WO2017091038A1 - (meth)acrylic amphipathic anisotropic powder and cosmetic composition comprising same - Google Patents

(meth)acrylic amphipathic anisotropic powder and cosmetic composition comprising same Download PDF

Info

Publication number
WO2017091038A1
WO2017091038A1 PCT/KR2016/013712 KR2016013712W WO2017091038A1 WO 2017091038 A1 WO2017091038 A1 WO 2017091038A1 KR 2016013712 W KR2016013712 W KR 2016013712W WO 2017091038 A1 WO2017091038 A1 WO 2017091038A1
Authority
WO
WIPO (PCT)
Prior art keywords
anisotropic powder
amphipathic
group
meth
polymer
Prior art date
Application number
PCT/KR2016/013712
Other languages
French (fr)
Korean (ko)
Inventor
남진
김영선
안순애
강병영
한상훈
Original Assignee
(주)아모레퍼시픽
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150167391A external-priority patent/KR20170062044A/en
Priority claimed from KR1020150167374A external-priority patent/KR20170062034A/en
Application filed by (주)아모레퍼시픽 filed Critical (주)아모레퍼시픽
Publication of WO2017091038A1 publication Critical patent/WO2017091038A1/en

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the present specification discloses a (meth) acrylic amphiphilic anisotropic powder, a cosmetic composition comprising the same, and a method of preparing the same.
  • the surfactant forms a curved surface in the oil or water phase depending on the packing parameters, one part of the surfactant is hydrated to the water phase, and the other part is solvated by oil, thus being water-in-oil type (w / o). Or form an oil-in-water (o / w) emulsion.
  • picking emulsions using spherical solid powders are w / o or o / w depending on the degree of wetting at the interface of the solid powder surface, that is, the degree of lipophilic or hydrophilicity.
  • To form an emulsion As a factor that determines the directionality of the membrane, there is a contact angle, and when the contact angle is smaller than 90 degrees, a large part of the surface of the particle exists as an aqueous phase to generate o / w. If the contact angle is larger than 90 degrees, it is present on the oil side to generate w / o. Create
  • One such application is a pickling emulsion that can form stabilized large emulsified particles using fine spherical particles (FIG. 1).
  • the contact angle ⁇ is different between the aqueous phase and the oil phase, and O / W emulsified particles are formed at ⁇ ⁇ 90 °, and W / O emulsified particles are formed at ⁇ > 90 °.
  • pickling emulsions are capable of producing larger emulsion particles compared to conventional surfactant systems, and the resulting emulsion particles form stabilized emulsion particles by preventing coalescence due to physical stabilization. Therefore, the method of changing the physical properties of the emulsified particles according to the particle size and the properties of the pickling solid particles, and the physical properties have been studied. However, pickering solid particles retain a hydrophilic or lipophilic surface but do not retain amphoteric like surfactants.
  • the problem to be solved by the present invention is to provide an amphiphilic anisotropic powder that maximizes the chemical surface activity and the physical surface activity by adjusting the degree of geometric shape, chemical hydrophilicity.
  • the problem to be solved by the present invention is to provide a method for producing amphiphilic anisotropic powder is simple and maximized yield is possible mass production.
  • the problem to be solved by the present invention is to include an amphiphilic anisotropic powder maximized chemical and physical surfactant activity by introducing the amphiphilic interfacial properties into the anisotropic polymer powder, excellent emulsification power and stabilized It is to provide a cosmetic composition for forming an emulsion.
  • the technology disclosed herein includes a hydrophilic first polymeric spheroid and a hydrophobic second polymeric spheroid, wherein the first polymeric spheroid and the second polymeric spheroid at least partially form a relative polymeric spheroid.
  • the first polymer spheroid and the second polymer spheroid provides an amphiphilic anisotropic powder comprising a (meth) acrylate-based polymer.
  • the (meth) acrylate-based polymer may include a polymer of a (meth) acrylate-based monomer having an alkyl group.
  • the (meth) acrylate-based monomer having an alkyl group may include an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.
  • the first polymer spheroid may be introduced with a hydrophilic functional group.
  • the hydrophilic functional group may be at least one selected from the group consisting of carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydroxyl group. .
  • the amphiphilic anisotropic powder may have a symmetrical shape, an asymmetrical snowman shape, or an asymmetrical inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are bonded to each other. Can be.
  • the amphiphilic anisotropic powder may have a particle size of 100 to 2500 nm.
  • the amphiphilic anisotropic powder may form large emulsified particles of 2 to 200 ⁇ m.
  • the technique disclosed herein is a method of preparing the amphipathic anisotropic powder, which method comprises: (1) preparing a first polymer spheroid by stirring a first monomer and a polymerization initiator; And (2) stirring the prepared first polymer spheroid with a second monomer and a polymerization initiator to prepare an anisotropic powder having a second polymer spheroid formed thereon.
  • (2) after (3) may further include introducing a hydrophilic functional group to the anisotropic powder prepared in (2).
  • the first monomer and the polymerization initiator in (1) may be mixed in a weight ratio of 100 to 1000: 1.
  • the second monomer and the polymerization initiator in (2) may be mixed in a weight ratio of 150 to 250: 1.
  • the second monomer content in (2) may be mixed to 40 to 300 parts by weight when the first polymer spheroid weight is 100 parts by weight.
  • the hydrophilic functional group in (3) may be introduced using a silane coupling agent and a reaction modifier.
  • the silane coupling agent may be N- [3- (trimethoxysilyl) propyl] ethylenediamine.
  • the reaction modifier may be ammonium hydroxide.
  • the technology disclosed herein is a cosmetic composition, wherein the composition comprises an amphiphilic anisotropic powder, the powder comprises a hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid, the agent The first polymer spheroid and the second polymer spheroid are bound at least partially to penetrate the relative polymer spheroid, and the first polymer spheroid and the second polymer spheroid include a (meth) acrylate-based polymer. It provides a cosmetic composition.
  • the technology disclosed herein is a method of preparing the cosmetic composition, wherein the amphipathic anisotropic powder is (1) stirring the first monomer and the polymerization initiator to prepare a first polymer spheroid; (2) stirring the prepared first polymer spheroid with a second monomer and a polymerization initiator to prepare an anisotropic powder having a second polymer spheroid formed thereon; And (3) emulsifying using the prepared amphiphilic anisotropic powder; provides a method for producing a cosmetic composition comprising a.
  • the technique disclosed in the present specification by adjusting the geometric properties of the amphiphilic and macromolecular particles characteristic of the conventional surfactant, to maximize the chemical surfactant and physical surfactant activity at the same time to maximize the amphiphilic anisotropic powder It is effective to provide.
  • the technology disclosed herein is simple and excellent in yield, enabling mass production, and has an effect of providing a method for preparing amphipathic anisotropic powders capable of controlling particle size to about 100 to 2500 nm.
  • the technology disclosed herein contains an amphipathic anisotropic powder that maximizes chemical and physical surfactant properties by adjusting the geometric properties of the amphiphilic and macromolecular particles that are characteristic of existing surfactants, It has the effect of providing a cosmetic composition that is excellent in emulsifying power and forms a stabilized emulsion.
  • the technology disclosed herein has the effect of providing a cosmetic composition that can be prepared in a variety of formulations and has a matte feeling without the stickiness or irritation of existing surfactants.
  • 1 is a schematic diagram showing the formulation of the formulation of the pickling emulsion according to the change in contact angle at the interface of the spherical solid powder.
  • Figure 2 is a schematic diagram of forming an amphiphilic anisotropic powder according to an embodiment of the present invention.
  • FIG. 3 is a photograph and a schematic diagram of a cylindrical rotary reactor used in the preparation of amphipathic anisotropic powder according to an embodiment of the present invention.
  • Figure 4 is an electron micrograph (scale bar 1 ⁇ m) of the first polymer spheroid according to an embodiment of the present invention.
  • FIG. 5 is an electron micrograph of an amphiphilic anisotropic powder according to an embodiment of the present invention, which is an amphiphilic anisotropic powder having a size of 350 nm (scale bar 1 ⁇ m).
  • FIG. 6 is an electron micrograph of an amphipathic anisotropic powder according to an embodiment, which is an amphipathic anisotropic powder having a size of 2 ⁇ m (scale bar 10 ⁇ m).
  • FIG. 7 is a schematic diagram showing an emulsified form of the amphipathic anisotropic powder according to an embodiment of the present invention.
  • FIG. 8 is a table showing a silane coupling agent compound used in Example 2.
  • (meth) acryl may mean acryl and / or methacryl.
  • the particle size of the amphiphilic anisotropic powder is a measure of the maximum length, which is the longest length in the powder particles.
  • the average powder size herein means the average value of the particle sizes of the amphipathic anisotropic powders.
  • the technology disclosed herein includes a hydrophilic first polymeric spheroid and a hydrophobic second polymeric spheroid, wherein the first polymeric spheroid and the second polymeric spheroid at least partially form a relative polymeric spheroid.
  • the first polymer spheroid and the second polymer spheroid provides an amphiphilic anisotropic powder comprising a (meth) acrylate-based polymer.
  • a spheroid is a body composed of a polymer, and may be, for example, a sphere, globoid, or oval shape, and based on the longest length in the body cross section. Or have a long axis length in nano units.
  • the (meth) acrylate-based polymer may include a polymer of a (meth) acrylate-based monomer having an alkyl group.
  • the (meth) acrylate-based monomer having an alkyl group may include an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.
  • an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.
  • the first polymer spheroid may be introduced with a hydrophilic functional group.
  • the hydrophilic functional group may be a functional group having a negative or positive charge or polyethylene glycol (PEG) series, a carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, It may be at least one selected from the group consisting of a polyethylene glycol group and a hydroxyl group.
  • PEG polyethylene glycol
  • the amphiphilic anisotropic powder may have a symmetrical shape, an asymmetrical snowman shape, or an asymmetrical inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are bonded to each other.
  • the snowman shape means that the first and second polymer spheroids having different sizes are bonded to each other.
  • the amphiphilic anisotropic powder may have a particle size of 100 to 2500 nm.
  • the amphipathic anisotropic powder may have a particle size of 100 to 1500 nm, 100 to 500 nm, or 200 to 300 nm.
  • the amphiphilic anisotropic powder has a particle size of 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, 170 nm or more, 180 nm or more, 190 nm Or more, 200 nm or more, 210 nm or more, 220 nm or more, 230 nm or more, 240 nm or more, or 250 nm or more, 2500 nm or less, 2450 nm or less, 2400 nm or less, 2350 nm or less, 2300 nm or less, 2250 nm 2200 nm or less, 2150 nm or less, 2100 nm or less, 2050 nm or less, 2000 nm or less, 1950 nm or less, 1900 nm or less, 1850 nm or less, 1800 nm or less, 1750 n
  • the amphiphilic anisotropic powder may form large emulsified particles of 2 to 200 ⁇ m.
  • the amphipathic anisotropic powder may be to form large emulsified particles of 5 to 200 ⁇ m, 10 to 100 ⁇ m, 10 to 50 ⁇ m, or 25 ⁇ m.
  • the amphiphilic anisotropic powder is at least 2 ⁇ m, at least 3 ⁇ m, at least 4 ⁇ m, at least 5 ⁇ m, at least 6 ⁇ m, at least 7 ⁇ m, at least 8 ⁇ m, at least 9 ⁇ m, at least 10 ⁇ m, at least 11 ⁇ m, 12 13 ⁇ m or more, 13 ⁇ m or more, 14 ⁇ m or more, 15 ⁇ m or more, 16 ⁇ m or more, 17 ⁇ m or more, 18 ⁇ m or more, 19 ⁇ m or more, 20 ⁇ m or more, 21 ⁇ m or more, 22 ⁇ m or more, 23 ⁇ m or more, 24 ⁇ m or more At least 25 ⁇ m, at least 26 ⁇ m, at least 27 ⁇ m, at least 28 ⁇ m, at least 29 ⁇ m, at least 30 ⁇ m, at least 31 ⁇ m, at least 32 ⁇ m, at least 33 ⁇ m, at least 34 ⁇ m, at least 35 ⁇ m, at least 36
  • the hydrophobic and hydrophilic portions of the amphiphilic anisotropic powder have different orientations with respect to the interface to form large emulsion particles, thereby enabling the implementation of a formulation having excellent usability.
  • Conventional molecular-level surfactants have made it difficult to produce stabilized large emulsion particles having a particle diameter of several tens of micrometers, and the surface thickness of the surfactant was about several nm, whereas the surface thickness of the amphiphilic anisotropic powder disclosed herein Is increased to about several hundred nm and the emulsion stability can be greatly improved as the stabilized interfacial film is formed due to the strong bonding between the powders.
  • the amphipathic anisotropic powder is prepared by polymerizing a first monomer to prepare a core of a first polymer spheroid, and coating a core of the first polymer spheroid to the first polymer sp of the core-shell structure It may be prepared to prepare the Lloyd, and reacting the first polymer spheroid and the first monomer of the core-shell structure to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.
  • Figure 2 is a schematic diagram showing the principle of formation of amphipathic anisotropic powder according to an embodiment of the present invention.
  • the core of the first polymer spheroid may be penetrated through the shell of the first polymer spheroid, and then powdered to form a second polymer spheroid.
  • the method of producing the amphipathic anisotropic powder comprises the steps of (1) preparing a first polymer spheroid by stirring the first monomer and the polymerization initiator; And (2) stirring the first polymer spheroid prepared above with a second monomer and a polymerization initiator to provide an anisotropic powder having a second polymer spheroid formed thereon.
  • (3) may further include introducing a hydrophilic functional group to the prepared anisotropic powder.
  • the stirring may be rotational stirring. Rotational agitation is preferred because uniform mechanical mixing is required along with chemical modification to produce uniform particles.
  • the rotary stirring may be rotary stirring in a cylindrical rotary reactor, but the rotary stirring method is not limited thereto.
  • the size and location of the baffles in the cylindrical rotary reactor and the degree of spacing with the impeller greatly affect the uniformity of the particles produced. It is desirable to minimize the blade gap between the inner wing and the impeller to equalize the convective flow and its strength, and to supply the powder reaction liquid below the wing length and maintain the impeller rotation speed at a high speed. It may be rotated at a highway of 200 rpm or more, and the ratio of the length of the diameter and the height of the reactor may be 1 to 3: 1 to 5, more specifically, 10 to 30 cm in diameter and 10 to 50 cm in height. The reactor size can vary in proportion to the reaction capacity. In addition, the material of the cylindrical rotary reactor may be a ceramic, glass, and the like, the temperature of the stirring is preferably 50 to 90 °C.
  • the simple rotary method enables the production of uniform particles and is a low energy method that requires less energy, and has a characteristic of enabling mass production by maximizing reaction efficiency.
  • the tumbling method in which the reactor itself rotates in the related art requires high energy and rotates the reactor at a predetermined angle, thus requiring high energy and restricting the size of the reactor. Due to the limitations of the reactor size, the amount produced is also limited to small amounts of about several hundred mg to several g, making it unsuitable for mass production.
  • the first monomer and the second monomer may be the same or different, and specifically, may be a (meth) acrylate monomer.
  • the polymerization initiator used in each step may be the same or different, and the crosslinking agent used in each step may be the same or different.
  • the (meth) acrylate monomer may include an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.
  • an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.
  • the polymerization initiator may be a radical polymerization initiator, specifically, may be a peroxide-based, azo-based or a mixture thereof. Moreover, ammonium persulfate, sodium persulfate, potassium persulfate can also be used.
  • the polymerization initiator may be azobisisobutyronitrile, but is not limited thereto.
  • the first monomer and the polymerization initiator in (1) may be mixed in a weight ratio of 100 to 1000: 0.1 to 2.
  • 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.
  • the first monomer, the polymerization initiator, and the crosslinking agent may be added.
  • the first monomer, the polymerization initiator and the crosslinking agent may be mixed in a weight ratio of 80 to 150: 0.5 to 2: 0.5 to 2, for example, 100: 1: 1.
  • the crosslinking agent may be a (meth) acrylate-based crosslinking agent, and may be, for example, one or more of allyl methacrylate and ethylene glycol dimthacrylate. Specifically, it may be allyl methacrylate.
  • the size and shape of the amphiphilic anisotropic powder are influenced by the first polymer spheroid size control of the initial stage (1), and the first polymer spheroid size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator and the crosslinking agent. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
  • the stabilizer may be further added in (1) to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 20.
  • the stabilizer may be an ionic vinyl polymer, specifically one or more of polyvinylpyrollidone and polyvinyl alcohol, for example polyvinylpi It may be ralidone.
  • Ionic polymers reduce the fluidity of powders by increasing the viscosity of the trauma phase by expansion of the macromolecular chain. This allows the powders produced by polymer polymerization to maintain a uniform size to prevent entanglement and coalescence (bonding) of each other.
  • the weight ratio of the first monomer, the polymerization initiator and the crosslinking agent is 110 to 130: 1: 1 to 5, specifically 115 to 125: 1: 1 to 2-4. It can be prepared from the first polymer spheroid.
  • the weight ratio of the first monomer, the polymerization initiator and the crosslinking agent is 100 to 150: 0.5 to 2: 0 to 2, specifically 115 to 125: 1: 0 It can be prepared from the first polymer spheroid.
  • amphipathic anisotropic powder of the asymmetrical snowman shape is made of a weight ratio of the first monomer, the polymerization initiator, and the crosslinking agent is 100 to 200: 0.1 to 1: 5 to 15, specifically 110 to 130: 1: 9 to 11 It can be prepared from 1 polymer spheroid.
  • the asymmetric inverse snowman-shaped amphiphilic anisotropic powder is a first monomer, a polymerization initiator and a crosslinking agent having a weight ratio of 100 to 200: 1: 1 to 10, specifically 110 to 130: 1: 1 to 2-4 It can be prepared from polymeric spheroids.
  • the second monomer and the polymerization initiator in (2) may be mixed in a weight ratio of 100 to 300: 1.
  • the second monomer and the polymerization initiator are 160 to 250: 1, or 170 to 250: 1, or 180 to 250: 1, or 190 to 250: 1, or 200 to 250: 1, or 210 to 250 It can be mixed in a weight ratio of: 1, or 220 to 250: 1, or 230 to 250: 1, or 240 to 250: 1.
  • the second monomer, the polymerization initiator and the crosslinking agent may be mixed in a weight ratio of 100 to 300: 1: 1: 0.001 to 10 by further adding a crosslinking agent in the above (2).
  • a crosslinking agent in the above (2).
  • the crosslinking agent may be a (meth) acrylate-based crosslinking agent, and may be, for example, one or more of allyl methacrylate and ethylene glycol dimthacrylate.
  • allyl methacrylate ethylene glycol dimthacrylate may be used.
  • ethylene glycol dimethacrylate may be used.
  • the stabilizer may be further added in (2) to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 20.
  • the stabilizer may be an ionic vinyl polymer, specifically, one or more of polyvinylpyrollidone and polyvinyl alcohol, for example, polyvinyl alcohol Can be.
  • the second monomer content in the step (2) may be mixed to 40 to 300 parts by weight when the first polymer spheroid weight is 100 parts by weight.
  • the second monomer content is 20 to 100 parts by weight when the weight of the first polymer spheroid is 100 parts by weight, an asymmetrical snowman type powder is obtained, and when it is 100 to 150 parts by weight, or 110 to 150 parts by weight, a symmetrical shape Powder is obtained, and when it is 150 to 300 parts by weight, or 160 to 300 parts by weight, an asymmetric reverse snowman type powder is obtained.
  • the weight ratio of the said range there exists an effect which can raise the uniformity of anisotropic powder.
  • the hydrophilic functional group in (3) is not limited thereto, but may be introduced using a silane coupling agent and a reaction modifier.
  • the silane coupling agent is (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl ) Propyl] ethylenediammonium chloride, (N-succinyl-3-aminopropyl) trimethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea and 3-[(trimethoxysilyl) propyloxy ] -1,2-propanediol may be one or more selected from the group consisting of, specifically N- [3- (trimethoxysilyl) propyl] ethylenediamine.
  • the silane coupling agent may be mixed in an amount of 35 parts by weight to 65 parts by weight, for example, 40 parts by weight to 60 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (2).
  • Hydrophilization can be suitably made within the said range.
  • the reaction modifier may be ammonium hydroxide.
  • the reaction control agent may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example, 90 parts by weight to 110 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in (2). Hydrophilization can be suitably made within the said range.
  • the technology disclosed herein provides a cosmetic composition wherein the composition comprises an amphipathic anisotropic powder.
  • amphipathic anisotropic powder is as described above, a description thereof will be omitted.
  • the amphiphilic anisotropic powder may be contained in an amount of 0.1 to 15% by weight based on the total weight of the cosmetic composition. It is possible to provide a cosmetic composition having excellent emulsifying power within the above range and forming a stabilized emulsion.
  • the method of manufacturing a cosmetic composition according to an embodiment of the present invention may include preparing the amphiphilic anisotropic powder and emulsifying the oil phase part and the water phase using the prepared amphipathic anisotropic powder.
  • the cosmetic composition contains an amphiphilic anisotropic powder that maximizes chemical and physical surfactant properties by adjusting the geometric properties of the amphipathic and macromolecular particles, which are the characteristics of the existing surfactants, to provide excellent emulsification and stabilization. Emulsions may be formed.
  • the cosmetic composition can be prepared in a variety of formulations and has the effect of providing a cosmetic composition having a matte feeling without the stickiness or irritation of the existing surfactant.
  • composition according to this embodiment can provide a stable emulsion formulation without including an excess of surfactant, it can be excellent skin stability.
  • composition according to the present embodiment may exhibit emulsion stability over time in a wide temperature range, and the temperature may be, for example, -15 ° C to 60 ° C.
  • composition according to the present embodiment may include a large emulsified particle to provide a flexible and soft feeling.
  • Cosmetic compositions according to embodiments of the present invention may be formulated containing a cosmetically or dermatologically acceptable medium or base. It is any formulation suitable for topical application, in the form of suspensions, microemulsions, microcapsules, microgranules or ionic (liposomal) and nonionic vesicle dispersants or creams, skins, lotions, powders, ointments, sprays or concealers. It may be provided in the form of a stick. It may also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions can be prepared according to conventional methods in the art.
  • the cosmetic composition according to the embodiments of the present invention may be a powder, a fatty substance, an organic solvent, a dissolving agent, a thickening agent, a gelling agent, a softening agent, an antioxidant, a suspending agent, a stabilizer, a foaming agent, a fragrance, a surfactant.
  • ionic or nonionic emulsifiers fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics It may contain adjuvants conventionally used in the cosmetic or dermatological fields, such as any other ingredients used. Such adjuvants are introduced in amounts generally used in the cosmetic or dermatological arts.
  • the cosmetic composition according to the embodiments of the present invention may further contain a skin absorption promoting substance to increase the skin improving effect.
  • a dispersion solution was prepared by mixing 80 g of water, 20 g of methanol and polyvinylpyrrolidone (PVP, Mw 360,000) as a stabilizer, and 10 g of methyl methacrylate, 0.1 azobisisobutyronitrile (AIBN) as a polymerization initiator.
  • a monomer solution is prepared by mixing 0.1 g of allyl methacrylate as a g alc crosslinking agent. The monomer solution was added to the dispersion solution and purged with nitrogen for 30 minutes, followed by reaction at 62 ° C for 12 hours. The reaction was stirred in a cylindrical rotary reactor, the cylindrical rotary reactor was 11 cm in diameter, 17 cm in height, glass, and was rotated at a speed of 500 rpm.
  • the reaction was carried out in a cylindrical rotary reactor, after which methanol was added and washed three times for 60 minutes at 12000 rpm with a centrifugal separator. After drying at room temperature with a vacuum pump, the mixture was ground with a mortar to prepare a powder. Amphipathic anisotropic powder of about 350 nm size was prepared and a micrograph is shown in FIG. 5.
  • Amphiphilic anisotropic powder was prepared in the same manner as in Example 1, except that the content of each used ingredient was changed as shown in Table 1 below.
  • Amphipathic anisotropic powder of about 2 ⁇ m in size was prepared and a micrograph is shown in FIG. 6.
  • An emulsion cosmetic composition using the amphipathic anisotropic powder obtained in Preparation Example 2 was prepared. Multiple formulations of oil-in-water (O / W), water-in-oil (W / O), W / O / W, O / W / O were prepared, and specific compositions are shown in Tables 2 to 4 below.
  • Example 1 (O / W)
  • Example 2 (W / O) Puresyn4 25 75 Cetoskd 0.8 0.5 DB 0.3 0.25 C981 0.2 - PE 0.4 0.3 TAU 0.1 - Water up to 100 up to 100
  • Example 3 (W / O / W)
  • Example 2 (W / O) 16 DB 0.5 C981
  • Example 4 (O / W / O) Puresyn4 85
  • Example 1 (O / W) 7 DB 0.5 C981 (1%) - PE 0.2 TAU - Water up to 100
  • Puresyn4 Hydrogenated poly (C6-14) olefin (oil)
  • CetosKD Cetearyl alcohol (wax)
  • TAU Tromethamine (acid regulator)

Abstract

The present specification discloses a (meth)acrylic amphipathic anisotropic powder, a cosmetic composition comprising same and a method for producing the powder. In one aspect, the technology disclosed in the present specification controls amphipathic properties, which are characteristics of conventional surfactants, and geometric properties, which are characteristics of coarse powder particles, thereby providing an amphipathic anisotropic powder having simultaneously maximized chemical surface-active properties and physical surface-active properties. In another aspect, the technology disclosed in the present specification can provide a cosmetic composition which comprises an amphipathic anisotropic powder having maximized chemical surface-active properties and physical surface-active properties obtained by controlling amphipathic properties, which are characteristics of conventional surfactants, and geometric properties, which are characteristics of coarse powder particles, and thus can form an emulsion having stability and excellent emulsifying capacity.

Description

(메트)아크릴계 양친매성 이방성 분체 및 이를 포함하는 화장료 조성물(Meth) acrylic amphiphilic anisotropic powder and cosmetic composition comprising the same
본 명세서에는 (메트)아크릴계 양친매성 이방성 분체, 이를 포함하는 화장료 조성물, 및 이들의 제조방법이 개시된다.The present specification discloses a (meth) acrylic amphiphilic anisotropic powder, a cosmetic composition comprising the same, and a method of preparing the same.
계면활성제는 기하학적인 형상(packing parameter)에 따라 오일 또는 수상 방향으로 곡면을 형성하게 되고 계면활성제의 한 부분은 수상으로 수화 작용을, 다른 부분은 오일에 의한 용매화가 이루어져서 유중수형(w/o) 또는 수중유형(o/w) 에멀젼을 형성한다. The surfactant forms a curved surface in the oil or water phase depending on the packing parameters, one part of the surfactant is hydrated to the water phase, and the other part is solvated by oil, thus being water-in-oil type (w / o). Or form an oil-in-water (o / w) emulsion.
다양한 형태 및 크기의 미세 입자(나노, 마이크로 사이즈)들의 다양한 제조방법들이 보고되어 왔다. 특히, 고분자로 이루어진 구형 미세 입자는 그 제조방법에 따라서 사이즈와 형태가 조절됨에 따라 응용 가능성이 확대되고 있다. Various methods of preparing fine particles (nano, micro size) of various shapes and sizes have been reported. In particular, as the spherical fine particles made of a polymer is adjusted in size and shape in accordance with the manufacturing method, the application possibilities are expanding.
한편, 기존 분자형 계면활성제와는 달리 구형 고체 분체를 이용한 피커링 에멀젼(Pickering emulsion)은 고체 분체 표면의 계면에서의 젖음성 정도에 따라서, 즉 친유성 또는 친수성의 정도에 따라 w/o 또는 o/w 에멀젼을 형성한다. 면막의 방향성을 결정하는 인자로서 접촉각이 있고, 접촉각이 90도보다 작으면 입자 표면의 많은 부분이 수상으로 존재하여 o/w를 생성하고, 접촉각이 90도보다 크면 오일쪽에 존재하여 w/o를 생성한다.On the other hand, unlike conventional molecular surfactants, picking emulsions using spherical solid powders are w / o or o / w depending on the degree of wetting at the interface of the solid powder surface, that is, the degree of lipophilic or hydrophilicity. To form an emulsion. As a factor that determines the directionality of the membrane, there is a contact angle, and when the contact angle is smaller than 90 degrees, a large part of the surface of the particle exists as an aqueous phase to generate o / w. If the contact angle is larger than 90 degrees, it is present on the oil side to generate w / o. Create
그 응용 예들 중에 하나로 미세 구형 입자를 이용하여 안정화된 거대 유화 입자를 형성할 수 있는 피커링 에멀젼이 있다(도 1). 구형 입자의 친수성/소수성 정도에 따라서 수상과 유상 사이에 접촉각(θ)이 차이가 나고 θ<90°에서는 O/W 유화 입자를 형성하고 θ>90°에서는 W/O 유화 입자를 형성한다. One such application is a pickling emulsion that can form stabilized large emulsified particles using fine spherical particles (FIG. 1). Depending on the degree of hydrophilicity / hydrophobicity of the spherical particles, the contact angle θ is different between the aqueous phase and the oil phase, and O / W emulsified particles are formed at θ <90 °, and W / O emulsified particles are formed at θ> 90 °.
일반적으로 피커링 에멀젼은 기존 계면활성제 시스템에 비하여 거대한 유화 입자 생성이 가능하고 생성된 유화 입자들은 물리적 안정화에 따른 합일(coalescence)을 방지하여 안정화된 유화 입자를 형성한다. 따라서, 피커링 고체 입자들의 입자 크기와 성질에 따른 유화 입자들의 물리적 성질의 변화 방법 및 그에 따른 물성 연구 등이 진행되어 왔다. 그러나, 피커링 고체 입자는 친수성 또는 친유성 표면을 보유하기는 하지만 계면활성제처럼 양쪽성을 보유하지는 않는다.In general, pickling emulsions are capable of producing larger emulsion particles compared to conventional surfactant systems, and the resulting emulsion particles form stabilized emulsion particles by preventing coalescence due to physical stabilization. Therefore, the method of changing the physical properties of the emulsified particles according to the particle size and the properties of the pickling solid particles, and the physical properties have been studied. However, pickering solid particles retain a hydrophilic or lipophilic surface but do not retain amphoteric like surfactants.
좀 더 나아가서는 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, 형태학적 이방성일지라도 전체적으로 소수성이거나 친수성이어서 화학적 이방성에 한계가 있었다. Furthermore, there have been attempts to produce new anisotropic powders by imparting amphiphilic properties having both hydrophilicity and hydrophobicity to the fine spherical particles. An example is Janus spherical particles. However, these spherical morphological limitations limit chemical anisotropy. In other words, even though morphological anisotropy is hydrophobic or hydrophilic as a whole, there is a limit to chemical anisotropy.
이에 기하학적인 형태 조절과 함께 화학적인 이방성을 부여함으로써 계면활성력을 가지는 이방성 분체의 제조가 시도되어 왔으나, 양친매성 이방성 분체의 그 응용가능성이 크다는 장점에도 불구하고 현재까지는 그 대량 생산이 가능한 제조방법이 구체적으로 개발되지 못하였고, 산업적으로 균일하게 대량 생산하기 어렵다는 문제점이 있어 실질적인 산업적인 응용이 이루어지지 않았다.This has been attempted to produce anisotropic powders having an interfacial activity by providing chemical anisotropy with geometrical shape control, but the production method that can be mass-produced so far despite the advantage that the amphipathic anisotropic powders have great applicability This has not been specifically developed, there is a problem that it is difficult to mass-produce industrially uniformly, and practical industrial applications have not been achieved.
일 측면에서, 본 발명이 해결하고자 하는 과제는 기하학적 형태, 화학적인 친수성 정도를 조절함으로써 화학적 계면활성력 및 물리적인 계면활성력을 극대화시킨 양친매성 이방성 분체를 제공하는 것이다.In one aspect, the problem to be solved by the present invention is to provide an amphiphilic anisotropic powder that maximizes the chemical surface activity and the physical surface activity by adjusting the degree of geometric shape, chemical hydrophilicity.
다른 측면에서, 본 발명이 해결하고자 하는 과제는 간단하고 수율이 극대화되어 대량 생산이 가능한 양친매성 이방성 분체의 제조방법을 제공하는 것이다.In another aspect, the problem to be solved by the present invention is to provide a method for producing amphiphilic anisotropic powder is simple and maximized yield is possible mass production.
또 다른 측면에서, 본 발명이 해결하고자 하는 과제는 양친성 계면 성질을 이방성 고분자 분체에 도입하여 화학적 계면활성력 및 물리적 계면활성력을 극대화시킨 양친매성 이방성 분체를 함유함으로써, 유화력이 우수하고 안정화된 에멀젼을 형성하는 화장료 조성물을 제공하는 것이다.In another aspect, the problem to be solved by the present invention is to include an amphiphilic anisotropic powder maximized chemical and physical surfactant activity by introducing the amphiphilic interfacial properties into the anisotropic polymer powder, excellent emulsification power and stabilized It is to provide a cosmetic composition for forming an emulsion.
일 측면에서, 본 명세서에 개시된 기술은 친수성인 제1 고분자 스페로이드 및 소수성인 제2 고분자 스페로이드를 포함하며, 상기 제1 고분자 스페로이드 및 제2 고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하고, 상기 제1 고분자 스페로이드와 제2 고분자 스페로이드는 (메트)아크릴레이트계 고분자를 포함하는, 양친매성 이방성 분체를 제공한다.In one aspect, the technology disclosed herein includes a hydrophilic first polymeric spheroid and a hydrophobic second polymeric spheroid, wherein the first polymeric spheroid and the second polymeric spheroid at least partially form a relative polymeric spheroid. Combined into a penetrating structure, the first polymer spheroid and the second polymer spheroid provides an amphiphilic anisotropic powder comprising a (meth) acrylate-based polymer.
예시적인 일 구현예에 따르면, 상기 (메트)아크릴레이트계 고분자는 알킬기를 갖는 (메트)아크릴레이트계 모노머의 중합체를 포함할 수 있다.According to an exemplary embodiment, the (meth) acrylate-based polymer may include a polymer of a (meth) acrylate-based monomer having an alkyl group.
예시적인 일 구현예에 따르면, 상기 알킬기를 갖는 (메트)아크릴레이트계 모노머는 비치환된 탄소수 1~20의 선형 또는 분지형의 알킬기를 갖는 (메트)아크릴산 에스테르를 포함할 수 있다.According to an exemplary embodiment, the (meth) acrylate-based monomer having an alkyl group may include an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.
예시적인 일 구현예에 따르면, 상기 제1 고분자 스페로이드는 친수성 관능기가 추가적으로 도입될 수 있다.According to an exemplary embodiment, the first polymer spheroid may be introduced with a hydrophilic functional group.
예시적인 일 구현예에 따르면, 상기 친수성 관능기는 카르복실산기, 설폰기, 포스페이트기, 아미노기, 알콕시기, 에스테르기, 아세테이트기, 폴리에틸렌글리콜기 및 하이드록실기로 이루어진 군에서 선택되는 1 이상일 수 있다.According to an exemplary embodiment, the hydrophilic functional group may be at least one selected from the group consisting of carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydroxyl group. .
예시적인 일 구현예에 따르면, 상기 양친매성 이방성 분체는 제1 고분자 스페로이드 및 제2 고분자 스페로이드가 결합된 결합부를 기준으로 대칭 형상, 비대칭 스노우맨(snowman) 형상 또는 비대칭 역스노우맨 형상을 가질 수 있다.According to an exemplary embodiment, the amphiphilic anisotropic powder may have a symmetrical shape, an asymmetrical snowman shape, or an asymmetrical inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are bonded to each other. Can be.
예시적인 일 구현예에 따르면, 상기 양친매성 이방성 분체는 입자 크기가 100 내지 2500 nm일 수 있다.According to one exemplary embodiment, the amphiphilic anisotropic powder may have a particle size of 100 to 2500 nm.
예시적인 일 구현예에 따르면, 상기 양친매성 이방성 분체는 2 내지 200 ㎛의 거대 유화 입자를 형성할 수 있다.According to one exemplary embodiment, the amphiphilic anisotropic powder may form large emulsified particles of 2 to 200 ㎛.
다른 측면에서, 본 명세서에 개시된 기술은 상기 양친매성 이방성 분체의 제조방법으로서, 상기 방법은 (1) 제1모노머 및 중합 개시제를 교반하여 제1고분자 스페로이드를 제조하고; 그리고 (2) 상기 제조된 제1고분자 스페로이드를, 제2모노머 및 중합 개시제와 교반하여 제2고분자 스페로이드가 형성된 이방성 분체를 제조하는 것을 포함할 수 있다.In another aspect, the technique disclosed herein is a method of preparing the amphipathic anisotropic powder, which method comprises: (1) preparing a first polymer spheroid by stirring a first monomer and a polymerization initiator; And (2) stirring the prepared first polymer spheroid with a second monomer and a polymerization initiator to prepare an anisotropic powder having a second polymer spheroid formed thereon.
예시적인 일 구현예에 따르면, 상기 (2) 이후에 (3) 상기 (2) 에서 제조된 이방성 분체에 친수성 관능기를 도입하는 것을 더 포함할 수 있다.According to one exemplary embodiment, (2) after (3) may further include introducing a hydrophilic functional group to the anisotropic powder prepared in (2).
예시적인 일 구현예에 따르면, 상기 (1)에서 제1 모노머 및 중합 개시제는 100 내지 1000 : 1의 중량비로 혼합할 수 있다. According to one exemplary embodiment, the first monomer and the polymerization initiator in (1) may be mixed in a weight ratio of 100 to 1000: 1.
예시적인 일 구현예에 따르면, 상기 (2)에서 제2 모노머 및 중합 개시제는 150 내지 250 : 1의 중량비로 혼합할 수 있다.According to an exemplary embodiment, the second monomer and the polymerization initiator in (2) may be mixed in a weight ratio of 150 to 250: 1.
예시적인 일 구현예에 따르면, 상기 (2)에서 제2 모노머 함량은 제1고분자 스페로이드 중량이 100 중량부일 때 40 내지 300 중량부로 혼합할 수 있다.According to one exemplary embodiment, the second monomer content in (2) may be mixed to 40 to 300 parts by weight when the first polymer spheroid weight is 100 parts by weight.
예시적인 일 구현예에 따르면, 상기 (3)에서 친수성 관능기는 실란 커플링제와 반응 조절제를 이용하여 도입할 수 있다.According to one exemplary embodiment, the hydrophilic functional group in (3) may be introduced using a silane coupling agent and a reaction modifier.
예시적인 일 구현예에 따르면, 상기 실란 커플링제는 N-[3-(트리메톡시실릴)프로필]에틸렌디아민일 수 있다.According to an exemplary embodiment, the silane coupling agent may be N- [3- (trimethoxysilyl) propyl] ethylenediamine.
예시적인 일 구현예에 따르면, 상기 반응 조절제는 암모늄 하이드록사이드일 수 있다.According to one exemplary embodiment, the reaction modifier may be ammonium hydroxide.
일 측면에서, 본 명세서에 개시된 기술은 화장료 조성물에 있어서, 상기 조성물은 양친매성 이방성 분체를 포함하고, 상기 분체는 친수성인 제1 고분자 스페로이드 및 소수성인 제2 고분자 스페로이드를 포함하며, 상기 제1 고분자 스페로이드 및 제2 고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하며, 상기 제1고분자 스페로이드와 제2고분자 스페로이드는 (메트)아크릴레이트계 고분자를 포함하는, 화장료 조성물을 제공한다.In one aspect, the technology disclosed herein is a cosmetic composition, wherein the composition comprises an amphiphilic anisotropic powder, the powder comprises a hydrophilic first polymer spheroid and a hydrophobic second polymer spheroid, the agent The first polymer spheroid and the second polymer spheroid are bound at least partially to penetrate the relative polymer spheroid, and the first polymer spheroid and the second polymer spheroid include a (meth) acrylate-based polymer. It provides a cosmetic composition.
다른 측면에서, 본 명세서에 개시된 기술은 상기 화장료 조성물의 제조방법으로서, 상기 방법은 상기 양친매성 이방성 분체는 (1) 제1모노머 및 중합 개시제를 교반하여 제1고분자 스페로이드를 제조하고; (2) 상기 제조된 제1고분자 스페로이드를, 제2모노머 및 중합 개시제와 교반하여 제2고분자 스페로이드가 형성된 이방성 분체를 제조하고; 그리고 (3) 상기 제조된 양친매성 이방성 분체를 이용하여 유화하는 단계;를 포함하는 화장료 조성물의 제조방법을 제공한다.In another aspect, the technology disclosed herein is a method of preparing the cosmetic composition, wherein the amphipathic anisotropic powder is (1) stirring the first monomer and the polymerization initiator to prepare a first polymer spheroid; (2) stirring the prepared first polymer spheroid with a second monomer and a polymerization initiator to prepare an anisotropic powder having a second polymer spheroid formed thereon; And (3) emulsifying using the prepared amphiphilic anisotropic powder; provides a method for producing a cosmetic composition comprising a.
일 측면에서, 본 명세서에 개시된 기술은 기존 계면활성제의 특징인 양친매성과 거대 분체 입자의 특징인 기하학적 성질을 조절함으로써, 화학적 계면활성력 및 물리적인 계면활성력을 동시에 극대화시킨 양친매성 이방성 분체를 제공하는 효과가 있다.In one aspect, the technique disclosed in the present specification by adjusting the geometric properties of the amphiphilic and macromolecular particles characteristic of the conventional surfactant, to maximize the chemical surfactant and physical surfactant activity at the same time to maximize the amphiphilic anisotropic powder It is effective to provide.
다른 측면에서, 본 명세서에 개시된 기술은 간단하고 수율이 우수하여 대량 생산이 가능하며, 100 내지 2500 nm 내외로 입자 크기를 조절할 수 있는 양친매성 이방성 분체의 제조방법을 제공하는 효과가 있다.In another aspect, the technology disclosed herein is simple and excellent in yield, enabling mass production, and has an effect of providing a method for preparing amphipathic anisotropic powders capable of controlling particle size to about 100 to 2500 nm.
일 측면에서, 본 명세서에 개시된 기술은 기존 계면활성제의 특징인 양친매성과 거대 분체 입자의 특징인 기하학적 성질을 조절하여 화학적 계면활성력 및 물리적 계면활성력을 극대화시킨 양친매성 이방성 분체를 함유함으로써, 유화력이 우수하고 안정화된 에멀젼을 형성하는 화장료 조성물을 제공하는 효과가 있다.In one aspect, the technology disclosed herein contains an amphipathic anisotropic powder that maximizes chemical and physical surfactant properties by adjusting the geometric properties of the amphiphilic and macromolecular particles that are characteristic of existing surfactants, It has the effect of providing a cosmetic composition that is excellent in emulsifying power and forms a stabilized emulsion.
다른 측면에서, 본 명세서에 개시된 기술은 다양한 제형으로 제조가 가능하고 기존 계면활성제의 끈적임이나 자극감이 없이 매트한 사용감을 갖는 화장료 조성물을 제공하는 효과가 있다.In another aspect, the technology disclosed herein has the effect of providing a cosmetic composition that can be prepared in a variety of formulations and has a matte feeling without the stickiness or irritation of existing surfactants.
도 1은 구형 고체 분체의 계면에서의 접촉각 변화에 따른 피커링 에멀젼의 제형 형성 원리를 나타내는 모식도이다.1 is a schematic diagram showing the formulation of the formulation of the pickling emulsion according to the change in contact angle at the interface of the spherical solid powder.
도 2는 본 발명의 일 실시예에 따른 양친매성 이방성 분체를 형성하는 모식도이다.Figure 2 is a schematic diagram of forming an amphiphilic anisotropic powder according to an embodiment of the present invention.
도 3은 본 발명의 일 실시예에 따른 양친매성 이방성 분체의 제조시 사용되는 원통형 회전 반응기의 사진 및 모식도이다.3 is a photograph and a schematic diagram of a cylindrical rotary reactor used in the preparation of amphipathic anisotropic powder according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 제1고분자 스페로이드의 전자현미경 사진(스케일바 1㎛)이다.Figure 4 is an electron micrograph (scale bar 1㎛) of the first polymer spheroid according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 양친매성 이방성 분체의 전자현미경 사진으로, 350nm 크기의 양친매성 이방성 분체 (스케일바 1㎛)이다.5 is an electron micrograph of an amphiphilic anisotropic powder according to an embodiment of the present invention, which is an amphiphilic anisotropic powder having a size of 350 nm (scale bar 1 μm).
도 6은 일 실시예에 따른 양친매성 이방성 분체의 전자현미경 사진으로, 2㎛ 크기의 양친매성 이방성 분체 (스케일바 10㎛)이다.6 is an electron micrograph of an amphipathic anisotropic powder according to an embodiment, which is an amphipathic anisotropic powder having a size of 2 μm (scale bar 10 μm).
도 7은 본 발명의 일 실시예에 따른 양친매성 이방성 분체의 유화 형태를 나타내는 모식도이다.7 is a schematic diagram showing an emulsified form of the amphipathic anisotropic powder according to an embodiment of the present invention.
도 8은 실시예 2에서 사용한 실란 커플링제 화합물을 나타낸 표이다.8 is a table showing a silane coupling agent compound used in Example 2. FIG.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 명세서에서 “치환된”은 별도의 정의가 없는 한, 본 발명의 작용기 중 하나 이상의 수소 원자가 할로겐 (F, Cl, Br 또는 I), 히드록시기, 니트로기, 이미노기(=NH, =NR, R은 탄소수 1-10의 알킬기이다), 아미디노기, 히드라진 또는 히드라존기, 카르복시기, 치환 또는 비치환된 탄소수 1-20의 알킬기, 치환 또는 비치환된 탄소수 3-30의 헤테로아릴기, 치환 또는 비치환된 탄소수 2-30의 헤테로시클로알킬기로 치환되는 것을 의미할 수 있다.As used herein, unless otherwise defined, "substituted" means that one or more hydrogen atoms of the functional groups of the present invention are halogen (F, Cl, Br or I), hydroxy, nitro, imino (= NH, = NR, R Is an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted It may mean substituted with a heterocycloalkyl group having 2 to 30 ring carbon atoms.
본 명세서에서 본 명세서에서 "(메트)아크릴"은 아크릴(acryl) 및/또는 메타크릴(methacryl)을 의미할 수 있다.As used herein, "(meth) acryl" may mean acryl and / or methacryl.
본 명세서에서 양친매성 이방성 분체의 입자 크기는 분체 입자에서 가장 긴 길이인 최장경(maximum length)을 측정한 것이다.In the present specification, the particle size of the amphiphilic anisotropic powder is a measure of the maximum length, which is the longest length in the powder particles.
본 명세서에서 평균 분체 크기는 양친매성 이방성 분체들의 입자 크기들의 평균 값을 의미한다.The average powder size herein means the average value of the particle sizes of the amphipathic anisotropic powders.
일 측면에서, 본 명세서에 개시된 기술은 친수성인 제1 고분자 스페로이드 및 소수성인 제2 고분자 스페로이드를 포함하며, 상기 제1 고분자 스페로이드 및 제2 고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하고, 상기 제1 고분자 스페로이드와 제2 고분자 스페로이드는 (메트)아크릴레이트계 고분자를 포함하는, 양친매성 이방성 분체를 제공한다.In one aspect, the technology disclosed herein includes a hydrophilic first polymeric spheroid and a hydrophobic second polymeric spheroid, wherein the first polymeric spheroid and the second polymeric spheroid at least partially form a relative polymeric spheroid. Combined into a penetrating structure, the first polymer spheroid and the second polymer spheroid provides an amphiphilic anisotropic powder comprising a (meth) acrylate-based polymer.
본 명세서에서 스페로이드는 고분자로 구성된 하나의 몸체로서, 예를 들어 구형체(sphere), 구상체(globoid) 또는 타원형체(oval shape)일 수 있으며, 몸체 단면에서 가장 긴 길이를 기준으로 마이크로 단위 또는 나노 단위의 장축 길이를 가질 수 있다.As used herein, a spheroid is a body composed of a polymer, and may be, for example, a sphere, globoid, or oval shape, and based on the longest length in the body cross section. Or have a long axis length in nano units.
예시적인 일 구현예에 따르면, 상기 (메트)아크릴레이트계 고분자는 알킬기를 갖는 (메트)아크릴레이트계 모노머의 중합체를 포함할 수 있다.According to an exemplary embodiment, the (meth) acrylate-based polymer may include a polymer of a (meth) acrylate-based monomer having an alkyl group.
예시적인 일 구현예에 따르면, 상기 알킬기를 갖는 (메트)아크릴레이트계 모노머는 비치환된 탄소수 1~20의 선형 또는 분지형의 알킬기를 갖는 (메트)아크릴산 에스테르를 포함할 수 있다. 예를 들어, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 이소-부틸(메트)아크릴레이트, 펜틸(메트)아크릴레이트, 헥실(메트)아크릴레이트, 헵틸(메트)아크릴레이트, 에틸헥실(메트)아크릴레이트, 옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 노닐(메트)아크릴레이트, 데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트 등을 포함할 수 있다. According to an exemplary embodiment, the (meth) acrylate-based monomer having an alkyl group may include an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylic Latex, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) Acrylate, decyl (meth) acrylate, lauryl (meth) acrylate and the like.
예시적인 일 구현예에 따르면, 상기 제1 고분자 스페로이드는 친수성 관능기가 추가적으로 도입될 수 있다.According to an exemplary embodiment, the first polymer spheroid may be introduced with a hydrophilic functional group.
예시적인 일 구현예에 따르면, 상기 친수성 관능기는 음전하 또는 양전하를 가진 관능기 또는 PEG(Polyethylene glycol) 계열일 수 있으며, 카르복실산기, 설폰기, 포스페이트기, 아미노기, 알콕시기, 에스테르기, 아세테이트기, 폴리에틸렌글리콜기 및 하이드록실기로 이루어진 군에서 선택되는 1 이상일 수 있다.According to one exemplary embodiment, the hydrophilic functional group may be a functional group having a negative or positive charge or polyethylene glycol (PEG) series, a carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, It may be at least one selected from the group consisting of a polyethylene glycol group and a hydroxyl group.
예시적인 일 구현예에 따르면, 상기 양친매성 이방성 분체는 제1 고분자 스페로이드 및 제2 고분자 스페로이드가 결합된 결합부를 기준으로 대칭 형상, 비대칭 스노우맨(snowman) 형상 또는 비대칭 역스노우맨 형상을 가질 수 있다. 상기 스노우맨 형상은 결합되는 서로 크기가 상이한 제1 및 제2 고분자 스페로이드가 결합된 것을 의미한다.According to an exemplary embodiment, the amphiphilic anisotropic powder may have a symmetrical shape, an asymmetrical snowman shape, or an asymmetrical inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are bonded to each other. Can be. The snowman shape means that the first and second polymer spheroids having different sizes are bonded to each other.
예시적인 일 구현예에 따르면, 상기 양친매성 이방성 분체는 입자 크기가 100 내지 2500 nm일 수 있다. 다른 측면에서, 상기 양친매성 이방성 분체는 입자 크기가 100 내지 1500 nm, 100 내지 500 nm, 또는 200 내지 300 nm일 수 있다. 구체적으로, 상기 양친매성 이방성 분체는 입자 크기가 100 nm 이상, 110 nm 이상, 120 nm 이상, 130 nm 이상, 140 nm 이상, 150 nm 이상, 160 nm 이상, 170 nm 이상, 180 nm 이상, 190 nm 이상, 200 nm 이상, 210 nm 이상, 220 nm 이상, 230 nm 이상, 240 nm 이상, 또는 250 nm 이상이고, 2500 nm 이하, 2450 nm 이하, 2400 nm 이하, 2350 nm 이하, 2300 nm 이하, 2250 nm 이하, 2200 nm 이하, 2150 nm 이하, 2100 nm 이하, 2050 nm 이하, 2000 nm 이하, 1950 nm 이하, 1900 nm 이하, 1850 nm 이하, 1800 nm 이하, 1750 nm 이하, 1700 nm 이하, 1650 nm 이하, 1600 nm 이하, 1550 nm 이하, 1500 nm 이하, 1450 nm 이하, 1400 nm 이하, 1350 nm 이하, 1300 nm 이하, 1250 nm 이하, 1200 nm 이하, 1150 nm 이하, 1100 nm 이하, 1050 nm 이하, 1000 nm 이하, 950 nm 이하, 900 nm 이하, 850 nm 이하, 800 nm 이하, 750 nm 이하, 700 nm 이하, 650 nm 이하, 600 nm 이하, 550 nm 이하, 500 nm 이하, 450 nm 이하, 400 nm 이하, 350 nm 이하, 또는 300 nm 이하일 수 이다According to one exemplary embodiment, the amphiphilic anisotropic powder may have a particle size of 100 to 2500 nm. In another aspect, the amphipathic anisotropic powder may have a particle size of 100 to 1500 nm, 100 to 500 nm, or 200 to 300 nm. Specifically, the amphiphilic anisotropic powder has a particle size of 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, 170 nm or more, 180 nm or more, 190 nm Or more, 200 nm or more, 210 nm or more, 220 nm or more, 230 nm or more, 240 nm or more, or 250 nm or more, 2500 nm or less, 2450 nm or less, 2400 nm or less, 2350 nm or less, 2300 nm or less, 2250 nm 2200 nm or less, 2150 nm or less, 2100 nm or less, 2050 nm or less, 2000 nm or less, 1950 nm or less, 1900 nm or less, 1850 nm or less, 1800 nm or less, 1750 nm or less, 1700 nm or less, 1650 nm or less, 1600 nm or less, 1550 nm or less, 1500 nm or less, 1450 nm or less, 1400 nm or less, 1350 nm or less, 1300 nm or less, 1250 nm or less, 1200 nm or less, 1150 nm or less, 1100 nm or less, 1050 nm or less, 1000 nm 950 nm or less, 900 nm or less, 850 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 500 nm or less, 450 nm or less, 400 nm or less A number equal to or less than 350 nm or less, or 300 nm
예시적인 일 구현예에 따르면, 상기 양친매성 이방성 분체는 2 내지 200 ㎛의 거대 유화 입자를 형성할 수 있다. 다른 측면에서, 상기 양친매성 이방성 분체는 5 내지 200 ㎛, 10 내지 100 ㎛, 10 내지 50 ㎛, 또는 25 ㎛의 거대 유화 입자를 형성하는 것일 수 있다. 구체적으로, 상기 양친매성 이방성 분체는 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, 31 ㎛ 이상, 32 ㎛ 이상, 33 ㎛ 이상, 34 ㎛ 이상, 35 ㎛ 이상, 36 ㎛ 이상, 37 ㎛ 이상, 38 ㎛ 이상, 39 ㎛ 이상, 40 ㎛ 이상, 41 ㎛ 이상, 42 ㎛ 이상, 43 ㎛ 이상, 44 ㎛ 이상, 45 ㎛ 이상, 46 ㎛ 이상, 47 ㎛ 이상, 48 ㎛ 이상, 49 ㎛ 이상, 50 ㎛ 이상, 80 ㎛ 이상, 100 ㎛ 이상, 130 ㎛ 이상, 150 ㎛ 이상 또는 180 ㎛ 이상이고, 200 ㎛ 이하, 190 ㎛ 이하, 180 ㎛ 이하, 170 ㎛ 이하, 160 ㎛ 이하, 150㎛ 이하 , 130㎛ 이하, 100㎛ 이하, 80㎛ 이하, 50㎛ 이하, 40㎛ 이하, 30㎛ 이하, 25㎛ 이하, 20㎛ 이하, 15㎛ 이하, 10㎛ 이하, 또는 5 ㎛ 이하의 유화 입자를 형성할 수 있다.  According to one exemplary embodiment, the amphiphilic anisotropic powder may form large emulsified particles of 2 to 200 ㎛. In another aspect, the amphipathic anisotropic powder may be to form large emulsified particles of 5 to 200 ㎛, 10 to 100 ㎛, 10 to 50 ㎛, or 25 ㎛. Specifically, the amphiphilic anisotropic powder is at least 2 μm, at least 3 μm, at least 4 μm, at least 5 μm, at least 6 μm, at least 7 μm, at least 8 μm, at least 9 μm, at least 10 μm, at least 11 μm, 12 13 μm or more, 13 μm or more, 14 μm or more, 15 μm or more, 16 μm or more, 17 μm or more, 18 μm or more, 19 μm or more, 20 μm or more, 21 μm or more, 22 μm or more, 23 μm or more, 24 μm or more At least 25 μm, at least 26 μm, at least 27 μm, at least 28 μm, at least 29 μm, at least 30 μm, at least 31 μm, at least 32 μm, at least 33 μm, at least 34 μm, at least 35 μm, at least 36 μm, 37 At least 38 μm, at least 38 μm, at least 39 μm, at least 40 μm, at least 41 μm, at least 42 μm, at least 43 μm, at least 44 μm, at least 45 μm, at least 46 μm, at least 47 μm, at least 48 μm, at least 49 μm. At least 50 μm, at least 80 μm, at least 100 μm, at least 130 μm, at least 150 μm, or at least 180 μm, at most 200 μm, at most 190 μm, at most 180 μm, at most 170 μm, at most 160 μm, at most 150 μm, 130 μm or less, 100 μm or less, Emulsified particles of 80 µm or less, 50 µm or less, 40 µm or less, 30 µm or less, 25 µm or less, 20 µm or less, 15 µm or less, 10 µm or less, or 5 µm or less can be formed.
상기 양친매성 이방성 분체의 소수성 부분 및 친수성 부분이 계면에 대한 상이한 방향성을 가짐으로써 거대 유화 입자를 형성하고, 사용감이 우수한 제형의 구현이 가능하다. 종래 분자 수준의 계면활성제로는 수십 ㎛의 입경을 갖는 안정화된 거대 유화 입자를 만들기가 어려웠고, 계면활성제의 계면막 두께가 약 수 nm였던 반면, 본 명세서에 개시된 양친매성 이방성 분체의 경우 계면막 두께가 약 수백 nm로 증가하고 분체간 강한 결합으로 인해 안정화된 계면막을 형성함에 따라 유화 안정도가 크게 향상될 수 있다.The hydrophobic and hydrophilic portions of the amphiphilic anisotropic powder have different orientations with respect to the interface to form large emulsion particles, thereby enabling the implementation of a formulation having excellent usability. Conventional molecular-level surfactants have made it difficult to produce stabilized large emulsion particles having a particle diameter of several tens of micrometers, and the surface thickness of the surfactant was about several nm, whereas the surface thickness of the amphiphilic anisotropic powder disclosed herein Is increased to about several hundred nm and the emulsion stability can be greatly improved as the stabilized interfacial film is formed due to the strong bonding between the powders.
본 발명 일 실시예에서, 상기 양친매성 이방성 분체는 제1모노머를 중합하여 제1고분자 스페로이드의 코어를 제조하고, 상기 제1고분자 스페로이드의 코어를 코팅하여 코어-쉘 구조의 제1고분자 스페로이드를 제조하고, 상기 코어-쉘 구조의 제1고분자 스페로이드와 제1모노머를 반응시켜 제2고분자 스페로이드가 형성된 양친매성 이방성 분체를 제조하는 것을 포함하여 제조될 수 있다.In one embodiment of the present invention, the amphipathic anisotropic powder is prepared by polymerizing a first monomer to prepare a core of a first polymer spheroid, and coating a core of the first polymer spheroid to the first polymer sp of the core-shell structure It may be prepared to prepare the Lloyd, and reacting the first polymer spheroid and the first monomer of the core-shell structure to prepare an amphiphilic anisotropic powder in which the second polymer spheroid is formed.
도 2는 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.Figure 2 is a schematic diagram showing the principle of formation of amphipathic anisotropic powder according to an embodiment of the present invention. According to the manufacturing method, the core of the first polymer spheroid may be penetrated through the shell of the first polymer spheroid, and then powdered to form a second polymer spheroid.
본 실시예에서, 상기 양친매성 이방성 분체의 제조방법으로서, 상기 방법은 (1) 제1모노머 및 중합 개시제를 교반하여 제1고분자 스페로이드를 제조하고; 그리고 (2) 상기 제조된 제1고분자 스페로이드를, 제2모노머 및 중합 개시제와 교반하여 제2고분자 스페로이드가 형성된 이방성 분체를 제조하는 것을 포함하는 양친매성 이방성 분체의 제조방법을 제공한다.In this embodiment, the method of producing the amphipathic anisotropic powder, the method comprises the steps of (1) preparing a first polymer spheroid by stirring the first monomer and the polymerization initiator; And (2) stirring the first polymer spheroid prepared above with a second monomer and a polymerization initiator to provide an anisotropic powder having a second polymer spheroid formed thereon.
예시적인 일 구현예에 따르면, 상기 (2)의 이방성 분체를 제조한 후에, (3) 상기 제조된 이방성 분체에 친수성 관능기를 도입하는 것을 더 포함할 수 있다.According to an exemplary embodiment, after preparing the anisotropic powder of (2), (3) may further include introducing a hydrophilic functional group to the prepared anisotropic powder.
상기 (1) 및 (2) 에서 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 (1) and (2), the stirring may be rotational stirring. Rotational agitation is preferred because uniform mechanical mixing is required along with chemical modification to produce uniform particles. The rotary stirring may be rotary stirring in a cylindrical rotary reactor, but the rotary stirring method is not limited thereto.
이때, 반응기 내부 디자인은 분체 형성에 큰 영향을 미친다. 원통형 회전 반응기 내 날개(baffles)의 크기와 위치, 및 임펠러(impeller)와의 간격 정도는 생성되는 입자의 균일성에 큰 영향을 미친다. 내부 날개와 임펠러의 블레이드(blade) 간격을 최소화하여 대류 흐름과 그 세기를 균일화하고, 분체 반응액은 날개 길이 이하로 투입되며 임펠러 회전속도는 고속을 유지하는 것이 바람직하다. 200 rpm 이상의 고속도로 회전될 수 있고, 반응기의 지름과 높이의 길이 비율은 1 내지 3 : 1 내지 5, 더욱 구체적으로 지름 10 내지 30 cm 및 높이 10 내지 50 cm일 수 있다. 반응기 크기는 반응 용량에 비례하여 변화가 가능하다. 또한, 원통형 회전 반응기의 재질은 세라믹, 유리 등일 수 있고, 교반시 온도는 50 내지 90 ℃인 것이 바람직하다.At this time, the design inside the reactor has a great influence on the powder formation. The size and location of the baffles in the cylindrical rotary reactor and the degree of spacing with the impeller greatly affect the uniformity of the particles produced. It is desirable to minimize the blade gap between the inner wing and the impeller to equalize the convective flow and its strength, and to supply the powder reaction liquid below the wing length and maintain the impeller rotation speed at a high speed. It may be rotated at a highway of 200 rpm or more, and the ratio of the length of the diameter and the height of the reactor may be 1 to 3: 1 to 5, more specifically, 10 to 30 cm in diameter and 10 to 50 cm in height. The reactor size can vary in proportion to the reaction capacity. In addition, the material of the cylindrical rotary reactor may be a ceramic, glass, and the like, the temperature of the stirring is preferably 50 to 90 ℃.
원통형 회전 반응기에서 단순 회전법은 균일한 입자의 생성을 가능하게 하고 에너지가 적게 소요되는 저에너지 방법이면서 반응 효율이 극대화되어 대량 생산을 가능하게 하는 특징이 있다. 종래 사용되었던 반응기 자체가 회전하는 텀블링 방식은 반응기 전체를 일정한 각도로 기울여서 고속으로 회전시켜야 하므로 고에너지가 필요하고 반응기의 크기가 제한적이었다. 반응기 크기의 한계 때문에 생성되는 양 또한 약 수백 mg 내지 수 g 정도의 소량으로 제한적이어서 대량 생산에 부적합하였다.In the cylindrical rotary reactor, the simple rotary method enables the production of uniform particles and is a low energy method that requires less energy, and has a characteristic of enabling mass production by maximizing reaction efficiency. The tumbling method in which the reactor itself rotates in the related art requires high energy and rotates the reactor at a predetermined angle, thus requiring high energy and restricting the size of the reactor. Due to the limitations of the reactor size, the amount produced is also limited to small amounts of about several hundred mg to several g, making it unsuitable for mass production.
예시적인 일 구현예에 따르면, 상기 제1모노머와 제2모노머는 동일 또는 상이할 수 있으며, 구체적으로 (메트)아크릴레이트계 모노머일 수 있다. 또한, 각 단계에서 사용되는 중합 개시제는 동일 또는 상이할 수 있고, 각 단계에서 사용되는 가교제는 동일 또는 상이할 수 있다.According to an exemplary embodiment, the first monomer and the second monomer may be the same or different, and specifically, may be a (meth) acrylate monomer. In addition, the polymerization initiator used in each step may be the same or different, and the crosslinking agent used in each step may be the same or different.
예시적인 일 구현예에 따르면, 상기 (메트)아크릴레이트계 모노머는 비치환된 탄소수 1~20의 선형 또는 분지형의 알킬기를 갖는 (메트)아크릴산 에스테르를 포함할 수 있다. 예를 들어, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 이소-부틸(메트)아크릴레이트, 펜틸(메트)아크릴레이트, 헥실(메트)아크릴레이트, 헵틸(메트)아크릴레이트, 에틸헥실(메트)아크릴레이트, 옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 노닐(메트)아크릴레이트, 데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트 등을 포함할 수 있으며, 예를 들어, 메틸메타크릴레이트일 수 있다.According to an exemplary embodiment, the (meth) acrylate monomer may include an (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylic Latex, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) Acrylate, decyl (meth) acrylate, lauryl (meth) acrylate and the like, and may be, for example, methyl methacrylate.
예시적인 일 구현예에 따르면, 상기 중합 개시제는 라디칼 중합 개시제일 수 있으며, 구체적으로, 퍼옥사이드계, 아조계 또는 이들의 혼합물일 수 있다. 또한, 과황산암모늄, 과황산나트륨, 과황산칼륨도 사용 가능하다. 예를 들어 상기 중합 개시제는 아조비스이소부티로니트릴일 수 있으나 이에 제한되지 않는다.According to one exemplary embodiment, the polymerization initiator may be a radical polymerization initiator, specifically, may be a peroxide-based, azo-based or a mixture thereof. Moreover, ammonium persulfate, sodium persulfate, potassium persulfate can also be used. For example, the polymerization initiator may be azobisisobutyronitrile, but is not limited thereto.
예시적인 일 구현예에 따르면, 상기 (1)에서 제1 모노머 및 중합 개시제는 100 내지 1000 : 0.1 내지 2 의 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.According to an exemplary embodiment, the first monomer and the polymerization initiator in (1) may be mixed in a weight ratio of 100 to 1000: 0.1 to 2. 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)에서 제1모노머, 중합 개시제 및 가교제를 첨가할 수 있다. 제1모노머, 중합 개시제 및 가교제를 중량비로 80~150: 0.5~2:0.5~2 예를 들어, 100:1:1로 혼합할 수 있다.In another aspect, in (1), the first monomer, the polymerization initiator, and the crosslinking agent may be added. The first monomer, the polymerization initiator and the crosslinking agent may be mixed in a weight ratio of 80 to 150: 0.5 to 2: 0.5 to 2, for example, 100: 1: 1.
예시적인 일 구현예에 따르면, 상기 가교제는 (메트)아크릴레이트계 가교제일 수 있으며, 예를 들어 알릴메타크릴레이트(Allyl methacrylate) 및 에틸렌글리콜디메타크릴레이트(ethylene glycol dimthacrylate) 중 하나 이상일 수 있으며, 구체적으로 알릴메타크릴레이트일 수 있다.According to an exemplary embodiment, the crosslinking agent may be a (meth) acrylate-based crosslinking agent, and may be, for example, one or more of allyl methacrylate and ethylene glycol dimthacrylate. Specifically, it may be allyl methacrylate.
양친매성 이방성 분체의 사이즈 및 형태는 초기 (1)의 제1 고분자 스페로이드 사이즈 조절에 의하여 영향받고, 제1 고분자 스페로이드 사이즈는 제1 모노머, 중합 개시제 및 가교제의 중량비에 따라 조절될 수 있다. 또한, 상기 범위의 중량비로 혼합함으로써, 이방성 분체의 균일도를 높일 수 있는 효과가 있다.The size and shape of the amphiphilic anisotropic powder are influenced by the first polymer spheroid size control of the initial stage (1), and the first polymer spheroid size can be adjusted according to the weight ratio of the first monomer, the polymerization initiator and the crosslinking agent. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
다른 측면에서, 상기 (1)에서 안정화제를 더 첨가하여 제1 모노머, 중합 개시제 및 안정화제를 100 내지 1000 : 1 : 0.001 내지 20의 중량비로 혼합할 수 있다. In another aspect, the stabilizer may be further added in (1) to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 20.
예시적인 일 구현예에 따르면, 상기 안정화제는 이온성 비닐 고분자일 수 있으며, 구체적으로 폴리비닐피롤리돈(polyvinylpyrollidone) 및 폴리비닐알코올(polyvinyl alcohol) 중 하나 이상일 수 있으며, 예를 들어 폴리비닐피롤리돈일 수 있다. 이온성 고분자는 거대 분자쇄의 팽창에 의해서 외상의 점도를 상승시켜 분체들의 유동성을 감소시킨다. 이는 고분자 중합으로 생성되는 분체들이 상호간의 엉김, 합일(결합)등을 방지, 균일한 사이즈를 유지할 수 있도록 한다. According to one exemplary embodiment, the stabilizer may be an ionic vinyl polymer, specifically one or more of polyvinylpyrollidone and polyvinyl alcohol, for example polyvinylpi It may be ralidone. Ionic polymers reduce the fluidity of powders by increasing the viscosity of the trauma phase by expansion of the macromolecular chain. This allows the powders produced by polymer polymerization to maintain a uniform size to prevent entanglement and coalescence (bonding) of each other.
또한, 양친매성 이방성 분체가 300 내지 400 nm의 크기를 가질 경우, 제1모노머, 중합 개시제 및 가교제의 중량비가 110 내지 130 : 1 : 1 내지 5, 구체적으로 115 내지 125 : 1 : 2 내지 4인 제1고분자 스페로이드로부터 제조될 수 있다. In addition, when the amphiphilic anisotropic powder has a size of 300 to 400 nm, the weight ratio of the first monomer, the polymerization initiator and the crosslinking agent is 110 to 130: 1: 1 to 5, specifically 115 to 125: 1: 1 to 2-4. It can be prepared from the first polymer spheroid.
또한, 양친매성 이방성 분체가 1100 내지 2500 nm의 크기를 가질 경우, 제1모노머, 중합 개시제 및 가교제의 중량비가 100 내지 150 : 0.5 내지 2 : 0 내지 2, 구체적으로 115 내지 125 : 1 : 0인 제1고분자 스페로이드로부터 제조될 수 있다. In addition, when the amphiphilic anisotropic powder has a size of 1100 to 2500 nm, the weight ratio of the first monomer, the polymerization initiator and the crosslinking agent is 100 to 150: 0.5 to 2: 0 to 2, specifically 115 to 125: 1: 0 It can be prepared from the first polymer spheroid.
또한, 비대칭 스노우맨 형상의 양친매성 이방성 분체는 제1 모노머, 중합 개시제 및 가교제의 중량비가 100 내지 200 : 0.1 내지 1 : 5 내지 15, 구체적으로 110 내지 130 : 1 : 9 내지 11 로 제조된 제1 고분자 스페로이드로부터 제조될 수 있다. In addition, the amphipathic anisotropic powder of the asymmetrical snowman shape is made of a weight ratio of the first monomer, the polymerization initiator, and the crosslinking agent is 100 to 200: 0.1 to 1: 5 to 15, specifically 110 to 130: 1: 9 to 11 It can be prepared from 1 polymer spheroid.
또한, 비대칭 역스노우맨 형상의 양친매성 이방성 분체는 제1 모노머, 중합 개시제 및 가교제의 중량비가 100 내지 200 : 1 : 1 내지 10, 구체적으로 110 내지 130 : 1 : 2 내지 4로 제조된 제1 고분자 스페로이드로부터 제조될 수 있다.In addition, the asymmetric inverse snowman-shaped amphiphilic anisotropic powder is a first monomer, a polymerization initiator and a crosslinking agent having a weight ratio of 100 to 200: 1: 1 to 10, specifically 110 to 130: 1: 1 to 2-4 It can be prepared from polymeric spheroids.
예시적인 일 구현예에 따르면, 상기 (2)에서 제2모노머 및 중합 개시제는 100 내지 300 : 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.According to an exemplary embodiment, the second monomer and the polymerization initiator in (2) may be mixed in a weight ratio of 100 to 300: 1. In another aspect, the second monomer and the polymerization initiator are 160 to 250: 1, or 170 to 250: 1, or 180 to 250: 1, or 190 to 250: 1, or 200 to 250: 1, or 210 to 250 It can be mixed in a weight ratio of: 1, or 220 to 250: 1, or 230 to 250: 1, or 240 to 250: 1.
다른 측면에서, 상기 (2)에서 가교제를 더 첨가하여 제2 모노머, 중합 개시제 및 가교제를 100 내지 300 : 1 : 0.001 내지 10의 중량비로 혼합할 수 있다. 상기 범위의 중량비로 혼합함으로써, 이방성 분체의 균일도를 높일 수 있는 효과가 있다.In another aspect, the second monomer, the polymerization initiator and the crosslinking agent may be mixed in a weight ratio of 100 to 300: 1: 1: 0.001 to 10 by further adding a crosslinking agent in the above (2). By mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
예시적인 일 구현예에 따르면, 상기 가교제는 (메트)아크릴레이트계 가교제일 수 있으며, 예를 들어 알릴메타크릴레이트(Allyl methacrylate) 및 에틸렌글리콜디메타크릴레이트(ethylene glycol dimthacrylate) 중 하나 이상일 수 있으며, 구체적으로 에틸렌글리콜디메타크릴레이트일 수 있다.According to an exemplary embodiment, the crosslinking agent may be a (meth) acrylate-based crosslinking agent, and may be, for example, one or more of allyl methacrylate and ethylene glycol dimthacrylate. For example, ethylene glycol dimethacrylate may be used.
다른 측면에서, 상기 (2)에서 안정화제를 더 첨가하여 제1 모노머, 중합 개시제 및 안정화제를 100 내지 1000 : 1 : 0.001 내지 20의 중량비로 혼합할 수 있다. In another aspect, the stabilizer may be further added in (2) to mix the first monomer, the polymerization initiator, and the stabilizer in a weight ratio of 100 to 1000: 1: 0.001 to 20.
예시적인 일 구현예에 따르면, 상기 안정화제는 이온성 비닐 고분자일 수 있으며, 구체적으로 폴리비닐피롤리돈(polyvinylpyrollidone) 및 폴리비닐알코올(polyvinyl alcohol) 중 하나 이상일 수 있으며, 예를 들어 폴리비닐알코올일 수 있다.According to one exemplary embodiment, the stabilizer may be an ionic vinyl polymer, specifically, one or more of polyvinylpyrollidone and polyvinyl alcohol, for example, polyvinyl alcohol Can be.
예시적인 일 구현예에 따르면, 상기 (2)단계에서 제2모노머 함량은 제1 고분자 스페로이드 중량이 100 중량부일 때 40 내지 300 중량부로 혼합할 수 있다. 구체적으로, 제2모노머 함량이 제1 고분자 스페로이드 중량이 100 중량부일 때 20 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.According to one exemplary embodiment, the second monomer content in the step (2) may be mixed to 40 to 300 parts by weight when the first polymer spheroid weight is 100 parts by weight. Specifically, when the second monomer content is 20 to 100 parts by weight when the weight of the first polymer spheroid is 100 parts by weight, an asymmetrical snowman type powder is obtained, and when it is 100 to 150 parts by weight, or 110 to 150 parts by weight, a symmetrical shape Powder is obtained, and when it is 150 to 300 parts by weight, or 160 to 300 parts by weight, an asymmetric reverse snowman type powder is obtained. Moreover, by mixing in the weight ratio of the said range, there exists an effect which can raise the uniformity of anisotropic powder.
예시적인 일 구현예에 따르면, 상기 (3)에서 친수성 관능기는 이에 제한하는 것은 아니나, 실란 커플링제와 반응 조절제를 이용하여 도입할 수 있다.According to an exemplary embodiment, the hydrophilic functional group in (3) is not limited thereto, but may be introduced using a silane coupling agent and a reaction modifier.
예시적인 일 구현예에 따르면, 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.According to one exemplary embodiment, the silane coupling agent is (3-aminopropyl) trimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl ) Propyl] ethylenediammonium chloride, (N-succinyl-3-aminopropyl) trimethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea and 3-[(trimethoxysilyl) propyloxy ] -1,2-propanediol may be one or more selected from the group consisting of, specifically N- [3- (trimethoxysilyl) propyl] ethylenediamine.
예시적인 일 구현예에 따르면, 상기 실란 커플링제는 상기 (2)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.According to an exemplary embodiment, the silane coupling agent may be mixed in an amount of 35 parts by weight to 65 parts by weight, for example, 40 parts by weight to 60 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in step (2). . Hydrophilization can be suitably made within the said range.
예시적인 일 구현예에 따르면, 상기 반응 조절제는 암모늄 하이드록사이드일 수 있다.According to one exemplary embodiment, the reaction modifier may be ammonium hydroxide.
예시적인 일 구현예에 따르면, 상기 반응 조절제는 상기 (2)에서 제조된 이방성 분체 100중량부에 대하여 85중량부 내지 115중량부, 예를 들어 90중량부 내지 110중량부로 혼합할 수 있다. 상기 범위 내에서 친수화가 적절하게 이루어질 수 있다.According to an exemplary embodiment, the reaction control agent may be mixed in an amount of 85 parts by weight to 115 parts by weight, for example, 90 parts by weight to 110 parts by weight, based on 100 parts by weight of the anisotropic powder prepared in (2). Hydrophilization can be suitably made within the said range.
종래 피커링에 사용되는 구형 분체 입자들에 양친성 계면활성력을 부여하여 그 계면활성력을 증가시키려는 시도들이 이루어져 왔고 그 예로 야누스 구형 입자가 있으나, 기하학적인 한계성 및 균일한 대량 생산이 어려운 문제점이 있어 실질적인 응용이 이루어지지 않았다. 반면, 본 명세서에 개시된 상기 양친매성 이방성 분체의 제조방법은 가교제를 사용하지 않아 제조상 엉김이 없어 수율이 높고 균일하며, 단순 교반 방법을 이용하여 텀블링 방법에 비해 대량 생산이 용이하다. 특히, 400 nm 이하 크기의 나노 사이즈를 수십 g 내지 수십 kg 단위로 대량 생산할 수 있는 이점이 있다.Attempts have been made to increase the interfacial activity by imparting an amphiphilic surfactant to spherical powder particles used in conventional pickling. Examples are Janus spherical particles, but geometric limitations and uniform mass production are difficult. No practical application has been made. On the other hand, the method of manufacturing the amphiphilic anisotropic powder disclosed in the present specification does not use a crosslinking agent, there is no entanglement in production, the yield is high and uniform, and mass production is easier than the tumbling method using a simple stirring method. In particular, there is an advantage that can be mass-produced in a unit of several tens g to several tens of kilograms of nano size of 400 nm or less.
일 측면에서, 본 명세서에 개시된 기술은 화장료 조성물에 있어서, 상기 조성물은 양친매성 이방성 분체를 포함는 화장료 조성물을 제공한다.In one aspect, the technology disclosed herein provides a cosmetic composition wherein the composition comprises an amphipathic anisotropic powder.
상기 양친매성 이방성 분체는 상술한 바와 같으므로 설명을 생략한다.Since the amphipathic anisotropic powder is as described above, a description thereof will be omitted.
상기 양친매성 이방성 분체는 화장료 조성물 전체 중량을 기준으로 0.1 내지 15 중량% 함유될 수 있다. 상기 범위 내에서 유화력이 우수하고 안정화된 에멀젼을 형성하는 화장료 조성물을 제공할 수 있다.The amphiphilic anisotropic powder may be contained in an amount of 0.1 to 15% by weight based on the total weight of the cosmetic composition. It is possible to provide a cosmetic composition having excellent emulsifying power within the above range and forming a stabilized emulsion.
본 발명 일 실시예에 따른 화장료 조성물의 제조방법은 상기 양친매성 이방성 분체를 제조하고, 상기 제조된 양친매성 이방성 분체를 이용하여 유상부 및 수상부를 유화하는 것을 포함할 수 있다.The method of manufacturing a cosmetic composition according to an embodiment of the present invention may include preparing the amphiphilic anisotropic powder and emulsifying the oil phase part and the water phase using the prepared amphipathic anisotropic powder.
상기 양친매성 이방성 분체의 제조는 상술한 바와 같으므로 설명을 생략한다.Since the preparation of the amphipathic anisotropic powder is as described above, the description is omitted.
도 6은 본 발명의 일 실시예에 따른 양친매성 이방성 분체를 이용한 유화 형태를 나타내는 모식도이다. 상기 화장료 조성물은 기존 계면활성제의 특징인 양친매성과 거대 분체 입자의 특징인 기하학적 성질을 조절하여 화학적 계면활성력 및 물리적 계면활성력을 극대화시킨 양친매성 이방성 분체를 함유함으로써, 유화력이 우수하고 안정화된 에멀젼을 형성할 수 있다. 6 is a schematic diagram showing an emulsified form using amphiphilic anisotropic powder according to an embodiment of the present invention. The cosmetic composition contains an amphiphilic anisotropic powder that maximizes chemical and physical surfactant properties by adjusting the geometric properties of the amphipathic and macromolecular particles, which are the characteristics of the existing surfactants, to provide excellent emulsification and stabilization. Emulsions may be formed.
상기 화장료 조성물은 다양한 제형으로 제조가 가능하고 기존 계면활성제의 끈적임이나 자극감이 없이 매트한 사용감을 갖는 화장료 조성물을 제공하는 효과가 있다.The cosmetic composition can be prepared in a variety of formulations and has the effect of providing a cosmetic composition having a matte feeling without the stickiness or irritation of the existing surfactant.
본 실시예에 따른 조성물은 과량의 계면활성제를 포함하지 않고도 안정한 유화 제형을 제공할 수 있어, 피부 안정성이 우수할 수 있다.The composition according to this embodiment can provide a stable emulsion formulation without including an excess of surfactant, it can be excellent skin stability.
본 실시예에 따른 조성물은 넓은 온도 범위에서 경시 유화 안정성을 나타낼 수 있으며, 상기 온도는 예를 들어 -15℃ 내지 60℃일 수 있다.The composition according to the present embodiment may exhibit emulsion stability over time in a wide temperature range, and the temperature may be, for example, -15 ° C to 60 ° C.
본 실시예에 따른 조성물은 거대 유화입자를 포함하여 유연하고 부드러운 사용감을 제공할 수 있다.The composition according to the present embodiment may include a large emulsified particle to provide a flexible and soft feeling.
본 발명의 실시예들에 따른 화장료 조성물은 화장품학 또는 피부과학적으로 허용가능한 매질 또는 기제를 함유하여 제형화될 수 있다. 이는 국소적용에 적합한 모든 제형으로서, 현탁액, 마이크로에멀젼, 마이크로캡슐, 미세과립구 또는 이온형(리포좀) 및 비이온형의 소낭 분산제의 형태로, 또는 크림, 스킨, 로션, 파우더, 연고, 스프레이 또는 콘실 스틱의 형태로 제공될 수 있다. 또한 포말(foam)의 형태로 또는 압축된 추진제를 더 함유한 에어로졸 조성물의 형태로도 사용될 수 있다. 이들 조성물은 당해 분야의 통상적인 방법에 따라 제조될 수 있다.Cosmetic compositions according to embodiments of the present invention may be formulated containing a cosmetically or dermatologically acceptable medium or base. It is any formulation suitable for topical application, in the form of suspensions, microemulsions, microcapsules, microgranules or ionic (liposomal) and nonionic vesicle dispersants or creams, skins, lotions, powders, ointments, sprays or concealers. It may be provided in the form of a stick. It may also be used in the form of a foam or in the form of an aerosol composition further containing a compressed propellant. These compositions can be prepared according to conventional methods in the art.
또한, 본 발명의 실시예들에 따른 화장료 조성물은 분체, 지방 물질, 유기용매, 용해제, 농축제, 겔화제, 연화제, 항산화제, 현탁화제, 안정화제, 발포제(foaming agent), 방향제, 계면활성제, 물, 이온형 또는 비이온형 유화제, 충전제, 금속이온봉쇄제, 킬레이트화제, 보존제, 비타민, 차단제, 습윤화제, 필수 오일, 염료, 안료, 친수성 또는 친유성 활성제, 지질 소낭 또는 화장품에 통상적으로 사용되는 임의의 다른 성분과 같은 화장품학 또는 피부과학 분야에서 통상적으로 사용되는 보조제를 함유할 수 있다. 상기 보조제는 화장품학 또는 피부과학 분야에서 일반적으로 사용되는 양으로 도입된다. 본 발명의 실시예들에 따른 화장료 조성물은 피부 개선 효과를 증가시키기 위하여 피부 흡수 촉진 물질을 더 함유할 수 있다.In addition, the cosmetic composition according to the embodiments of the present invention may be a powder, a fatty substance, an organic solvent, a dissolving agent, a thickening agent, a gelling agent, a softening agent, an antioxidant, a suspending agent, a stabilizer, a foaming agent, a fragrance, a surfactant. Commonly used in water, ionic or nonionic emulsifiers, fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles or cosmetics It may contain adjuvants conventionally used in the cosmetic or dermatological fields, such as any other ingredients used. Such adjuvants are introduced in amounts generally used in the cosmetic or dermatological arts. The cosmetic composition according to the embodiments of the present invention may further contain a skin absorption promoting substance to increase the skin improving effect.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples.
[[ 실시예Example 1]  One] 양친매성Amphipathic 이방성  Anisotropy 분체의Powder 제조 Produce
1-1. 1-1. 폴리메틸메타크릴레이트Polymethyl methacrylate (PMMA) 제1 고분자 (PMMA) first polymer 스페로이드Spheroid 제조 Produce
물 80g, 메탄올 20g 및 안정화제로서 폴리비닐피롤리돈(PVP, Mw 360,000)를 혼합하여 분산 용액을 제조하고, 메틸메타크릴레이트 10g, 중합 개시제로서 아조비스이소부티로니트릴(Azobisisobutyronitrile, AIBN) 0.1g alc 가교제로서 알릴메타크릴레이트 0.1g을 혼합하여 모노머 용액을 제조한다. 모노머 용액을 분산 용액에 첨가하고 30분간 질소 퍼징한 후, 62℃ 12시간동안 반응시켰다. 반응은 원통형 회전 반응기에서 교반하였으며, 원통형 회전 반응기는 지름 11cm, 높이 17cm, 유리재질이고, 500 rpm의 속도로 회전시켰다.A dispersion solution was prepared by mixing 80 g of water, 20 g of methanol and polyvinylpyrrolidone (PVP, Mw 360,000) as a stabilizer, and 10 g of methyl methacrylate, 0.1 azobisisobutyronitrile (AIBN) as a polymerization initiator. A monomer solution is prepared by mixing 0.1 g of allyl methacrylate as a g alc crosslinking agent. The monomer solution was added to the dispersion solution and purged with nitrogen for 30 minutes, followed by reaction at 62 ° C for 12 hours. The reaction was stirred in a cylindrical rotary reactor, the cylindrical rotary reactor was 11 cm in diameter, 17 cm in height, glass, and was rotated at a speed of 500 rpm.
얻어진 제1고분자 스페로이드에 메탄올을 넣어 원심분리기로 12000rpm에서 60분씩 3회 세척하고, 감압펌프로 상온 건조 후 막자사발로 분쇄하여 분체로 제조하였다. 도 4에 제조된 제1고분자 스페로이드의 전자현미경 사진을 나타낸다.Methanol was added to the obtained first polymer spheroid and washed three times at 12000 rpm for 60 minutes using a centrifugal separator. The mixture was dried at room temperature with a vacuum pump, and then ground in a mortar to prepare a powder. An electron micrograph of the first polymer spheroid prepared in FIG. 4 is shown.
1-2. 1-2. 양친매성Amphipathic 이방성  Anisotropy 분체Powder 제조 Produce
물 37g 및 안정화제로 폴리비닐알코올 1.38g을 혼합하여 분산용액을 제조한다. 상기 제조예 1에서 제조된 제1고분자 스페로이드 0.5g과 상기 분산용액을 혼합하여 상온, 500rpm으로 한시간 동안 혼합하고, 여기에 메틸메타크릴레이트 5.0g, 가교제로서 에틸렌글리콜디메타크릴레이트 0.5g 및 중합 개시제로서 아조비스이소부티로니트릴 0.05g의 혼합물을 첨가하여 상온에서 500rpm으로 24시간 동안 반응시킨다. 저해제로서 하이드로퀴논(hydroquinone) 0.025g을 첨가하고 75℃, 500rpm으로 24시간 동안 반응 시킨다. 반응은 원통형 회전 반응기에서 수행하였고, 이후 메탄올을 넣어 원심분리기로 12000rpm에서 60분씩 3회 세척하고, 감압펌프로 상온 건조 후 막자사발로 분쇄하여 분체로 제조하였다. 약 350nm 크기의 양친매성 이방성 분체가 제조되었으며, 현미경 사진을 도 5에 나타낸다.37 g of water and 1.38 g of polyvinyl alcohol were mixed with a stabilizer to prepare a dispersion solution. 0.5 g of the first polymer spheroid prepared in Preparation Example 1 and the dispersion solution were mixed and mixed at room temperature and 500 rpm for one hour, and therein, 5.0 g of methyl methacrylate, 0.5 g of ethylene glycol dimethacrylate as a crosslinking agent, and A mixture of 0.05 g of azobisisobutyronitrile was added as a polymerization initiator and reacted at 500 rpm for 24 hours at room temperature. 0.025 g of hydroquinone is added as an inhibitor and reacted at 75 ° C. and 500 rpm for 24 hours. The reaction was carried out in a cylindrical rotary reactor, after which methanol was added and washed three times for 60 minutes at 12000 rpm with a centrifugal separator. After drying at room temperature with a vacuum pump, the mixture was ground with a mortar to prepare a powder. Amphipathic anisotropic powder of about 350 nm size was prepared and a micrograph is shown in FIG. 5.
[[ 실시예Example 2]  2] 친수화Hydrophilization 처리 된Processed 양친매성Amphipathic 이방성  Anisotropy 분체의Powder 제조 Produce
상기 실시예 1에서 얻어진 양친매성 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 교반하였다. 상기 실란 커플링제로 이용된 화합물은 도 8에 나타내었다. 30 g of N- [3- (trimethoxysilyl) propyl] ethylenediamine (N- [3- (trimethoxysilyl) propyl] ethylenediamine) as a silane coupling agent in 600 g of the aqueous dispersion solution of the amphiphilic anisotropic powder obtained in Example 1; As a reaction regulator, 60 g of ammonium hydroxide was mixed and reacted at 25 ° C. for 24 hours to introduce a hydrophilic functional group. The reaction was stirred in a cylindrical rotary reactor. The compound used as the silane coupling agent is shown in FIG. 8.
[[ 실시예Example 3]  3] 양친매성Amphipathic 이방성  Anisotropy 분체Powder 제조 Produce
각 사용 성분의 함량을 하기 표 1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 방법으로 양친매성 이방성 분체를 제조하였다.Amphiphilic anisotropic powder was prepared in the same manner as in Example 1, except that the content of each used ingredient was changed as shown in Table 1 below.
약 2㎛ 크기의 양친매성 이방성 분체가 제조되었으며, 현미경 사진을 도 6에 나타낸다.Amphipathic anisotropic powder of about 2 μm in size was prepared and a micrograph is shown in FIG. 6.
Figure PCTKR2016013712-appb-T000001
Figure PCTKR2016013712-appb-T000001
[[ 실시예Example 4~7] 유화  4 ~ 7] oil painting 화장료Cosmetics 조성물의 제조 Preparation of the composition
상기 제조예 2에서 얻어진 양친매성 이방성 분체를 이용한 에멀젼 화장료 조성물을 제조하였다. 수중유형(O/W), 유중수형(W/O), W/O/W, O/W/O의 멀티플 제형을 각각 제조하였고, 구체적인 조성은 하기 표 2~4와 같다.An emulsion cosmetic composition using the amphipathic anisotropic powder obtained in Preparation Example 2 was prepared. Multiple formulations of oil-in-water (O / W), water-in-oil (W / O), W / O / W, O / W / O were prepared, and specific compositions are shown in Tables 2 to 4 below.
중량%weight% 실시예 1 (O/W)Example 1 (O / W) 실시예 2 (W/O)Example 2 (W / O)
Puresyn4Puresyn4 2525 7575
CetosKDCetoskd 0.80.8 0.50.5
DBDB 0.30.3 0.250.25
C981C981 0.20.2 --
PEPE 0.40.4 0.30.3
TAUTAU 0.10.1 --
WaterWater up to 100up to 100 up to 100up to 100
중량%weight% 실시예 3 (W/O/W)Example 3 (W / O / W)
실시예 2(W/O)Example 2 (W / O) 1616
DBDB 0.50.5
C981C981 1One
TAUTAU 0.10.1
PEPE 0.050.05
WaterWater up to 100up to 100
중량%weight% 실시예 4 (O/W/O)Example 4 (O / W / O)
Puresyn4Puresyn4 8585
실시예1(O/W)Example 1 (O / W) 77
DBDB 0.50.5
C981 (1%)C981 (1%) --
PEPE 0.20.2
TAUTAU --
WaterWater up to 100up to 100
Puresyn4 : Hydrogenated poly(C6-14) olefin (오일)Puresyn4: Hydrogenated poly (C6-14) olefin (oil)
CetosKD : Cetearyl alcohol (왁스)CetosKD: Cetearyl alcohol (wax)
TAU : Tromethamine (산도조절제)TAU: Tromethamine (acid regulator)
PE : Phenoxyethanol (보존제)PE: Phenoxyethanol (preservative)
C981 : Polyacrylate (점증제)C981: Polyacrylate (Thickener)
DB : 양친매성 이방성 분체DB: Amphiphilic Anisotropic Powder
이상, 본 발명내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시태양일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의해 정의된다고 할 것이다.As described above, specific portions of the present disclosure have been described in detail, and for those skilled in the art, these specific techniques are merely preferred embodiments, and the scope of the present disclosure is not limited thereto. Will be obvious. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (20)

  1. 친수성인 제1 고분자 스페로이드 및 소수성인 제2 고분자 스페로이드를 포함하며,A hydrophilic first polymeric spheroid and a hydrophobic second polymeric spheroid,
    상기 제1 고분자 스페로이드 및 제2 고분자 스페로이드는 적어도 부분적으로 상대 고분자 스페로이드를 침투하는 구조로 결합하고,The first polymer spheroid and the second polymer spheroid are combined at least partially in a structure penetrating the relative polymer spheroid,
    상기 제1 고분자 스페로이드와 제2 고분자 스페로이드는 (메트)아크릴레이트계 고분자를 포함하는, 양친매성 이방성 분체.Amphiphilic anisotropic powder, wherein the first polymer spheroid and the second polymer spheroid contains a (meth) acrylate-based polymer.
  2. 제1항에 있어서,The method of claim 1,
    상기 (메트)아크릴레이트계 고분자는 알킬기를 갖는 (메트)아크릴레이트계 모노머의 중합체인 것을 특징으로 하는 양친매성 이방성 분체.Amphiphilic anisotropic powder, characterized in that the (meth) acrylate polymer is a polymer of a (meth) acrylate monomer having an alkyl group.
  3. 제2항에 있어서,The method of claim 2,
    상기 알킬기를 갖는 (메트)아크릴레이트계 모노머는 비치환된 탄소수 1~20의 선형 또는 분지형의 알킬기를 갖는 (메트)아크릴산 에스테르를 포함하는 양친매성 이방성 분체.Amphiphilic anisotropic powder comprising the (meth) acrylate monomer having an alkyl group comprises a (meth) acrylic acid ester having an unsubstituted linear or branched alkyl group of 1 to 20 carbon atoms.
  4. 제1항에 있어서,The method of claim 1,
    상기 제1고분자 스페로이드는 친수성 관능기가 추가로 도입된 것인, 양친매성 이방성 분체.Amphiphilic anisotropic powder is the first polymer spheroid is further introduced with a hydrophilic functional group.
  5. 제1항에 있어서,The method of claim 1,
    상기 친수성 관능기는 카르복실산기, 설폰기, 포스페이트기, 아미노기, 알콕시기, 에스테르기, 아세테이트기, 폴리에틸렌글리콜기 및 하이드록실기로 이루어진 군에서 선택되는 1 이상인 것을 특징으로 하는 양친매성 이방성 분체.Amphiphilic anisotropic powder, characterized in that the hydrophilic functional group is at least one selected from the group consisting of carboxylic acid group, sulfone group, phosphate group, amino group, alkoxy group, ester group, acetate group, polyethylene glycol group and hydroxyl group.
  6. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체는 제1 고분자 스페로이드 및 제2 고분자 스페로이드가 결합된 결합부를 기준으로 대칭 형상, 비대칭 스노우맨(snowman) 형상 또는 비대칭 역스노우맨 형상을 갖는 것을 특징으로 양친매성 이방성 분체.The amphipathic anisotropic powder has an amphipathic anisotropic powder, characterized in that it has a symmetrical shape, an asymmetrical snowman shape or an asymmetric inverse snowman shape based on the bonding portion where the first polymer spheroid and the second polymer spheroid are bonded.
  7. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체는 입자 크기가 100 내지 2500 nm인 것을 특징으로 하는 양친매성 이방성 분체.The amphipathic anisotropic powder is an amphipathic anisotropic powder, characterized in that the particle size of 100 to 2500 nm.
  8. 제1항에 있어서,The method of claim 1,
    상기 양친매성 이방성 분체는 2 내지 200 ㎛의 거대 유화 입자를 형성하는 것을 특징으로 하는 양친매성 이방성 분체.The amphipathic anisotropic powder is an amphipathic anisotropic powder, characterized in that to form large emulsion particles of 2 to 200 ㎛.
  9. 제1항 내지 제8항 중 어느 한 항의 양친매성 이방성 분체의 제조방법으로서, 상기 방법은The method for producing the amphipathic anisotropic powder according to any one of claims 1 to 8, wherein the method
    (1) 제1모노머 및 중합 개시제를 교반하여 제1 고분자 스페로이드를 제조하고; 그리고(1) stirring a first monomer and a polymerization initiator to prepare a first polymer spheroid; And
    (2) 상기 제조된 제1고분자 스페로이드를, 제2모노머 및 중합 개시제와 교반하여 제2고분자 스페로이드가 형성된 이방성 분체를 제조하는 것을 포함하는양친매성 이방성 분체의 제조방법. (2) A method for producing an amphipathic anisotropic powder comprising stirring the prepared first polymer spheroid with a second monomer and a polymerization initiator to produce an anisotropic powder having a second polymer spheroid.
  10. 제9항에 있어서,The method of claim 9,
    상기 (1)에서 제1 모노머 및 중합 개시제는 100 내지 1000 : 1의 중량비로 혼합하는, 양친매성 이방성 분체의 제조방법.The method of producing an amphipathic anisotropic powder in (1), wherein the first monomer and the polymerization initiator are mixed in a weight ratio of 100 to 1000: 1.
  11. 제9항에 있어서,The method of claim 9,
    상기 (2)에서 제2 모노머 및 중합 개시제는 150 내지 250 : 1의 중량비로 혼합하는, 양친매성 이방성 분체의 제조방법.The method of producing an amphipathic anisotropic powder in (2), wherein the second monomer and the polymerization initiator are mixed in a weight ratio of 150 to 250: 1.
  12. 제9항에 있어서,The method of claim 9,
    상기 (2)에서 제2 모노머 함량은 제1 고분자 스페로이드 중량이 100 중량부일 때 40 내지 300 중량부로 혼합하는 것을 특징으로 하는 양친매성 이방성 분체의 제조방법.The method of producing an amphipathic anisotropic powder is characterized in that the second monomer content in (2) is mixed to 40 to 300 parts by weight when the first polymer spheroid weight is 100 parts by weight.
  13. 제9항에 있어서,The method of claim 9,
    상기 (2) 단계 이후에,After the step (2),
    (3) 상기 제조된 이방성 분체에 친수성 관능기를 도입하는 것을 더 포함하는 양친매성 이방성 분체의 제조방법.(3) A method for producing an amphipathic anisotropic powder further comprising introducing a hydrophilic functional group into the prepared anisotropic powder.
  14. 제13항에 있어서,The method of claim 13,
    상기 (3)에서 친수성 관능기는 실란 커플링제와 반응 조절제를 이용하여 도입하는 것을 특징으로 하는 양친매성 이방성 분체의 제조방법.The method of producing an amphiphilic anisotropic powder, characterized in that the hydrophilic functional group in (3) is introduced using a silane coupling agent and a reaction regulator.
  15. 제14항에 있어서,The method of claim 14,
    상기 실란 커플링제는 N-[3-(트리메톡시실릴)프로필]에틸렌디아민인 것을 특징으로 하는 양친매성 이방성 분체의 제조방법.The silane coupling agent is N- [3- (trimethoxysilyl) propyl] ethylenediamine. The method for producing an amphipathic anisotropic powder.
  16. 제 14항에 있어서,The method of claim 14,
    상기 반응 조절제는 암모늄 하이드록사이드인 것을 특징으로 하는 양친매성 이방성 분체의 제조방법.The reaction control agent is a method for producing amphipathic anisotropic powder, characterized in that the ammonium hydroxide.
  17. 제1항 내지 제16항 중 어느 한 항에 따른 양친매성 이방성 분체를 포함하는 화장료 조성물.A cosmetic composition comprising an amphipathic anisotropic powder according to any one of claims 1 to 16.
  18. 제17항에 있어서,The method of claim 17,
    상기 양친매성 이방성 분체는 2 내지 200 ㎛의 거대 유화 입자를 형성하는 것을 특징으로 하는 화장료 조성물.The amphipathic anisotropic powder is a cosmetic composition, characterized in that to form large emulsion particles of 2 to 200 ㎛.
  19. 제17항에 있어서,The method of claim 17,
    상기 화장료 조성물은 수중유형(O/W), 유중수형(W/O), W/O/W 또는 O/W/O의 멀티플 제형을 갖는 유화 조성물인 것을 특징으로 하는 화장료 조성물.The cosmetic composition is an oil-in-water type (O / W), water-in-oil type (W / O), W / O / W or O / W / O cosmetic composition, characterized in that the emulsion composition having a multiple formulation.
  20. 제17항에 있어서,The method of claim 17,
    상기 양친매성 이방성 분체는 화장료 조성물 전체 중량을 기준으로 0.1 내지 15 중량% 함유된 것을 특징으로 하는 화장료 조성물.The amphipathic anisotropic powder is a cosmetic composition, characterized in that contained 0.1 to 15% by weight based on the total weight of the cosmetic composition.
PCT/KR2016/013712 2015-11-27 2016-11-25 (meth)acrylic amphipathic anisotropic powder and cosmetic composition comprising same WO2017091038A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020150167391A KR20170062044A (en) 2015-11-27 2015-11-27 (meth)acryl cosmetic composition comprising amphiphilic anisotropic particles and method for manufacturing the same
KR10-2015-0167391 2015-11-27
KR1020150167374A KR20170062034A (en) 2015-11-27 2015-11-27 (meth)acryl amphiphilic anisotropic particles and method for manufacturing the same
KR10-2015-0167374 2015-11-27

Publications (1)

Publication Number Publication Date
WO2017091038A1 true WO2017091038A1 (en) 2017-06-01

Family

ID=58764194

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/013712 WO2017091038A1 (en) 2015-11-27 2016-11-25 (meth)acrylic amphipathic anisotropic powder and cosmetic composition comprising same

Country Status (1)

Country Link
WO (1) WO2017091038A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008058297A2 (en) * 2006-11-10 2008-05-15 Harvard University Non-spherical particles
US8241651B2 (en) * 2004-11-10 2012-08-14 The Regents Of The University Of Michigan Multiphasic biofunctional nano-components and methods for use thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8241651B2 (en) * 2004-11-10 2012-08-14 The Regents Of The University Of Michigan Multiphasic biofunctional nano-components and methods for use thereof
WO2008058297A2 (en) * 2006-11-10 2008-05-15 Harvard University Non-spherical particles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KIM, JIN-WOONG ET AL.: "Synthesis of Nonspherical Colloidal Particles with Anisotropic Properties", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 128, no. 44, 2006, pages 14374 - 14377, XP055385991 *
PARK, JIN-GYU ET AL.: "High-yield Synthesis of Monodisperse Dumbbell-shaped Polymer Nanopartictes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 132, no. 17, 2010, pages 5960 - 5961, XP055385995 *
PENG, BO ET AL.: "Synthesis of Fluorescent Monodisperse Non-spherical Dumbbell-like Model Colloids", JOURNAL OF MATERIALS CHEMISTRY, vol. 22, no. 41, 2012, pages 21893 - 21900, XP055385992 *

Similar Documents

Publication Publication Date Title
WO2015183042A1 (en) Cosmetic composition containing amphiphilic anisotropic powder and method for preparing same
WO2017090998A1 (en) Bi-continuous phase emulsion composition containing amphiphilic anisotropic powder
WO2017091038A1 (en) (meth)acrylic amphipathic anisotropic powder and cosmetic composition comprising same
WO2017090990A1 (en) Silicone-in-water type emulsified cosmetic composition comprising silicone oil, and method for preparing same
WO2017090974A1 (en) Emulsion cosmetic composition containing inorganic uv blocker and method for preparing same
WO2018056750A1 (en) Oil-in-water type cosmetic material composition comprising inorganic salt and preparation method therefor
WO2018199594A1 (en) Oil-in-water type emulsion composition containing emulsion particle clusters and preparation method therefor
WO2017091037A1 (en) Emulsion cosmetic composition containing pigment powder and method for preparing same
WO2017090999A1 (en) Emulsion cosmetic composition containing ceramide and method for preparing same
WO2019108008A1 (en) Emulsion composition comprising amphiphilic anisotropic powder and having improved stability
WO2017090981A1 (en) Emulsion cosmetic composition containing solid butter and method for preparing same
WO2016108579A1 (en) Chemically anisotropic powder, and cosmetic composition containing same
WO2016108659A1 (en) Surface-modified amphiphilic anisotropic powder, emulsion composition containing same, and method for preparing same
WO2016108567A1 (en) Co-emulsification composition containing various emulsification particle sizes and method for preparing same
WO2017090989A1 (en) Emulsion cosmetic composition comprising optical interference pigment and method for preparing same
WO2015183040A1 (en) Amphiphilic anisotropic powder and method for manufacturing same
WO2016108583A1 (en) Chemically asymmetric anisotropic powder and water-in-oil (w/o) emulsification composition containing same
WO2017090972A1 (en) Emulsion cosmetic composition comprising polar organic solvent and method for preparing same
WO2016108661A1 (en) Chemical anisotropic powder and cosmetic composition, containing the same, with stabilized effective raw material
CN115466346B (en) Preparation method of polymer thickener in polar solvent
WO2017090983A1 (en) Emulsion cosmetic composition containing fine wax particles and preparation method therefor
KR20210111638A (en) Acrylic graft copolymer cosmetic composition and method for manufacturing the same
KR102645441B1 (en) A emulsion type composition of enhanced stability comprising amphiphilic anisotropic particles
CN109535350A (en) The synthetic method and application of POSS grafted fluoropolymer styrene-acrylic composite emulsion
JPH1059824A (en) Cosmetic material containing powder-resin complex

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16868934

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16868934

Country of ref document: EP

Kind code of ref document: A1