WO2020222411A1 - Compound, and cosmetic composition for near-infrared blocker, comprising same - Google Patents

Compound, and cosmetic composition for near-infrared blocker, comprising same Download PDF

Info

Publication number
WO2020222411A1
WO2020222411A1 PCT/KR2020/002622 KR2020002622W WO2020222411A1 WO 2020222411 A1 WO2020222411 A1 WO 2020222411A1 KR 2020002622 W KR2020002622 W KR 2020002622W WO 2020222411 A1 WO2020222411 A1 WO 2020222411A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
composition
formula
substituted
unsubstituted
Prior art date
Application number
PCT/KR2020/002622
Other languages
French (fr)
Korean (ko)
Inventor
오희묵
이지현
김수지
이준배
박명삼
Original Assignee
코스맥스(주)
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
Application filed by 코스맥스(주) filed Critical 코스맥스(주)
Publication of WO2020222411A1 publication Critical patent/WO2020222411A1/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
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/63—Steroids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • 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
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
    • 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
    • A61K8/0295—Liquid crystals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26—Optical properties

Definitions

  • It relates to a compound and a cosmetic composition for a near-infrared blocking agent thereof.
  • NIR near-infrared
  • Near-infrared rays promote the formation of skin wrinkles by a mechanism different from that of skin wrinkles generated by ultraviolet rays. Therefore, the currently used sunscreen alone cannot effectively block skin wrinkles.
  • the mechanism of skin wrinkles caused by near infrared rays is as follows.
  • Near-infrared rays have the ability to penetrate the epidermis, dermis and subcutaneous tissues of the skin. Thermal energy induced by infrared radiation transmitted to the skin layer promotes the expression of dermal fibroblasts and matrix metalloproteinases (MMPs) in the skin layer. MMPs exist in the dermis and are enzymes that degrade matrix proteins that support the strength and shape of the skin, causing the denaturation of matrix proteins (such as collagen). For this reason, when near-infrared rays penetrate the skin, skin wrinkles and skin aging may occur.
  • MMPs matrix metalloproteinases
  • Titanium dioxide is mainly used as a material for blocking near-infrared rays, but due to the nature of the material, a white clouding phenomenon occurs. This lowers the consumer's desire to purchase. In addition, since it has a photocatalytic property, there is a concern of inducing inflammation in the body when it penetrates the dermal layer or when inhaled through a respiratory system.
  • the pitch of the cholesteric liquid crystal can be freely adjusted according to the composition of the mixture to block near infrared rays of a wide range of wavelengths, and between inorganic powders of metal oxides such as titanium dioxide, which is an existing near infrared ray blocking material. It is to provide a composition that does not cause a clouding phenomenon caused by aggregation.
  • X represents a halogen group
  • Y represents an ester group or a moiety including a carbonate group
  • a particle comprising the composition is provided.
  • a cosmetic composition for a near-infrared blocker comprising the composition.
  • the composition comprising the compounds of Formula 1 and Formula according to an embodiment is transparent by selectively reflecting near infrared rays, and the pitch of the cholesteric liquid crystal can be freely adjusted according to the composition of the mixture, thereby blocking near infrared rays of a wide range of wavelengths.
  • Cloudiness caused by aggregation between inorganic powders of metal oxides such as titanium dioxide, an existing near-infrared ray blocking material does not occur, and the possibility of skin oxidation due to the photocatalytic phenomenon of titanium dioxide, an existing material, can be prevented.
  • the possibility of accumulation of metal oxides in the body due to inhalation of titanium dioxide micro and nano particles in the lungs can also be prevented.
  • FIG. 1 is a polarization microscope photograph showing that a liquid crystal composition according to an embodiment of the present invention is a cholesteric phase.
  • FIG. 2 is a diagram showing a structure of a cholesteric liquid crystal phase according to an embodiment of the present invention.
  • FIG. 3 is a diagram showing a reflection wavelength according to a cholesteric liquid crystal pitch.
  • FIG. 6 is a graph showing reflectance of a liquid crystal composition in a near infrared region according to an exemplary embodiment.
  • FIG. 7 is an image of microcapsules observed with a polarization microscope according to an embodiment of the present invention.
  • a composition according to one aspect comprises Formula 1 and Formula 2:
  • X represents a halogen group
  • Y represents a moiety including an ester group or a carbonate group
  • R and R' are each independently a substituted or unsubstituted C 1 -C 60 alkyl group Show.
  • X may be Cl, Br or I.
  • X is Cl.
  • R 1 and R 2 is each independently a substituted or unsubstituted C 1 -C 60 alkyl group, a substituted or unsubstituted C 2 -C 60 alkenyl group, a substituted or unsubstituted C 2 -C 60 alkynyl group, a substituted or unsubstituted C 1 -C 60 alkoxy group, substituted or unsubstituted C 3 -C 10 cycloalkyl group, substituted or unsubstituted C 1 -C 10 heterocycloalkyl group, substituted or unsubstituted C 3 -C 10 cycloalkenyl group and substituted or It may be selected from unsubstituted C 1 -C 10 heterocycloalkenyl groups.
  • Y may be an organic radical or organic radicals
  • R and R'in Formulas 1 and 2 may be represented by Formula 2a:
  • * represents a bond with a neighboring atom.
  • R 1 may be represented by the following Formula 3a
  • R 2 may be represented by the following Formula 3b:
  • * represents a bond with a neighboring atom.
  • R 2 represents Cl
  • R represents the following Formula 2a
  • R'in Formula 2 represents the following Formula 2a
  • R 2 can be represented by the following formula 3b:
  • the composition may include 20 to 40% by weight of the compound of Formula 1, and 60 to 80% by weight of the compound of Formula 2.
  • the composition includes 30 to 35% by weight of the compound of Formula 1, and 65 to 70% by weight of the compound of Formula 2.
  • the weight% ratio of the compound of Formula 1 and the compound of Formula 2 may be 1:1 to 1:4.
  • the weight percent ratio of the compound of formula 1 and the compound of formula 2 is 1:1 to 1:3.
  • the composition may be a composition having cholesteric liquid crystal properties.
  • Having a cholesteric liquid crystal property means that when the liquid crystal molecules are in a cholesteric phase, a twist is added to the molecules oriented in a certain direction to form a spiral shape in a direction perpendicular to the layer as a whole. This is schematically shown in FIG. 2.
  • FIG. 3 is a diagram showing a reflection wavelength according to a cholesteric liquid crystal pitch.
  • n e is the ideal refractive index, and n o is the normal refractive index.
  • the liquid crystal molecules When light enters the liquid crystal molecules, it has a different refractive index depending on the polarization direction, so the speed of progress changes. For example, if the refractive index of a specific liquid crystal molecule in the direction of the long axis of the molecule is large (ideal refractive index, n e ), and the refractive index in the direction perpendicular to the long axis of the molecule is small (normal refractive index, n o ), the light incident on the molecule is the long axis The light in the polarization direction horizontal to and horizontal will be delayed, and the light in the polarization direction perpendicular to the long axis will have little delay.
  • n e ideal refractive index
  • n o normal refractive index
  • the refractive index is (speed of light in vacuum) ⁇ (speed of light in medium). For this reason, birefringence of light occurs. If such birefringence occurs in the cholesteric phase of the liquid crystal, light having a wavelength corresponding to the equation of ⁇ is n ⁇ P is continuously phase delayed along the helical structure of the liquid crystal.
  • the cholesteric liquid crystal has a left-handed helical structure
  • light incident on the left circularly polarized light is reflected, and light incident on the right circularly polarized light passes through the liquid crystal as it is.
  • the wavelength of light conforming to the above principle varies according to the pitch of the cholesteric liquid crystal, the wavelength of light to be reflected can be selected by adjusting the pitch.
  • the average refractive index (n) may also change according to the composition of the liquid crystal mixture.
  • the area of the reflection wavelength which is the product of the refractive index and the liquid crystal pitch, is in the near-infrared area. Accordingly, it may have a characteristic of reflecting near infrared rays.
  • the refractive index of the composition having cholesteric liquid crystal properties may be 1.1 to 1.9 at 25°C to 40°C, and a liquid crystal pitch may be 400 to 600 nm.
  • the wavelength range reflected by the composition may be specifically 700 to 1800 nm.
  • the wavelength range that the composition reflects is 700 to 1100 nm.
  • Microcapsules according to another aspect may contain the composition.
  • the microcapsules can be manufactured by a generally known method, and for detailed manufacturing methods, see Examples.
  • the microcapsules may be lipozoohms.
  • the cosmetic composition for a near-infrared blocker comprising according to another aspect may include the composition.
  • the composition may be present in particles (eg, microcapsules).
  • the cosmetic composition for the near-infrared blocking agent may include particles (eg, microcapsules), and the particles (eg, microcapsules) may include a composition including compounds of Formulas 1 and 2.
  • the cosmetic composition for the near-infrared ray blocking agent is generally used in cosmetics in addition to particles (eg, microcapsules) containing the compounds of Formulas 1 and 2, carriers containing at least one oil phase, covalent agents, fats and waxes , Stabilizers, thickeners, biologically active ingredients, film-forming agents, fragrances, colorants, pearlescent agents, preservatives, pigments, electrolytes (eg, magnesium sulfate), pH adjusters, antioxidants, surfactants, etc. , But is not limited thereto.
  • the C 1 -C 60 alkyl group refers to a linear or branched aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and specific examples include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl Group, ter-butyl group, pentyl group, iso-amyl group, hexyl group, and the like.
  • a C 1 -C 60 alkylene group refers to a divalent group having the same structure as the C 1 -C 60 alkyl group.
  • the C 2 -C 60 alkenyl group refers to a hydrocarbon group including one or more carbon double bonds in the middle or terminal of the C 2 -C 60 alkyl group, and specific examples thereof include ethenyl group, propenyl group, butenyl group And the like.
  • the C 2 -C 60 alkenylene group refers to a divalent group having the same structure as the C 2 -C 60 alkenyl group.
  • the C 2 -C 60 alkynyl group refers to a hydrocarbon group including one or more carbon triple bonds in the middle or terminal of the C 2 -C 60 alkyl group, and specific examples thereof include an ethynyl group, a propynyl group, and the like. Included.
  • the C 2 -C 60 alkynylene group refers to a divalent group having the same structure as the C 2 -C 60 alkynyl group.
  • the C 1 -C 60 alkoxy group refers to a monovalent group having the formula of -OA 101 (here, A 101 is the C 1 -C 60 alkyl group), and specific examples thereof include a methoxy group, an ethoxy group And an isopropyloxy group.
  • the C 3 -C 10 cycloalkyl group refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo And heptyl group.
  • a C 3 -C 10 cycloalkylene group refers to a divalent group having the same structure as the C 3 -C 10 cycloalkyl group.
  • the C 1 -C 10 heterocycloalkyl group refers to a monovalent monocyclic group having 1 to 10 carbon atoms including at least one hetero atom selected from N, O, Si, P and S as a ring-forming atom, and , Specific examples thereof include 1,2,3,4-oxatriazolidinyl group (1,2,3,4-oxatriazolidinyl), tetrahydrofuranyl, tetrahydrothiophenyl group, and the like.
  • the C 1 -C 10 heterocycloalkylene group refers to a divalent group having the same structure as the C 1 -C 10 heterocycloalkyl group.
  • the C 3 -C 10 cycloalkenyl group is a monovalent monocyclic group having 3 to 10 carbon atoms, and refers to a group having at least one double bond in the ring, but not having aromaticity. Examples include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like.
  • the C 3 -C 10 cycloalkenylene group refers to a divalent group having the same structure as the C 3 -C 10 cycloalkenyl group.
  • the C 1 -C 10 heterocycloalkenyl group is a monovalent monocyclic group having 1 to 10 carbon atoms including at least one hetero atom selected from N, O, Si, P and S as a ring-forming atom, and Has at least one double bond within.
  • Specific examples of the C 1 -C 10 heterocycloalkenyl group include 4,5-dihydro-1,2,3,4-oxatriazolyl group, 2,3-dihydrofuranyl group, and 2,3-dihydro And a thiophenyl group.
  • the C 1 -C 10 heterocycloalkenylene group refers to a divalent group having the same structure as the C 1 -C 10 heterocycloalkenyl group.
  • a substituted C 1 -C 60 alkyl group, a substituted C 2 -C 60 alkenyl group, a substituted C 2 -C 60 alkynyl group, a substituted C 1 -C 60 alkoxy group, a substituted C 3 -C 10 At least one of the substituents of a cycloalkyl group, a substituted C 1 -C 10 heterocycloalkyl group, a substituted C 3 -C 10 cycloalkenyl group, and a substituted C 1 -C 10 heterocycloalkenyl group,
  • Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 3 -C 10 cycloalkyl group, C 1 -C 10 hetero cycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heteroaryl cycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 aryl come T, C 1 -C 60 heteroaryl group, monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed heteropolycyclic group, -Si(Q 11 )(Q 12 )(Q 13 ), -N(Q 11 )(Q 12 ), -B(Q 11 )(Q 12 ), -C( O)(Q 11 ), -S(
  • the Q 11 to Q 13 , Q 21 to Q 23 and Q 31 to Q 33 are independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, ami Dino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent non-aromatic A condensed polycyclic group, a monovalent non-aromatic heterocondensed polycyclic group, a C 1 -C 60 alky
  • * and *' mean a bonding site with a neighboring atom in the corresponding formula.
  • Particles according to another aspect include a composition comprising the compounds of Formula 1 and Formula 2.
  • the composition including the compounds of Formulas 1 and 2 may be encapsulated in particles.
  • the particles may be microcapsules.
  • the particles may be a biodegradable polymer.
  • the biodegradable polymer are polystyrene (polystyrene), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polytetrafluoro Ethylene (PTFE), aliphatic polyester polymer, poly(L-lactic acid) (PLLA), poly(D,L-lactic acid) (PDLLA), poly(glycolic acid) (PGA), poly(caprolactone) (PCL) ), poly(hydroxyalkanoate), polydioxanone (PDS), polytrimethylene carbonate, or a copolymer of these units poly(lactic acid-co-glycolic acid) (PLGA), poly(L -Lactic acid-co-caprolactone) (PLCL), poly(glycolic acid-co-caprolactone) (PGCL), derivatives thereof, and
  • a cosmetic composition comprising the compounds of Formulas 1 and 2, or a skin external preparation or cosmetic composition comprising the particles (eg, microparticles).
  • the composition comprising the compounds of Formula 1 and Formula 2 has a near-infrared blocking effect, and may be usefully used in the external preparation for skin or cosmetic composition. Therefore, the skin external preparation or cosmetic composition may be a near-infrared blocking skin external preparation or a cosmetic composition.
  • the cosmetic composition of the present invention may be formulated as, for example, a liquid product, lotion, essence, cream, sun lotion, sun cream, makeup base, foundation, BB cream, stick-shaped product, or balm type product, etc. It is not limited thereto.
  • oil, water, surfactants, moisturizers, lower alcohols, thickeners, chelating agents, preservatives, fragrances, etc. may be additionally selected and added according to the formulation to be prepared.
  • a sunscreen agent, a light scattering agent, and the like may be included, and the formulation and additive components thereof are not limited to the above contents.
  • the above ingredients may be introduced in amounts generally used in the field of dermatology.
  • the cosmetic composition includes additional ingredients commonly used in cosmetics, such as thickeners, dispersants, flavors, fillers, preservatives, preservatives, neutralizing agents, sweeteners, vitamins, free-radical scavengers, metal ion sequestering agents, functional ingredients, and these Any conventional cosmetic ingredients that may be selected from mixtures of may further be included.
  • the external preparation for skin may be a cream, gel, ointment, skin emulsifier, skin suspension, transdermal delivery patch, drug-containing bandage, lotion, or a combination thereof.
  • the external preparation for skin may be prepared and used in the form of an ointment, lotion, spray, patch, cream, powder, suspension, gel or gel.
  • the above skin external preparations are ingredients commonly used in external preparations for skin such as cosmetics and pharmaceuticals, such as aqueous ingredients, oily ingredients, powder ingredients, alcohols, moisturizers, thickeners, ultraviolet absorbers, whitening agents, preservatives, antioxidants, surfactants, fragrances. , Colorants, various skin nutrients, or combinations thereof and may be appropriately formulated according to need.
  • the external preparations for skin include metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, and gluconic acid, caffeine, tannin, bellapamil, licorice extract, glavidine, and caline.
  • Hot water extract of fruit, various herbal medicines, drugs such as tocopherol acetate, glytilithic acid, tranexamic acid and derivatives or salts thereof, vitamin C, magnesium ascorbate, glucoside ascorbic acid, arbutin, kojic acid, glucose, fructose, Sugars such as trehalose can also be appropriately blended.
  • a method for blocking near-infrared rays of an individual comprising the step of applying a composition comprising the compounds of Formula 1 and Formula 2, particles comprising the same, or a skin external preparation or cosmetic composition comprising the same to the skin. .
  • composition is the same as described above.
  • the subject may be a mammal, for example a human, cow, horse, pig, dog, sheep, goat, or cat.
  • a cholesteric liquid crystal compound of the following compounds CC (Cholesteryl chloride, Sigma-Aldrich) and COC (Cholesteryl oleyl carbonate, Sigma-Aldrich) was prepared.
  • a composition was prepared by mixing CC and COC in the ratio shown in Table 1.
  • CC and COC were put in the same container at the weight% ratio of Table 1 Heat above the phase transition temperature to become a phosphorus liquid. After that, it is sufficiently stirred so that CC and COC are homogeneously mixed.
  • FIG. 1 is a photograph of an orientation structure of a liquid crystal composition according to an embodiment of the present invention observed with a polarization microscope.
  • the characteristic polarization image texture shown in FIG. 1 is Example 3 Indicates that the composition of is in the cholesteric phase at that temperature.
  • a typical temperature range of room temperature or body temperature is 25°C to 36.5°C.
  • the phase transition temperature which is the temperature at which the cholesteric phase becomes an isotropic liquid, is preferably higher than 25°C.
  • the phase transition temperature from the isotropic liquid to the cholesteric phase is preferably higher than 25°C.
  • phase transition temperature of the compositions of Examples 1, 2, and 3 is higher than 25°C. If it has an appropriate composition ratio, it is possible to reflect near-infrared rays in a desired temperature range.
  • FIG. 4 is a graph showing a change in a central reflection wavelength versus temperature according to a mixture composition of Formulas 1 and 2 according to an embodiment of the present invention
  • FIG. 6 is a graph showing a reflectance according to a wavelength of a liquid crystal composition according to an embodiment of the present invention. to be.
  • the range of the reflection wavelength varies depending on the mixing composition ratio of the compounds of Formula 1 and Formula 2 according to an embodiment of the present invention.
  • composition was stirred at 38° C. and 300 rpm for 10 hours to evaporate DCM and then cooled to room temperature.
  • composition was washed with distilled water and decanting was repeated 3 times to obtain microcapsules.
  • FIG. 7 is an image of microcapsules observed with a polarization microscope according to an embodiment of the present invention. Referring to FIG. 7, it can be seen that a bright shape is confirmed due to the liquid crystal in the microcapsules in the polarized picture. This means that the liquid crystal composition is properly encapsulated in the microcapsules.
  • Cosmetics prepared in this way may also have an effect of blocking near-infrared rays due to the liquid crystal contained in the microcapsules.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Disclosed are: a composition comprising compounds of chemical formulas 1 and 2; particles comprising same; and a cosmetic composition for a near-infrared blocker.

Description

화합물 및 이를 포함하는 근적외선 차단제용 화장료 조성물Compound and cosmetic composition for near-infrared blocking agent containing the same
화합물 및 이를 근적외선 차단제용 화장료 조성물에 관한 것이다. It relates to a compound and a cosmetic composition for a near-infrared blocking agent thereof.
최근 연구에 의하면, 지표면으로 입사하는 태양광 파장 중 한 종류인 근적외선(NIR)이 피부 유해성을 가지고 있음이 밝혀지고 있다. 적외선으로 간주되는 파장인 760nm에서 1mm파장 가운데 760 ~ 1400nm와 1400 ~ 3000nm의 파장대는 각각 IR-A와 IR-B로 분류되기도 하며, IR-A와 IR-B영역이 근적외선으로 통용된다.According to a recent study, it has been revealed that near-infrared (NIR), one of the wavelengths of sunlight incident on the surface of the earth, is harmful to the skin. Among the wavelengths of 760nm to 1mm, which are considered infrared rays, the wavelength bands of 760 ~ 1400nm and 1400 ~ 3000nm are classified into IR-A and IR-B, respectively, and IR-A and IR-B regions are commonly used as near infrared rays.
근적외선은 자외선이 발생시키는 피부 주름 생성 기전과는 다른 기전으로 피부 주름 생성을 촉진시킨다. 그 때문에 현재 사용되고 있는 자외선차단제 만으로는 피부 주름 생성 현상 등을 효과적으로 차단할 수 없다. 근적외선이 일으키는 피부 주름 생성 기전은 다음과 같다.Near-infrared rays promote the formation of skin wrinkles by a mechanism different from that of skin wrinkles generated by ultraviolet rays. Therefore, the currently used sunscreen alone cannot effectively block skin wrinkles. The mechanism of skin wrinkles caused by near infrared rays is as follows.
근적외선은 피부의 표피와 진피, 피하조직까지 침투가 가능한 특성을 가진다. 피부층으로 전달된 적외선의 복사에너지가 유발한 열에너지는 섬유아세포(dermal fibroblasts)와 피부 층 내에 Matrix metalloproteinases (MMPs)의 발현을 촉진시킨다. MMPs는 진피에 존재하며 피부의 강도와 형태를 지지해주는 역할을 하는 기질단백질의 분해하는 효소로써 기질단백질(콜라겐 등)의 변성을 일으킨다. 이 때문에 근적외선이 피부에 침투할 경우 피부 주름, 피부 노화 현상을 수반할 수 있다. Near-infrared rays have the ability to penetrate the epidermis, dermis and subcutaneous tissues of the skin. Thermal energy induced by infrared radiation transmitted to the skin layer promotes the expression of dermal fibroblasts and matrix metalloproteinases (MMPs) in the skin layer. MMPs exist in the dermis and are enzymes that degrade matrix proteins that support the strength and shape of the skin, causing the denaturation of matrix proteins (such as collagen). For this reason, when near-infrared rays penetrate the skin, skin wrinkles and skin aging may occur.
근적외선을 차단하기 위한 소재로는 티타늄디옥사이드가 주로 사용되나 소재의 특성상 피부가 하얗게 보이는 백탁현상이 발생한다. 이는 소비자의 구매욕구를 저하시킨다. 또한 광촉매 성질을 가지기 때문에 진피층 침투 시, 또는 호흡기로 흡입 시에는 체내 염증 유발의 우려가 존재한다.Titanium dioxide is mainly used as a material for blocking near-infrared rays, but due to the nature of the material, a white clouding phenomenon occurs. This lowers the consumer's desire to purchase. In addition, since it has a photocatalytic property, there is a concern of inducing inflammation in the body when it penetrates the dermal layer or when inhaled through a respiratory system.
최근 근적외선을 차단할 물질로써 Polymethylmethacrylate(PMMA)를 금속산화물인 세륨 옥사이드/알루미늄 옥사이드 등으로 코팅한 복합분체가 연구된 바 있다. 또 다른 예로 지르코늄디옥사이드 표면에 실리카가 코팅된 복합분체가 연구된 바 있다.Recently, a composite powder coated with polymethylmethacrylate (PMMA) as a material to block near infrared rays with a metal oxide such as cerium oxide/aluminum oxide has been studied. As another example, a composite powder coated with silica on the surface of zirconium dioxide has been studied.
근적외선을 선택 반사시킴으로 투명하고, 혼합물의 조성에 따라 콜레스테릭 액정의 피치를 자유자재로 조절 가능하여 광범위한 파장의 근적외선 차단이 가능하며, 기존 근적외선 차단 소재인 티타늄디옥사이드와 같은 금속산화물의 무기 분체 간 응집으로 인해 발생하는 백탁현상이 발생하지 않는 조성물 등을 제공하는 것이다.It is transparent by selectively reflecting near infrared rays, and the pitch of the cholesteric liquid crystal can be freely adjusted according to the composition of the mixture to block near infrared rays of a wide range of wavelengths, and between inorganic powders of metal oxides such as titanium dioxide, which is an existing near infrared ray blocking material. It is to provide a composition that does not cause a clouding phenomenon caused by aggregation.
일 측면에 따르면,According to one aspect,
하기 화학식 1 및 화학식 2를 포함하는 조성물이 제공된다:There is provided a composition comprising Formula 1 and Formula 2:
<화학식 1><Formula 1>
Figure PCTKR2020002622-appb-I000001
Figure PCTKR2020002622-appb-I000001
<화학식 2><Formula 2>
Figure PCTKR2020002622-appb-I000002
Figure PCTKR2020002622-appb-I000002
상기 화학식 1 및 2에서, X는 할로겐기를 나타내고, Y는 에스테르기 또는 카보네이트기를 포함하는 모이어티를 나타내며, R 및 R'는 각각 독립적으로 치환 또는 비치환된 C1-C60알킬기를 나타낸다.In Formulas 1 and 2, X represents a halogen group, Y represents an ester group or a moiety including a carbonate group, and R and R'each independently represent a substituted or unsubstituted C 1 -C 60 alkyl group.
다른 일 측면에 따르면, 상기 조성물을 포함하는 입자가 제공된다.According to another aspect, a particle comprising the composition is provided.
또 다른 일 측면에 따르면, 상기 조성물을 포함하는 근적외선 차단제용 화장료 조성물이 제공된다. According to another aspect, there is provided a cosmetic composition for a near-infrared blocker comprising the composition.
일 구현예에 따른 화학식 1 및 화학식의 화합물을 포함하는 조성물은 근적외선을 선택 반사시킴으로 투명하고, 혼합물의 조성에 따라 콜레스테릭 액정의 피치를 자유자재로 조절 가능하여 광범위한 파장의 근적외선 차단이 가능하며, 기존 근적외선 차단 소재인 티타늄디옥사이드와 같은 금속산화물의 무기 분체 간 응집으로 인해 발생하는 백탁현상이 발생하지 않으며, 기존 소재인 티타늄디옥사이드의 광촉매 현상으로 인한 피부 산화 발생 가능성을 예방할 수 있으며, 기존 소재인 티타늄디옥사이드 마이크로, 나노 입자의 폐 흡입으로 인한 금속 산화물의 체내 축적 가능성도 예방 할 수 있다.The composition comprising the compounds of Formula 1 and Formula according to an embodiment is transparent by selectively reflecting near infrared rays, and the pitch of the cholesteric liquid crystal can be freely adjusted according to the composition of the mixture, thereby blocking near infrared rays of a wide range of wavelengths. , Cloudiness caused by aggregation between inorganic powders of metal oxides such as titanium dioxide, an existing near-infrared ray blocking material, does not occur, and the possibility of skin oxidation due to the photocatalytic phenomenon of titanium dioxide, an existing material, can be prevented. The possibility of accumulation of metal oxides in the body due to inhalation of titanium dioxide micro and nano particles in the lungs can also be prevented.
도 1은 본 발명의 일 실시예에 따른 액정 조성물이 콜레스테릭상임을 나타내는 편광현미경 사진이다.1 is a polarization microscope photograph showing that a liquid crystal composition according to an embodiment of the present invention is a cholesteric phase.
도 2는 본 발명의 일 실시예에 따른 콜레스테릭 액정상 구조를 나타낸 도면이다.2 is a diagram showing a structure of a cholesteric liquid crystal phase according to an embodiment of the present invention.
도 3은 콜레스테릭 액정 피치에 따른 반사 파장을 나타낸 도면이다.3 is a diagram showing a reflection wavelength according to a cholesteric liquid crystal pitch.
도 4는 본 발명의 일 실시예에 따른 화학식 1 및 화학식 2의 혼합 조성에 따른 온도 대비 중심 반사 파장 변화를 나타낸 그래프이다.4 is a graph showing a change in center reflection wavelength versus temperature according to a mixture composition of Formulas 1 and 2 according to an embodiment of the present invention.
도 5는 화학식 1의 화합물 및 화학식 2의 화합물의 실시예에 따른 다양한 조성의 혼합물들의 상전이 온도를 나타낸 그래프이다.5 is a graph showing the phase transition temperatures of mixtures of various compositions according to examples of the compound of Formula 1 and the compound of Formula 2;
도 6은 일 구체예에 따른 액정 조성물의 근적외선 영역에서의 반사율을 나타낸 그래프이다.6 is a graph showing reflectance of a liquid crystal composition in a near infrared region according to an exemplary embodiment.
도 7은 본 발명의 일 실시예에 따른 마이크로캡슐을 편광 현미경으로 관찰한 이미지이다.7 is an image of microcapsules observed with a polarization microscope according to an embodiment of the present invention.
일 측면에 따른 조성물은 하기 화학식 1 및 화학식 2를 포함한다:A composition according to one aspect comprises Formula 1 and Formula 2:
<화학식 1><Formula 1>
Figure PCTKR2020002622-appb-I000003
Figure PCTKR2020002622-appb-I000003
<화학식 2><Formula 2>
Figure PCTKR2020002622-appb-I000004
Figure PCTKR2020002622-appb-I000004
상기 화학식 1 및 2에서, X는 할로겐기를 나타내고, Y는 에스테르기 또는 카보네이트기를 포함하는 모이어티(moiety)를 나타내며, R 및 R'는 각각 독립적으로 치환 또는 비치환된 C1-C60알킬기를 나타낸다. In Formulas 1 and 2, X represents a halogen group, Y represents a moiety including an ester group or a carbonate group, and R and R'are each independently a substituted or unsubstituted C 1 -C 60 alkyl group Show.
일 구현예에 따르면, 상기 화학식 1에서 X는 Cl, Br 또는 I일 수 있다. 예를 들어 상기 화학식 1에서 X는 Cl이다.According to an embodiment, in Formula 1, X may be Cl, Br or I. For example, in Formula 1, X is Cl.
일 구현예에 따르면, 상기 화학식 2에서 에스테르기를 포함하는 모이어티는 R1(C=O)O-이고, 카보네이트기를 포함하는 모이어티는 R2O(C=O)O-이며, R1 및 R2는 각각 독립적으로 치환 또는 비치환된 C1-C60알킬기, 치환 또는 비치환된 C2-C60알케닐기, 치환 또는 비치환된 C2-C60알키닐기, 치환 또는 비치환된 C1-C60알콕시기, 치환 또는 비치환된 C3-C10시클로알킬기, 치환 또는 비치환된 C1-C10헤테로시클로알킬기, 치환 또는 비치환된 C3-C10시클로알케닐기 및 치환 또는 비치환된 C1-C10헤테로시클로알케닐기 중에서 선택될 수 있다. 예를 들어, Y는 1 이상의 이중 결합을 포함하는 알케닐기일 수 있으며, 상기 이중 결합은 시스(cis) 형태일 수 있다.According to an embodiment, in Formula 2, the moiety including an ester group is R 1 (C=O)O-, and the moiety including a carbonate group is R 2 O(C=O)O-, R 1 and R 2 is each independently a substituted or unsubstituted C 1 -C 60 alkyl group, a substituted or unsubstituted C 2 -C 60 alkenyl group, a substituted or unsubstituted C 2 -C 60 alkynyl group, a substituted or unsubstituted C 1 -C 60 alkoxy group, substituted or unsubstituted C 3 -C 10 cycloalkyl group, substituted or unsubstituted C 1 -C 10 heterocycloalkyl group, substituted or unsubstituted C 3 -C 10 cycloalkenyl group and substituted or It may be selected from unsubstituted C 1 -C 10 heterocycloalkenyl groups. For example, Y may be an alkenyl group including one or more double bonds, and the double bond may be in a cis form.
일 구현예에 따르면, 상기 화학식 1 및 화학식 2에서 R 및 R'는 하기 화학식 2a로 나타내질 수 있다:According to an embodiment, R and R'in Formulas 1 and 2 may be represented by Formula 2a:
Figure PCTKR2020002622-appb-I000005
Figure PCTKR2020002622-appb-I000005
화학식 2a에서 *는 이웃 원자와의 결합을 나타낸다.In Formula 2a, * represents a bond with a neighboring atom.
일 구현예에 따르면, 상기 R1은 하기 화학식 3a로 나타내지고, R2는 하기 화학식 3b로 나타내질 수 있다:According to an embodiment, R 1 may be represented by the following Formula 3a, and R 2 may be represented by the following Formula 3b:
Figure PCTKR2020002622-appb-I000006
Figure PCTKR2020002622-appb-I000006
화학식 3a 및 3b에서 *는 이웃 원자와의 결합을 나타낸다.In Formulas 3a and 3b, * represents a bond with a neighboring atom.
일 구현예에 따르면, 상기 화학식 1에서, X는 Cl을 나타내고, R은 하기 화학식 2a를 나타내고, 화학식 2에서 R'은 하기 화학식 2a를 나타내고, Y는 R2O(C=O)O-이고 R2는 하기 화학식 3b로 나타낼 수 있다:According to an embodiment, in Formula 1, X represents Cl, R represents the following Formula 2a, R'in Formula 2 represents the following Formula 2a, and Y is R 2 O(C=O)O-, R 2 can be represented by the following formula 3b:
Figure PCTKR2020002622-appb-I000007
Figure PCTKR2020002622-appb-I000007
Figure PCTKR2020002622-appb-I000008
Figure PCTKR2020002622-appb-I000008
화학식 2a 및 3a에서 *는 이웃 원자와의 결합을 나타낸다.In Formulas 2a and 3a, * represents a bond with a neighboring atom.
즉, 화학식 1 및 2의 화합물은 각각 하기 화학식 3 및 4로 나타내질 수 있다:That is, the compounds of Formulas 1 and 2 may be represented by Formulas 3 and 4, respectively:
<화학식 3><Formula 3>
Figure PCTKR2020002622-appb-I000009
Figure PCTKR2020002622-appb-I000009
<화학식 4><Formula 4>
Figure PCTKR2020002622-appb-I000010
Figure PCTKR2020002622-appb-I000010
일 구현예에 따르면, 상기 조성물은 화학식 1의 화합물을 20 내지 40 중량% 포함하고, 화학식 2의 화합물을 60 내지 80 중량% 포함할 수 있다. 예를 들어, 상기 조성물은 화학식 1의 화합물을 30 내지 35 중량% 포함하고, 화학식 2의 화합물을 65 내지 70 중량% 포함한다.According to one embodiment, the composition may include 20 to 40% by weight of the compound of Formula 1, and 60 to 80% by weight of the compound of Formula 2. For example, the composition includes 30 to 35% by weight of the compound of Formula 1, and 65 to 70% by weight of the compound of Formula 2.
일 구현예에 따르면, 상기 조성물에서 화학식 1의 화합물 및 화학식 2의 화합물의 중량% 비는 1:1 내지 1:4일 수 있다. 예를 들어, 화학식 1의 화합물 및 화학식 2의 화합물의 중량% 비는 1:1 내지 1:3이다.According to an embodiment, in the composition, the weight% ratio of the compound of Formula 1 and the compound of Formula 2 may be 1:1 to 1:4. For example, the weight percent ratio of the compound of formula 1 and the compound of formula 2 is 1:1 to 1:3.
일 구현예에 따르면, 상기 조성물은 콜레스테릭 액정 성질을 갖는 조성물일 수 있다. 콜레스테릭 액정 성질을 갖는다는 것은 액정 분자가 콜레스테릭상일 때일정한 방향으로 배향되어 있는 분자에 비틀림이 더해져 전체적으로 층과 수직의 방향으로 나선 모양을 이루는 상태임을 말한다. 이를 도식적으로 나타내면 도 2와 같다. According to one embodiment, the composition may be a composition having cholesteric liquid crystal properties. Having a cholesteric liquid crystal property means that when the liquid crystal molecules are in a cholesteric phase, a twist is added to the molecules oriented in a certain direction to form a spiral shape in a direction perpendicular to the layer as a whole. This is schematically shown in FIG. 2.
콜레스테릭 액정은 비등방성인 불투명한 콜레스테릭 상으로 존재할 때 도 2와 같이 분자들이 주기적으로 꼬여 있는 구조를 가진다. 따라서, 액정의 피치를 조절함에 의해 브래그 법칙(Bragg's law)에 근거하여 다음과 같은 λ(반사파장) = n(평균 액정 굴절률)×P(액정pitch)에 근거하여 입사광을 선택적으로 반사시키는 것이 가능하다. 예를 들어, 콜레스테릭 액정의 평균 굴절률을 1.5로 가정하면(25℃), 액정 피치를 507 nm 이상으로 증가시키면 입사광의 선택반사파장을 760nm 이상 범위의 근적외선 영역으로 이동시키는 것이 가능하다. 한편, 액정의 피치 조절은 서로 다른 콜레스테릭 액정 화합물을 특정한 비율로 혼합하면 가능하다. Cholesteric liquid crystals have a structure in which molecules are periodically twisted as shown in FIG. 2 when present in an anisotropic, opaque cholesteric phase. Therefore, by adjusting the pitch of the liquid crystal, it is possible to selectively reflect incident light based on the following λ (reflection wavelength) = n (average liquid crystal refractive index) x P (liquid crystal pitch) based on Bragg's law. Do. For example, assuming that the average refractive index of the cholesteric liquid crystal is 1.5 (25°C), if the liquid crystal pitch is increased to 507 nm or more, it is possible to move the selective reflection wavelength of the incident light to the near infrared region in the range of 760 nm or more. On the other hand, the pitch of the liquid crystal can be adjusted by mixing different cholesteric liquid crystal compounds in a specific ratio.
도 3은 콜레스테릭 액정 피치에 따른 반사 파장을 나타낸 도면이다.3 is a diagram showing a reflection wavelength according to a cholesteric liquid crystal pitch.
도 3을 참조하면, 반사되는 파장 범위 △λ는 n△×P(pitch)로 나타내질 수 있으며, 여기서, △n = ne - no 이다. ne는 이상굴절률이고, no 은 정상굴절률이다.Referring to FIG. 3, the reflected wavelength range Δλ may be expressed as nΔ×P (pitch), where Δn = n e -n o . n e is the ideal refractive index, and n o is the normal refractive index.
빛이 액정 분자로 입사하면 편광 방향에 따라 다른 굴절률을 가지므로 진행속도가 달라진다. 예를 들어 특정 액정 분자의 분자의 장축 방향의 굴절률이 크고 (이상굴절률, ne), 분자의 장축에 수직한 방향의 굴절률이 작다면 (정상굴절률, no), 분자에 입사된 빛은 장축과 수평한 편광방향의 빛은 지연되고 장축과 수직한 편광방향의 빛은 지연이 거의 되지 않을 것이다. 굴절률은 (진공에서의 빛의 속도) ÷ (매질에서의 빛의 속도) 이다. 이 때문에 빛의 복굴절 현상이 발생하게 된다. 이러한 복굴절 현상이 액정의 콜레스테릭상에서 일어나게 된다면 λ는 n×P의 식에 부합되는 파장의 빛이 액정의 나선 구조를 따라 연속적으로 위상지연된다.When light enters the liquid crystal molecules, it has a different refractive index depending on the polarization direction, so the speed of progress changes. For example, if the refractive index of a specific liquid crystal molecule in the direction of the long axis of the molecule is large (ideal refractive index, n e ), and the refractive index in the direction perpendicular to the long axis of the molecule is small (normal refractive index, n o ), the light incident on the molecule is the long axis The light in the polarization direction horizontal to and horizontal will be delayed, and the light in the polarization direction perpendicular to the long axis will have little delay. The refractive index is (speed of light in vacuum) ÷ (speed of light in medium). For this reason, birefringence of light occurs. If such birefringence occurs in the cholesteric phase of the liquid crystal, light having a wavelength corresponding to the equation of λ is n×P is continuously phase delayed along the helical structure of the liquid crystal.
이때 콜레스테릭 액정이 좌선성 나선구조를 가진다면 좌원편광으로 입사된 빛은 반사되고, 우원편광으로 입사된 빛은 액정을 그대로 투과한다. 이것이 콜레스테릭 액정이 빛을 선택적으로 반사하는 원리이다. 앞서 서술한대로 콜레스테릭 액정의 피치에 따라 위 원리에 부합하는 빛의 파장이 달라지므로 피치를 조절함으로써 반사시키고자 하는 빛의 파장을 선택할 수 있다. At this time, if the cholesteric liquid crystal has a left-handed helical structure, light incident on the left circularly polarized light is reflected, and light incident on the right circularly polarized light passes through the liquid crystal as it is. This is the principle that cholesteric liquid crystals selectively reflect light. As described above, since the wavelength of light conforming to the above principle varies according to the pitch of the cholesteric liquid crystal, the wavelength of light to be reflected can be selected by adjusting the pitch.
또한 액정 화합물들은 모두 고유한 굴절률을 가지고 있으므로 액정 혼합물 조성에 따라 평균 굴절률(n) 역시 변화할 수 있다.In addition, since all of the liquid crystal compounds have their own refractive index, the average refractive index (n) may also change according to the composition of the liquid crystal mixture.
본 발명의 일 구현예에 따른 상기 조성물에서 화학식 1의 화합물 및 화학식 2의 화합물이 각각 상기 중량% 범위로서 상기 중량% 비를 가지는 경우, 굴절률과 액정 피치를 곱한 값인 반사 파장의 영역이 근적외선 영역에 해당하여 근적외선을 반사시키는 특성을 가질 수 있다. In the composition according to an embodiment of the present invention, when the compound of Formula 1 and the compound of Formula 2 each have the weight% ratio as the weight% range, the area of the reflection wavelength, which is the product of the refractive index and the liquid crystal pitch, is in the near-infrared area. Accordingly, it may have a characteristic of reflecting near infrared rays.
일 구현예에 따르면, 콜레스테릭 액정 성질을 갖는 상기 조성물의 굴절률은 25℃ 내지 40℃에서 1.1 내지 1.9이고, 액정 피치(pitch)가 400 내지 600nm일 수 있다. According to one embodiment, the refractive index of the composition having cholesteric liquid crystal properties may be 1.1 to 1.9 at 25°C to 40°C, and a liquid crystal pitch may be 400 to 600 nm.
일 구현예에 따르면, 상기 조성물이 반사하는 파장 범위는 구체적으로 700 내지 1800nm일 수 있다. 예를 들어, 상기 조성물이 반사하는 파장 범위는 700 내지 1100nm이다.According to one embodiment, the wavelength range reflected by the composition may be specifically 700 to 1800 nm. For example, the wavelength range that the composition reflects is 700 to 1100 nm.
다른 측면에 따른 마이크로캡슐은 상기 조성물을 포함할 수 있다. 마이크로 캡슐은 일반적으로 알려진 방법으로 제조될 수 있으며, 상세한 제조 방법은 실시예를 참조한다. 예를 들어, 상기 마이크로 캡슐은 리포조옴일 수 있다. Microcapsules according to another aspect may contain the composition. The microcapsules can be manufactured by a generally known method, and for detailed manufacturing methods, see Examples. For example, the microcapsules may be lipozoohms.
또 다른 측면에 따른 포함하는 근적외선 차단제용 화장료 조성물은 상기 조성물을 포함할 수 있다. 상기 조성물은 입자(예를 들어, 마이크로캡슐) 내에 존재할 수 있다.The cosmetic composition for a near-infrared blocker comprising according to another aspect may include the composition. The composition may be present in particles (eg, microcapsules).
상기 근적외선 차단제용 화장료 조성물은 입자(예를 들어, 마이크로캡슐)를 포함할 수 있고, 상기 입자(예를 들어, 마이크로캡슐)는 화학식 1 및 화학식 2의 화합물을 포함하는 조성물을 포함할 수 있다. 상기 근적외선 차단제용 화장료 조성물은 화학식 1 및 화학식 2의 화합물을 포함하는 입자(예를 들어, 마이크로캡슐) 이외에 일반적으로 화장료에 사용되는 물, 1이상의 오일상을 포함하는 담체, 공유화제, 지방 및 왁스, 안정제, 후화제, 생물성 활성 성분, 필름 형성제, 방향제, 착색제, 진주광제, 방부제, 안료, 전해액(예를 들면, 황산마그네슘), pH 조절제, 산화 방지제, 계면 활성제 등을 포함할 수 있으나, 이에 제한되지는 않는다.The cosmetic composition for the near-infrared blocking agent may include particles (eg, microcapsules), and the particles (eg, microcapsules) may include a composition including compounds of Formulas 1 and 2. The cosmetic composition for the near-infrared ray blocking agent is generally used in cosmetics in addition to particles (eg, microcapsules) containing the compounds of Formulas 1 and 2, carriers containing at least one oil phase, covalent agents, fats and waxes , Stabilizers, thickeners, biologically active ingredients, film-forming agents, fragrances, colorants, pearlescent agents, preservatives, pigments, electrolytes (eg, magnesium sulfate), pH adjusters, antioxidants, surfactants, etc. , But is not limited thereto.
본 발명의 화학식에 사용된 치환기에 대해서 설명한다. The substituents used in the formula of the present invention will be described.
본 명세서 중 C1-C60알킬기는, 탄소수 1 내지 60의 선형 또는 분지형 지방족 탄화수소 1가(monovalent) 그룹을 의미하며, 구체적인 예에는, 메틸기, 에틸기, 프로필기, 이소부틸기, sec-부틸기, ter-부틸기, 펜틸기, iso-아밀기, 헥실기 등이 포함된다. 본 명세서 중 C1-C60알킬렌기는 상기 C1-C60알킬기와 동일한 구조를 갖는 2가(divalent) 그룹을 의미한다. In the present specification, the C 1 -C 60 alkyl group refers to a linear or branched aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and specific examples include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl Group, ter-butyl group, pentyl group, iso-amyl group, hexyl group, and the like. In the present specification, a C 1 -C 60 alkylene group refers to a divalent group having the same structure as the C 1 -C 60 alkyl group.
본 명세서 중 C2-C60알케닐기는, 상기 C2-C60알킬기의 중간 또는 말단에 하나 이상의 탄소 이중 결합을 포함한 탄화수소 그룹을 의미하며, 이의 구체적인 예에는, 에테닐기, 프로페닐기, 부테닐기 등이 포함된다. 본 명세서 중 C2-C60알케닐렌기는 상기 C2-C60알케닐기와 동일한 구조를 갖는 2가 그룹을 의미한다. In the present specification, the C 2 -C 60 alkenyl group refers to a hydrocarbon group including one or more carbon double bonds in the middle or terminal of the C 2 -C 60 alkyl group, and specific examples thereof include ethenyl group, propenyl group, butenyl group And the like. In the present specification, the C 2 -C 60 alkenylene group refers to a divalent group having the same structure as the C 2 -C 60 alkenyl group.
본 명세서 중 C2-C60알키닐기는, 상기 C2-C60알킬기의 중간 또는 말단에 하나 이상의 탄소 삼중 결합을 포함한 탄화수소 그룹을 의미하며, 이의 구체적인 예에는, 에티닐기, 프로피닐기, 등이 포함된다. 본 명세서 중 C2-C60알키닐렌기는 상기 C2-C60알키닐기와 동일한 구조를 갖는 2가 그룹을 의미한다. In the present specification, the C 2 -C 60 alkynyl group refers to a hydrocarbon group including one or more carbon triple bonds in the middle or terminal of the C 2 -C 60 alkyl group, and specific examples thereof include an ethynyl group, a propynyl group, and the like. Included. In the present specification, the C 2 -C 60 alkynylene group refers to a divalent group having the same structure as the C 2 -C 60 alkynyl group.
본 명세서 중 C1-C60알콕시기는, -OA101(여기서, A101은 상기 C1-C60알킬기임)의 화학식을 갖는 1가 그룹을 의미하며, 이의 구체적인 예에는, 메톡시기, 에톡시기, 이소프로필옥시기 등이 포함된다. In the present specification, the C 1 -C 60 alkoxy group refers to a monovalent group having the formula of -OA 101 (here, A 101 is the C 1 -C 60 alkyl group), and specific examples thereof include a methoxy group, an ethoxy group And an isopropyloxy group.
본 명세서 중 C3-C10시클로알킬기는, 탄소수 3 내지 10의 1가 포화 탄화수소 모노시클릭 그룹을 의미하며, 이의 구체예에는는 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기, 시클로헵틸기 등이 포함된다. 본 명세서 중 C3-C10시클로알킬렌기는 상기 C3-C10시클로알킬기와 동일한 구조를 갖는 2가 그룹을 의미한다.In the present specification, the C 3 -C 10 cycloalkyl group refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo And heptyl group. In the present specification, a C 3 -C 10 cycloalkylene group refers to a divalent group having the same structure as the C 3 -C 10 cycloalkyl group.
본 명세서 중 C1-C10헤테로시클로알킬기는, N, O, Si, P 및 S 중에서 선택된 적어도 하나의 헤테로 원자를 고리-형성 원자로서 포함한 탄소수 1 내지 10의 1가 모노시클릭 그룹을 의미하며, 이의 구체예에는 1,2,3,4-옥사트리아졸리디닐기(1,2,3,4-oxatriazolidinyl), 테트라히드로퓨라닐기(tetrahydrofuranyl), 테트라히드로티오페닐기 등이 포함된다. 본 명세서 중 C1-C10헤테로시클로알킬렌기는 상기 C1-C10헤테로시클로알킬기와 동일한 구조를 갖는 2가 그룹을 의미한다.In the present specification, the C 1 -C 10 heterocycloalkyl group refers to a monovalent monocyclic group having 1 to 10 carbon atoms including at least one hetero atom selected from N, O, Si, P and S as a ring-forming atom, and , Specific examples thereof include 1,2,3,4-oxatriazolidinyl group (1,2,3,4-oxatriazolidinyl), tetrahydrofuranyl, tetrahydrothiophenyl group, and the like. In the present specification, the C 1 -C 10 heterocycloalkylene group refers to a divalent group having the same structure as the C 1 -C 10 heterocycloalkyl group.
본 명세서 중 C3-C10시클로알케닐기는 탄소수 3 내지 10의 1가 모노시클릭 그룹으로서, 고리 내에 적어도 하나의 이중 결합을 가지나, 방향족성(aromaticity)을 갖지 않는 그룹을 의미하며, 이의 구체예에는 시클로펜테닐기, 시클로헥세닐기, 시클로헵테닐기 등이 포함된다. 본 명세서 중 C3-C10시클로알케닐렌기는 상기 C3-C10시클로알케닐기와 동일한 구조를 갖는 2가 그룹을 의미한다.In the present specification, the C 3 -C 10 cycloalkenyl group is a monovalent monocyclic group having 3 to 10 carbon atoms, and refers to a group having at least one double bond in the ring, but not having aromaticity. Examples include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like. In the present specification, the C 3 -C 10 cycloalkenylene group refers to a divalent group having the same structure as the C 3 -C 10 cycloalkenyl group.
본 명세서 중 C1-C10헤테로시클로알케닐기는 N, O, Si, P 및 S 중에서 선택된 적어도 하나의 헤테로 원자를 고리-형성 원자로서 포함한 탄소수 1 내지 10의 1가 모노시클릭 그룹으로서, 고리 내에 적어도 하나의 이중 결합을 갖는다. 상기 C1-C10헤테로시클로알케닐기의 구체예에는, 4,5-디히드로-1,2,3,4-옥사트리아졸일기, 2,3-디히드로퓨라닐기, 2,3-디히드로티오페닐기 등이 포함된다. 본 명세서 중 C1-C10헤테로시클로알케닐렌기는 상기 C1-C10헤테로시클로알케닐기와 동일한 구조를 갖는 2가 그룹을 의미한다.In the present specification, the C 1 -C 10 heterocycloalkenyl group is a monovalent monocyclic group having 1 to 10 carbon atoms including at least one hetero atom selected from N, O, Si, P and S as a ring-forming atom, and Has at least one double bond within. Specific examples of the C 1 -C 10 heterocycloalkenyl group include 4,5-dihydro-1,2,3,4-oxatriazolyl group, 2,3-dihydrofuranyl group, and 2,3-dihydro And a thiophenyl group. In the present specification, the C 1 -C 10 heterocycloalkenylene group refers to a divalent group having the same structure as the C 1 -C 10 heterocycloalkenyl group.
본 명세서 중, 치환된 C1-C60알킬기, 치환된 C2-C60알케닐기, 치환된 C2-C60알키닐기, 치환된 C1-C60알콕시기, 치환된 C3-C10시클로알킬기, 치환된 C1-C10헤테로시클로알킬기, 치환된 C3-C10시클로알케닐기 및 치환된 C1-C10헤테로시클로알케닐기의 치환기 중 적어도 하나는, In the present specification, a substituted C 1 -C 60 alkyl group, a substituted C 2 -C 60 alkenyl group, a substituted C 2 -C 60 alkynyl group, a substituted C 1 -C 60 alkoxy group, a substituted C 3 -C 10 At least one of the substituents of a cycloalkyl group, a substituted C 1 -C 10 heterocycloalkyl group, a substituted C 3 -C 10 cycloalkenyl group, and a substituted C 1 -C 10 heterocycloalkenyl group,
중수소(-D), -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기 및 C1-C60알콕시기; Deuterium (-D), -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2- C 60 alkenyl group, C 2 -C 60 alkynyl group and C 1 -C 60 alkoxy group;
중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q11)(Q12)(Q13), -N(Q11)(Q12), -B(Q11)(Q12), -C(=O)(Q11), -S(=O)2(Q11) 및 -P(=O)(Q11)(Q12) 중에서 선택된 적어도 하나로 치환된, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기 및 C1-C60알콕시기; Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 3 -C 10 cycloalkyl group, C 1 -C 10 hetero cycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heteroaryl cycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 aryl come T, C 1 -C 60 heteroaryl group, monovalent non-aromatic condensed polycyclic group, monovalent non-aromatic condensed heteropolycyclic group, -Si(Q 11 )(Q 12 )(Q 13 ), -N(Q 11 )(Q 12 ), -B(Q 11 )(Q 12 ), -C(=O)(Q 11 ), -S(=O) 2 (Q 11 ) and -P(=O)(Q 11 )(Q 12 ) Substituted with at least one selected from, a C 1 -C 60 alkyl group, a C 2 -C 60 alkenyl group, a C 2 -C 60 alkynyl group, and a C 1 -C 60 alkoxy group;
C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹;C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryl An oxy group, a C 6 -C 60 arylthio group, a C 1 -C 60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group and a monovalent non-aromatic condensed heteropolycyclic group;
중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, -Si(Q21)(Q22)(Q23), -N(Q21)(Q22), -B(Q21)(Q22), -C(=O)(Q21), -S(=O)2(Q21) 및 -P(=O)(Q21)(Q22) 중에서 선택된 적어도 하나로 치환된, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C6-C60아릴옥시기, C6-C60아릴티오기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹 및 1가 비-방향족 헤테로축합다환 그룹; 및Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group , C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocyclo alkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 arylthio, C 1 -C 60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non- -Aromatic heterocondensed polycyclic group, -Si(Q 21 )(Q 22 )(Q 23 ), -N(Q 21 )(Q 22 ), -B(Q 21 )(Q 22 ), -C(=O) (Q 21 ), -S(=O) 2 (Q 21 ) and -P(=O)(Q 21 )(Q 22 ) substituted with at least one selected from, C 3 -C 10 cycloalkyl group, C 1 -C 10 come heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heteroaryl cycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy, C 6 -C 60 aryl tea, A C 1 -C 60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group; And
-Si(Q31)(Q32)(Q33), -N(Q31)(Q32), -B(Q31)(Q32), -C(=O)(Q31), -S(=O)2(Q31) 및 -P(=O)(Q31)(Q32); -Si(Q 31 )(Q 32 )(Q 33 ), -N(Q 31 )(Q 32 ), -B(Q 31 )(Q 32 ), -C(=O)(Q 31 ), -S (=O) 2 (Q 31 ) and -P(=O) (Q 31 ) (Q 32 );
중에서 선택되고,Is selected from,
상기 Q11 내지 Q13, Q21 내지 Q23 및 Q31 내지 Q33은 서로 독립적으로, 수소, 중수소, -F, -Cl, -Br, -I, 히드록실기, 시아노기, 니트로기, 아미디노기, 히드라지노기, 히드라조노기, C1-C60알킬기, C2-C60알케닐기, C2-C60알키닐기, C1-C60알콕시기, C3-C10시클로알킬기, C1-C10헤테로시클로알킬기, C3-C10시클로알케닐기, C1-C10헤테로시클로알케닐기, C6-C60아릴기, C1-C60헤테로아릴기, 1가 비-방향족 축합다환 그룹, 1가 비-방향족 헤테로축합다환 그룹, 중수소, -F 및 시아노기 중에서 선택된 적어도 하나로 치환된 C1-C60알킬기, 중수소, -F 및 시아노기 중에서 선택된 적어도 하나로 치환된 C6-C60아릴기, 비페닐기 및 터페닐기 중에서 선택될 수 있다.The Q 11 to Q 13 , Q 21 to Q 23 and Q 31 to Q 33 are independently of each other, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, ami Dino group, hydrazino group, hydrazono group, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 10 cycloalkyl group, C 1 -C 10 heterocycloalkyl group, C 3 -C 10 cycloalkenyl group, C 1 -C 10 heterocycloalkenyl group, C 6 -C 60 aryl group, C 1 -C 60 heteroaryl group, monovalent non-aromatic A condensed polycyclic group, a monovalent non-aromatic heterocondensed polycyclic group, a C 1 -C 60 alkyl group substituted with at least one selected from deuterium, -F and a cyano group, C 6 -substituted with at least one selected from deuterium, -F and a cyano group It may be selected from a C 60 aryl group, a biphenyl group, and a terphenyl group.
본 명세서 중 * 및 *'은, 다른 정의가 없는 한, 해당 화학식 중 이웃한 원자와의 결합 사이트를 의미한다.In the present specification, * and *', unless otherwise defined, mean a bonding site with a neighboring atom in the corresponding formula.
다른 일 측면에 따른 입자는, 상기 화학식 1 및 화학식 2의 화합물을 포함하는 조성물을 포함한다. Particles according to another aspect include a composition comprising the compounds of Formula 1 and Formula 2.
일 구현예에 따르면, 상기 화학식 1 및 화학식 2의 화합물을 포함하는 조성물은 입자 내에 캡슐화된 것일 수 있다. 상기 입자는 마이크로캡슐일 수 있다.According to one embodiment, the composition including the compounds of Formulas 1 and 2 may be encapsulated in particles. The particles may be microcapsules.
다른 구체예에 있어서, 상기 입자는 생분해성 고분자일 수 있다. 상기 생분해성 고분자의 예는 폴리스티렌(polystyrene), 폴리메틸메타크릴레이트(PMMA), 폴리에틸렌 테레프탈레이트(PET), 폴리비닐클로라이트(PVC), 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리테트라플루오르에틸렌(PTFE), 지방족 폴리에스테르계 고분자로서, 폴리(L-락트산)(PLLA), 폴리(D,L-락트산）(PDLLA), 폴리(글리콜산)(PGA), 폴리(카프로락톤)(PCL), 폴리(하이드록시알카노에이트), 폴리다이옥산온(PDS), 폴리트라이메틸렌카보네이트 중에서 선택된 1 종이거나, 또는 이들 단위들의 공중합체인 폴리(락트산-co-글리콜산)(PLGA), 폴리(L-락트산-co-카프로락톤)(PLCL), 폴리(글리콜산-co-카프로락톤)(PGCL), 이들의 유도체 등을 포함할 수 있다. In another embodiment, the particles may be a biodegradable polymer. Examples of the biodegradable polymer are polystyrene (polystyrene), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polytetrafluoro Ethylene (PTFE), aliphatic polyester polymer, poly(L-lactic acid) (PLLA), poly(D,L-lactic acid) (PDLLA), poly(glycolic acid) (PGA), poly(caprolactone) (PCL) ), poly(hydroxyalkanoate), polydioxanone (PDS), polytrimethylene carbonate, or a copolymer of these units poly(lactic acid-co-glycolic acid) (PLGA), poly(L -Lactic acid-co-caprolactone) (PLCL), poly(glycolic acid-co-caprolactone) (PGCL), derivatives thereof, and the like.
본 발명의 일 측면에 따르면, 상기 화학식 1 및 화학식 2의 화합물을 포함하는 화장료 조성물, 또는 상기 입자(예를 들면, 마이크로 입자)를 포함하는 피부 외용제 또는 화장료 조성물을 제공한다. According to an aspect of the present invention, there is provided a cosmetic composition comprising the compounds of Formulas 1 and 2, or a skin external preparation or cosmetic composition comprising the particles (eg, microparticles).
일 구체예에 있어서, 상기 화학식 1 및 화학식 2의 화합물을 포함하는 조성물은 근적외선 차단 효과를 가져, 상기 피부 외용제 또는 화장료 조성물에 유용하게 사용될 수 있다. 따라서, 상기 피부 외용제 또는 화장료 조성물은 근적외선 차단용 피부 외용제 또는 화장료 조성물일 수 있다. In one embodiment, the composition comprising the compounds of Formula 1 and Formula 2 has a near-infrared blocking effect, and may be usefully used in the external preparation for skin or cosmetic composition. Therefore, the skin external preparation or cosmetic composition may be a near-infrared blocking skin external preparation or a cosmetic composition.
본 발명의 화장료 조성물은, 예를 들어 액상 제품, 로션, 에센스, 크림, 선로션, 선크림, 메이크업 베이스, 파운데이션, 비비크림, 스틱상 제품 또는 밤(Balm) 타입 제품 등으로 제형화될 수 있으나, 이에 한정되는 것은 아니다. 또한, 제조하고자 하는 제형에 따라 추가로 유분, 물, 계면활성제, 보습제, 저급 알콜, 증점제, 킬레이트제, 방부제, 향료 등을 선택하여 배합 첨가할 수 있다. 또한 자외선 차단제, 광산란제 등을 포함할 수 있으며, 그 제형 및 첨가성분이 상기 내용에 한정되는 것은 아니다. 또한 상기 성분들은 피부 과학 분야에서 일반적으로 사용되는 양으로 도입될 수 있다.The cosmetic composition of the present invention may be formulated as, for example, a liquid product, lotion, essence, cream, sun lotion, sun cream, makeup base, foundation, BB cream, stick-shaped product, or balm type product, etc. It is not limited thereto. In addition, oil, water, surfactants, moisturizers, lower alcohols, thickeners, chelating agents, preservatives, fragrances, etc. may be additionally selected and added according to the formulation to be prepared. In addition, a sunscreen agent, a light scattering agent, and the like may be included, and the formulation and additive components thereof are not limited to the above contents. In addition, the above ingredients may be introduced in amounts generally used in the field of dermatology.
상기 화장료 조성물은 화장품에 통상 사용되는 추가 성분, 예컨대, 점증제, 분산제, 향료, 충전제, 보존제, 방부제, 중성화제, 감미료, 비타민, 자유-라디칼 스케빈저, 금속 이온 봉쇄제, 기능성 성분 및 이들의 혼합물로부터 선택될 수 있는 임의의 통상적 미용 성분을 더 포함할 수 있다.The cosmetic composition includes additional ingredients commonly used in cosmetics, such as thickeners, dispersants, flavors, fillers, preservatives, preservatives, neutralizing agents, sweeteners, vitamins, free-radical scavengers, metal ion sequestering agents, functional ingredients, and these Any conventional cosmetic ingredients that may be selected from mixtures of may further be included.
당업자는 본 명세서에 따른 조성물의 유리한 특성이 예상된 첨가에 의해 악영향을 받지 않거나 실질적으로 받지 않도록, 임의의 추가 성분 및/또는 이의 양을 선택할 수 있다.One of skill in the art can select any additional ingredients and/or amounts thereof so that the advantageous properties of the composition according to the present specification are not adversely affected or substantially unaffected by the expected addition.
본 명세서에서, 상기 피부외용제는 크림, 겔, 연고, 피부 유화제, 피부 현탁액, 경피전달성 패치, 약물 함유 붕대, 로션, 또는 그 조합일 수 있다. 상기 피부외용제는 연고제, 로션제, 스프레이제, 패취제, 크림제, 산제, 현탁제, 겔제 또는 젤의 형태로 제조되어 사용될 수 있다. 상기 피부외용제는 통상 화장품이나 의약품 등의 피부외용제에 사용되는 성분, 예를 들면 수성성분, 유성성분, 분말성분, 알코올류, 보습제, 증점제, 자외선흡수제, 미백제, 방부제, 산화방지제, 계면활성제, 향료, 색제, 각종 피부 영양제, 또는 이들의 조합과 필요에 따라서 적절하게 배합될 수 있다. 상기 피부외용제는, 에데트산이나트륨, 에데트산삼나트륨, 시트르산나트륨, 폴리인산나트륨, 메타인산나트륨, 글루콘산 등의 금속봉쇄제, 카페인, 탄닌, 벨라파밀, 감초추출물, 글라블리딘, 칼린의 과실의 열수추출물, 각종생약, 아세트산토코페롤, 글리틸리틴산, 트라넥삼산 및 그 유도체 또는 그 염등의 약제, 비타민 C, 아스코르브산인산마그네슘, 아스코르브산글루코시드, 알부틴, 코지산, 글루코스, 프룩토스, 트레할로스 등의 당류등도 적절하게 배합할 수 있다.In the present specification, the external preparation for skin may be a cream, gel, ointment, skin emulsifier, skin suspension, transdermal delivery patch, drug-containing bandage, lotion, or a combination thereof. The external preparation for skin may be prepared and used in the form of an ointment, lotion, spray, patch, cream, powder, suspension, gel or gel. The above skin external preparations are ingredients commonly used in external preparations for skin such as cosmetics and pharmaceuticals, such as aqueous ingredients, oily ingredients, powder ingredients, alcohols, moisturizers, thickeners, ultraviolet absorbers, whitening agents, preservatives, antioxidants, surfactants, fragrances. , Colorants, various skin nutrients, or combinations thereof and may be appropriately formulated according to need. The external preparations for skin include metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, and gluconic acid, caffeine, tannin, bellapamil, licorice extract, glavidine, and caline. Hot water extract of fruit, various herbal medicines, drugs such as tocopherol acetate, glytilithic acid, tranexamic acid and derivatives or salts thereof, vitamin C, magnesium ascorbate, glucoside ascorbic acid, arbutin, kojic acid, glucose, fructose, Sugars such as trehalose can also be appropriately blended.
또한, 일 측면에 따르면, 상기 화학식 1 및 화학식 2의 화합물을 포함하는 조성물, 그를 포함하는 입자 또는 이들을 포함하는 피부외용제 또는 화장료 조성물을 피부에 도포하는 단계를 포함하는 개체의 근적외선 차단 방법을 제공한다. In addition, according to an aspect, there is provided a method for blocking near-infrared rays of an individual comprising the step of applying a composition comprising the compounds of Formula 1 and Formula 2, particles comprising the same, or a skin external preparation or cosmetic composition comprising the same to the skin. .
상기 조성물에 대해서는 상술한 바와 동일하다. 상기 개체는 포유동물, 예를 들면, 사람, 소, 말, 돼지, 개, 양, 염소, 또는 고양이일 수 있다. The composition is the same as described above. The subject may be a mammal, for example a human, cow, horse, pig, dog, sheep, goat, or cat.
이하에서, 실시예를 들어, 본 발명의 일 구현예에 따른 조성물, 이를 포함하는 입자(예를 들어, 마이크로캡슐) 및 이를 포함하는 화장료 조성물에 대하여 보다 구체적으로 설명한다. 그러나, 이들 도면 및 실시예는 본 발명을 예시적으로 설명하기 위한 것으로 본 발명의 범위가 이들 도면 및 실시예에 한정되는 것은 아니다.Hereinafter, for example, a composition according to an embodiment of the present invention, a particle (eg, microcapsule) containing the same, and a cosmetic composition containing the same will be described in more detail. However, these drawings and examples are for illustrative purposes only, and the scope of the present invention is not limited to these drawings and examples.
[실시예][Example]
콜레스테릭 액정 화합물 준비Preparation of cholesteric liquid crystal compounds
하기 화합물 CC(Cholesteryl chloride, Sigma-Aldrich) 및 COC(Cholesteryl oleyl carbonate, Sigma-Aldrich)의 콜레스테릭 액정 화합물을 준비하였다.A cholesteric liquid crystal compound of the following compounds CC (Cholesteryl chloride, Sigma-Aldrich) and COC (Cholesteryl oleyl carbonate, Sigma-Aldrich) was prepared.
Figure PCTKR2020002622-appb-I000011
Figure PCTKR2020002622-appb-I000011
CC(cholesteryl chloride) CC (cholesteryl chloride)
Figure PCTKR2020002622-appb-I000012
Figure PCTKR2020002622-appb-I000012
COC(cholesteryl oleyl carbonate) Cholesteryl oleyl carbonate (COC)
콜레스테릭 액정 조성물 제조Preparation of cholesteric liquid crystal composition
CCCC COCCOC
실시예 1Example 1 25 중량%25% by weight 75 중량%75% by weight
실시예 2Example 2 30 중량%30% by weight 70 중량%70% by weight
실시예 3Example 3 33 중량%33% by weight 67 중량%67% by weight
상기 표 1에 나타난 비율로 CC 및 COC를 혼합하여 조성물을 제조하였다.실시예 1,2,3의 혼합물이 각각 균질하게 혼합되기 위해서는 CC 및 COC를 표 1의 중량% 비로 동일 용기에 넣은 후 등방성인 액체가 되는 상전이 온도 이상으로 가열한다. 그 후 충분히 교반하여 CC 및COC가 균질하게 혼합되도록 한다. A composition was prepared by mixing CC and COC in the ratio shown in Table 1. In order for the mixtures of Examples 1,2 and 3 to be homogeneously mixed, respectively, CC and COC were put in the same container at the weight% ratio of Table 1 Heat above the phase transition temperature to become a phosphorus liquid. After that, it is sufficiently stirred so that CC and COC are homogeneously mixed.
혼합된 액정 혼합물을 슬라이드 글라스 위에 한 방울 떨어뜨린 후 커버글라스를 덮는다. 커버글라스를 손가락으로 수 차례 약하게 누르면 유리 표면과 평행하게 액정이 배향된다. 그리고 액정의 온도를 핫스테이지를 사용해 조절해 가며 편광 현미경으로 편광 이미지를 촬영하고 이를 통해 상전이 온도를 측정한다. After dropping the mixed liquid crystal mixture on the slide glass, cover the cover glass. When the cover glass is gently pressed several times with a finger, the liquid crystal is aligned parallel to the glass surface. Then, the temperature of the liquid crystal is adjusted using a hot stage, and a polarized image is taken with a polarizing microscope, and the phase transition temperature is measured through it.
액정이 일정한 온도 이상으로 승온되면 더 이상 액정 특유의 규칙적인 구조를 유지하지 못하고 투명한 등방성인 액체 상태가 된다. 그에 따라 액정상일 때 보이던 불투명한 콜레스테릭상의 특징적인 편광 이미지가 관찰되지 않게 된다. 따라서, 편광 현미경을 이용해 교차 편광판 사이에 위치한 콜레스테릭 액정의 온도에 따른 이미지 촬영은 조성물이 어떤 상으로 존재하는지를 알아 볼 수 있는 유용한 방법이다. 도 1은 본 발명의 일 실시예에 따른 액정 조성물의 배향구조를 편광현미경으로 관찰한 사진이다. 도1의 이미지는 실시예 3의 COC:CC = 67:33 액정 혼합물이 직교 편광(Anaylzer,Polarizer 수직)하에서 35℃에서 촬영된 편광 이미지로서, 도 1에 나타난 특유의 편광 이미지 texture는 실시예 3의 조성물이 해당 온도에서 콜레스테릭 상임을 나타낸다.When the liquid crystal is heated above a certain temperature, it no longer maintains the regular structure peculiar to the liquid crystal and becomes a transparent isotropic liquid state. Accordingly, the characteristic polarized image of the opaque cholesteric phase, which was seen in the liquid crystal phase, is not observed. Therefore, taking an image according to the temperature of the cholesteric liquid crystal positioned between the cross polarizing plates using a polarizing microscope is a useful method to find out which phase the composition exists. 1 is a photograph of an orientation structure of a liquid crystal composition according to an embodiment of the present invention observed with a polarization microscope. The image of FIG. 1 is a polarized image of the COC:CC = 67:33 liquid crystal mixture of Example 3 taken at 35° C. under orthogonal polarization (Anaylzer, Polarizer vertical). The characteristic polarization image texture shown in FIG. 1 is Example 3 Indicates that the composition of is in the cholesteric phase at that temperature.
통상적인 상온 또는 체온의 온도 구간은 25 ℃ 내지 36.5 ℃이다. 콜레스테릭 액정을 이용한 근적외선 차단제 조성물이 상온 또는 피부의 체온 범위에서 근적외선을 반사하기 위해서는 콜레스테릭 상에서 등방성 액체가 되는 온도인 상전이 온도가 25 ℃보다 높은 것이 바람직 하다. 또한 콜레스테릭 액정을 포함하는 근적외선 차단제 조성물이 냉각될 때 등방성 액체에서 콜레스테릭상으로 되는 상전이 온도가 25 ℃보다 높은 것이 바람직 하다. A typical temperature range of room temperature or body temperature is 25°C to 36.5°C. In order for the near-infrared blocking agent composition using a cholesteric liquid crystal to reflect near-infrared rays at room temperature or in the body temperature range of the skin, the phase transition temperature, which is the temperature at which the cholesteric phase becomes an isotropic liquid, is preferably higher than 25°C. In addition, when the near-infrared blocking agent composition containing a cholesteric liquid crystal is cooled, the phase transition temperature from the isotropic liquid to the cholesteric phase is preferably higher than 25°C.
실시예 1, 2, 3 의 조성물의 상전이 온도가 25℃보다 높은 온도임을 도 5를 통해 나타내었다. 적절한 조성비를 가지는 경우, 원하는 온도 범위에서 근적외선을 반사할 수 있다.It is shown through FIG. 5 that the phase transition temperature of the compositions of Examples 1, 2, and 3 is higher than 25°C. If it has an appropriate composition ratio, it is possible to reflect near-infrared rays in a desired temperature range.
도 4는 본 발명의 일 실시예에 따른 화학식 1 및 화학식 2의 혼합 조성에 따른 온도 대비 중심 반사 파장 변화를 나타낸 그래프이고, 도 6은 일 구체예에 따른 액정 조성물의 파장에 따른 반사율을 나타낸 그래프이다.4 is a graph showing a change in a central reflection wavelength versus temperature according to a mixture composition of Formulas 1 and 2 according to an embodiment of the present invention, and FIG. 6 is a graph showing a reflectance according to a wavelength of a liquid crystal composition according to an embodiment of the present invention. to be.
본 발명의 일 실시예에 따른 화학식 1 및 화학식 2의 화합물의 혼합 조성비에 따라, 도 4, 6으로부터 반사 파장의 범위가 달라진다는 것을 알 수 있다.It can be seen from FIGS. 4 and 6 that the range of the reflection wavelength varies depending on the mixing composition ratio of the compounds of Formula 1 and Formula 2 according to an embodiment of the present invention.
콜레스테릭 액정 조성물을 포함하는 마이크로캡슐 제조Preparation of microcapsules containing cholesteric liquid crystal composition
실시예 1의 혼합 조성물 500mg, PCL(Polycaprolactone, Mn 45,000, Sigma-Aldrich) 375mg, 및 DCM(Dichloromethane, Sigma-Aldrich) 5ml를 바이알에 넣고 볼텍스로 균질화한 후, 상기 조성물을 PVA(Poly(vinyl alcohol), -(CH2CHOH)n-: n = approx. 2000, TCI) 50ml에 첨가하고, 25℃, 1500rpm에서 20분 동안 교반하여 수중유적형(O/W) 에멀젼을 제조하였다. 500 mg of the mixed composition of Example 1, PCL (Polycaprolactone, M n 45,000, Sigma-Aldrich) 375 mg, and DCM (Dichloromethane, Sigma-Aldrich) 5 ml were placed in a vial and homogenized with a vortex, and the composition was PVA (Poly (vinyl alcohol), -(CH 2 CHOH) n -: n = approx. 2000, TCI) was added to 50 ml, and stirred at 25° C. and 1500 rpm for 20 minutes to prepare an oil-in-water (O/W) emulsion.
계속해서, 상기 조성물을 38℃, 300rpm에서 10 시간 동안 교반하여 DCM을 기화시킨 후 상온으로 냉각시켰다.Subsequently, the composition was stirred at 38° C. and 300 rpm for 10 hours to evaporate DCM and then cooled to room temperature.
상기 조성물을 증류수로 세척 및 디켄팅(decanting)을 3회 반복하여 마이크로캡슐을 얻었다.The composition was washed with distilled water and decanting was repeated 3 times to obtain microcapsules.
도 7은 본 발명의 일 실시예에 따른 마이크로캡슐을 편광 현미경으로 관찰한 이미지이다. 도 7을 참조하면, 편광 사진에서 마이크로캡슐 속의 액정으로 인하여 밝은 형상이 확인됨을 알 수 있다. 이는 마이크로캡슐 내에 액정 조성물이 적절하게 캡슐화되었음을 의미한다.7 is an image of microcapsules observed with a polarization microscope according to an embodiment of the present invention. Referring to FIG. 7, it can be seen that a bright shape is confirmed due to the liquid crystal in the microcapsules in the polarized picture. This means that the liquid crystal composition is properly encapsulated in the microcapsules.
이렇게 제조된 화장품 또한 마이크로캡슐 속에 포함된 액정으로 인하여 근적외선을 차단하는 효과를 가질 수 있다. Cosmetics prepared in this way may also have an effect of blocking near-infrared rays due to the liquid crystal contained in the microcapsules.

Claims (13)

  1. 하기 화학식 1 및 화학식 2를 포함하는 조성물:A composition comprising Formula 1 and Formula 2:
    <화학식 1><Formula 1>
    Figure PCTKR2020002622-appb-I000013
    Figure PCTKR2020002622-appb-I000013
    <화학식 2><Formula 2>
    Figure PCTKR2020002622-appb-I000014
    Figure PCTKR2020002622-appb-I000014
    상기 화학식 1 및 2에서, X는 할로겐기를 나타내고, Y는 에스테르기 또는 카보네이트기를 포함하는 모이어티(moiety)를 나타내며, R 및 R'는 각각 독립적으로 치환 또는 비치환된 C1-C60알킬기를 나타낸다. In Formulas 1 and 2, X represents a halogen group, Y represents a moiety including an ester group or a carbonate group, and R and R'are each independently a substituted or unsubstituted C 1 -C 60 alkyl group Show.
  2. 제1항에 있어서, 상기 화학식 1에서 X는 Cl, Br 또는 I인 조성물.The composition of claim 1, wherein X in Formula 1 is Cl, Br or I.
  3. 제1항에 있어서, 상기 화학식 2에서 에스테르기를 포함하는 모이어티는 R1(C=O)O-이고, 카보네이트기를 포함하는 모이어티는 R2O(C=O)O-이며, R1 및 R2는 각각 독립적으로 치환 또는 비치환된 C1-C60알킬기, 치환 또는 비치환된 C2-C60알케닐기, 치환 또는 비치환된 C2-C60알키닐기, 치환 또는 비치환된 C1-C60알콕시기, 치환 또는 비치환된 C3-C10시클로알킬기, 치환 또는 비치환된 C1-C10헤테로시클로알킬기, 치환 또는 비치환된 C3-C10시클로알케닐기 및 치환 또는 비치환된 C1-C10헤테로시클로알케닐기 중에서 선택되는 조성물.The method of claim 1, wherein the moiety including an ester group in Formula 2 is R 1 (C=O)O-, and the moiety including a carbonate group is R 2 O(C=O)O-, R 1 and R 2 is each independently a substituted or unsubstituted C 1 -C 60 alkyl group, a substituted or unsubstituted C 2 -C 60 alkenyl group, a substituted or unsubstituted C 2 -C 60 alkynyl group, a substituted or unsubstituted C 1 -C 60 alkoxy group, substituted or unsubstituted C 3 -C 10 cycloalkyl group, substituted or unsubstituted C 1 -C 10 heterocycloalkyl group, substituted or unsubstituted C 3 -C 10 cycloalkenyl group and substituted or A composition selected from unsubstituted C 1 -C 10 heterocycloalkenyl groups.
  4. 제1항에 있어서, 상기 화학식 1 및 화학식 2에서 R 및 R'는 하기 화학식 2a로 나타내지는 조성물:The composition of claim 1, wherein R and R'in Formulas 1 and 2 are represented by the following Formula 2a:
    Figure PCTKR2020002622-appb-I000015
    Figure PCTKR2020002622-appb-I000015
    화학식 2a에서 *는 이웃 원자와의 결합을 나타낸다.In Formula 2a, * represents a bond with a neighboring atom.
  5. 제3항에 있어서, 상기 R1은 하기 화학식 3a로 나타내지고, R2는 하기 화학식 3b로 나타내지는 조성물:The composition of claim 3, wherein R 1 is represented by the following formula 3a, and R 2 is represented by the following formula 3b:
    Figure PCTKR2020002622-appb-I000016
    Figure PCTKR2020002622-appb-I000016
    화학식 3a 및 3b에서 *는 이웃 원자와의 결합을 나타낸다.In Formulas 3a and 3b, * represents a bond with a neighboring atom.
  6. 제1항에 있어서, The method of claim 1,
    상기 화학식 1에서, X는 Cl이고 R은 하기 화학식 2a를 나타내고, In Formula 1, X is Cl and R represents the following Formula 2a,
    상기 화학식 2에서, R'은 하기 화학식 2a를 나타내고, Y는 R2O(C=O)O-이고 R2는 하기 화학식 3b를 나타내는 조성물:In Formula 2, R'represents the following formula 2a, Y is R 2 O(C=O)O-, and R 2 represents the following formula 3b
    Figure PCTKR2020002622-appb-I000017
    Figure PCTKR2020002622-appb-I000017
    Figure PCTKR2020002622-appb-I000018
    Figure PCTKR2020002622-appb-I000018
    화학식 2a 및 3a에서 *는 이웃 원자와의 결합을 나타낸다.In Formulas 2a and 3a, * represents a bond with a neighboring atom.
  7. 제1항에 있어서, 화학식 1의 화합물을 20 내지 40 중량% 포함하고, 화학식 2의 화합물을 60 내지 80 중량% 포함하는 조성물.The composition of claim 1, comprising 20 to 40% by weight of the compound of Formula 1 and 60 to 80% by weight of the compound of Formula 2.
  8. 제1항에 있어서, 화학식 1의 화합물 및 화학식 2의 화합물의 중량% 비가 1:1 내지 1:4인 조성물.The composition of claim 1, wherein the weight percent ratio of the compound of Formula 1 and the compound of Formula 2 is 1:1 to 1:4.
  9. 제1항의 조성물이 콜레스테릭 액정 성질을 갖는 조성물.The composition of claim 1 has cholesteric liquid crystal properties.
  10. 제9항에 있어서, 콜레스테릭 액정 성질을 갖는 상기 조성물의 굴절률이 25℃ 내지 40℃ 범위에서 1.1 내지 1.9이고, 액정 피치(pitch)가 400 내지 600nm인 조성물.The composition according to claim 9, wherein the composition having a cholesteric liquid crystal property has a refractive index of 1.1 to 1.9 in the range of 25°C to 40°C, and a liquid crystal pitch of 400 to 600 nm.
  11. 제9항에 있어서, 상기 조성물이 반사하는 파장 범위가 700 내지 1800nm인 조성물.The composition of claim 9, wherein the composition has a reflective wavelength range of 700 to 1800 nm.
  12. 제1항의 조성물을 포함하는 입자.Particles comprising the composition of claim 1.
  13. 제1항의 조성물을 포함하는 근적외선 차단제용 화장료 조성물.A cosmetic composition for a near-infrared blocking agent comprising the composition of claim 1.
PCT/KR2020/002622 2019-04-30 2020-02-24 Compound, and cosmetic composition for near-infrared blocker, comprising same WO2020222411A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2019-0050998 2019-04-30
KR1020190050998A KR102174527B1 (en) 2019-04-30 2019-04-30 Compound and Cosmetic composition comprising the same for blocking the near infrared rays

Publications (1)

Publication Number Publication Date
WO2020222411A1 true WO2020222411A1 (en) 2020-11-05

Family

ID=73028861

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/002622 WO2020222411A1 (en) 2019-04-30 2020-02-24 Compound, and cosmetic composition for near-infrared blocker, comprising same

Country Status (2)

Country Link
KR (1) KR102174527B1 (en)
WO (1) WO2020222411A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2681143B2 (en) * 1988-03-24 1997-11-26 ポーラ化成工業株式会社 Cholesteric liquid crystal composition and cosmetics containing the same
WO2009079546A1 (en) * 2007-12-19 2009-06-25 Avon Products, Inc. Cholesteric liquid crystal coloring compositions and articles produced therefrom
KR20150062261A (en) * 2013-11-28 2015-06-08 주식회사 진영바이오 Cholesterol derivatives-based liquid crystal and capsule containing the liquid crystal
KR20170138930A (en) * 2016-06-08 2017-12-18 주식회사 엘지생활건강 Cosmetic Composition Comprising Cholesteric Liquid Crystal Particles and Manufacturing Method thereof
KR20180053458A (en) * 2016-11-11 2018-05-23 주식회사 케이피티 Preparation method of cholesteric liquid crystal and cosmetic composition comprising the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012017854A1 (en) 2012-09-08 2014-05-28 Kronos International, Inc. Infrared-reflecting pigment based on titanium dioxide and process for its preparation
KR20140095736A (en) 2013-01-25 2014-08-04 주식회사 엘지생활건강 Complex powder for reflecting near infrared rays
WO2016171383A1 (en) 2015-04-22 2016-10-27 코스맥스 주식회사 Method of evaluating effectiveness of infrared ray blocking material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2681143B2 (en) * 1988-03-24 1997-11-26 ポーラ化成工業株式会社 Cholesteric liquid crystal composition and cosmetics containing the same
WO2009079546A1 (en) * 2007-12-19 2009-06-25 Avon Products, Inc. Cholesteric liquid crystal coloring compositions and articles produced therefrom
KR20150062261A (en) * 2013-11-28 2015-06-08 주식회사 진영바이오 Cholesterol derivatives-based liquid crystal and capsule containing the liquid crystal
KR20170138930A (en) * 2016-06-08 2017-12-18 주식회사 엘지생활건강 Cosmetic Composition Comprising Cholesteric Liquid Crystal Particles and Manufacturing Method thereof
KR20180053458A (en) * 2016-11-11 2018-05-23 주식회사 케이피티 Preparation method of cholesteric liquid crystal and cosmetic composition comprising the same

Also Published As

Publication number Publication date
KR102174527B1 (en) 2020-11-06

Similar Documents

Publication Publication Date Title
KR101434073B1 (en) Skin lightening compositions
DE60314404T2 (en) Body care mix with color change indicator
ES2856080T3 (en) Dispersions containing encapsulated materials and compositions using the same
CN1235617C (en) Skin lightening composition containing magnesium ascorbyl phosphate and uniontan-U34 TM (extract formulation of cucumber extract and lemon extract)
KR101715542B1 (en) Substrate with near infra-red (nir) light-emitting material
AU2008349470A1 (en) Topical compositions containing citrus jabara extract
KR20150092311A (en) Cosmetic compositions with near infra-red (nir) light-emitting material and methods therefor
KR20150092313A (en) Cosmetic compositions with near infra-red (nir) light-emitting material and methods therefor
CA3016619C (en) Resveratrol glycolate and tartrate derivatives and synthetic methods therefor
CA2901306A1 (en) Compositions with thermally-regulating material
US20080112991A1 (en) Method of enhancing skin absorption of nutrients and active agents
ES2355734T3 (en) COSMETIC COMPOSITIONS CONTAINING FLUORESCENT COLORS FOR THE NATURAL APPEARANCE OF THE SKIN.
US7153517B2 (en) Cosmetic composition structured by a thermotropic liquid crystal polymer
KR20150092312A (en) Cosmetic compositions with near infra-red (nir) light-emitting material and methods therefor
KR20150092310A (en) Cosmetic compositions with near infra-red (nir) light-emitting material and methods therefor
WO2020222411A1 (en) Compound, and cosmetic composition for near-infrared blocker, comprising same
CN111343966B (en) Composition comprising baicalin and specific acrylic polymer
JPH08268839A (en) Zinc oxide-coated extender pigment and cosmetics containing it
WO2018052260A1 (en) Makeup cosmetic composition containing scoria powder
KR100684367B1 (en) Cosmetic composition containing UV-screening polysilsesquioxane sphere
WO2010143802A1 (en) Stable reverse-phase emulsion
KR20200135579A (en) Surfactant free silicone emulsion
WO2022075657A1 (en) Method for preparing cosmetic composition containing micelle composite formed using natural moisturizing factor, and cosmetic composition prepared therefrom
US6333026B1 (en) Use of an indigoid compound in a cosmetic composition, in particular a make-up composition, in order to confer on it antimicrobial properties and the property of lengthy hold over time
KR20140081125A (en) W/O type make up cosmetic composition having temperature sensitive to clensing

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: 20799320

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: 20799320

Country of ref document: EP

Kind code of ref document: A1