsion particles are formed at a temperature of 90 ° or less depending on the degree of hydrophilicity / hydrophobicity of the spherical particles.
  • a problem to be solved by the present invention is to provide an emulsified composition excellent in emulsion stability.
  • a problem to be solved by the present invention is to provide an emulsified composition including an amphiphilic anisotropic powder and having excellent stability at a low viscosity with time.
  • the present invention provides an emulsified composition
  • the hydrophilic one of the shells comprises a functional group
  • the emulsion composition comprises two phases, and the phases have mutually opposite electric potentials, Thereby providing an emulsified composition.
  • the present invention can provide an emulsified composition having excellent low viscosity emulsion stability.
  • the present invention can provide an emulsified composition having an excellent stability at a low viscosity including an amphiphilic anisotropic powder.
  • FIG. 1 is a schematic diagram for forming an amphiphilic anisotropic powder according to an embodiment of the present invention.
  • FIG. 2 shows the pH-dependent change of the aqueous phase of hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) according to an embodiment of the present invention.
  • FIG. 3 is a graph showing the difference in thin film formation according to the degree of neutralization of the increment agent of hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) according to an embodiment of the present invention.
  • Fig. 4 shows the results of comparing emulsion formation differences according to the presence or absence of electric potential of the oil phase of the compositions of Reference Example 10 and Reference Example 9.
  • Fig. The left side is the reference example 10, and the right side is the reference example 9.
  • FIG. 5 is a graph showing that the (-) z-potential value of the amphiphilic anisotropic powder shifts in the (+) z-potential direction while bonding with the emollient, confirming that the amphiphilic anisotropic powder binds with the emollient Lt; / RTI >
  • the red color in the lower graph is the z-potential value when bound with hexyldecyl myristoyl methylaminopropionate under the same conditions as the amphoteric anisotropic powder, and the green is the value when the pH is adjusted.
  • 6A is a schematic view of an emulsified particle using only a substance having a positive potential and a substance having a negative potential.
  • FIG. 6B is a schematic diagram of emulsified particles of an emulsified composition comprising a substance having a positive potential, a substance having a negative potential, and an amphiphilic anisotropic powder according to an embodiment of the present invention.
  • FIG. 6B is a schematic diagram of emulsified particles of an emulsified composition comprising a substance having a positive potential, a substance having a negative potential, and an amphiphilic anisotropic powder according to an embodiment of the present invention.
  • 7A is a photomicrograph of the emulsified particles after 4 weeks of preparation of the composition using only the carbomer of Comparative Example 1 and hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE).
  • FIG. 7B is a photomicrograph of the emulsified particles after four weeks of preparation of a composition containing the carbomer, hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) and amphipathic anisotropic powder of Example 1.
  • FIG. 7B is a photomicrograph of the emulsified particles after four weeks of preparation of a composition containing the carbomer, hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) and amphipathic anisotropic powder of Example 1.
  • FIG. 7B is a photomicrograph of the emulsified particles after four weeks of preparation of a composition containing the carbomer, hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOY
  • FIG. 7C is a photomicrograph of the emulsified particles after 4 weeks of preparation of the composition containing the carbomer of Comparative Example 2.
  • an emulsified composition comprising a substance having dislocations, and a double spiroid type polymeric amphipathic powder comprising a hydrophilic one-side and a hydrophobic one, wherein the powder has a hydrophobic side partially embedded in the hydrophilic one side
  • the hydrophilic one of the shells comprises a functional group
  • the emulsion composition comprises two phases, and the phases have mutually opposite electric potentials.
  • the substance having the dislocation may include at least one of a substance having a positive potential and a substance having a negative potential.
  • the present invention provides an emulsified composition comprising a substance having a positive potential, a substance having a negative potential, and a bispolide amphiphilic anisotropic powder comprising a hydrophilic one-side and a hydrophobic one, wherein the hydrophilic one of the shells comprises a functional group, the emulsion composition comprises two phases, and the phase comprises an emulsifying composition having a mutual potential opposite to that of the other, .
  • the two phases may include an aqueous phase and an oil phase.
  • the emulsion composition may include, for example, W / O, O / W phase, but is not limited thereto.
  • the interface is stabilized due to interactions between charges, so that the coagulation, fusion, or creaming of the emulsion particles in the emulsion composition can be prevented.
  • the substance having the positive potential may include an emollient
  • the substance having the negative potential may include an increasing agent
  • the emulsifying composition may be in water or in water.
  • the emulsified composition may be a water-in-oil type.
  • the substance having the positive potential can interact with the substance having the negative potential to form a film. Since the two phases contain a material having opposite potentials, the two phases exhibit opposite potentials and exhibit charge interactions at the interface between the two phases.
  • Figure 6a shows the formation of regions (denoted in the figure as ion charge interaction zones) in the formulations containing materials having opposite potentials in two phases, representing interactions between the charges at the interface. It is possible to exhibit excellent interfacial stability by the film formed in the region showing the interaction between the charges.
  • FIG. 6B is a schematic diagram of a formulation in which an amphiphilic anisotropic powder is present in a film formed in a region showing charge-charge interaction.
  • the amphipathic anisotropic powder can form stable emulsified particles by having the hydrophobic part and the hydrophilic part have different directions to the interface.
  • the emulsion particle formed by introducing an amphiphilic anisotropic powder into the interfacial membrane increases the thickness of the interfacial membrane to several hundreds nm, while the interfacial film formed by the general molecular-level surfactant forms a dynamic emulsion state. A solid interfacial film is formed.
  • an amphiphilic anisotropic powder is introduced into the stabilized interface through the interaction with the charge, so that a more stable emulsified composition can be formed.
  • the amphiphilic anisotropic powder may be present at the interface with the substance having the disposition.
  • an amphiphilic anisotropic powder may be combined with a substance having a positive potential.
  • the emulsion stability can be improved through the formation of the interfacial film, and the emulsion composition according to the present invention can have more stability.
  • the emulsified particles according to the present invention can form a stable emulsified formulation in a wide range of viscosity and can provide a soft feeling feeling with a low viscosity.
  • the substance having a positive potential can be any substance exhibiting a positive potential, but can include, for example, a emollient having a positive potential, and can include, for example, a compound containing an amine group .
  • the substance having a positive potential may include at least one selected from an aliphatic amine compound, an aromatic amine compound and an amine group-containing silicone compound.
  • the compound containing an amine group may be, for example, a compound having a functional group such as -N ⁇ , -NH-, -NH 2, or the like.
  • a compound having a functional group such as an aliphatic amine compound, an aromatic amine compound, but are not limited to, species.
  • the compound containing an amine group may be an alkylamine containing a linear or branched alkyl group having 6 to 30 carbon atoms, an aliphatic amine compound such as an alkanolamine containing a linear or branched alkanol group having 6 to 30 carbon atoms, , aromatic amine compounds such as o-toluidine, 2,4,6-trimethylaniline, anisidine and N-methylaniline, bisamodimethicone, amodimethicone, aminopropyldimethicone ( aminopropyl dimethicone), and the like.
  • the substance having the positive potential may be contained in the oil phase of the emulsified composition.
  • the emulsified composition may contain 0.01% to 75% by weight of the substance having the positive potential relative to the total weight of the composition.
  • the material having a positive potential is included in the above range, emulsion stability can be excellent, and stability with time can be excellent especially at a low viscosity.
  • the substance having a negative electric potential may be any substance exhibiting a negative electric potential, but may include an aging agent having a negative electric potential, for example, an anionic polymer.
  • the anionic polymer compound may be, for example, a polymer compound having a carboxylic acid group, a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group as a functional group.
  • a polymer compound having a carboxylic acid group, a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group as a functional group may be selected from an acrylic acid polymer, a polysaccharide polymer and a sulfonic polymer But is not limited thereto.
  • the anionic polymer compound may be selected from the group consisting of polyacrylic acid, polymethacrylic acid, polymethylmethacrylic acid, methylmethacrylate-acrylic acid copolymer, vinylpyrrolidone-acrylic acid copolymer, hydroxyethyl acrylate / sodium acrylate
  • An acrylic acid polymer such as a hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, an acrylate / C10-30 alkyl acrylate cross polymer (ACRYLATES / C10-30 ALKYL ACRYLATE CROSSPOLYMER), a carbomer
  • Polysaccharide polymer compounds such as alginic acid, pectin and polygalacturonic acid
  • sulfonic acid-based polymer compounds such as polystyrene sulfonic acid.
  • hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer acrylate / C10-30 alkyl acrylate crosspolymer (ACRYLATES / C10-30 ALKYL ACRYLATE CROSSPOLYMER), acrylate / And carbomers may be used.
  • the material having a negative potential may be a carbomer.
  • the material having a negative potential may have a pH of 7 or less and lower the pH of the overall composition.
  • the carbomer may lower the pH of the overall composition.
  • the substance having the negative electric potential may be contained in the water phase of the emulsified composition.
  • the emulsified composition may contain 0.01 to 10% by weight of the substance having the negative potential with respect to the total weight of the composition. Preferably from 0.1 to 0.4% by weight, based on the total weight of the composition. Within this range, the emulsified composition may have excellent stability at low viscosity.
  • the emulsified composition may have a pH of 7 or less, for example, a pH of 3 to 7. Within this range, the emulsified composition may have excellent stability at low viscosity.
  • the emulsified composition may have a pH of less than 7, less than pH 6.5, less than pH 6, less than pH 5.5, less than pH 5, less than pH 4.5, less than pH 4.0, or less than pH 3.5, PH 4.0 or higher, pH 4.5 or higher, pH 5.0 or higher, pH 5.5 or higher, pH 6.0 or higher, or pH 6.5 or higher.
  • the magnitude of the positive potential of a substance having a positive potential may vary depending on the pH of the composition, for example, the lower the pH, the larger the potential.
  • the bispulo-type polymeric amphipathic anisotropic powder may be present at the interfaces of the two phases.
  • the amphiphilic anisotropic powder may be a double-sphere type polymeric amphipathic anisotropic powder consisting of a hydrophilic one-side and a hydrophobic one.
  • the powder may have a structure in which the hydrophobic other part partially penetrates into the inside of the hydrophilic one to form a hydrophilic one of the cores, and the hydrophilic one may include a functional group.
  • the amphiphilic anisotropic powder includes a hydrophilic one (first polymer spoloid) and a hydrophobic other (second polymer spoloid), the hydrophilic one having a core-shell structure, the hydrophobic one having a hydrophilic one- At least partially penetrating into the inside of the hydrophilic core to form a hydrophilic one of the cores, and the hydrophilic one shell may contain a functional group.
  • FIG. 1 is a schematic view showing the principle of formation of an amphiphilic anisotropic powder according to an embodiment of the present invention.
  • the core of the first polymer spolide may be formed through the shell of the first polymer spolide and may be grown to form a second polymer spoloid by the above manufacturing method.
  • the powder may be in the form of a double sparoid, that is, a three-dimensional nephroid having a shape in which two spheroids are combined, and a symmetrical shape, asymmetric snowman snowman-shaped or asymmetric inverse snowman shape.
  • the shape of the snowman means that the first and second polymer spheroids having different sizes are combined.
  • the spheroid may be, for example, a sphere, a globoid, or an oval shape, and may have a major axis length in microns or nanometers based on the longest length in the body cross-section. have.
  • the hydrophilic one may be a core-shell structure in which the core is made of the same polymer as the hydrophobic base, and the hydrophilic one and the hydrophobic one may each take one spoloid shape of the double spoil.
  • the binding portion between the two sphereoids of the double sphere may have a continuous structure from the hydrophilic core to the hydrophobic one.
  • the hydrophilic one-side core and the hydrophobic one include a vinyl polymer
  • the hydrophilic one-side shell may include a copolymer of a vinyl monomer and a monomer containing a functional group
  • the vinyl polymer may be a vinyl aromatic polymer, and may be, for example, 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 functional group-containing monomer may be a siloxane-containing (meth) acrylate, and specifically includes 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, vinyl Triethoxysilane, vinyltrimethoxysilane, or a mixture thereof.
  • the hydrophilic one-side shell may further include a hydrophilic functional group.
  • the hydrophilic functional group may be a functional group having a negative or positive potential or a PEG (polyethylene glycol) group, and may be a carboxylic acid group, a sulfonic group, a phosphate group, an amino group, an alkoxy group, an ester group, an acetate group, a polyethylene glycol group, And a hydroxyl group.
  • PEG polyethylene glycol
  • the hydrophilic one-side shell may further include a sugar-containing functional group.
  • the functional group containing the sugar is selected from the group consisting of N- ⁇ N- (3-triethoxysilylpropyl) aminoethyl ⁇ gluconamide, N- (3-triethoxysilylpropyl) - (3-triethoxysilylpropyl) aminoethyl ⁇ -oligo-hyaluronamide, and the like.
  • the amphiphilic anisotropic powder may have a particle size of 100 to 1500 nm.
  • the amphiphilic anisotropic powder may have a particle size of 100 to 500 nm, or 200 to 300 nm.
  • the amphiphilic anisotropic powder preferably 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, 1200 nm or more, 1200 nm or more, 1300 nm or more or 1400 nm or more and 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 and 800 nm or less , 700 nm or less, 600 nm or less.
  • the particle size of the amphiphilic anisotropic powder herein is the maximum length measured as the longest length of the powder particle.
  • the particle size range of the amphiphilic anisotropic powder herein means that at least 95% of the amphipathic anisotropic powder present in the composition falls within this range.
  • the amphiphilic anisotropic powder may be prepared by polymerizing a first monomer to prepare a core of a first polymer spoloid, coating the core of the first polymer spoloid to form a core- And preparing an amphiphilic anisotropic powder in which the second polymer spolide is formed by reacting the first polymer spolide of the core-shell structure with the first monomer.
  • FIG. 1 is a schematic view showing the principle of formation of an amphiphilic anisotropic powder according to an embodiment of the present invention.
  • the core of the first polymer spolide may be formed through the shell of the first polymer spolide and may be grown to form a second polymer spoloid by the above manufacturing method.
  • the amphiphilic anisotropic powder is prepared by (1) stirring the first monomer and the polymerization initiator to prepare a core of the first polymer spolide; (2) stirring the prepared core of the first polymer spolide with a monomer containing a first monomer, a polymerization initiator and a functional group to prepare a first polymer spolide having a coated core-shell structure; (3) preparing an amphiphilic anisotropic powder in which the second polymer spolide is formed by stirring the first polymer spoloid of the prepared core-shell structure with the second monomer and the polymerization initiator.
  • stirring may be rotary stirring. It is preferable to rotate and stir because chemical mechanical modification and homogeneous mechanical mixing are required for producing uniform particles.
  • the rotational stirring may be performed in a cylindrical rotating reactor, but the rotational stirring method is not limited thereto.
  • the design inside the reactor has a great influence on powder formation.
  • the size and location of the baffles in the cylindrical rotating reactor and the degree of spacing between the impeller and the baffles greatly influence the uniformity of the particles produced. It is desirable to minimize the interval between the blades of the inner wing and the impeller to equalize the convection flow and the strength thereof, and to feed the powder reaction liquid below the wing length and to maintain the impeller rotation speed at a high speed.
  • 200 rpm, and the length to diameter ratio 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 be varied in proportion to the reaction capacity.
  • the material of the cylindrical rotating reactor may be ceramics, glass, etc., and the temperature at the time of stirring is preferably 50 to 90 ° C.
  • the simple rotation method is capable of producing uniform particles, and is a low energy method requiring less energy and maximizing the reaction efficiency, enabling mass production.
  • the conventional tumbling method in which the reactor itself rotates requires high energy and restricts the size of the reactor since the entire reactor must be tilted at a constant angle and rotated at high speed.
  • the amount produced due to reactor size limitations was also limited to small quantities of the order of several hundreds of milligrams to several grams, making them unsuitable for mass production.
  • the first monomer and the second monomer may be the same or different, and may be specifically vinyl monomers.
  • the first monomer added in the step (2) is the same as the first monomer used in the step (1), and 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, a peroxide type, an azo type, or a mixture thereof. Ammonium persulfate, sodium persulfate and potassium persulfate may also be used.
  • the first monomer and the polymerization initiator may be mixed at 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 in the step (1) 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 first polymer spoil size adjustment in the initial stage (1), and the first polymer spoil size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator, and the stabilizer. Further, by mixing at the weight ratio within the above range, the shape and uniformity of the anisotropic powder can be remarkably increased.
  • the stabilizer may be an ionic vinyl monomer, and specifically sodium 4-vinylbenzene sulfonate may be used. Stabilizers prevent swelling of the resulting particles and provide positive or negative charge on the powder surface to electrostatically prevent interactions (bonds) during grain formation.
  • the weight ratio of the first monomer, the polymerization initiator and the stabilizer is 80 to 135: 1: 1 to 5, specifically 95 to 120: 1: 2 to 4, when the amphiphilic anisotropic powder has a size of 200 to 250 nm. 1 < / RTI > polymer spolide.
  • the weight ratio of the first monomer, the polymerization initiator and the stabilizer is in the range of 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 3 , ≪ / RTI > the first polymeric spheroids.
  • 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 ≪ / RTI >
  • the amphiphilic anisotropic powder having an asymmetric snowman shape is preferably an amorphous powder having 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 Can be prepared from polymeric sphereoids.
  • the amphiphilic anisotropic powder having an asymmetric reverse snowman shape is preferably an amphipathic powder having a weight ratio of the first monomer, the polymerization initiator and the stabilizer of 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 2 to 4 1 < / RTI > polymer spolide.
  • the monomer containing a functional group in the step (2) may be a siloxane-containing (meth) acrylate.
  • a siloxane-containing (meth) acrylate examples thereof include 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) Methacrylate, vinyltriethoxysilane, vinyltrimethoxysilane, or a mixture 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 30 to 100: 0.2 to 1.0: 1 to 20. In another aspect, the monomer containing the first monomer, the polymerization initiator and the functional group may be mixed at a weight ratio of 150 to 300: 1: 6 to 40.
  • the degree of coating can be controlled according to the weight ratio, and the shape of the amphipathic anisotropic powder is determined according to the degree of coating, and when the weight ratio is adjusted, the coating thickness is increased to about 10 to 30%, specifically about 20% And the coating is too thick, so that the pulverization does not proceed or the pulverization is proceeded well without the problem that the pulverization is too thin.
  • the uniformity of the anisotropic powder can be increased.
  • step (3) a part of the core of the first polymer spolide is protruded from the one side of the first polymer spolide of the core-shell structure through the shell and the protrusions are grown by the polymer of the second monomer, Can be formed.
  • 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 may be present in an amount of from 160 to 250: 1, or from 170 to 250: 1, or from 180 to 250: 1, or from 190 to 250: 1, or from 200 to 250: : 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 mixed in a weight ratio of 150: 250: 1: 0.001 to 5 by adding the second monomer and the polymerization initiator together with the stabilizer in the step (3).
  • Specific types of stabilizers are as described above.
  • the second monomer content may be 40 to 300 parts by weight when the weight of the first polymer spoil 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 first polymer spoil weight of the core-shell structure is 100 parts by weight, the asymmetric snowman type powder is obtained, and 100 to 150 parts by weight, or 110 to 150 parts by weight, When the weight is in the range of 150 to 300 parts by weight or in the range of 160 to 300 parts by weight, an asymmetric reverse snowman type powder is obtained. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.
  • the step (3) may further include the step of (4) introducing a hydrophilic functional group into the produced 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 control agent.
  • the silane coupling agent is selected from the group consisting of (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) (Trimethoxysilyl) propyl] urea and 3 - [(trimethoxysilyl) propyloxy] -1,2 (trimethylsilyl) Propanediol, and specifically may be at least one selected from the group consisting of N- [3- (trimethoxysilyl) propyl] ethylenediamine.
  • the silane coupling agent may be added 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 the step (3). Within this range, hydrophilization can be appropriately performed.
  • reaction modifier may be ammonium hydroxide.
  • reaction modifier may be added in an amount of 85 to 115 parts by weight, for example, 90 to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3).
  • hydrophilization can be appropriately performed.
  • the step (3) is followed by (4) a step of introducing a sugar-containing functional group into the produced anisotropic powder .
  • the functional group containing sugar is not limited thereto, but may be introduced using a sugar-containing silane coupling agent and a reaction control agent.
  • the sugar-containing silane coupling agent is selected from the group consisting of N- ⁇ N- (3-triethoxysilylpropyl) aminoethyl ⁇ gluconamide, N- (3-triethoxysilylpropyl) And N- ⁇ N- (3-triethoxysilylpropyl) aminoethyl ⁇ -oligo-hyaluronamide.
  • the reaction modifier may be ammonium hydroxide.
  • reaction modifier may be added in an amount of 85 to 115 parts by weight, for example, 90 to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3).
  • the introduction of a sugar-containing functional group within the above range can be suitably performed.
  • the preparation of the amphiphilic anisotropic powder according to the above method does not use a cross-linking agent, so there is no production entanglement.
  • the yield is high and uniform, and mass production is easier than the tumbling method using a simple agitation method.
  • the size of the emulsified particles may be from 1 ⁇ m to 100 ⁇ m in average particle size, for example from 10 ⁇ m to 30 ⁇ m.
  • the average particle diameter is 1 ⁇ ⁇ or more, 2 ⁇ ⁇ or more, 3 ⁇ ⁇ or more, 4 ⁇ ⁇ or more, 5 ⁇ ⁇ or more, 6 ⁇ ⁇ or more, 7 ⁇ ⁇ or more, 8 ⁇ ⁇ or more, At least 15 ⁇ , at least 16 ⁇ , at least 17 ⁇ , at least 18 ⁇ , at least 19 ⁇ , at least 20 ⁇ , at least 21 ⁇ , at least 22 ⁇ , at least 23 ⁇ , at least 24 ⁇ At least 25 ⁇ , at least 26 ⁇ , at least 27 ⁇ , at least 28 ⁇ , at least 29 ⁇ , at least 30 ⁇ , at least 35 ⁇ , at least 40 ⁇ , at least 45 ⁇ , at least 50 ⁇ , at least 55 ⁇ ,
  • the average particle diameter may be 100 ⁇ ,
  • the average particle diameter of the emulsified particles means an average value of the diameter of a single particle.
  • the particle diameter of the emulsion particle is not uniform, and the emulsion particle having a particle diameter in the wide range of 0.1 to 2000 ⁇ m coexists.
  • the mean particle diameter of the macro emulsion particles may be, for example, 20 mu m.
  • the composition may comprise the amphiphilic anisotropic powder in an amount of 0.01 to 10% by weight, preferably 0.1 to 1% by weight, based on the total weight of the composition. More specifically, it is preferable that the content of the inorganic filler is 0.01 wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% %, Up to 9 wt.%, Up to 8 wt.%, Up to 7 wt.%, Up to 6 wt.%, Up to 5 wt.%, Up to 4 wt.%, Or up to 3 wt.%, Or less, 2 wt% or less, or 1 wt% or less.
  • the composition may comprise the amphiphilic anisotropic powder in an amount of 0.1% to 20% by weight, for example, 0.1% to 1%, and in one embodiment 0.5% by weight based on the total weight of the composition .
  • Stable emulsion particles can be formed within the above range, and emulsion particles having an appropriate size can be formed.
  • the ratio of the substance having the positive potential to the substance having the negative potential: amphiphilic anisotropic powder can be included in a weight ratio of 100: 1 to 20: 1-10.
  • the weight ratio is 100: 1.5-18: 1.2-9, 100: 2-16: 1.4-8, 100: 2.5-14: 1.6-7, 100: 3-12: 1.8-6, 100: 3.5 -10: 2-5, 100: 4-8: 2.2-4, or 100: 4.5-6: 2.4-4 and the weight ratio is 100: 1.5-20: 1-9, 100: 20: 1-8, 100: 2.5-20: 1-7, 100: 3-20: 1-7, 100: 3.5-20: 1-6, 100: 4-20: 1-5, or 100: 4.5 -20: 1-4, and the weight ratio is 100: 1-18: 2-10, 100: 1-16: 3-10, 100: 1-14: 4-10, 100: 1-12 : 5-10, 100: 1-10: 6-10, 100: 1-8: 7-10.
  • the emulsifying composition may comprise a pH adjusting agent.
  • the water phase of the emulsified composition may further comprise an acid.
  • the acid may be included in any acid used in cosmetics.
  • the acid may be one or more selected from the group consisting of lactic acid, glycolic acid, ethyl ascorbic acid, ascorbic acid, and glutamic acid. But is not limited thereto.
  • the viscosity of the composition may be 100-100,000 cps, for example, the viscosity of the composition may be 2,000-15,000 cps. Since the composition according to this embodiment does not require stabilization through an incremental increase, it is possible to provide a composition having a wide range of viscosity regardless of viscosity.
  • the viscosity of the composition can be measured using a BROOKFIELD Viscometer.
  • the viscosity of the composition may be controlled by the content of a substance having a positive potential or the content of a substance having a negative potential, for example the composition may have a viscosity of at least 15000 cps.
  • the composition may have a viscosity of, for example, greater than 200 cps, greater than 300 cps, greater than 400 cps, greater than 500 cps, greater than 600 cps, greater than 700 cps, greater than 800 cps, greater than 900 cps, greater than 1000 cps, At least 1200 cps, at least 1300 cps, at least 1400 cps, at least 1500 cps, at least 1600 cps, at least 1700 cps, at least 1800 cps, at least 1900 cps, at least 2000 cps, at least 2100 cps, at least 2200 cps, at least 2300 cps, More than 2400 cps, greater than 2500 cps, greater than 2600 cps, greater than 2700 cps, greater than 2800 cps, greater than 2900 cps, greater than 3000 cp
  • the composition may have excellent emulsion stability at a viscosity of 100-100,000 cps, and in particular, the composition may have a low viscosity at a low viscosity of 2000-15000 cps, for example at a low viscosity of 3000-10000 cps.
  • the composition may further comprise a surfactant for emulsification.
  • a surfactant for emulsification examples include lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cyclopentasiloxane * PEG-10, and the like.
  • the surfactant examples include, but are not limited to, Dimethicone * Distearimonium Hectorite, Cetyl PEG.PPG-10/1 Dimethicone (Cetyl Dimethicone Copolyol; Cetyl PEG.PPG-10/1 Dimethicone (Cetyl Dimethicone * Copolyol, etc.), arachidyl alcohol / behenyl alcohol / arachidyl glucoside (ARACHIDYL ALCOHOL / BEHENYL ALCOHOL / ARACHIDYL GLUCOSIDE), cetearyl alcohol * CETEARYL ALCOHOL * CETEARYL GLUCOSIDE), C14-22 alcohol * C12-20 alkyl glucoside (C14-22 ALCOHOLS * C12-20 ALKYL GLUCOSIDE), glyceryl stearate * PEG-100 stearate (Glyceryl Stearate * PEG- W You The like of a surfact
  • the surfactant may be included in an amount of 0 to 20% by weight, 0 to 10% by weight, or 0 to 5% by weight based on the total weight of the composition. In this embodiment, it is possible to stabilize the emulsified formulation while containing a small amount of surfactant.
  • the composition according to embodiments of the present invention may be a cosmetic composition.
  • the cosmetic composition may be formulated containing a cosmetically or dermatologically acceptable medium or base. It may be in the form of a suspension, a microemulsion, a microcapsule, a microgranule or an ionic (liposome) and a non-ionic follicular dispersion, or a cream, a skin, a lotion, a powder, an ointment, a spray, May be provided in the form of a stick. It can also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions may be prepared according to conventional methods in the art.
  • the cosmetic composition according to embodiments of the present invention may be in the form of powders, fatty substances, organic solvents, solubilizers, thickeners, gelling agents, softeners, antioxidants, suspending agents, stabilizers, foaming agents, , Water, ionic or nonionic emulsifiers, fillers, sequestering agents, chelating agents, preservatives, vitamins, barrier agents, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics And any other ingredients used, such as cosmetics or adjuvants commonly used in the field of dermatology. Such adjuvants are introduced in amounts commonly used in the cosmetics or dermatological fields.
  • 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.
  • Production Examples 1-1 to 1-4 were prepared according to the composition shown in Table 1 below. Specific methods are described below.
  • SVBS Sodium vinyl benzene sulfonate (stabilizer)
  • PS Polystyrene (polymer bead)
  • AIBN Azobisisobutyronitrile (polymerization initiator)
  • styrene as a monomer
  • 1.0 g of sodium 4-vinylbenzenesulfonate as a stabilizer
  • 0.5 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were mixed in a water bath at 75 DEG C For 8 hours.
  • the reaction was stirred in a cylindrical rotating reactor.
  • the cylindrical rotating reactor was 11 cm in diameter, 17 cm in height, made of glass, and rotated at a speed of 200 rpm.
  • the emulsion composition of the present invention was examined for changes in the physical properties of a substance having a positive potential (emollient) depending on the pH of the aqueous phase, and the effect of the type of acid affecting the pH was examined.
  • the substance having a positive potential was purchased from Nippon Emulsion Co., Ltd., and HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE, which is a trade name AMITER MA-HD, was used, Lithospermi Radix ) extract And hexyldecyl myristoyl methylaminopropionate were used. Water, glycolic acid, and ethyl ascorbic acid were used as the water phase. Extracts of B. pertussis were used as a reddish oil-soluble material to facilitate visual confirmation of film formation and emulsification. There is no influence on the formation of the formulations even when the pigment is changed to another oil-soluble dye. When the layer separation occurs, the red layer is identified with a bright red color, and when the emulsification occurs, it appears to be light pink.
  • each raw material of acid was put into the water as shown in Table 2, prepared by titrating to the corresponding pH, and the oil phase and the water phase were hand-mixed.
  • the layer separation is performed by the behavior of a substance having a general positive potential (Referential Examples 1 and 3, (1) and (3) in FIG. 2) It was confirmed that the tertiary amine moiety of the substance having a positive electric potential has a positive electric potential through the base reaction and serves as a surfactant (Reference Examples 2 and 4, (2) and (4) in FIG. 2). Further, it was confirmed that there was no influence depending on the type of acid.
  • 0.1 wt% of carbomer as a substance having a negative potential was added to the aqueous phase.
  • tromethamine was neutralized with neutralizing agent to pH 3, 4, 5, and 6 in each reference example. After neutralization, hexyldecyl myristoyl methyl aminopropionate was slowly poured without mixing to observe the thin film layer on the surface.
  • the positive potential of the substance having a positive potential differs depending on the pH level.
  • Positive potentials of counter-positively charged positive potentials which can bind to carbomers with negative potential, increase with decreasing pH, and thus the difference in the degree of formation of the thin film layer due to charge interactions . It was confirmed that a transparent thin film was formed at pH 6 (Reference Example 8), from which it is expected that the thin film layer becomes unstable in a formulation of pH 7 or more.
  • Comparative Example 1 was prepared by mixing a squalane extract with a common oil having no dislocation.
  • Example 1 emulsion helixdecyl myristoyl methyl aminopropionate having a positive potential varying with pH, The extracts were mixed and prepared.
  • Water containing the amphiphilic anisotropic powder prepared in Preparation Example 1-3 was prepared as an aqueous phase, and the aqueous phase was pH 5 without any pH adjustment.
  • the oil phase was added to the liquid phase (pH 5) of the amphiphilic anisotropic powder without pH adjustment of the water phase and observed by hand mixing. A photograph of the composition is shown in FIG.
  • the Z-potential of the amphiphilic anisotropic powder and the change in the numerical value after the binding of the amphiphilic anisotropic powder and hexyldecyl myristoyl methyl aminopropionate are shown in FIG. Specifically, the composition containing the amphiphilic anisotropic powder in the composition of Table 5 and the composition containing the amphiphilic anisotropic powder and hexyldecyl myristoyl methylaminopropionate were measured for Z-potential using a Zetasizer (Malvern) Respectively.
  • Figure 5 shows that the (-) z-potential value of the amphiphilic anisotropic powder itself (upper graph) is lower than that of the amphiphilic anisotropic powder in the (+) direction while the amphiphilic anisotropic powder and hexyldecyl myristoyl methylaminopropionate bind in the lower graph. Which indicates the binding of the amphiphilic anisotropic powder to the emollient.
  • a formulation using only carbomer and hexyldecyl myristoyl methyl aminopropionate and a particle varying with an amphipathic anisotropic powder are compared and observed.
  • the viscosity of the emulsion composition prepared in the contents of Table 6 was measured at 30 ° C on the next day of manufacture using a viscosity meter (BROOKFIELD Viscometer, SPINDLE # 3, 12RPM, 30 ° C, the next day).
  • FIG. 7A, 7B, and 7C are photographs of micrographs of emulsion particles observed after the compositions of Comparative Example 1, Example 1, and Comparative Example 2 were stored at 30 DEG C for 4 weeks, respectively.
  • the emulsion formulations of Comparative Example 1 ) And the amphiphilic anisotropic powder of Example 1 (Fig. 7B) were the same formulation except that Example 1 contained 0.5 wt% of the amphiphilic anisotropic powder, and Comparative Example 2 (Fig. 7C) Powder, and positive displacement material.
  • Example 1 it was confirmed that the amphiphilic anisotropic powder is located at a site where the film is formed by the interaction between charges, and the particles are made large.
  • Comparative Example 2 did not achieve 4-week stability in the pilot scale, but Example 1 (Fig. 7B) in which amphipathic anisotropic powder was combined had 4000 cps and formed large particles, And it was confirmed that it has stability.

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Abstract

Disclosed is an emulsion composition comprising a material having a positive potential, a material having a negative potential, and a double spheroidal polymer amphiphilic anisotropic powder composed of one side with hydrophilicity and the other side with hydrophobicity, wherein the powder has a structure in which the other side with hydrophobicity partially infiltrates into the inside of the one side with hydrophilicity to form a core of the one side with hydrophilicity, a shell of the one side with hydrophilicity comprising a functional group, and wherein the emulsion composition comprises two phases, the phases having potentials opposite to each other.

Description

양친매성 이방성 분체를 포함하며 안정도가 향상된 유화 조성물An emulsion composition comprising an amphiphilic anisotropic powder and having improved stability
본 명세서는 양전위를 갖는 물질, 양친매성 이방성 분체, 및 음전위를 갖는 물질을 포함하는 유화 조성물에 관한 것이다.The present disclosure relates to emulsified compositions comprising a substance having a positive potential, an amphiphilic anisotropic powder, and a substance having a negative potential.
계면활성제를 사용하는 유화시스템에서는 계면활성제의 HLB(Hydrophile-Lipophile Balance)값에 따라 수상과 유상을 혼합하여 유화하여 내상과 외상이 구분되는 경시적으로 안정한 유화 시스템을 형성하는 것이다.In an emulsification system using a surfactant, an aqueous emulsion is formed by mixing an aqueous phase with an aqueous phase according to the HLB (Hydrophile-Lipophile Balance) value of the surfactant to emulsify the internal phase and the external phase.
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.It has been difficult to form a dual emulsion type emulsion using a conventional surfactant because it can be realized only at a composition ratio of a ternary system (water, oil, surfactant) and is difficult to stabilize due to the fluidity of emulsified interface film.
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. The size and shape of the spherical fine particles made of the polymer are controlled according to the manufacturing method, and thus the application possibility is expanded. One of its applications is Pickering emulsion which can form stabilized macroporous particles using micro spherical particles. O / W emulsified particles are formed at a contact angle of 90 ° or more, and W / O emulsion particles are formed at a temperature of 90 ° or less depending on the degree of hydrophilicity / hydrophobicity of the spherical particles.
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, both hydrophilic and hydrophobic, to the microspheres. An example is the Janus spherical particles. However, due to the morphological limitations of these spheres, there is a limit to the chemical anisotropy. In other words, although it is morphologically anisotropic, it is totally hydrophobic or hydrophilic, 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.It has been attempted to produce anisotropic powders having surface activity by imparting chemical anisotropy together with geometric shape control. However, despite the advantage of its applicability of amphiphilic anisotropic powder, up to now, Has not been specifically developed, and there is a problem that it is difficult to mass-produce uniformly in the industry, so that no practical industrial application has been made.
일 관점에서, 본 발명이 해결하고자 하는 과제는 유화 안정성이 우수한 유화 조성물을 제공하는 것이다.From the viewpoint of one aspect, a problem to be solved by the present invention is to provide an emulsified composition excellent in emulsion stability.
또 다른 관점에서, 본 발명이 해결하고자 하는 과제는 양친매성 이방성 분체를 포함하여 저점도 경시 안정성이 우수한 유화 조성물을 제공하는 것이다.In another aspect, a problem to be solved by the present invention is to provide an emulsified composition including an amphiphilic anisotropic powder and having excellent stability at a low viscosity with time.
일 관점에서, 본원 발명은 양전위를 갖는 물질, 음전위를 갖는 물질, 및 친수성 일방 및 소수성 타방으로 이루어진 이중 스페로이드형 고분자 양친매성 이방성 분체;를 포함하는, 유화 조성물로서, 상기 분체는 소수성 타방이 상기 친수성 일방의 내부로 부분적으로 침투하여 친수성 일방의 코어를 형성하는 구조이며, 상기 친수성 일방의 쉘은 관능기를 포함하고, 상기 유화 조성물은 2 개의 상을 포함하며, 상기 상은 서로 반대 전위를 갖는, 유화 조성물을 제공한다.In one aspect, the present invention provides an emulsified composition comprising a substance having a positive potential, a substance having a negative potential, and a bispolide amphiphilic anisotropic powder having a hydrophilic one-side and a hydrophobic side, wherein the powder has a hydrophobic other side Wherein the hydrophilic one of the shells comprises a functional group, the emulsion composition comprises two phases, and the phases have mutually opposite electric potentials, Thereby providing an emulsified composition.
일 관점에서, 본 발명은 저점도 유화 안정성이 우수한 유화 조성물을 제공할 수 있다.In one aspect, the present invention can provide an emulsified composition having excellent low viscosity emulsion stability.
또 다른 관점에서, 본 발명은 양친매성 이방성 분체를 포함하여 저점도 경시 안정성이 우수한 유화 조성물을 제공할 수 있다.From another viewpoint, the present invention can provide an emulsified composition having an excellent stability at a low viscosity including an amphiphilic anisotropic powder.
도 1은 본 발명의 일 실시예에 따른 양친매성 이방성 분체를 형성하는 모식도이다.1 is a schematic diagram for forming an amphiphilic anisotropic powder according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 헥실데실 미리스토일 메틸 아미노프로피오네이트(HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE)의 수상의 pH에 따른 변화를 나타낸 것이다.FIG. 2 shows the pH-dependent change of the aqueous phase of hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) according to an embodiment of the present invention.
도 3은 본 발명의 일 실시예에 따른 헥실데실 미리스토일 메틸 아미노프로피오네이트(HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE)의 점증제의 중화 정도에 따른 박막 형성 차이를 나타낸 것이다.FIG. 3 is a graph showing the difference in thin film formation according to the degree of neutralization of the increment agent of hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) according to an embodiment of the present invention.
도 4는 참조예 10과 참조예 9 조성물의 유상부의 전위 유무에 따른 유화 형성 차이를 비교한 결과를 나타낸다. 좌측이 참조예 10, 우측이 참조예 9이다. Fig. 4 shows the results of comparing emulsion formation differences according to the presence or absence of electric potential of the oil phase of the compositions of Reference Example 10 and Reference Example 9. Fig. The left side is the reference example 10, and the right side is the reference example 9. [
도 5는 양친매성 이방성 분체의 (-) z-포텐셜 값이 에몰리언트와 결합하면서 (+) z-포텐셜 방향으로 시프트 되는 것을 나타낸 그래프로서, 이를 통하여 양친매성 이방성 분체가 에몰리언트와 결합함을 확인할 수 있음을 나타낸 것이다. 하단 그래프의 붉은색은 양친매성 이방성 분체와 동일 조건에서 헥실데실미리스토일메틸아미노프로피오네이트와 결합된 경우의 z-포텐셜 값이며, 녹색은 pH가 조절된 경우의 값이다. FIG. 5 is a graph showing that the (-) z-potential value of the amphiphilic anisotropic powder shifts in the (+) z-potential direction while bonding with the emollient, confirming that the amphiphilic anisotropic powder binds with the emollient Lt; / RTI > The red color in the lower graph is the z-potential value when bound with hexyldecyl myristoyl methylaminopropionate under the same conditions as the amphoteric anisotropic powder, and the green is the value when the pH is adjusted.
도 6a는 양전위를 갖는 물질 및 음전위를 갖는 물질 만을 사용한 유화 입자의 모식도이다.6A is a schematic view of an emulsified particle using only a substance having a positive potential and a substance having a negative potential.
도 6b는 본 발명의 일 실시예에 따른 양전위를 갖는 물질, 음전위를 갖는 물질 및 양친매성 이방성 분체를 포함하는 유화 조성물의 유화 입자의 모식도이다.FIG. 6B is a schematic diagram of emulsified particles of an emulsified composition comprising a substance having a positive potential, a substance having a negative potential, and an amphiphilic anisotropic powder according to an embodiment of the present invention. FIG.
도 7a는 비교예 1의 카보머와 헥실데실 미리스토일 메틸 아미노프로피오네이트(HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE)만을 사용한 조성물의 제조 4주 후 유화 입자의 현미경 사진이다.7A is a photomicrograph of the emulsified particles after 4 weeks of preparation of the composition using only the carbomer of Comparative Example 1 and hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE).
도 7b는 실시예 1의 카보머, 헥실데실 미리스토일 메틸 아미노프로피오네이트(HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) 및 양친매성 이방성 분체를 함유한 조성물의 제조 4주 후 유화 입자의 현미경 사진이다.FIG. 7B is a photomicrograph of the emulsified particles after four weeks of preparation of a composition containing the carbomer, hexyldecyl myristoyl methyl aminopropionate (HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE) and amphipathic anisotropic powder of Example 1. FIG.
도 7c는 비교예 2의 카보머를 함유한 조성물의 제조 4주 후 유화입자의 현미경 사진이다.7C is a photomicrograph of the emulsified particles after 4 weeks of preparation of the composition containing the carbomer of Comparative Example 2. Fig.
이하, 본 발명의 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. 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, embodiments of the present invention will be described in more detail. However, the techniques disclosed in the present application are not limited to the embodiments described herein but may be embodied in other forms. It should be understood, however, that the embodiments disclosed herein are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention.
본 발명의 일 측면에서, 전위를 갖는 물질, 및 친수성 일방 및 소수성 타방으로 이루어진 이중 스페로이드형 고분자 양친매성 이방성 분체를 포함하는 유화 조성물로서, 상기 분체는 소수성 타방이 상기 친수성 일방의 내부로 부분적으로 침투하여 친수성 일방의 코어를 형성하는 구조이며, 상기 친수성 일방의 쉘은 관능기를 포함하고, 상기 유화 조성물은 2 개의 상을 포함하며, 상기 상은 서로 반대 전위를 갖는 유화 조성물을 제공한다.In one aspect of the present invention, there is provided an emulsified composition comprising a substance having dislocations, and a double spiroid type polymeric amphipathic powder comprising a hydrophilic one-side and a hydrophobic one, wherein the powder has a hydrophobic side partially embedded in the hydrophilic one side Wherein the hydrophilic one of the shells comprises a functional group, the emulsion composition comprises two phases, and the phases have mutually opposite electric potentials.
상기 전위를 갖는 물질은 양전위를 갖는 물질 및 음전위를 갖는 물질 중 하나 이상을 포함할 수 있다.The substance having the dislocation may include at least one of a substance having a positive potential and a substance having a negative potential.
일 구체예에서, 본 발명은 양전위를 갖는 물질, 음전위를 갖는 물질, 및 친수성 일방 및 소수성 타방으로 이루어진 이중 스페로이드형 고분자 양친매성 이방성 분체를 포함하는 유화 조성물로서, 상기 분체는 소수성 타방이 상기 친수성 일방의 내부로 부분적으로 침투하여 친수성 일방의 코어를 형성하는 구조이며, 상기 친수성 일방의 쉘은 관능기를 포함하고, 상기 유화 조성물은 2 개의 상을 포함하며, 상기 상은 서로 반대 전위를 갖는 유화 조성물을 제공한다.In one embodiment, the present invention provides an emulsified composition comprising a substance having a positive potential, a substance having a negative potential, and a bispolide amphiphilic anisotropic powder comprising a hydrophilic one-side and a hydrophobic one, Wherein the hydrophilic one of the shells comprises a functional group, the emulsion composition comprises two phases, and the phase comprises an emulsifying composition having a mutual potential opposite to that of the other, .
상기 2 개의 상은 수상 및 유상을 포함할 수 있다. 상기 유화 조성물은 예를 들어, W/O, O/W 상을 포함할 수 있으나, 이에 제한되지 않는다.The two phases may include an aqueous phase and an oil phase. The emulsion composition may include, for example, W / O, O / W phase, but is not limited thereto.
상기 유화 조성물은 2 개의 상이 서로 반대 전위를 가지기 때문에, 전하간 상호작용으로 인하여 계면이 안정화되어 유화 조성물에서 유화 입자의 응집, 융합 또는 크리밍(creaming) 현상을 방지할 수 있다. Since the two phases of the emulsion composition have mutual dislocations, the interface is stabilized due to interactions between charges, so that the coagulation, fusion, or creaming of the emulsion particles in the emulsion composition can be prevented.
일 측면에서, 상기 양전위를 갖는 물질은 에몰리언트를 포함할 수 있고, 상기 음전위를 갖는 물질은 점증제를 포함할 수 있다.In one aspect, the substance having the positive potential may include an emollient, and the substance having the negative potential may include an increasing agent.
일 측면에서, 상기 유화 조성물은 수중유형 또는 유중수형일 수 있다. 구체적으로, 상기 유화 조성물은 유중수형일 수 있다.In one aspect, the emulsifying composition may be in water or in water. Specifically, the emulsified composition may be a water-in-oil type.
상기 양전위를 갖는 물질은 상기 음전위를 갖는 물질과 상호작용하여 막을 형성할 수 있다. 2개의 상에서 서로 반대 전위를 가지는 물질을 포함하기 때문에 2 개의 상이 반대 전위를 나타내어 2 개의 상 사이의 계면에서 전하간 상호작용(charge interaction)을 나타내게 된다. 도 6a는 2 개의 상에서 서로 반대 전위를 가지는 물질을 포함한 제형에서 계면에 전하간 상호작용을 나타내는 영역(도면에서 ion charge interaction zone으로 표기함)이 형성되는 것을 도시한다. 상기 전하간 상호작용을 나타내는 영역에 형성된 막에 의하여 우수한 계면 안정성을 나타낼 수 있다.The substance having the positive potential can interact with the substance having the negative potential to form a film. Since the two phases contain a material having opposite potentials, the two phases exhibit opposite potentials and exhibit charge interactions at the interface between the two phases. Figure 6a shows the formation of regions (denoted in the figure as ion charge interaction zones) in the formulations containing materials having opposite potentials in two phases, representing interactions between the charges at the interface. It is possible to exhibit excellent interfacial stability by the film formed in the region showing the interaction between the charges.
도 6b는 전하간 상호작용을 나타내는 영역에 형성된 막에 양친매성 이방성 분체가 존재하는 제형의 모식도이다. 상기 양친매성 이방성 분체는 소수성 부분 및 친수성 부분이 계면에 대한 상이한 방향성을 가짐으로써 안정적인 유화 입자를 형성할 수 있다. 일반적인 분자 수준의 계면활성제에 의하여 형성되는 계면막이 동적 유화 상태를 이루는 반면, 계면 막에 양친매성 이방성 분체를 도입시킴으로써 형성되는 유화 입자는 계면막의 두께가 수백 nm로 증가하며, 분체 간의 강한 결합을 통하여 견고한 계면막을 형성하게 된다. 또한, 전하에 의한 상호작용을 통하여 안정화된 계면에 양친매성 이방성 분체가 도입되어 보다 안정적인 유화 조성물을 형성할 수 있다. 6B is a schematic diagram of a formulation in which an amphiphilic anisotropic powder is present in a film formed in a region showing charge-charge interaction. The amphipathic anisotropic powder can form stable emulsified particles by having the hydrophobic part and the hydrophilic part have different directions to the interface. The emulsion particle formed by introducing an amphiphilic anisotropic powder into the interfacial membrane increases the thickness of the interfacial membrane to several hundreds nm, while the interfacial film formed by the general molecular-level surfactant forms a dynamic emulsion state. A solid interfacial film is formed. In addition, an amphiphilic anisotropic powder is introduced into the stabilized interface through the interaction with the charge, so that a more stable emulsified composition can be formed.
일 예에서, 양친매성 이방성 분체는 상기 전위를 갖는 물질과 결합하여 계면에 존재할 수 있다. 예를 들어 양친매성 이방성 분체는 양전위를 갖는 물질과 결합할 수 있다. 이와 같은 계면막 형성을 통하여 유화 안정도가 향상될 수 있으며, 본 발명에 따른 유화 조성물은 더욱 안정성을 가질 수 있다. 본 발명에 따른 유화 입자에 의하여 넓은 범위의 점도에서 안정한 유화 제형을 형성할 수 있고, 또한 낮은 점도를 가지는 유연한 사용감의 유화 제형을 제공할 수 있다.In one example, the amphiphilic anisotropic powder may be present at the interface with the substance having the disposition. For example, an amphiphilic anisotropic powder may be combined with a substance having a positive potential. The emulsion stability can be improved through the formation of the interfacial film, and the emulsion composition according to the present invention can have more stability. The emulsified particles according to the present invention can form a stable emulsified formulation in a wide range of viscosity and can provide a soft feeling feeling with a low viscosity.
상기 양전위를 갖는 물질은 양전위를 나타내는 물질이라면 어느 것이든 사용할 수 있으나, 예를 들어 양전위를 갖는 연화제(emollient)를 포함할 수 있고, 예를 들어 아민기를 포함하는 화합물을 포함할 수 있다. The substance having a positive potential can be any substance exhibiting a positive potential, but can include, for example, a emollient having a positive potential, and can include, for example, a compound containing an amine group .
본 발명의 일 측면에서, 상기 양전위를 갖는 물질은 지방족 아민 화합물, 방향족 아민 화합물 및 아민기 함유 실리콘계 화합물 중에서 선택되는 1종 이상을 포함할 수 있다.In one aspect of the present invention, the substance having a positive potential may include at least one selected from an aliphatic amine compound, an aromatic amine compound and an amine group-containing silicone compound.
상기 아민기를 포함하는 화합물은 예를 들어 -N=, -NH-, -NH2 등을 작용기로 가지는 화합물일 수 있으며, 예를 들어 지방족 아민 화합물, 방향족 아민 화합물 및 아민기 함유 실리콘계 화합물 중에서 선택되는 1종 이상을 포함할 수 있으나, 이에 제한되지 않는다. 예를 들어 상기 아민기를 포함하는 화합물은 탄소수 6 내지 30의 선형 또는 분지형 알킬기를 함유하는 알킬아민, 탄소수 6 내지 30의 선형 또는 분지형 알칸올기를 함유하는 알칸올아민 등의 지방족 아민 화합물, 아닐린, o-톨루이딘, 2,4,6-트리메틸아닐린, 아니시딘, N-메틸아닐린 등의 방향족 아민 화합물, 비스아모디메티콘(bis amodimethicone), 아모디메티콘(amodimethicone), 아미노프로필디메티콘(aminopropyl dimethicone) 등의 아민기 함유 실리콘계 화합물일 수 있다. 예를 들어 헥실데실미리스토일메틸아미노프로피오네이트(Hexyldecyl Myristoyl Methylaminopropionate), 비스아모디메티콘(bis amodimethicone), 아모디메티콘(amodimethicone), 및 아미노프로필디메티콘(aminopropyl dimethicone) 중에서 선택되는 1종 이상일 수 있다.The compound containing an amine group may be, for example, a compound having a functional group such as -N═, -NH-, -NH 2, or the like. For example, a compound having a functional group such as an aliphatic amine compound, an aromatic amine compound, But are not limited to, species. For example, the compound containing an amine group may be an alkylamine containing a linear or branched alkyl group having 6 to 30 carbon atoms, an aliphatic amine compound such as an alkanolamine containing a linear or branched alkanol group having 6 to 30 carbon atoms, , aromatic amine compounds such as o-toluidine, 2,4,6-trimethylaniline, anisidine and N-methylaniline, bisamodimethicone, amodimethicone, aminopropyldimethicone ( aminopropyl dimethicone), and the like. For example, one selected from the group consisting of Hexyldecyl Myristoyl Methylaminopropionate, Bis amodimethicone, amodimethicone, and aminopropyl dimethicone. It can be more than a species.
일 측면에서, 상기 양전위를 갖는 물질은 유화 조성물의 유상에 함유될 수 있다.In one aspect, the substance having the positive potential may be contained in the oil phase of the emulsified composition.
본 발명의 일 측면에서, 상기 유화 조성물은 상기 양전위를 갖는 물질을 조성물 총 중량에 대하여 0.01 중량% 내지 75 중량%로 포함할 수 있다. 상기 양전위를 갖는 물질을 상기 범위로 포함하는 경우, 유화 안정성이 우수할 수 있으며, 특히 저점도에서 경시 안정성이 우수할 수 있다. 예를 들어, 0.01 중량% 이상, 0.05 중량% 이상, 0.1 중량% 이상, 0.5 중량% 이상, 1 중량% 이상, 2 중량% 이상, 4 중량% 이상, 6 중량% 이상, 8 중량% 이상, 10 중량% 이상, 12 중량% 이상, 14 중량% 이상, 16 중량% 이상, 18 중량% 이상, 20 중량% 이상, 22 중량% 이상, 24 중량% 이상, 26 중량% 이상, 28 중량% 이상, 30 중량% 이상, 32 중량% 이상, 34 중량% 이상, 36 중량% 이상, 38 중량% 이상, 40 중량% 이상, 42 중량% 이상, 44 중량% 이상, 46 중량% 이상, 48 중량% 이상, 또는 50 중량% 이상으로 포함할 수 있고, 75 중량% 이하, 74 중량% 이하, 72 중량% 이하, 70 중량% 이하, 68 중량% 이하, 66 중량% 이하, 64 중량% 이하, 62 중량% 이하, 60 중량% 이하, 58 중량% 이하, 56 중량% 이하, 54 중량% 이하, 52 중량% 이하, 50 중량% 이하, 48 중량% 이하, 46 중량% 이하, 44 중량% 이하, 42 중량% 이하, 40 중량% 이하, 38 중량% 이하, 36 중량% 이하, 34 중량% 이하, 32 중량% 이하, 30 중량% 이하, 28 중량% 이하, 26 중량% 이하, 24 중량% 이하, 22 중량% 이하, 또는 20 중량% 이하로 포함할 수 있다.In one aspect of the present invention, the emulsified composition may contain 0.01% to 75% by weight of the substance having the positive potential relative to the total weight of the composition. When the material having a positive potential is included in the above range, emulsion stability can be excellent, and stability with time can be excellent especially at a low viscosity. At least 0.01% by weight, at least 0.05% by weight, at least 0.1% by weight, at least 0.5% by weight, at least 1% by weight, at least 2% by weight, at least 4% by weight, at least 6% by weight, at least 8% At least 12 wt%, at least 14 wt%, at least 16 wt%, at least 18 wt%, at least 20 wt%, at least 22 wt%, at least 24 wt%, at least 26 wt%, at least 28 wt% At least 32 wt%, at least 34 wt%, at least 36 wt%, at least 38 wt%, at least 40 wt%, at least 42 wt%, at least 44 wt%, at least 46 wt%, at least 48 wt% 75 wt% or less, 74 wt% or less, 72 wt% or less, 70 wt% or less, 68 wt% or less, 66 wt% or less, 64 wt% or less, 62 wt% or less, Up to 60 wt%, up to 58 wt%, up to 56 wt%, up to 54 wt%, up to 52 wt% up to 50 wt% up to 48 wt% up to up to 46 wt% up to up to 42 wt% 40 wt% or less, 38 wt% or less, Up to 36 weight percent, up to 34 weight percent, up to 32 weight percent, up to 30 weight percent, up to 28 weight percent, up to 26 weight percent, up to 24 weight percent, up to 22 weight percent, or up to 20 weight percent .
상기 음전위를 갖는 물질은 음전위를 나타내는 물질이라면 어느 것이든 사용할 수 있으나, 예를 들어 음전위를 갖는 점증제를 포함할 수 있고, 예를 들어 음이온성 고분자 화합물을 포함할 수 있다.The substance having a negative electric potential may be any substance exhibiting a negative electric potential, but may include an aging agent having a negative electric potential, for example, an anionic polymer.
상기 음이온성 고분자 화합물은 예를 들어 카르복실산기, 술폰산기, 황산에스테르기, 인산에스테르기 작용기로 가진 고분자 화합물일 수 있으며, 예를 들어 아크릴산계 고분자 화합물, 다당류 고분자 화합물 및 술폰산계 고분자 화합물 중에서 선택되는 1종 이상을 포함할 수 있으나, 이에 제한되지 않는다. 예를 들어 상기 음이온성 고분자 화합물은 폴리아크릴산, 폴리메타크릴산, 폴리메틸메타크릴산, 메틸메타크릴레이트-아크릴산 코폴리머, 비닐피롤리돈-아크릴산 코폴리머, 하이드록시에틸아크릴레이트/소듐아크릴로일디메틸타우레이트 코폴리머(Hydroxyethyl Acrylate/Sodium Acryloyldimethyl Taurate Copolymer), 아크릴레이트/C10-30 알킬아크릴레이트크로스폴리머(ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER), 카보머(carbomer) 등의 아크릴산계 고분자 화합물, 알긴산, 펙틴, 폴리갈락투론산 등의 다당류 고분자 화합물, 폴리스티렌 술폰산 등의 술폰산계 고분자 화합물일 수 있다. 예를 들어 하이드록시에틸아크릴레이트/소듐아크릴로일디메틸타우레이트 코폴리머(Hydroxyethyl Acrylate/Sodium Acryloyldimethyl Taurate Copolymer), 아크릴레이트/C10-30 알킬아크릴레이트크로스폴리머(ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER), 및 카보머(carbomer) 중에서 선택되는 1 종 이상을 사용할 수 있다. 일 실시예에서, 상기 음전위를 갖는 물질은 카보머(carbomer)일 수 있다.The anionic polymer compound may be, for example, a polymer compound having a carboxylic acid group, a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group as a functional group. For example, it may be selected from an acrylic acid polymer, a polysaccharide polymer and a sulfonic polymer But is not limited thereto. For example, the anionic polymer compound may be selected from the group consisting of polyacrylic acid, polymethacrylic acid, polymethylmethacrylic acid, methylmethacrylate-acrylic acid copolymer, vinylpyrrolidone-acrylic acid copolymer, hydroxyethyl acrylate / sodium acrylate An acrylic acid polymer such as a hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, an acrylate / C10-30 alkyl acrylate cross polymer (ACRYLATES / C10-30 ALKYL ACRYLATE CROSSPOLYMER), a carbomer, Polysaccharide polymer compounds such as alginic acid, pectin and polygalacturonic acid, and sulfonic acid-based polymer compounds such as polystyrene sulfonic acid. For example, hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, acrylate / C10-30 alkyl acrylate crosspolymer (ACRYLATES / C10-30 ALKYL ACRYLATE CROSSPOLYMER), acrylate / And carbomers may be used. In one embodiment, the material having a negative potential may be a carbomer.
일 실시예에서, 상기 음전위를 갖는 물질은 pH 7 이하를 가질 수 있으며, 전체 조성물의 pH를 낮출 수 있다. 예를 들어, 상기 카보머(carbomer)는 전체 조성물의 pH를 낮출 수 있다.In one embodiment, the material having a negative potential may have a pH of 7 or less and lower the pH of the overall composition. For example, the carbomer may lower the pH of the overall composition.
일 측면에서, 상기 음전위를 갖는 물질은 유화 조성물의 수상에 함유될 수 있다.In one aspect, the substance having the negative electric potential may be contained in the water phase of the emulsified composition.
본 발명의 일 측면에서, 상기 유화 조성물은 상기 음전위를 갖는 물질을 조성물 총 중량에 대하여 0.01 내지 10 중량%로 포함할 수 있다. 바람직하게, 조성물 총 중량에 대하여 0.1 내지 0.4 중량%로 포함할 수 있다. 상기 범위에서 유화 조성물은 우수한 저점도 경시 안정성을 가질 수 있다.In one aspect of the present invention, the emulsified composition may contain 0.01 to 10% by weight of the substance having the negative potential with respect to the total weight of the composition. Preferably from 0.1 to 0.4% by weight, based on the total weight of the composition. Within this range, the emulsified composition may have excellent stability at low viscosity.
예를 들어, 0.01 중량% 이상, 0.05 중량% 이상, 0.1 중량% 이상, 0.15 중량% 이상, 0.2 중량% 이상, 0.25 중량% 이상, 0.30 중량% 이상, 0.35 중량% 이상, 0.4 중량% 이상, 0.45 중량% 이상, 0.5 중량% 이상, 0.6 중량% 이상, 0.7 중량% 이상, 0.8 중량% 이상, 0.9 중량% 이상, 1.0 중량% 이상, 1.5 중량% 이상, 2.0 중량% 이상, 2.5 중량% 이상, 3.0 중량% 이상, 3.5 중량% 이상, 4.0 중량% 이상, 4.5 중량% 이상, 5.0 중량% 이상, 5.5 중량% 이상, 6.0 중량% 이상, 6.5 중량% 이상, 7.0 중량% 이상, 7.5 중량% 이상, 8.0 중량% 이상, 8.5 중량% 이상 또는 9.0 중량% 이상으로 포함할 수 있고, 10 중량% 이하, 9.5 중량% 이하, 9.0 중량% 이하, 8.5 중량% 이하, 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, 4.0 중량% 이하, 3.5 중량% 이하, 3.0 중량% 이하, 2.5 중량% 이하, 2.0 중량% 이하, 1.5 중량% 이하, 1.0 중량% 이하, 0.9 중량% 이하, 0.8 중량% 이하, 0.7 중량% 이하, 0.6 중량% 이하, 0.5 중량% 이하, 0.45 중량% 이하, 0.4 중량% 이하,0.35 중량% 이하, 0.30 중량% 이하, 0.25 중량% 이하, 0.20 중량% 이하, 0.15 중량% 이하, 0.1 중량% 이하, 또는 0.05 중량% 이하로 포함할 수 있다.For example, at least 0.01%, at least 0.05%, at least 0.1%, at least 0.15%, at least 0.2%, at least 0.25%, at least 0.30%, at least 0.35%, at least 0.4% At least 0.5% by weight, at least 0.6% by weight, at least 0.7% by weight, at least 0.8% by weight, at least 0.9% by weight, at least 1.0% by weight, at least 1.5% by weight, at least 2.0% by weight, at least 2.5% At least 3.5 wt%, at least 4.0 wt%, at least 4.5 wt%, at least 5.0 wt%, at least 5.5 wt%, at least 6.0 wt%, at least 6.5 wt%, at least 7.0 wt%, at least 7.5 wt% Up to 9.5 wt.%, Up to 9.0 wt.%, Up to 8.5 wt.%, Up to 8.0 wt.%, Up to 7.5 wt.%, Up to 7.0 wt.% Up to 6.5 wt.%, Up to 6.0 wt.%, Up to 5.5 wt.%, Up to 5.0 wt.%, Up to 4.5 wt.%, Up to 4.0 wt.%, Up to 3.5 wt. Not more than 2.0%, not more than 1.5%, not more than 1.0%, not more than 0.9%, not more than 0.8%, not more than 0.7%, not more than 0.6%, not more than 0.5%, not more than 0.45%, not more than 0.4% Up to 0.35 weight percent, up to 0.30 weight percent, up to 0.25 weight percent, up to 0.20 weight percent, up to 0.15 weight percent, up to 0.1 weight percent, or up to 0.05 weight percent.
본 발명의 일 관점에서, 상기 유화 조성물은 pH 7 이하, 예를 들어 pH 3 내지 7로 가질 수 있다. 상기 범위에서 유화 조성물은 우수한 저점도 경시 안정성을 가질 수 있다.In one aspect of the present invention, the emulsified composition may have a pH of 7 or less, for example, a pH of 3 to 7. Within this range, the emulsified composition may have excellent stability at low viscosity.
예를 들어, 상기 유화 조성물은 pH 7 이하, pH 6.5 이하, pH 6 이하, pH 5.5 이하, pH 5 이하, pH 4.5 이하, pH 4.0 이하, 또는 pH 3.5 이하 일 수 있고, pH 3 이상, pH 3.5 이상, pH 4.0 이상, pH 4.5 이상, pH 5.0 이상, pH 5.5 이상, pH 6.0 이상, 또는 pH 6.5 이상일 수 있다.For example, the emulsified composition may have a pH of less than 7, less than pH 6.5, less than pH 6, less than pH 5.5, less than pH 5, less than pH 4.5, less than pH 4.0, or less than pH 3.5, PH 4.0 or higher, pH 4.5 or higher, pH 5.0 or higher, pH 5.5 or higher, pH 6.0 or higher, or pH 6.5 or higher.
일예에서, 양전위를 갖는 물질의 양전위 크기는 조성물 pH에 따라 달라질 수 있으며, 예를 들어 pH가 낮아질수록 양전위가 커질 수 있다.In one example, the magnitude of the positive potential of a substance having a positive potential may vary depending on the pH of the composition, for example, the lower the pH, the larger the potential.
일 관점에서, 상기 이중 스페로이드형 고분자 양친매성 이방성 분체는 상기 2 개의 상의 계면에 존재할 수 있다. In one aspect, the bispulo-type polymeric amphipathic anisotropic powder may be present at the interfaces of the two phases.
본 실시예에서, 상기 양친매성 이방성 분체는 친수성 일방 및 소수성 타방으로 이루어진 이중 스페로이드형 고분자 양친매성 이방성 분체일 수 있다.In the present embodiment, the amphiphilic anisotropic powder may be a double-sphere type polymeric amphipathic anisotropic powder consisting of a hydrophilic one-side and a hydrophobic one.
상기 분체는 소수성 타방이 상기 친수성 일방의 내부로 부분적으로 침투하여 친수성 일방의 코어를 형성하는 구조이며, 상기 친수성 일방은 관능기를 포함할 수 있다.The powder may have a structure in which the hydrophobic other part partially penetrates into the inside of the hydrophilic one to form a hydrophilic one of the cores, and the hydrophilic one may include a functional group.
일 예에서, 상기 양친매성 이방성 분체는 친수성 일방(제1고분자 스페로이드)과 소수성 타방(제2고분자 스페로이드)을 포함하고, 상기 친수성 일방은 코어-쉘 구조를 가지며, 소수성 타방이 상기 친수성 일방의 내부로 적어도 부분적으로 침투하여 친수성 일방의 코어를 형성하는 구조이며, 상기 친수성 일방의 쉘은 관능기를 포함할 수 있다.In one example, the amphiphilic anisotropic powder includes a hydrophilic one (first polymer spoloid) and a hydrophobic other (second polymer spoloid), the hydrophilic one having a core-shell structure, the hydrophobic one having a hydrophilic one- At least partially penetrating into the inside of the hydrophilic core to form a hydrophilic one of the cores, and the hydrophilic one shell may contain a functional group.
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 분체화 되어 제2고분자 스페로이드를 형성할 수 있다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the principle of formation of an amphiphilic anisotropic powder according to an embodiment of the present invention. FIG. The core of the first polymer spolide may be formed through the shell of the first polymer spolide and may be grown to form a second polymer spoloid by the above manufacturing method.
상기 분체는 이중(二重) 스페로이드형, 즉 2개의 스페로이드가 결합된 형상을 가지는 3차원의 네프로이드(nephroid) 형상일 수 있으며, 상기 결합된 결합부를 기준으로 대칭형상, 비대칭 스노우맨(snowman) 형상 또는 비대칭 역스노우맨 형상일 수 있다. 상기 스노우맨 형상은 결합되는 서로 크기가 상이한 제1 및 제2 고분자 스페로이드가 결합된 것을 의미한다.The powder may be in the form of a double sparoid, that is, a three-dimensional nephroid having a shape in which two spheroids are combined, and a symmetrical shape, asymmetric snowman snowman-shaped or asymmetric inverse snowman shape. The shape of the snowman means that the first and second polymer spheroids having different sizes are combined.
상기 스페로이드는, 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.The spheroid may be, for example, a sphere, a globoid, or an oval shape, and may have a major axis length in microns or nanometers based on the longest length in the body cross-section. have.
일예에서, 상기 친수성 일방은 그 코어가 소수성 타방과 동일한 고분자로 이루어진 코어-쉘 구조일 수 있으며, 친수성 일방과 소수성 타방은 이중 스페로이드 중의 각각 하나의 스페로이드 형상을 이룰 수 있다. 이중 스페로이드의 양 스페로이드 간의 결합부는 친수성 일방의 코어로부터 소수성 타방으로 연속하는 구조로 이루어질 수 있다.In one embodiment, the hydrophilic one may be a core-shell structure in which the core is made of the same polymer as the hydrophobic base, and the hydrophilic one and the hydrophobic one may each take one spoloid shape of the double spoil. The binding portion between the two sphereoids of the double sphere may have a continuous structure from the hydrophilic core to the hydrophobic one.
일예에서, 상기 친수성 일방의 코어와 소수성 타방은 비닐 고분자를 포함하며, 상기 친수성 일방의 쉘은 비닐 모노머와 관능기를 함유하는 모노머의 공중합체를 포함할 수 있다.In one embodiment, the hydrophilic one-side core and the hydrophobic one include a vinyl polymer, and the hydrophilic one-side shell 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 example, the vinyl polymer may be a vinyl aromatic polymer, and may be, for example, 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 example, 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 functional group-containing monomer may be a siloxane-containing (meth) acrylate, and specifically includes 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, vinyl Triethoxysilane, vinyltrimethoxysilane, or a mixture thereof.
일예에서, 상기 친수성 일방의 쉘은 친수성 관능기가 추가적으로 도입될 수 있다.In one embodiment, the hydrophilic one-side shell may further include a hydrophilic functional group.
일예에서, 상기 친수성 관능기는 음전위 또는 양전위를 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 functional group having a negative or positive potential or a PEG (polyethylene glycol) group, and may be a carboxylic acid group, a sulfonic group, a phosphate group, an amino group, an alkoxy group, an ester group, an acetate group, a polyethylene glycol group, And a hydroxyl group.
일예에서, 상기 친수성 일방의 쉘은 당을 함유하는 관능기가 추가적으로 도입될 수 있다.In one embodiment, the hydrophilic one-side shell may further include a sugar-containing functional group.
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 functional group containing the sugar is selected from the group consisting of N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) - (3-triethoxysilylpropyl) aminoethyl} -oligo-hyaluronamide, and the like.
일예에서, 상기 양친매성 이방성 분체는 입자 크기가 100 내지 1500 nm일 수 있다. 예를 들어, 상기 양친매성 이방성 분체는 입자 크기가 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 또는 1400 nm 이상이고, 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. 예를 들어, 상기 양친매성 이방성 분체의 평균 입자 크기는 약 270 nm 일 수 있다.In one embodiment, the amphiphilic anisotropic powder may have a particle size of 100 to 1500 nm. For example, the amphiphilic anisotropic powder may have a particle size of 100 to 500 nm, or 200 to 300 nm. Specifically, the amphiphilic anisotropic powder preferably 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, 1200 nm or more, 1200 nm or more, 1300 nm or more or 1400 nm or more and 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 and 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. For example, the average particle size of the amphiphilic anisotropic powder may be about 270 nm.
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 amphiphilic anisotropic powder herein is the maximum length measured as the longest length of the powder particle. The particle size range of the amphiphilic anisotropic powder herein means that at least 95% of the amphipathic anisotropic powder present in the composition falls within this range.
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 amphiphilic anisotropic powder may be prepared by polymerizing a first monomer to prepare a core of a first polymer spoloid, coating the core of the first polymer spoloid to form a core- And preparing an amphiphilic anisotropic powder in which the second polymer spolide is formed by reacting the first polymer spolide of the core-shell structure with the first monomer.
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.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the principle of formation of an amphiphilic anisotropic powder according to an embodiment of the present invention. FIG. The core of the first polymer spolide may be formed through the shell of the first polymer spolide and may be grown to form a second polymer spoloid by the above manufacturing method.
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 is prepared by (1) stirring the first monomer and the polymerization initiator to prepare a core of the first polymer spolide; (2) stirring the prepared core of the first polymer spolide with a monomer containing a first monomer, a polymerization initiator and a functional group to prepare a first polymer spolide having a coated core-shell structure; (3) preparing an amphiphilic anisotropic powder in which the second polymer spolide is formed by stirring the first polymer spoloid of the prepared core-shell structure with the second monomer and the polymerization initiator.
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 above steps (1), (2) and (3), stirring may be rotary stirring. It is preferable to rotate and stir because chemical mechanical modification and homogeneous mechanical mixing are required for producing uniform particles. The rotational stirring may be performed in a cylindrical rotating reactor, but the rotational 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 powder formation. The size and location of the baffles in the cylindrical rotating reactor and the degree of spacing between the impeller and the baffles greatly influence the uniformity of the particles produced. It is desirable to minimize the interval between the blades of the inner wing and the impeller to equalize the convection flow and the strength thereof, and to feed the powder reaction liquid below the wing length and to maintain the impeller rotation speed at a high speed. 200 rpm, and the length to diameter ratio 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 be varied in proportion to the reaction capacity. The material of the cylindrical rotating reactor may be ceramics, glass, etc., and the temperature at the time of stirring is preferably 50 to 90 ° C.
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 rotating reactor, the simple rotation method is capable of producing uniform particles, and is a low energy method requiring less energy and maximizing the reaction efficiency, enabling mass production. The conventional tumbling method in which the reactor itself rotates requires high energy and restricts the size of the reactor since the entire reactor must be tilted at a constant angle and rotated at high speed. The amount produced due to reactor size limitations was also limited to small quantities of the order of several hundreds of milligrams to several grams, making them 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, and may be specifically vinyl monomers. The first monomer added in the step (2) is the same as the first monomer used in the step (1), and 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, a peroxide type, an azo type, or a mixture thereof. Ammonium persulfate, sodium persulfate and potassium persulfate may 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 the step (1), the first monomer and the polymerization initiator may be mixed at 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 형상 및 균일도를 현저하게 높일 수 있는 효과가 있다.In another aspect, a stabilizer may be added together with the first monomer and the polymerization initiator in the step (1) 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 first polymer spoil size adjustment in the initial stage (1), and the first polymer spoil size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator, and the stabilizer. Further, by mixing at the weight ratio within the above range, the shape and uniformity of the anisotropic powder can be remarkably increased.
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, and specifically sodium 4-vinylbenzene sulfonate may be used. Stabilizers prevent swelling of the resulting particles and provide positive or negative charge on the powder surface to electrostatically prevent interactions (bonds) during grain formation.
양친매성 이방성 분체가 200 내지 250 nm의 크기를 가질 경우, 제 1모노머, 중합 개시제 및 안정화제의 중량비가 80 내지 135 : 1 : 1 내지 5, 구체적으로 95 내지 120 : 1 : 2 내지 4인 제1 고분자 스페로이드로부터 제조될 수 있다. The weight ratio of the first monomer, the polymerization initiator and the stabilizer is 80 to 135: 1: 1 to 5, specifically 95 to 120: 1: 2 to 4, when the amphiphilic anisotropic powder has a size of 200 to 250 nm. 1 < / RTI > polymer spolide.
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. 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 in the range of 225 to 240: 1: 1 to 3, specifically 230 to 235: 1: 1 to 3 , ≪ / RTI > the first polymeric spheroids.
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. 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 ≪ / RTI >
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. The amphiphilic anisotropic powder having an asymmetric snowman shape is preferably an amorphous powder having 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 Can be prepared from polymeric sphereoids.
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.The amphiphilic anisotropic powder having an asymmetric reverse snowman shape is preferably an amphipathic powder having a weight ratio of the first monomer, the polymerization initiator and the stabilizer of 100 to 140: 1: 1 to 5, specifically 110 to 130: 1: 2 to 4 1 < / RTI > polymer spolide.
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. Specific examples thereof include 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) Methacrylate, vinyltriethoxysilane, vinyltrimethoxysilane, or a mixture thereof.
일예에서, 상기 (2)단계에서 제1 모노머, 중합 개시제 및 관능기를 함유하는 모노머는 30 내지 100 : 0.2 내지 1.0 : 1 내지 20의 중량비로 혼합할 수 있다. 다른 측면에서, 상기 제1 모노머, 중합 개시제 및 관능기를 함유하는 모노머는 150 내지 300 : 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 embodiment, 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 30 to 100: 0.2 to 1.0: 1 to 20. In another aspect, the monomer containing the first monomer, the polymerization initiator and the functional group may be mixed at a weight ratio of 150 to 300: 1: 6 to 40. The degree of coating can be controlled according to the weight ratio, and the shape of the amphipathic anisotropic powder is determined according to the degree of coating, and when the weight ratio is adjusted, the coating thickness is increased to about 10 to 30%, specifically about 20% And the coating is too thick, so that the pulverization does not proceed or the pulverization is proceeded well without the problem that the pulverization is too thin. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.
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.According to the above step (3), a part of the core of the first polymer spolide is protruded from the one side of the first polymer spolide of the core-shell structure through the shell and the protrusions are grown by the polymer of the second monomer, Can be formed.
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.For 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 may be present in an amount of from 160 to 250: 1, or from 170 to 250: 1, or from 180 to 250: 1, or from 190 to 250: 1, or from 200 to 250: : 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, the second monomer, the polymerization initiator and the stabilizer may be mixed in a weight ratio of 150: 250: 1: 0.001 to 5 by adding the second monomer and the polymerization initiator together with the stabilizer in the step (3). Specific types of stabilizers are as described above. By mixing at a weight ratio within the above range, uniformity of the anisotropic powder can be enhanced.
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 embodiment, in the step (3), the second monomer content may be 40 to 300 parts by weight when the weight of the first polymer spoil 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 first polymer spoil weight of the core-shell structure is 100 parts by weight, the asymmetric snowman type powder is obtained, and 100 to 150 parts by weight, or 110 to 150 parts by weight, When the weight is in the range of 150 to 300 parts by weight or in the range of 160 to 300 parts by weight, an asymmetric reverse snowman type powder is obtained. In addition, by mixing at the weight ratio within the above range, there is an effect that the uniformity of the anisotropic powder can be increased.
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, in the production of an amphiphilic anisotropic powder according to an embodiment of the present invention, the step (3) may further include the step of (4) introducing a hydrophilic functional group into the produced anisotropic powder have.
일예에서, 상기 (4)단계에서 친수성 관능기는 이에 제한하는 것은 아니나, 실란 커플링제와 반응 조절제를 이용하여 도입할 수 있다.In one embodiment, the hydrophilic functional group in step (4) is not limited thereto, but may be introduced using a silane coupling agent and a reaction control agent.
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 selected from the group consisting of (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) (Trimethoxysilyl) propyl] urea and 3 - [(trimethoxysilyl) propyloxy] -1,2 (trimethylsilyl) Propanediol, and specifically may be at least one selected from the group consisting of 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.For example, the silane coupling agent may be added 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 the step (3). Within this range, hydrophilization can be appropriately performed.
일예에서, 상기 반응 조절제는 암모늄 하이드록사이드일 수 있다.In one example, 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.For example, the reaction modifier may be added in an amount of 85 to 115 parts by weight, for example, 90 to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3). Within this range, hydrophilization can be appropriately performed.
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, in the production of the amphiphilic anisotropic powder according to one embodiment of the present invention, the step (3) is followed by (4) a step of introducing a sugar-containing functional group into the produced anisotropic powder .
상기 (4)단계에서 당을 포함하는 관능기는 이에 제한하는 것은 아니나, 당 함유 실란커플링제와 반응 조절제를 이용하여 도입할 수 있다.In the step (4), the functional group containing sugar is not limited thereto, but may be introduced using a sugar-containing silane coupling agent and a reaction control agent.
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 selected from the group consisting of N- {N- (3-triethoxysilylpropyl) aminoethyl} gluconamide, N- (3-triethoxysilylpropyl) 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.For example, the reaction modifier may be added in an amount of 85 to 115 parts by weight, for example, 90 to 110 parts by weight based on 100 parts by weight of the anisotropic powder prepared in the step (3). The introduction of a sugar-containing functional group within the above range can be suitably performed.
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.The preparation of the amphiphilic anisotropic powder according to the above method does not use a cross-linking agent, so there is no production entanglement. Thus, the yield is high and uniform, and mass production is easier than the tumbling method using a simple agitation method. In particular, there is an advantage that a nano size of 300 nm or less can be mass-produced in a unit of tens g to several tens of kg.
일 실시예에서, 상기 유화 입자의 크기는 평균 입경 1㎛ 내지 100 ㎛, 예를 들어 10㎛ 내지 30㎛ 일 수 있다. 구체적으로, 평균 입경 1 ㎛ 이상, 2 ㎛ 이상, 3 ㎛ 이상, 4 ㎛ 이상, 5 ㎛ 이상, 6 ㎛ 이상, 7 ㎛ 이상, 8 ㎛ 이상, 9 ㎛ 이상, 10 ㎛ 이상, 11 ㎛ 이상, 12 ㎛ 이상, 13 ㎛ 이상, 14 ㎛ 이상, 15 ㎛ 이상, 16 ㎛ 이상, 17 ㎛ 이상, 18 ㎛ 이상, 19 ㎛ 이상, 20 ㎛ 이상, 21 ㎛ 이상, 22 ㎛ 이상, 23 ㎛ 이상, 24 ㎛ 이상, 25 ㎛ 이상, 26 ㎛ 이상, 27 ㎛ 이상, 28 ㎛ 이상, 29 ㎛ 이상, 30 ㎛ 이상, 35 ㎛ 이상, 40 ㎛ 이상, 45 ㎛ 이상, 50 ㎛ 이상, 55 ㎛ 이상, 60 ㎛ 이상, 65 ㎛ 이상, 70 ㎛ 이상, 75 ㎛ 이상, 80 ㎛ 이상, 85 ㎛ 이상, 90 ㎛ 이상, 또는 95 ㎛ 이상일 수 있고, 평균 입경 100 ㎛ 이하, 95 ㎛ 이하, 90 ㎛ 이하, 85 ㎛ 이하, 80 ㎛ 이하, 75 ㎛ 이하, 70 ㎛ 이하, 65 ㎛ 이하, 60 ㎛ 이하, 55 ㎛ 이하, 50 ㎛ 이하, 45 ㎛ 이하, 40 ㎛ 이하, 35 ㎛ 이하, 30 ㎛ 이하, 29 ㎛ 이하, 28 ㎛ 이하, 27 ㎛ 이하, 26 ㎛ 이하, 25 ㎛ 이하, 24 ㎛ 이하, 23 ㎛ 이하, 22 ㎛ 이하, 21 ㎛ 이하, 20 ㎛ 이하, 19 ㎛ 이하, 18 ㎛ 이하, 17 ㎛ 이하, 16 ㎛ 이하, 15 ㎛ 이하, 14 ㎛ 이하, 13 ㎛ 이하, 12 ㎛ 이하, 11 ㎛ 이하, 10 ㎛ 이하, 9 ㎛ 이하, 8 ㎛ 이하, 7 ㎛ 이하, 6 ㎛ 이하, 5 ㎛ 이하, 4 ㎛ 이하, 3 ㎛ 이하, 2 ㎛ 이하일 수 있다.In one embodiment, the size of the emulsified particles may be from 1 μm to 100 μm in average particle size, for example from 10 μm to 30 μm. Specifically, it is preferable that the average particle diameter is 1 占 퐉 or more, 2 占 퐉 or more, 3 占 퐉 or more, 4 占 퐉 or more, 5 占 퐉 or more, 6 占 퐉 or more, 7 占 퐉 or more, 8 占 퐉 or more, At least 15 탆, at least 16 탆, at least 17 탆, at least 18 탆, at least 19 탆, at least 20 탆, at least 21 탆, at least 22 탆, at least 23 탆, at least 24 탆 At least 25 탆, at least 26 탆, at least 27 탆, at least 28 탆, at least 29 탆, at least 30 탆, at least 35 탆, at least 40 탆, at least 45 탆, at least 50 탆, at least 55 탆, The average particle diameter may be 100 占 퐉 or less, 95 占 퐉 or less, 90 占 퐉 or less, 85 占 퐉 or less, 80 占 퐉 or less, 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 29 μm or less, 28 μm or less, or less than or equal to 30 μm, less than or equal to 75 μm, less than or equal to 70 μm, less than or equal to 65 μm, 27 탆 or less, 26 탆 or less, 25 탆 Not more than 24 μm, not more than 23 μm, not more than 22 μm, not more than 21 μm, not more than 20 μm, not more than 19 μm, not more than 18 μm, not more than 17 μm, not more than 16 μm, not more than 15 μm, not more than 14 μm, Or less, 11 μm or less, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less and 2 μm or less.
본 명세서에서 상기 유화 입자의 평균 입경은 단일 입자의 지름의 평균값을 의미한다. 상기 거대 유화 입자 상태에서는 유화 입자의 입경이 균일하지 않으며, 0.1㎛ 에서 2000㎛의 넓은 범위의 입경의 유화 입자가 공존한다. 상기 거대 유화 입자의 평균 입경은 예를 들어 20㎛일 수 있다.In the present specification, the average particle diameter of the emulsified particles means an average value of the diameter of a single particle. In the state of the large emulsion particle, the particle diameter of the emulsion particle is not uniform, and the emulsion particle having a particle diameter in the wide range of 0.1 to 2000 μm coexists. The mean particle diameter of the macro emulsion particles may be, for example, 20 mu m.
일 예에서, 상기 조성물은 상기 양친매성 이방성 분체를 조성물 총 중량에 대하여 0.01 내지 10 중량%로 포함할 수 있으며, 바람직하게 0.1 내지 1 중량%로 포함할 수 있다. 구체적으로, 0.01 중량% 이상, 0.1 중량% 이상, 0.2 중량% 이상, 0.3 중량% 이상, 0.4 중량% 이상, 0.5 중량% 이상, 0.6 중량% 이상, 0.7 중량% 이상, 0.8 중량% 이상, 0.9 중량% 이상, 또는 1.0 중량% 이상일 수 있고, 10 중량% 이하, 9 중량% 이하, 8 중량% 이하, 7 중량% 이하, 6 중량% 이하, 5 중량% 이하, 4 중량% 이하, 또는 3 중량% 이하, 2 중량% 이하, 또는 1 중량% 이하로 포함할 수 있다. 예를 들어 상기 조성물은 상기 양친매성 이방성 분체를 조성물 총 중량에 대하여 0.1% 내지 20중량%, 예를 들어 0.1% 내지 1%로 포함할 수 있으며, 일 실시예에서 0.5 중량%로 포함할 수 있다. 상기 범위 내에서 안정한 유화 입자 형성이 가능하며, 적절한 크기의 유화 입자를 형성할 수 있다.In one example, the composition may comprise the amphiphilic anisotropic powder in an amount of 0.01 to 10% by weight, preferably 0.1 to 1% by weight, based on the total weight of the composition. More specifically, it is preferable that the content of the inorganic filler is 0.01 wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% %, Up to 9 wt.%, Up to 8 wt.%, Up to 7 wt.%, Up to 6 wt.%, Up to 5 wt.%, Up to 4 wt.%, Or up to 3 wt.%, Or less, 2 wt% or less, or 1 wt% or less. For example, the composition may comprise the amphiphilic anisotropic powder in an amount of 0.1% to 20% by weight, for example, 0.1% to 1%, and in one embodiment 0.5% by weight based on the total weight of the composition . Stable emulsion particles can be formed within the above range, and emulsion particles having an appropriate size can be formed.
일 관점에 있어서, 상기 양전위를 갖는 물질 : 양친매성 이방성 분체 : 음전위를 갖는 물질의 비율은 100 : 1-20 : 1-10의 중량비로 포함될 수 있다. 구체적으로, 상기 중량 비율은 100 : 1.5-18 : 1.2-9, 100 : 2-16 : 1.4-8, 100 : 2.5-14 : 1.6-7, 100 : 3-12 : 1.8-6, 100 : 3.5-10 : 2-5, 100 : 4-8 : 2.2-4, 또는 100 : 4.5-6 : 2.4-4 일 수 있고, 또한 상기 중량 비율은 100 : 1.5-20 : 1-9, 100 : 2-20 : 1-8, 100 : 2.5-20 : 1-7, 100 : 3-20 : 1-7, 100 : 3.5-20 : 1-6, 100 : 4-20 : 1-5, 또는 100 : 4.5-20 : 1-4 일 수 있고, 또한 상기 중량 비율은 100 : 1-18 : 2-10, 100 : 1-16 : 3-10, 100 : 1-14 : 4-10, 100 : 1-12 : 5-10, 100 : 1-10 : 6-10, 100 : 1-8 : 7-10 일 수 있다.In one aspect, the ratio of the substance having the positive potential to the substance having the negative potential: amphiphilic anisotropic powder: can be included in a weight ratio of 100: 1 to 20: 1-10. Specifically, the weight ratio is 100: 1.5-18: 1.2-9, 100: 2-16: 1.4-8, 100: 2.5-14: 1.6-7, 100: 3-12: 1.8-6, 100: 3.5 -10: 2-5, 100: 4-8: 2.2-4, or 100: 4.5-6: 2.4-4 and the weight ratio is 100: 1.5-20: 1-9, 100: 20: 1-8, 100: 2.5-20: 1-7, 100: 3-20: 1-7, 100: 3.5-20: 1-6, 100: 4-20: 1-5, or 100: 4.5 -20: 1-4, and the weight ratio is 100: 1-18: 2-10, 100: 1-16: 3-10, 100: 1-14: 4-10, 100: 1-12 : 5-10, 100: 1-10: 6-10, 100: 1-8: 7-10.
일 관점에 있어서, 상기 유화 조성물은 pH 조절제를 포함할 수 있다.In one aspect, the emulsifying composition may comprise a pH adjusting agent.
일 관점에 있어서, 상기 유화 조성물의 수상은 산(acid)을 더 포함할 수 있다.In one aspect, the water phase of the emulsified composition may further comprise an acid.
구체적으로, 상기 산은 화장품 류에 사용되는 산 류라면 모두 포함될 수 있다. 예를 들어 상기 산은 젖산(lactic acid), 글리콜산(glycolic acid), 에틸 아스코르브산(ethyl ascorbic acid), 아스코르브산(ascorbic acid), 및 글루탐산(glutamic acid)로 구성되는 군에서 선택되는 하나 이상의 것일 수 있으나, 여기에 한정되는 것은 아니다.Specifically, the acid may be included in any acid used in cosmetics. For example, the acid may be one or more selected from the group consisting of lactic acid, glycolic acid, ethyl ascorbic acid, ascorbic acid, and glutamic acid. But is not limited thereto.
본 발명의 일 관점에서, 상기 조성물의 점도는 100-100,000 cps일 수 있으며, 예를 들어 상기 조성물의 점도는 2,000-15,000 cps일 수 있다. 본 실시예에 따른 조성물은 별도의 점증을 통한 안정화를 요하지 않기 때문에, 점도에 구애받지 않고 넓은 범위의 점도를 갖는 조성물을 제공할 수 있다. In one aspect of the present invention, the viscosity of the composition may be 100-100,000 cps, for example, the viscosity of the composition may be 2,000-15,000 cps. Since the composition according to this embodiment does not require stabilization through an incremental increase, it is possible to provide a composition having a wide range of viscosity regardless of viscosity.
상기 조성물의 점도는 점도측정기(BROOKFIELD Viscometer)를 이용하여 측정될 수 있다.The viscosity of the composition can be measured using a BROOKFIELD Viscometer.
일 실시예에서, 상기 조성물의 점도는 양전위를 갖는 물질의 함량 또는 음전위를 갖는 물질의 함량에 의하여 조절될 수 있으며, 예컨대 상기 조성물은 15000 cps 이상의 점도를 가질 수 있다.In one embodiment, the viscosity of the composition may be controlled by the content of a substance having a positive potential or the content of a substance having a negative potential, for example the composition may have a viscosity of at least 15000 cps.
예를 들어 상기 조성물은 점도가 예를 들어, 200 cps 이상, 300 cps 이상, 400 cps 이상, 500 cps 이상, 600 cps 이상, 700 cps 이상, 800 cps 이상, 900 cps 이상, 1000 cps 이상, 1100 cps 이상, 1200 cps 이상, 1300 cps 이상, 1400 cps 이상, 1500 cps 이상, 1600 cps 이상, 1700 cps 이상, 1800 cps 이상, 1900 cps 이상, 2000 cps 이상, 2100 cps 이상, 2200 cps 이상, 2300 cps 이상, 2400 cps 이상, 2500 cps 이상, 2600 cps 이상, 2700 cps 이상, 2800 cps 이상, 2900 cps 이상, 3000 cps 이상, 3100 cps 이상, 3200 cps 이상, 3300 cps 이상, 3400 cps 이상, 3500 cps 이상, 3600 cps 이상, 3700 cps 이상, 3800 cps 이상, 3900 cps 이상, 4000 cps 이상, 4100 cps 이상, 4200 cps 이상, 4300 cps 이상, 4400 cps 이상, 4500 cps 이상, 4600 cps 이상, 4700 cps 이상, 4800 cps 이상, 4900 cps 이상, 5000 cps 이상, 5100 cps 이상, 5200 cps 이상, 5300 cps 이상, 5400 cps 이상, 5500 cps 이상, 6000 cps 이상, 7000 cps 이상, 8000 cps 이상, 9000 cps 이상, 10000 cps 이상, 11000 cps 이상, 12000 cps 이상, 13000 cps 이상, 14000 cps 이상, 15000 cps 이상, 16000 cps 이상, 17000 cps 이상, 20000 cps 이상, 30000 cps 이상, 40000 cps 이상, 50000 cps 이상, 60000 cps 이상, 70000 cps 이상, 80000 cps 이상, 90000 cps 이상, 또는 100000 cps 이상일 수 있고, 100000 cps 이하, 90000 cps 이하, 80000 cps 이하, 70000 cps 이하, 60000 cps 이하, 50000 cps 이하, 40000 cps 이하, 30000 cps 이하, 20000 cps 이하, 17000 cps 이하, 16000 cps 이하, 15000 cps 이하, 14000 cps 이하, 13000 cps 이하, 12000 cps 이하, 11000 cps 이하, 10000 cps 이하, 9000 cps 이하, 8000 cps 이하, 7000 cps 이하, 6000 cps 이하, 5000 cps 이하, 4900 cps 이하, 4800 cps 이하, 4700 cps 이하, 4600 cps 이하, 4500 cps 이하, 4400 cps 이하, 4300 cps 이하, 4200 cps 이하, 4100 cps 이하, 4000 cps 이하, 3900 cps 이하, 3800 cps 이하, 3700 cps 이하, 3600 cps 이하, 3500 cps 이하, 3400 cps 이하, 3300 cps 이하, 3200 cps 이하, 3100 cps 이하, 3000 cps 이하, 2900 cps 이하, 2800 cps 이하, 2700 cps 이하, 2600 cps 이하, 2500 cps 이하, 2400 cps 이하, 2300 cps 이하, 2200 cps 이하, 2100 cps 이하, 2000 cps 이하, 1900 cps 이하, 1800 cps 이하, 1700 cps 이하, 1600 cps 이하, 1500 cps 이하, 1400 cps 이하, 1300 cps 이하, 1200 cps 이하, 1100 cps 이하, 1000 cps 이하, 900 cps 이하, 800 cps 이하, 700 cps 이하, 600 cps 이하, 500 cps 이하, 400 cps 이하, 300 cps 이하, 또는 200 cps 이하일 수 있다. 상기 조성물은 100-100,000 cps의 점도에서 우수한 유화 안정성을 가질 수 있으며, 특히 상기 조성물은 2000 내지 15000 cps의 저점도, 예를 들어 3000 내지 10000 cps의 저점도에서도 경시 안정성을 가질 수 있다.For example, the composition may have a viscosity of, for example, greater than 200 cps, greater than 300 cps, greater than 400 cps, greater than 500 cps, greater than 600 cps, greater than 700 cps, greater than 800 cps, greater than 900 cps, greater than 1000 cps, At least 1200 cps, at least 1300 cps, at least 1400 cps, at least 1500 cps, at least 1600 cps, at least 1700 cps, at least 1800 cps, at least 1900 cps, at least 2000 cps, at least 2100 cps, at least 2200 cps, at least 2300 cps, More than 2400 cps, greater than 2500 cps, greater than 2600 cps, greater than 2700 cps, greater than 2800 cps, greater than 2900 cps, greater than 3000 cps, greater than 3100 cps, greater than 3200 cps, greater than 3300 cps, greater than 3400 cps, greater than 3500 cps More than 3700 cps, greater than 3800 cps, greater than 3900 cps, greater than 4000 cps, greater than 4100 cps, greater than 4200 cps, greater than 4300 cps, greater than 4400 cps, greater than 4500 cps, greater than 4600 cps, greater than 4700 cps, greater than 4800 cps, More than 4900 cps, more than 5000 cps, more than 5100 cps, more than 5200 cps, more than 5300 cps, more than 5400 cps, more than 5500 cps, more than 6000 cps, 7000 cps More than 8000 cps, more than 9000 cps, more than 10,000 cps, more than 11000 cps, more than 12000 cps, more than 13000 cps, more than 14000 cps, more than 15000 cps, more than 16000 cps, more than 17000 cps, more than 20000 cps, more than 30000 cps cpm or more, 50000 cps or more, 60000 cps or more, 70000 cps or more, 80000 cps or more, 90000 cps or 100000 cps or less, 100000 cps or less, 90000 cps or less, 80000 cps or less, 70000 cps or less, No more than 10,000 cps, no more than 10,000 cps, no more than 10,000 cps, no more than 10,000 cps, no more than 50000 cps, no more than 40,000 cps, no more than 30000 cps, no more than 20,000 cps, no more than 17,000 cps, no more than 16,000 cps, no more than 15,000 cps, no more than 14,000 cps, Less than 8000 cps, less than 7000 cps, less than 6000 cps, less than 5000 cps, less than 4900 cps, less than 4800 cps, less than 4700 cps, less than 4600 cps, less than 4500 cps, less than 4400 cps, less than 4300 cps, less than 4200 cps, 4100 cps or less, 4000 cps or less, 3900 cps or less, 3800 cps or less, 3700 cps or less, 3600 cps or less, 3500 cps or less, 3400 cps or less, 3300 cps or less, 3200 cps or less, 3100 cps or less, 3000 cps or less, 2900 cps or less, 2800 cps or less, 2700 cps or less, 2600 cps or less, 2500 cps or less, 2400 cps or less, 2300 cps or less Less than 2200 cps, less than 2100 cps, less than 2000 cps, less than 1900 cps, less than 1800 cps, less than 1700 cps, less than 1600 cps, less than 1500 cps, less than 1400 cps, less than 1300 cps, less than 1200 cps, less than 1100 cps cps or less, 900 cps or less, 800 cps or less, 700 cps or less, 600 cps or less, 500 cps or less, 400 cps or less, 300 cps or less, or 200 cps or less. The composition may have excellent emulsion stability at a viscosity of 100-100,000 cps, and in particular, the composition may have a low viscosity at a low viscosity of 2000-15000 cps, for example at a low viscosity of 3000-10000 cps.
일 구체예에서 상기 조성물은 유화를 위한 계면활성제를 더 포함할 수 있다. 상기 계면활성제로는 기술 분야에서 통상적으로 사용하는 것이라면 제한 없이 사용할 수 있으며, 예를 들어 라우릴 PEG-9 폴리디메틸실록시에틸디메티콘(Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone), 시클로펜타실록산*PEG-10디메티콘*디스테아르디모늄헥토라이트(Cyclopentasiloxane*PEG-10 Dimethicone* Disteardimonium Hectorite), 세틸PEG.PPG-10/1디메티콘(세틸디메티콘 코폴리올; Cetyl PEG.PPG-10/1 Dimethicone(Cetyl Dimethicone Copolyol)) 등의 W/O 유화를 위해 사용되는 계면활성제, 아라키딜알코올/베헤닐알코올/아라키딜글루코사이드(ARACHIDYL ALCOHOL/BEHENYL ALCOHOL/ARACHIDYL GLUCOSIDE), 세테아릴알코올*세테아릴글루코사이드(CETEARYL ALCOHOL*CETEARYL GLUCOSIDE), C14-22알코올*C12-20알킬글루코사이드(C14-22 ALCOHOLS*C12-20 ALKYL GLUCOSIDE), 글리세릴스테아레이트*PEG-100스테아레이트(Glyceryl Stearate*PEG-100 Stearate) 등 O/W 유화를 위해 사용되는 계면활성제 등을 사용할 수 있으나 이에 제한되지 않는다. 상기 계면활성제는 조성물 총 중량에 대하여 0 내지 20중량%, 0 내지 10 중량%, 또는 0 내지 5 중량%로 포함될 수 있다. 본 실시예에서는 계면활성제를 소량으로 함유하면서도 유화 제형의 안정화가 가능하다.In one embodiment, the composition may further comprise a surfactant for emulsification. Examples of the surfactant include lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cyclopentasiloxane * PEG-10, and the like. Examples of the surfactant include, but are not limited to, Dimethicone * Distearimonium Hectorite, Cetyl PEG.PPG-10/1 Dimethicone (Cetyl Dimethicone Copolyol; Cetyl PEG.PPG-10/1 Dimethicone (Cetyl Dimethicone * Copolyol, etc.), arachidyl alcohol / behenyl alcohol / arachidyl glucoside (ARACHIDYL ALCOHOL / BEHENYL ALCOHOL / ARACHIDYL GLUCOSIDE), cetearyl alcohol * CETEARYL ALCOHOL * CETEARYL GLUCOSIDE), C14-22 alcohol * C12-20 alkyl glucoside (C14-22 ALCOHOLS * C12-20 ALKYL GLUCOSIDE), glyceryl stearate * PEG-100 stearate (Glyceryl Stearate * PEG- W You The like of a surfactant used, but is not limited thereto. The surfactant may be included in an amount of 0 to 20% by weight, 0 to 10% by weight, or 0 to 5% by weight based on the total weight of the composition. In this embodiment, it is possible to stabilize the emulsified formulation while containing a small amount of surfactant.
본 발명 실시예들에 따른 조성물은 화장료 조성물일 수 있다. 상기 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.The composition according to embodiments of the present invention may be a cosmetic composition. The cosmetic composition may be formulated containing a cosmetically or dermatologically acceptable medium or base. It may be in the form of a suspension, a microemulsion, a microcapsule, a microgranule or an ionic (liposome) and a non-ionic follicular dispersion, or a cream, a skin, a lotion, a powder, an ointment, a spray, May be provided in the form of a stick. It can also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions may 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 embodiments of the present invention may be in the form of powders, fatty substances, organic solvents, solubilizers, thickeners, gelling agents, softeners, antioxidants, suspending agents, stabilizers, foaming agents, , Water, ionic or nonionic emulsifiers, fillers, sequestering agents, chelating agents, preservatives, vitamins, barrier agents, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics And any other ingredients used, such as cosmetics or adjuvants commonly used in the field of dermatology. Such adjuvants are introduced in amounts commonly used in the cosmetics or dermatological fields. 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. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
하기 표 1의 조성에 따라 제조예 1-1 내지 1-4를 제조하였다. 구체적인 방법은 아래에 분술한다Production Examples 1-1 to 1-4 were prepared according to the composition shown in Table 1 below. Specific methods are described below.
하기 제조예에서 사용한 성분은 아래와 같다.The components used in the following Production Examples are as follows.
PS(1L 진탕형 반응조)PS (1L shaking reaction tank) CSCS DBDB
WaterWater 300300 PSPS 300300 CSCS 240240
MeOHMeOH 4040 WaterWater 250250 WaterWater 350350
StyreneStyrene 5050 TMSPATMSPA 66 AIBNAIBN 0.20.2
KPSKPS 0.50.5 StyreneStyrene 5050 StyreneStyrene 4040
SVBSSVBS 1.01.0 AIBNAIBN 0.20.2 SVBSSVBS 0.350.35
MeOH: Methanol 공용매(cosolvent)KPS: Potassium persulfate (개시제)MeOH: Methanol cosolvent KPS: Potassium persulfate (initiator)
SVBS: Sodium vinyl benzene sulfonate (안정화제)SVBS: Sodium vinyl benzene sulfonate (stabilizer)
PS: Polystyrene (고분자비드)PS: Polystyrene (polymer bead)
CS: 코어-쉘 구조의 코팅된 제1고분자 스페로이드CS: Coated first polymeric spheroid with core-shell structure
DB: 양친매성 이방성 분체 DB: Amphipathic anisotropic powder
TMSPA: Trimethoxysilyl propylacrylate (관능기)TMSPA: Trimethoxysilyl propylacrylate (functional group)
AIBN : Azobisisobutyronitrile (중합 개시제)AIBN: Azobisisobutyronitrile (polymerization initiator)
[제조예 1] 양친매성 이방성 분체 제조[Preparation Example 1] Preparation of an amphipathic anisotropic powder
제조예 1-1. 폴리스티렌(Polystyrene, PS) 제1 고분자 스페로이드 제조Production Example 1-1. Manufacture of Polystyrene (PS) First Polymer Spheroid
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 a water bath at 75 DEG C For 8 hours. The reaction was stirred in a cylindrical rotating reactor. The cylindrical rotating reactor was 11 cm in diameter, 17 cm in height, made of glass, and rotated at a speed of 200 rpm.
제조예 1-2. 코어-쉘(Core-Shell, CS) 구조의 코팅된 제1 고분자 스페로이드 제조Production Example 1-2. Preparation of Coated First Polymer Spheroid with 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.(Styrene), 6 g of TMSPA (3- (trimethoxysilyl) propylacrylate) as a monomer, and 0.2 g of azobisisobutyronitrile (AIBN) as a polymerization initiator were added to 300 g of the obtained first polymeric spolide of polystyrene ) Were mixed and reacted at 75 DEG C for 8 hours. The reaction was stirred in a cylindrical rotating reactor.
제조예 1-3. 양친매성 이방성 분체 (DB) 제조Production Example 1-3. Production of amphiphilic anisotropic powder (DB)
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 평균 입자 크기 235 ㎛의 양친매성 이방성 분체를 제조하였다.40 g of styrene as a monomer, 0.35 g of sodium 4-vinylbenzenesulfonate as a stabilizer, and 0.35 g of azobisisobutyronitrile as a polymerization initiator were added to 240 g of the polystyrene core shell (PS-CS) water dispersion solution obtained as a result of the reaction, And 0.2 g of azobisisobutyronitrile (AIBN) were mixed and heated at 75 캜 for 8 hours. The reaction was stirred in a cylindrical rotating reactor to produce an amphiphilic anisotropic powder having an average particle size of 235 탆.
제조예 1-4. 친수화된 양친매성 이방성 분체 제조Production Example 1-4. Preparation of Hydrophilic Amphiphilic Anisotropic Powder
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 as a silane coupling agent and 30 g of N- [3- (trimethoxysilyl) propyl] ethylenediamine were added to 600 g of the aqueous dispersion solution of the obtained anisotropic powder, (Ammmonium hydroxide) were mixed and reacted at 25 DEG C for 24 hours to introduce a hydrophilic functional group. The reaction was stirred in a cylindrical rotating reactor to prepare a hydrophilized amphipathic anisotropic powder.
[실험예 1] 에몰리언트의 수상 pH에 따른 변화 확인[Experimental Example 1] Confirmation of emollient change according to aqueous pH
본 발명의 유화 조성물의 수상 pH에 따른 양전위를 갖는 물질(에몰리언트)의 물성 변화를 확인하였으며, pH에 영향을 미치는 산의 종류에 따른 영향을 확인하고자 한다.The emulsion composition of the present invention was examined for changes in the physical properties of a substance having a positive potential (emollient) depending on the pH of the aqueous phase, and the effect of the type of acid affecting the pH was examined.
상기 양전위를 갖는 물질(에몰리언트)는 상표명 AMITER MA-HD인 헥실데실미리스토일메틸아미노프로피오네이트(HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE)을 니혼 에멀젼 사(社)에서 구입하여 사용하였으며, 유상부로서 자근초(Lithospermi Radix) 추출물 및 상기 헥실데실미리스토일메틸아미노프로피오네이트를 사용하였으며, 수상부로는 물, 글리콜산(glycolic acid), 및 에틸 아스코르브산(ethyl ascorbic acid)을 사용하였다. 자근초 추출물은 붉은색을 띠는 유용성 물질로 막형성 및 유화 형성 확인을 시각적으로 용이하게 하기 위해 사용되었다. 다른 유용성 색소로 변경하여 사용하여도 제형 형성에는 영향이 없다. 층분리가 일어날 경우 선명한 붉은색으로 수상 층이 확인되며, 유화가 일어날 경우 연한 분홍색으로 보이게 된다.The substance having a positive potential (Emollient) was purchased from Nippon Emulsion Co., Ltd., and HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE, which is a trade name AMITER MA-HD, was used, Lithospermi Radix ) extract And hexyldecyl myristoyl methylaminopropionate were used. Water, glycolic acid, and ethyl ascorbic acid were used as the water phase. Extracts of B. pertussis were used as a reddish oil-soluble material to facilitate visual confirmation of film formation and emulsification. There is no influence on the formation of the formulations even when the pigment is changed to another oil-soluble dye. When the layer separation occurs, the red layer is identified with a bright red color, and when the emulsification occurs, it appears to be light pink.
실험은 수상부에 각 산 원료를 표 2와 같이 투입하여 해당 pH로 적정하여 준비하였고, 유상부와 수상부를 핸드믹싱 하였다.In the experiment, each raw material of acid was put into the water as shown in Table 2, prepared by titrating to the corresponding pH, and the oil phase and the water phase were hand-mixed.
성분ingredient 참조예 1Reference Example 1 참조예 2Reference Example 2 참조예 3Reference Example 3 참조예 4Reference Example 4
HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATEHEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE 1010 1010 3030 3030
자근초 추출물Acanthopteran extract 1One 1One 1One 1One
water to 100to 100 to 100to 100 to 100to 100 to 100to 100
Glycolic acid Glycolic acid 00 pH 3 적정 pH 3 titration 00 00
Ethyl ascorbic acidEthyl ascorbic acid 00 00 00 pH 4 적정 pH 4 titration
현상phenomenon 층분리Layer separation 유화oil paint 층분리Layer separation 유화oil paint
그 결과는 도 2를 참조하여 확인할 수 있다. 구체적으로, 물과 양전위를 갖는 물질만 존재하는 경우에는 일반적인 양전위를 갖는 물질의 거동으로 층 분리가 이루어지지만(참조예 1 및 3, 도 2의 ① 및 ③), 산이 들어가게 되면서, 산-염기 반응을 통하여 양전위를 갖는 물질의 3차 아민 부분이 양전위를 갖게 되고, 계면활성제의 역할을 함을 확인할 수 있었다(참조예 2 및 4, 도 2의 ② 및 ④). 또한, 산의 종류에 따른 영향은 없는 것을 확인할 수 있었다.The results can be confirmed with reference to Fig. Specifically, when only a substance having water and a positive potential exists, the layer separation is performed by the behavior of a substance having a general positive potential (Referential Examples 1 and 3, (1) and (3) in FIG. 2) It was confirmed that the tertiary amine moiety of the substance having a positive electric potential has a positive electric potential through the base reaction and serves as a surfactant (Reference Examples 2 and 4, (2) and (4) in FIG. 2). Further, it was confirmed that there was no influence depending on the type of acid.
[실험예 2] pH에 따른 양전위를 갖는 물질과 점증제의 박막 형성 차이 확인[Experimental Example 2] Determination of thin film formation of a thickener and a substance having a positive electric potential according to pH
본 발명의 에멀젼에서 pH에 따른 양전위를 갖는 물질과 음전위를 갖는 물질의 박막층의 형성 정도의 차이를 확인 하고자 한다.In order to confirm the difference in the degree of formation of the thin film layer of the substance having positive electric potential and the substance having negative electric potential according to pH in the emulsion of the present invention.
음전위를 갖는 물질로서 카보머 0.1 중량%를 수상에 투입 하였다. 표 3에서 볼 수 있듯이, 각 참조예에서 pH 3, 4, 5, 및 6이 되도록 트로메타민(tromethamine)을 중화제로 하여 중화시켰다. 중화시킨 이후 헥실데실미리스토일메틸아미노프로피오네이트를 믹싱되지 않게 서서히 부어 표면에 생기는 박막층을 관찰하였다.0.1 wt% of carbomer as a substance having a negative potential was added to the aqueous phase. As shown in Table 3, tromethamine was neutralized with neutralizing agent to pH 3, 4, 5, and 6 in each reference example. After neutralization, hexyldecyl myristoyl methyl aminopropionate was slowly poured without mixing to observe the thin film layer on the surface.
성분(중량%)Component (% by weight) 참조예 5Reference Example 5 참조예 6Reference Example 6 참조예 7Reference Example 7 참조예 8Reference Example 8
HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATEHEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE 1010 1010 1010 1010
water to 100to 100 to 100to 100 to 100to 100 to 100to 100
카보머(carbomer)Carbomer 0.10.1 0.10.1 0.10.1 0.10.1
트로메타민(tromethamine)Tromethamine pH 적정하여 목표 pH 도달 확인Verify the target pH reached by titrating pH
pHpH 33 44 55 66
현상phenomenon 백색 막 형성White film formation 백색 막 형성White film formation 반투명 막 형성Semi-transparent film formation 투명막 형성Transparent film formation
그 결과는 도 3을 참조하여 확인할 수 있다. 구체적으로, 동일한 양전위를 갖는 물질을 사용하더라도, pH 수준에 따라서 양전위를 갖는 물질의 양전위가 달라진다. 음전위를 갖는 카보머와 결합할 수 있는 카운터-양전위화 된 양전위를 갖는 물질의 양전위가 pH가 낮아짐에 따라 증가하는 양상을 띄었고, 이에 따라 전하간 상호작용에 따른 박막층의 형성 정도의 차이가 발생한 것을 확인할 수 있었다. pH 6에서는 투명한 얇은 박막이 형성되는 것을 확인할 수 있었고(참조예 8), 이로부터 pH 7이상의 제형에서는 박막층이 불안해질 것으로 예상된다.The result can be confirmed with reference to FIG. Specifically, even if a substance having the same positive potential is used, the positive potential of the substance having a positive potential differs depending on the pH level. Positive potentials of counter-positively charged positive potentials, which can bind to carbomers with negative potential, increase with decreasing pH, and thus the difference in the degree of formation of the thin film layer due to charge interactions . It was confirmed that a transparent thin film was formed at pH 6 (Reference Example 8), from which it is expected that the thin film layer becomes unstable in a formulation of pH 7 or more.
[실험예 3] 유상부의 전위 유무에 따른 유화력 비교[Experimental Example 3] Comparison of emulsifying ability according to the presence or absence of dislocation in the upper part
전위를 띄지 않는 일반 오일 및 양전위를 갖는 헥실데실미리스토일메틸아미노프로피오네이트의 양친매성 이방성 분체에 대한 유화력을 비교하였다.The emulsifying powers of amphiphilic anisotropic powders of hexyldecyl myristoyl methyl aminopropionate having a dislocationless general oil and positive potential were compared.
유상부로 비교예 1은 전위를 띄지 않는 일반 오일로 스쿠알란에 자근초 추출물을 섞어서 준비하였고, 실시예 1은 pH에 따라 변화하는 양전위를 갖는 에몰리언트인 헥실데실미리스토일메틸아미노프로피오네이트에 자근초 추출물을 섞어서 준비하였다. As the oil phase, Comparative Example 1 was prepared by mixing a squalane extract with a common oil having no dislocation. In Example 1, emulsion helixdecyl myristoyl methyl aminopropionate having a positive potential varying with pH, The extracts were mixed and prepared.
상기 제조예 1-3에서 제조된 양친매성 이방성 분체를 포함하는 물을 수상부로 준비하였으며, 수상부는 별도의 pH 조정 없이 pH 5 이다. 수상부의 pH 조정 없는 양친성 이방성 분체 존재 액상(pH 5)에 유상부를 첨가하여 핸드믹싱 진행하여 관찰하였으며 조성물의 사진을 도 4에 제시한다.Water containing the amphiphilic anisotropic powder prepared in Preparation Example 1-3 was prepared as an aqueous phase, and the aqueous phase was pH 5 without any pH adjustment. The oil phase was added to the liquid phase (pH 5) of the amphiphilic anisotropic powder without pH adjustment of the water phase and observed by hand mixing. A photograph of the composition is shown in FIG.
성분ingredient 참조예 9Reference Example 9 참조예 10Reference Example 10
HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATEHEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE 1010 --
스쿠알란Squalane -- 1010
자근초 추출물Acanthopteran extract 1One 1One
water To 100To 100 To 100To 100
양친매성 이방성 분체(제조예 1-3)The amphiphilic anisotropic powder (Preparation Example 1-3) 0.50.5 0.50.5
pHpH 66 66
오일과 분체 결합을 통한 유화층 형성 여부Formation of emulsified layer through oil and powder bonding 형성formation 형성 없이 오일층으로 존재Exist as an oil layer without formation
그 결과는 도 4를 참조하여 확인할 수 있다. 구체적으로, 스쿠알란을 포함하는 참조예 10(좌측)의 경우 유화층이 형성되지 않고 오일층으로 존재하는 반면, 헥실데실미리스토일메틸아미노프로피오네이트를 포함하는 참조예 9(우측)의 경우 유화가 우수하게 진행된 것이 관찰된다. 이것은 음전위를 갖는 양친매성 이방성 분체가 양전위를 갖는 물질과 결합하여 유화력이 향상되어 일어나는 효과로 보여진다.The results can be confirmed with reference to FIG. Specifically, in Reference Example 10 (left side) including squalane, the emulsion layer was not formed but remained as an oil layer, whereas in Reference Example 9 (right side) containing hexyldecyl myristoyl methylaminopropionate, Is observed to be excellent. This is because the amphiphilic anisotropic powder having a negative electric potential is combined with a substance having a positive electric potential to enhance the emulsifying power.
[실험예 4] 양전위를 갖는 물질과 양친매성 이방성 분체의 결합 형성[Experimental Example 4] Bond formation of an amphipathic anisotropic powder and a substance having a positive potential
양친매성 이방성 분체의 Z-포텐셜과 양친매성 이방성 분체와 헥실데실미리스토일메틸아미노프로피오네이트의 결합 이후의 수치 변화를 확인하여 도 5에 나타낸다. 구체적으로, 표 5의 조성으로 양친매성 이방성 분체를 포함하는 조성물과 양친매성 이방성 분체 및 헥실데실미리스토일메틸아미노프로피오네이트를 포함하는 조성물에 대하여 Zetasizer (Malvern)를 이용하여 Z-포텐셜을 측정하였다.The Z-potential of the amphiphilic anisotropic powder and the change in the numerical value after the binding of the amphiphilic anisotropic powder and hexyldecyl myristoyl methyl aminopropionate are shown in FIG. Specifically, the composition containing the amphiphilic anisotropic powder in the composition of Table 5 and the composition containing the amphiphilic anisotropic powder and hexyldecyl myristoyl methylaminopropionate were measured for Z-potential using a Zetasizer (Malvern) Respectively.
성분ingredient 참조예 11 (하단 그래프)Reference Example 11 (lower graph) 참조예 12 (상단 그래프)Reference Example 12 (upper graph)
HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATEHEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE 2020 00
water To 100To 100 To 100To 100
양친매성 이방성 분체(제조예 1-3)The amphiphilic anisotropic powder (Preparation Example 1-3) 0.50.5 0.50.5
pHpH 66 66
도 5는 양친매성 이방성 분체의 자체의 (-) z-포텐셜 값 (상단 그래프)이 하단 그래프에서 양친매성 이방성 분체와 헥실데실미리스토일메틸아미노프로피오네이트가 결합하면서 (+) 방향의 z-포텐셜로 시프트 되는 것을 나타내며, 이로부터 양친매성 이방성 분체와 에몰리언트의 결합을 확인 할 수 있다.Figure 5 shows that the (-) z-potential value of the amphiphilic anisotropic powder itself (upper graph) is lower than that of the amphiphilic anisotropic powder in the (+) direction while the amphiphilic anisotropic powder and hexyldecyl myristoyl methylaminopropionate bind in the lower graph. Which indicates the binding of the amphiphilic anisotropic powder to the emollient.
[실험예 5] pilot 스케일 제형 안정도 확인[Experimental Example 5] Confirmation of stability of pilot scale formulation
본 발명의 유화 조성물에서 카보머와 헥실데실미리스토일메틸아미노프로피오네이트 만을 사용한 제형과 양친매성 이방성 분체를 함유함에 따라 달라지는 입자를 비교 관찰하고자 한다.In the emulsified composition of the present invention, a formulation using only carbomer and hexyldecyl myristoyl methyl aminopropionate and a particle varying with an amphipathic anisotropic powder are compared and observed.
표 6의 함량으로 제조된 유화 조성물은 제조된 익일에 30℃에서 점도측정기(BROOKFIELD Viscometer, SPINDLE #3,12RPM, 30℃, 익일)를 이용하여 점도를 측정하였다. The viscosity of the emulsion composition prepared in the contents of Table 6 was measured at 30 ° C on the next day of manufacture using a viscosity meter (BROOKFIELD Viscometer, SPINDLE # 3, 12RPM, 30 ° C, the next day).
성분ingredient 실시예 1Example 1 비교예 1Comparative Example 1 비교예 2Comparative Example 2
HEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATEHEXYLDECYL MYRISTOYL METHYL AMINOPROPIONATE 55 55 00
스쿠알란Squalane 55 55 1010
water To 100To 100 To 100To 100 To 100To 100
tromethamine트롬 메민 0.140.14 0.140.14 0.140.14
양친매성 이방성 분체 (제조예 1-3The amphiphilic anisotropic powder (Preparation Example 1-3 0.50.5 -- --
카보머Carbomer 0.20.2 0.20.2 0.20.2
pHpH 66 66 66
초기 점도Initial viscosity 40004000 45004500 50005000
4주 경시 안정도4-week time stability 유지maintain 유지maintain 하락degradation
유화 입자 사이즈Emulsion particle size 평균 20㎛ (10~30㎛)An average of 20 占 퐉 (10 to 30 占 퐉) 1~10㎛1 to 10 μm 1~10㎛1 to 10 μm
표면surface 양호Good 양호Good 표면에 오일띠 발생Oil band on surface
도 7a, 도 7b 및 도 7c는 각각 비교예 1, 실시예 1 및 비교예 2의 조성물을 30℃에서 4주간 보관한 후의 유화입자를 관찰한 현미경 사진이다.비교예 1의 유화 제형(도 7a)과 실시예 1의 양친매성 이방성 분체가 결합된 (도 7b)은 실시예 1이 양친매성 이방성 분체 0.5 중량%를 포함하는 것을 제외하고 동일 제형이며, 비교예 2(도 7c)는 양친매성 이방성 분체 및 양전위 물질을 제외한 제형이다.7A, 7B, and 7C are photographs of micrographs of emulsion particles observed after the compositions of Comparative Example 1, Example 1, and Comparative Example 2 were stored at 30 DEG C for 4 weeks, respectively. The emulsion formulations of Comparative Example 1 ) And the amphiphilic anisotropic powder of Example 1 (Fig. 7B) were the same formulation except that Example 1 contained 0.5 wt% of the amphiphilic anisotropic powder, and Comparative Example 2 (Fig. 7C) Powder, and positive displacement material.
실시예 1은 양친매성 이방성 분체가 전하간 상호작용에 의한 막을 형성하는 부위에 위치하면서 입자를 거대하게 만드는 것을 확인할 수 있었다.In Example 1, it was confirmed that the amphiphilic anisotropic powder is located at a site where the film is formed by the interaction between charges, and the particles are made large.
또한 비교예 2(도 7c)는 파일럿 스케일에서 4주 안정도를 확보하지 못하였으나, 양친매성 이방성 분체가 결합된 실시예 1(도 7b)은 4000cps를 가지며 거대 입자를 형성하면서도 파일럿 스케일에서 4주 이상의 안정도를 갖는 것을 확인할 수 있었다.In addition, Comparative Example 2 (Fig. 7C) did not achieve 4-week stability in the pilot scale, but Example 1 (Fig. 7B) in which amphipathic anisotropic powder was combined had 4000 cps and formed large particles, And it was confirmed that it has stability.

Claims (20)

  1. 양전위를 갖는 물질;A substance having a positive potential;
    음전위를 갖는 물질; 및A material having a negative potential; And
    친수성 일방 및 소수성 타방으로 이루어진 이중 스페로이드형 고분자 양친매성 이방성 분체;를 포함하는, 유화 조성물로서,An emulsifying composition comprising a hydrophilic one-sided and a hydrophobic two-sphere type polymeric amphiphilic anisotropic powder,
    상기 분체는 소수성 타방이 상기 친수성 일방의 내부로 부분적으로 침투하여 친수성 일방의 코어를 형성하는 구조이며, 상기 친수성 일방의 쉘은 관능기를 포함하고,Wherein the powder has a structure in which the hydrophobic part partially penetrates into the inside of the hydrophilic one to form a hydrophilic one of the cores, the hydrophilic one shell comprises a functional group,
    상기 유화 조성물은 2 개의 상을 포함하며, 상기 상은 서로 반대 전위를 갖는, 유화 조성물.Wherein the emulsion composition comprises two phases, the phases having opposite potentials.
  2. 제1항에 있어서,The method according to claim 1,
    상기 유화 조성물은 수중유형 또는 유중수형인, 유화 조성물.Wherein the emulsion composition is an aqueous or oil-in-water emulsion composition.
  3. 제1항에 있어서,The method according to claim 1,
    상기 이중 스페로이드형 고분자 양친매성 이방성 분체는 상기 2 개의 상의 계면에 존재하는 것인, 유화 조성물. Wherein the dual spheroidal polymeric amphiphilic anisotropic powder is present at the interfaces of the two phases.
  4. 제1항에 있어서,The method according to claim 1,
    상기 양전위를 갖는 물질은 지방족 아민 화합물, 방향족 아민 화합물 및 아민기 함유 실리콘계 화합물 중에서 선택되는 1종 이상을 포함하는, 유화 조성물.Wherein the substance having a positive potential comprises at least one selected from an aliphatic amine compound, an aromatic amine compound and an amine group-containing silicone compound.
  5. 제1항에 있어서,The method according to claim 1,
    상기 양전위를 갖는 물질은 헥실데실미리스토일메틸아미노프로피오네이트(Hexyldecyl Myristoyl Methylaminopropionate), 비스아모디메티콘(bis amodimethicone), 아모디메티콘(amodimethicone), 및 아미노프로필디메티콘(aminopropyl dimethicone) 중에서 선택되는 1종 이상을 포함하는, 유화 조성물.The substance having a positive potential is selected from the group consisting of hexyldecyl myristoyl methylaminopropionate, bis amodimethicone, amodimethicone, and aminopropyl dimethicone. Wherein the emulsifying composition comprises at least one selected from the group consisting of water,
  6. 제1항에 있어서,The method according to claim 1,
    상기 조성물은 상기 양전위를 갖는 물질을 조성물 총 중량에 대하여 0.01 중량% 내지 75 중량%로 포함하는, 유화 조성물.Wherein the composition comprises from 0.01% to 75% by weight of the substance having the positive potential relative to the total weight of the composition.
  7. 제1항에 있어서,The method according to claim 1,
    상기 음전위를 갖는 물질은 아크릴산계 고분자 화합물, 다당류 고분자 화합물 및 술폰산계 고분자 화합물 중에서 선택되는 1종 이상을 포함하는, 유화 조성물.Wherein the substance having a negative electric potential comprises at least one member selected from an acrylic acid-based polymer compound, a polysaccharide polymer compound and a sulfonic acid-based polymer compound.
  8. 제1항에 있어서,The method according to claim 1,
    상기 음전위를 갖는 물질은 폴리아크릴산, 폴리메타크릴산, 폴리메틸메타크릴산, 메틸메타크릴레이트-아크릴산 코폴리머, 비닐피롤리돈-아크릴산 코폴리머, 하이드록시에틸아크릴레이트/소듐아크릴로일디메틸타우레이트 코폴리머(Hydroxyethyl Acrylate/Sodium Acryloyldimethyl Taurate Copolymer), 아크릴레이트/C10-30 알킬아크릴레이트크로스폴리머(ACRYLATES/C10-30 ALKYL ACRYLATE CROSSPOLYMER), 카보머(carbomer), 알긴산, 펙틴, 폴리갈락투론산, 폴리스티렌 술폰산으로 구성되는 군에서 선택되는 하나 이상의 것인, 유화 조성물.The substance having a negative electric potential is selected from the group consisting of polyacrylic acid, polymethacrylic acid, polymethylmethacrylic acid, methylmethacrylate-acrylic acid copolymer, vinylpyrrolidone-acrylic acid copolymer, hydroxyethyl acrylate / sodium acryloyldimethyltaurate (ACRYLATES / C10-30 ALKYL ACRYLATE CROSSPOLYMER), carbomer, alginic acid, pectin, polygalacturonic acid, polyacrylic acid, polyacrylic acid, Polystyrene sulfonic acid, and polystyrene sulfonic acid.
  9. 제1항에 있어서,The method according to claim 1,
    상기 조성물은 상기 음전위를 갖는 물질을 조성물 총 중량에 대하여 0.01 중량% 내지 10 중량%로 포함하는, 유화 조성물.Wherein the composition comprises from 0.01% to 10% by weight, based on the total weight of the composition, of the substance having the negative potential.
  10. 제1항에 있어서,The method according to claim 1,
    상기 유화 조성물은 pH 7 이하인, 유화 조성물.Wherein the emulsion composition has a pH of 7 or less.
  11. 제1항에 있어서,The method according to claim 1,
    상기 관능기는 실록산인, 유화 조성물.Wherein the functional group is a siloxane.
  12. 제1항에 있어서,The method according to claim 1,
    상기 분체의 친수성 일방은 코어-쉘 구조이고,The hydrophilic one side of the powder is a core-shell structure,
    상기 친수성 일방의 코어와 소수성 타방은 비닐 방향족 고분자를 포함하고,Wherein the hydrophilic one of the cores and the hydrophobic one include a vinyl aromatic polymer,
    상기 친수성 일방의 쉘은 비닐 방향족 모노머; 및 관능기를 함유하는 모노머;의 공중합체를 포함하는, 유화 조성물.The hydrophilic one-side shell comprises a vinyl aromatic monomer; And a monomer containing a functional group.
  13. 제12항에 있어서,13. The method of claim 12,
    상기 관능기를 함유하는 모노머는 실록산 함유 (메트)아크릴레이트인, 유화 조성물.Wherein the functional group-containing monomer is a siloxane-containing (meth) acrylate.
  14. 제1항에 있어서,The method according to claim 1,
    상기 양친매성 이방성 분체는 입자크기가 100 내지 1500 nm 인, 유화 조성물.Wherein the amphiphilic anisotropic powder has a particle size of 100 to 1500 nm.
  15. 제1항에 있어서,The method according to claim 1,
    상기 양친매성 이방성 분체는 조성물 총 중량에 대하여 0.01 내지 10 중량%로 포함하는, 유화 조성물.Wherein the amphiphilic anisotropic powder comprises 0.01 to 10% by weight based on the total weight of the composition.
  16. 제1항에 있어서,The method according to claim 1,
    상기 양전위를 갖는 물질 : 양친매성 이방성 분체 : 음전위를 갖는 물질의 비율은 100 : 1-20 : 1-10의 중량비로 포함되는, 유화 조성물.Wherein the ratio of the material having the positive electric potential: the material having the amphiphilic anisotropic powder: the negative electric potential is contained in a weight ratio of 100: 1 to 20: 1-10.
  17. 제1항에 있어서,The method according to claim 1,
    상기 유화 조성물의 수상은 산(acid)을 더 포함하는 것인, 유화 조성물.Wherein the aqueous phase of the emulsified composition further comprises an acid.
  18. 제17항에 있어서,18. The method of claim 17,
    상기 산은 젖산(lactic acid), 글리콜산(glycolic acid), 에틸 아스코르브산(ethyl ascorbic acid), 아스코르브산(ascorbic acid), 및 글루탐산(glutamic acid)으로 구성되는 군에서 선택되는 하나 이상의 것인, 유화 조성물.Wherein the acid is at least one selected from the group consisting of lactic acid, glycolic acid, ethyl ascorbic acid, ascorbic acid, and glutamic acid, Composition.
  19. 제1항에 있어서,The method according to claim 1,
    상기 양전위를 갖는 물질은 상기 음전위를 갖는 물질과 상호작용하여 막을 형성하는 것인, 유화 조성물. Wherein the substance having the positive potential interacts with the substance having the negative potential to form a film.
  20. 제1항에 있어서,The method according to claim 1,
    상기 조성물의 점도는 100-100,000 cps인, 유화 조성물.Wherein the composition has a viscosity of 100-100,000 cps.
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