WO2015046968A1 - Organic/inorganic hybrid tio2 complex, cosmetic composition containing same, and method for manufacturing same - Google Patents

Organic/inorganic hybrid tio2 complex, cosmetic composition containing same, and method for manufacturing same Download PDF

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Publication number
WO2015046968A1
WO2015046968A1 PCT/KR2014/009051 KR2014009051W WO2015046968A1 WO 2015046968 A1 WO2015046968 A1 WO 2015046968A1 KR 2014009051 W KR2014009051 W KR 2014009051W WO 2015046968 A1 WO2015046968 A1 WO 2015046968A1
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Prior art keywords
acid
titanium dioxide
organic
inorganic hybrid
aminoethyl
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PCT/KR2014/009051
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French (fr)
Korean (ko)
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김진산
황대일
이창빈
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에이스틴 주식회사
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Publication of WO2015046968A1 publication Critical patent/WO2015046968A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/612—By organic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/651—The particulate/core comprising inorganic material

Definitions

  • the present invention relates to a surface-modified titanium dioxide fine particles and a composite of an organic material and a method for producing the same, and more particularly, titanium dioxide fine particles and the surface-modified titanium dioxide fine particles so that at least one functional group is introduced to the surface Organic / inorganic hybrid titanium dioxide complex (organic / inorganic hybrid TiO 2 complex) in the form of a chemically bonded organic material containing at least one active site (reactive site) that can react with the functional group of the present invention / Inorganic hybrid titanium dioxide composite has a safe and very good sunscreen effect, can be very useful as a sunscreen.
  • the present invention relates to a method for producing the organic / inorganic hybrid titanium dioxide complex, and a cosmetic composition comprising the complex and a method for producing the same.
  • the sun protection effect of cosmetics is usually expressed in terms of Sun Protection Factor (SPF) and Protection Grade of UV-A (PA) index, which was developed to indicate how well the product protects the skin from UV rays. If the SPF index is 30, it means that it takes 30 times longer for skin to redden (erythema formation) after sun exposure, and if it is bare skin, it takes 20 minutes. If it is, it means that it protects the skin from ultraviolet rays for 600 times (10 hours), which is 30 times, and the PA index is an index indicating the degree of blocking of ultraviolet rays A (UV-A). PA +++ has the best blocking effect of UVA.
  • sunscreens used in cosmetics are classified into organic sunscreens and inorganic sunscreens.
  • Organic sunscreens exhibit UV-blocking effects mainly by absorbing UV light, and there is a conjugation bond that can absorb UV light in the molecular structure of the sunscreen, and organic sunscreens include PABA (para-aminobenzoic acid) and PABA.
  • Organic compounds such as esters (PABA esters), salicylates, camphor derivatives and cinnamates, and dibenzoylmethane, anthranilate and benzo, which block UV-A.
  • Phenone (benzophenone), triazole (triazole) is mainly used in a mixed form, but there are disadvantages such as skin toxicity, allergies and discoloration occurs.
  • an inorganic sunscreen is mainly used.
  • Inorganic sunscreens exhibit an ultraviolet-blocking effect mainly by reflecting and scattering ultraviolet light, including titanium dioxide (TiO 2 ), zinc oxide (ZnO), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), or zirconium oxide (ZrO).
  • Metal oxides such as c), ferric chloride, talc, kaolin, and ichthymol (ichthyol) are mainly used.
  • Inorganic sunscreens generally have a larger UV protection effect as the size of inorganic particles, the main component of which is a major component, is known to be toxic to humans through animal experiments. Accordingly, the National Institute for Occupational Safety and Health (NIOSH), and the tolerance and limit the taking of the inorganic particles in the nanoparticle size to 0.1mg / m 2, the Korean KFDA for cosmetics containing nanomaterials of 100 nm or less It indicates that nanomaterials are used and requires that safety proof data be provided that they are harmless to humans.
  • NIOSH National Institute for Occupational Safety and Health
  • a stable sunscreen composition including an organic sunscreen and a chelate of metal ions and improved sunscreen performance (Japanese Patent Publication No. 2010-510170) has been proposed.
  • a new formulation system that can increase the protection index for the same amount of sunscreen while reducing the amount of sunscreen, including two immiscible phases stabilized with one or more anionic surfactants and anionic surfactants and cationic or A cosmetic composition (Korean Patent Publication No. 2001-0023743) further comprising a zwitterionic amphiphilic compound has been presented.
  • the present invention is to solve the existing problems as described above, while maintaining the excellent ultraviolet protection effect of the existing sunscreen containing an inorganic nanoparticles, a new sunscreen and a method of manufacturing the same does not occur safety problems due to small particle size
  • the purpose is to provide.
  • Another object of the present invention is to provide a cosmetic composition comprising the novel sunscreen according to the present invention and a method for producing the same.
  • the present invention provides an organic / inorganic hybrid titanium dioxide composite and a sunscreen cosmetic composition comprising the same covalently bonded to titanium dioxide fine particles and organic matter.
  • the titanium dioxide fine particles are preferably surface-modified to have at least one functional group that can be covalently bonded to an organic material, and the organic material contained in the organic / inorganic hybrid titanium dioxide composite is a functional group of the surface-modified titanium dioxide fine particles. It is characterized in that it comprises at least one active site capable of reacting.
  • the present invention also provides a method for preparing a titanium dioxide particle, comprising the steps of: (a) surface modifying the titanium dioxide fine particles so that at least one functional group is introduced to the surface; And (b) mixing an organic material having at least one active site capable of bonding with a functional group on the surface-modified titanium dioxide fine particle surface.
  • the present invention provides an organic / inorganic hybrid titanium dioxide composite composed of titanium dioxide fine particles and an organic material.
  • the 'organic / inorganic hybrid titanium dioxide composite' means a substance or aggregate of such substances in which titanium dioxide fine particles and an organic substance are combined by a covalent bond, preferably covalently.
  • the titanium dioxide fine particles are surface-modified to introduce a functional group (functional group) for bonding with an organic material to the surface.
  • a functional group functional group
  • the titanium dioxide fine particles surface-modified by the silane coupling agent include at least one functional group selected from the group consisting of at least one amine group, vinyl group, epoxy group, acryloxy group, amino group, ureide group and isocyanate group on the surface. can do.
  • the surface-modified titanium dioxide fine particles according to the present invention is preferably introduced with a functional group having a structure such as formula (1) on the surface thereof.
  • the present invention is not limited thereto, and any material capable of introducing a functional group capable of binding to an organic material may be used for surface modification, and thus, any functional group capable of binding to an organic material may be introduced to the surface of the titanium dioxide fine particles. Is obvious to the skilled person.
  • R 1 represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms
  • R 2 represents hydrogen or 1 carbon atom. 10 to 10, preferably an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
  • the surface modification introduces one or more functional groups on the surface of the titanium dioxide fine particles
  • the surface-modified titanium dioxide fine particles can form a complex with one or more organic substances.
  • the aminosilane that may be used in the present invention is N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N- (2-Aminoethyl) -3-aminopropylmethyldimethoxysilane) , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane), preferably 3-aminopropyltrimethoxysilane and 3 3-aminopropyltrialkoxysilane, such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxys
  • the organic material in the present invention is characterized in that it comprises an active site capable of chemically bonding with the functional groups on the surface of the titanium dioxide fine particles.
  • the active site is a carboxylic acid, acyl halide, aldehyde, amine, carboxylate cyanate, ester, imine, sulfo Sulfonic acid, sulfoxide, thiol, alcohol, isocyanate, etc., for example, a surface-modified functional group with aminosilane
  • -COOH or -COOR or the like can be used as the active site of the organic material.
  • R may be exemplified by halogen, C 1-5 alkyl, C 6-12 aryl, alkali metal, alkaline earth metal, or -NCO, but is not limited thereto.
  • the alkali metal or alkaline earth metal is preferably selected from Na, K, Mg, but is not limited thereto.
  • Organic materials that can be used in the present invention are polyacrylic acid (Polyacrylic acid (PAA)), sodium acrylate (Sodium Polyacrylate), hexanoic acid (Hexanoic acid), polymethylene polyphenyl polyisocyanate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic, acid, azelaic acid acid, sebacic acid, undecanedioic acid, phthalic acid, maleic acid, fumaric acid, glutaconic acid, trauma Traumatic acid, muconic acid, poly (ethyleneglycol) -bis (carboxymethyl) ether, poly (ethyleneglycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride anhydride, citric acid, aconitic acid, Tricarballylic acid, trimesic acid, 2-phosphonobutane-1,2,3-tricarboxylic acid, 1,4
  • a complex is formed through a chemical bond between a functional group on the surface-modified titanium dioxide particulate surface and an active site present in the organic material.
  • the content of titanium dioxide in the organic / inorganic hybrid titanium dioxide composite is preferably 60 to 99.5 wt% based on the total weight of the composite. If the content of titanium dioxide is less than 60% by weight, the titanium dioxide content is too small to reduce the sunscreen effect. If the content of more than 99.5% by weight of organic matter is less, there is a possibility that the feeling of use is lowered and cloudiness occurs.
  • the average particle size (Dv50) of the organic / inorganic hybrid titanium dioxide composite is 0.1 to 50 ⁇ m, preferably 0.5 to 30 ⁇ m, and most preferably 1 to 20 ⁇ m.
  • the average particle size of the organic / inorganic hybrid titanium dioxide composite according to the present invention while solving the safety problems such as human hazards that may occur due to the use of small size nanoparticles (100 nm or less), organic / inorganic hybrid dioxide Since the titanium composite contains nano-sized inorganic material, that is, metal oxide, there is an advantage that the titanium composite can exhibit the same or improved performance as the sunscreen using the nano-sized inorganic material.
  • the present invention provides a method for producing the organic / inorganic hybrid titanium dioxide composite in another aspect.
  • the materials, properties, sizes, and types and properties of organic materials used for surface modification of titanium dioxide fine particles are the same as described in the organic / inorganic hybrid titanium dioxide composite.
  • the content of the titanium dioxide in the prepared organic / inorganic hybrid titanium dioxide composite, the size of the composite is also the same as described in the organic / inorganic hybrid titanium dioxide composite.
  • Surface modification of the titanium dioxide fine particles according to the step (a) is 5 to 120 minutes, preferably 10 to 60 minutes by mixing titanium dioxide particles (particulates) in one or more solutions selected from distilled water, alcohol, such as ethanol or methanol, More preferably, the mixture is stirred for 20 to 40 minutes, by adding aminosilane dissolved in a solvent such as ethanol or methanol, and stirred for 0.5 to 6 hours, preferably 1 to 5 hours, and more preferably 2 to 4 hours. Can be achieved.
  • the titanium dioxide fine particles used for the surface modification are suitably in the size of 10 to 70 nm, preferably 20 to 50 nm.
  • the method may further include adding and stirring ammonia water. Subsequent filtration, washing with alcohol and / or distilled water, and drying may additionally give fine particles of titanium dioxide surface-modified with aminosilane. All the stirring may be performed at a temperature of 10 to 50 °C, preferably 15 ⁇ 40 °C, more preferably 20 ⁇ 30 °C. "Room temperature" in the present invention means 20 ⁇ 30 °C, especially 25 °C.
  • step (b) is to prepare an organic / inorganic hybrid titanium dioxide composite
  • the organic material is added to the organic solvent and 5 to 120 minutes at 40 to 80 °C, preferably 50 to 70 °C, preferably 10 ⁇ 60 minutes, more preferably, 20 to 40 minutes of stirring to prepare an organic solution, which is mixed with an organic solvent in which the titanium dioxide fine particles obtained in step (a) are dispersed, added, and all are 10 to 50 ° C., Preferably 15 to 40 °C, more preferably 20 to 30 °C 4 to 40 hours, preferably 10 to 30 hours, more preferably 12 to 20 hours it can be made, including the step of stirring.
  • the organic solvent for dissolving the organic material is DMF (N, N-dimethylformamide), NMP (N-Methtylpyrrolidone), hexane (hexane), chloroform (chloroform), cyclohexane, benzene (benzene), toluene ), Dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, diethylether , Dimethylformamide, acetonitrile, dimethyl sulfoxide, propylene carbonate, methanol, methanol, ethanol, proranol, butanol,
  • One or more solvents selected from the group consisting of acetic acid and nitromethane may be used, but is not limited thereto, and any organic solvent may be used as long as it is suitable for the purpose of the present invention. Even it can be used.
  • the present invention provides a sunscreen cosmetic composition comprising an organic / inorganic hybrid titanium dioxide composite.
  • the sunscreen cosmetic composition including the organic / inorganic hybrid titanium dioxide composite in the present invention may be prepared by mixing a conventional O / W cream base composition and an organic / inorganic hybrid titanium dioxide composite, but are not limited thereto. It will be apparent to those skilled in the art that the components contained in the cosmetic composition commonly used in the art can be used.
  • the sunscreen cosmetic composition according to the present invention preferably contains about 0.1 to 30% by weight, preferably 0.5 to 25% by weight, and most preferably 1 to 20% by weight of the organic / inorganic hybrid titanium dioxide composite.
  • the cosmetic composition for sunscreen comprising an organic / inorganic hybrid titanium dioxide composite according to the present invention may additionally include aggregates of cationic organic / inorganic hybrid particles and anionic polymer.
  • the cosmetic composition for sunscreen is an organic / inorganic hybrid titanium dioxide composite, the aggregate of the cationic organic / inorganic hybrid particles and the anionic polymer in a weight ratio of 0.01: 99.99 to 20: 80, preferably 0.1: 99.9 to It is preferable to mix in the ratio of 10:90.
  • the "cationic organic / inorganic hybrid particles” are charged to have positive charges with inorganic materials such as metal oxides or surfaces such as metal oxides whose surfaces are modified to have cationic functional groups (functional groups).
  • CCA charge control agent
  • "cationic organic / inorganic hybrid particles” is to modify the surface of the inorganic, preferably metal oxide to have a cationic functional group, or positive charge with inorganic materials such as metal oxide It can be obtained by mixing a positively charged charge control agent to have a.
  • a method of modifying the surface of the cationic organic / inorganic hybrid particles to have a cationic functional group a method of introducing a cationic functional group to the surface of an inorganic material such as a metal oxide, preferably a surface modification with an aminosilane, Alternatively, a method of modifying the surface of an inorganic material such as a metal oxide to have an anionic functional group and then reacting a material having a polycationic functional group is preferable, but is not limited thereto.
  • the inorganic material that can be used for the cationic organic / inorganic hybrid particles is preferably a metal oxide, but is not limited thereto. It will be apparent to those skilled in the art that any inorganic material that can achieve the object of the present invention can be used.
  • the metal oxide that can be used in the present invention is at least one selected from the group consisting of titanium dioxide (TiO 2 ), zinc oxide (ZnO), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ) and zirconium oxide (ZrO). Titanium dioxide or zinc oxide is preferred.
  • the inorganic material in the present invention preferably cationic functional groups that can be introduced to the surface of the metal oxide preferably has a structure such as formula (1) or formula (2), but is not limited thereto.
  • aminosilanes that may be used for surface modification of inorganics, preferably metal oxides, in the present invention are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane), preferably 3-aminopropyltrimethoxy 3-aminopropyltrialkoxysilane, N-phenyl-3-aminoprop
  • Surface-modified inorganic materials such as metal oxides to have anionic functional groups and then reacted with a material having a polycationic functional group to modify them to have cationic functional groups on the surface of the particles, such as aminosilane, Reacting a cationic organic / inorganic hybrid particle with a material having a polyanionic functional group and modifying its surface to have an anionic functional group, and then reacting with a material having a polycationic functional group, or A method of modifying a metal oxide surface with a material having a polyanionic functional group to have a direct anionic functional group, and then reacting with a material having a polycationic functional group may be used.
  • the anionic functional group include, but are not limited to, carboxylic acid groups, phosphoric acid groups, sulfuric acid groups, sulfate groups, and the like.
  • the material having a polycationic functional group is a polyamine, preferably ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, N-methylethylenediamine, 1,4-diaminobutane , 3- (methylamino) propylamine, N, N'-dimethylethylenediamine, N, N-dimethylethylenediamine, trimethylenetetraamine, triethylenetetraamine, phenylenediamine, hexamethylenetetraamine, diaminocyclohexane
  • One or more materials selected from the group consisting of, aminobenzylamine and tetraethylenepentaamine can be used, but are not limited thereto.
  • polyacid, polyacid derivatives, or anhydrous compounds of polyacid may be used, and specifically, oxalic acid and malonic acid.
  • a positively charged charge control agent that has a positive charge is preferably used ammonium salts, especially quaternary ammonium salts, which are quaternary ammonium salts. This is because it does not affect the advantage.
  • the amount of the positively charged charge control agent is too small, since the ionicity of the organic / inorganic hybrid particles produced is not present, 0.5 wt% or more, preferably 1 wt% or more, may be included relative to the weight of the final particles to be manufactured, and about 40 wt% It is preferably used in% or less.
  • the anionic polymer may be used without limitation as long as it can form an aggregate through ionic interaction with the cationic organic / inorganic hybrid particles.
  • Pyrrolidone-acrylic acid copolymer, Methyl methacrylate-acrylic acid copolymer, Methyl methacrylate-methacrylic acid copolymer , Polyacrylic acid (PAA), polymethacrylic acid (polymethacrylic acid) and carboxymethyl cellulose (carboxymethylcellolulose) is preferably at least one selected from the group consisting of, polyacrylic acid is most preferred.
  • Cosmetic compositions according to the invention can be prepared in various cosmetic forms. For example, it may be prepared in the form of cream, lotion, stick, foundation, emulsion, wax, oil, spray, aerosol, lotion, essence, pack, powder, gel and the like, but is not limited thereto. It will be apparent to those skilled in the art that any form commonly used in the art can be used.
  • an organic / inorganic hybrid titanium dioxide complex or an organic / inorganic hybrid titanium dioxide complex and a sunscreen cosmetic composition comprising an aggregate of an anionic polymer with titanium dioxide fine particles surface-modified to have a cationic functional group
  • a sunscreen cosmetic composition comprising an aggregate of an anionic polymer with titanium dioxide fine particles surface-modified to have a cationic functional group
  • the manufacturing method of the sunscreen cosmetics according to the present invention according to the product form of the cosmetic composition, such as cream, lotion, stick, foundation, emulsion, wax, oil, spray, aerosol lotion, essence, pack, powder, gel, etc.
  • Suitable excipients, dispersants, emulsifiers, pigments, oils, humectants, surfactants and the like may be mixed and formulated.
  • Example 1-1 Preparation Example 1 of Organic / Inorganic Hybrid Titanium Dioxide Composite
  • Titanium dioxide fine particles (TiO 2 ) (VK-T25, Xuancheng Jingrui New Material Co., Ltd.) 100.0 with an average particle diameter of 40 nm were mixed with 409.0 g of distilled water and 45.0 g of ethanol (Samjeon Chemical) for 30 minutes at room temperature. Stirred. Then, 10.0 g of 35% ammonia water was added, followed by stirring for 30 minutes. Thereafter, 3.0 g of 3-aminopropyltriethoxysilane (Aldrich) dissolved in 90.0 g of ethanol was added for 30 minutes, followed by stirring at room temperature for 3 hours.
  • Aldrich 3-aminopropyltriethoxysilane
  • the prepared aminosilane-treated titanium dioxide fine particles were measured by ZEN-3690 (Malvern Instruments Ltd), a dynamic light scattering method, and the average particle diameter was 130 nm.
  • polyacrylic acid Carbopol 981, Lubrizol, Mw 1,250,000
  • DMF N, N-Dimethylformamide, Samjeon Chemical
  • DCC N, N'-Dicyclohexylcarbodiimide, Samjeon Chemical
  • 20.0 g of aminosilane-treated titanium dioxide fine particles were added to a solution of 80.0 g of NMP (N-Methtylpyrrolidone), and the mixture was stirred at room temperature for 16 hours.
  • the reaction was then filtered / washed with 1M aqueous HCl solution, distilled water and acetone and dried to obtain 18.7 g of an organic / inorganic hybrid titanium dioxide composite.
  • the resulting organic / inorganic hybrid titanium dioxide composite was measured by Microtrac S3000 (Microtrac Inc.), and the average particle diameter was found to be 9.1 ⁇ m.
  • Example 1-2 Preparation Example 2 of Organic / Inorganic Hybrid Titanium Dioxide Composite
  • An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in the production method of Example 1-1, except that 12.0 g was used instead of 0.1 g of polyacrylic acid. It was confirmed that the average particle diameter was 19.3 ⁇ m.
  • Example 1-3 Preparation Example 3 of Organic / Inorganic Hybrid Titanium Dioxide Composite
  • An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 0.04 g instead of 0.1 g of polyacrylic acid was used. It was confirmed that the average particle diameter was 5.1 ⁇ m.
  • Example 1-4 Preparation Example 4 of Organic / Inorganic Hybrid Titanium Dioxide Composite
  • An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 16.0 g instead of 0.1 g of polyacrylic acid was used. It was confirmed that the average particle diameter was 23.2 ⁇ m.
  • An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that sodium polyacrylate (Aldrich, Mw123,000) was used instead of 0.1 g of polyacrylic acid. It was confirmed that the average particle diameter was 8.1 mu m.
  • Example 1-6 Preparation Example 6 of Organic / Inorganic Hybrid Titanium Dioxide Composite
  • An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 0.05 g of hexanoic acid (Aldrich) and 0.05 g of polyacrylic acid were used instead of 0.1 g of polyacrylic acid. It was confirmed that the average particle diameter was 6.3 ⁇ m.
  • Example 1-7 Preparation Example 7 of Organic / Inorganic Hybrid Titanium Dioxide Composite
  • An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 0.1 g of polymethylene polyphenyl polyisocyanate (Aldrich, Mw 400) was used instead of 0.1 g of polyacrylic acid, and DCC was not used. It was. The average particle diameter was found to be 4.3 ⁇ m.
  • Table 1 shows the properties of the organic / inorganic hybrid titanium dioxide composite according to Examples 1-1 to 1-7.
  • 10 g of titanium dioxide fine particles surface-modified with aminosilane prepared in Example 1-1 (a) were added to 80 g of distilled water and mixed with an organic / inorganic hybrid titanium dioxide composite, and 10,000 rpm with a homogenizer (IKA T25).
  • 10 g of a solution of polyacrylic acid (Carbopol 981, Lubrizol, Mw 1,250,000) prepared as a 1% solution in distilled water and a dispersion prepared by stirring for 5 minutes and stirred for 30 minutes at 500rpm and the titanium dioxide fine particles surface-modified with aminosilane Aggregates of polyacrylic acid and dispersions containing the same were prepared.
  • the D50 of the aggregate of titanium dioxide fine particles and polyacrylic acid surface-modified with the prepared aminosilane was 7.8 ⁇ m, and the content was 1.0 wt.% Relative to titanium dioxide.
  • the sunscreen cream was prepared by mixing the organic / inorganic hybrid titanium dioxide composite prepared according to Examples 1-1 to 1-7 and the aggregate prepared according to Example 1-8 with an oil-in-water type (O / W) cream base composition. Prepared. After each component was added, water was finally added to 100 g. Comparative Example used nano titanium dioxide (Parsol TX, DSM). Specific compositions are as shown in Table 2 below. In Example 2-8, a dispersion containing 10% by weight of the aggregate prepared in Example 1-8 was used.
  • the in-vitro sunscreen index (SPF) test (model: SPF 290S, manufacturer: Optometrics) was carried out. 1 mg / cm 2 was applied to a transpore tape, and after 15 minutes of drying, the scan measurement was performed 12 times with an SPF290 analyzer (Optometrics, USA), and the average value was obtained by repeating the measurement three times.
  • the sunscreen (Examples 2-1, 2-2, 2-5, 2-6, 2-7, 2-8) containing the organic / inorganic hybrid titanium dioxide composite according to the present invention is Compared with the sunscreen agent containing nano titanium dioxide (Comparative Example 1) showed the same or better sunscreen performance, the feeling of use is greatly improved and the turbidity is also lowered.
  • the content of titanium dioxide in the organic / inorganic hybrid titanium dioxide composite is preferably 60 to 99.5% by weight of the composite. Do.
  • the organic / inorganic hybrid titanium dioxide composite according to the present invention has a safe and very excellent UV blocking effect, and can form a homogeneous and very thin film, so that the feeling of use and cloudiness are greatly improved. Can be.

Abstract

The present invention relates to a complex comprising surface-modified microparticles and an organic product, and a method for manufacturing same, and more specifically, to an organic/inorganic hybrid TiO2 complex comprising an organic material in the form of a chemical bond, the organic material comprising TiO2 microparticles which are surface-modified so that at least one functional group is introduced to the surface, and at least one active site capable of reacting with the functional group on the surface-modified TiO2 complex. The organic/inorganic hybrid TiO2 complex, according to the present invention, is safe and has an excellent ultraviolet ray-shielding effect, and thus can be very useful as a sunscreen agent. Also, the present invention relates to a method for manufacturing the organic/inorganic hybrid TiO2 complex, a cosmetic composition containing the complex, and a method for manufacturing same.

Description

유/무기 하이브리드 이산화티탄 복합체, 이를 포함하는 화장료 조성물 및 그 제조방법Organic / inorganic hybrid titanium dioxide complex, cosmetic composition comprising the same and method for producing same
본 발명은 표면개질된 이산화티탄 미립자와 유기물의 복합체 및 그 제조방법에 대한 것으로, 더욱 자세하게는 하나 이상의 작용기(functional group)가 표면에 도입되도록 표면개질된 이산화티탄 미립자와 상기 표면개질된 이산화티탄 미립자의 작용기와 반응할 수 있는 활성 사이트(active site)를 하나 이상 포함하는 유기물이 화학결합된 형태의 유/무기 하이브리드 이산화티탄 복합체(organic/inorganic hybrid TiO2 complex)에 대한 것으로, 본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체는 안전하면서도 매우 우수한 자외선 차단 효과를 가지고 있어, 자외선 차단제로서 매우 유용하게 사용될 수 있다.The present invention relates to a surface-modified titanium dioxide fine particles and a composite of an organic material and a method for producing the same, and more particularly, titanium dioxide fine particles and the surface-modified titanium dioxide fine particles so that at least one functional group is introduced to the surface Organic / inorganic hybrid titanium dioxide complex (organic / inorganic hybrid TiO 2 complex) in the form of a chemically bonded organic material containing at least one active site (reactive site) that can react with the functional group of the present invention / Inorganic hybrid titanium dioxide composite has a safe and very good sunscreen effect, can be very useful as a sunscreen.
또한, 본 발명은 상기 유/무기 하이브리드 이산화티탄 복합체의 제조방법 및 상기 복합체를 포함하는 화장료 조성물과 그 제조방법에 대한 것이다.In addition, the present invention relates to a method for producing the organic / inorganic hybrid titanium dioxide complex, and a cosmetic composition comprising the complex and a method for producing the same.
최근 외모에 대한 관심이 증가되는 추세와 함께, 각종 야외활동(outdoor activity), 특히 야외에서의 레포츠를 즐기는 인구가 증가함에 따라 자외선으로 인한 홍반 등의 피부 손상이나 화상을 방지하기 위한 자외선 차단 효과를 가지는 다양한 제품에 대한 수요가 지속적으로 증가하고 있다. With the recent trend of increasing interest in appearance, as the population enjoying various outdoor activities, especially outdoor sports, increases the sunscreen effect to prevent skin damage or burns such as erythema caused by ultraviolet rays. Eggplants are constantly growing in demand for various products.
화장품의 자외선 차단 효과는 일반적으로 SPF(Sun Protection Factor) 및 PA(Protection Grade of UV-A) 지수로 표시되는데, SPF 지수는 해당 제품이 얼마나 자외선으로부터 피부를 잘 보호해주는지를 나타내기 위해서 개발된 수치로, SPF 지수가 30 이면 햇볕에 노출된 후, 피부가 붉게 달아오르는데(홍반 형성)까지 걸리는 시간을 30배로 늘려준다는 뜻으로, 만약, 아무것도 바르지 않은 맨살 상태에서 홍반 형성까지 걸리는 시간이 20분이라면, 30배에 해당하는 600분 (10시간) 동안 자외선으로부터 피부를 지켜준다는 의미이며, PA 지수는 자외선 A(UV-A)의 차단 정도를 나타내는 지수로, PA+, PA++, PA+++의 3등급으로 구분되며, PA+++가 가장 자외선 A의 차단효과가 우수하다. The sun protection effect of cosmetics is usually expressed in terms of Sun Protection Factor (SPF) and Protection Grade of UV-A (PA) index, which was developed to indicate how well the product protects the skin from UV rays. If the SPF index is 30, it means that it takes 30 times longer for skin to redden (erythema formation) after sun exposure, and if it is bare skin, it takes 20 minutes. If it is, it means that it protects the skin from ultraviolet rays for 600 times (10 hours), which is 30 times, and the PA index is an index indicating the degree of blocking of ultraviolet rays A (UV-A). PA +++ has the best blocking effect of UVA.
일반적으로 화장품 용도로 사용되는 자외선 차단제는 유기계 자외선 차단제와 무기계 자외선 차단제로 구분된다. Generally, sunscreens used in cosmetics are classified into organic sunscreens and inorganic sunscreens.
유기계 자외선 차단제는 주로 자외선을 흡수함으로써 자외선 차단 효과를 나타내는데, 자외선 차단제 분자 구조 내에 자외선을 흡수할 수 있는 콘쥬게이션 결합이 존재하는 특성을 가지며, 유기계 자외선 차단제로는 PABA(para-aminobenzoic acid), PABA 에스테르(PABA esters), 살리시레이트(salicylates), 캄포 유도체(camphor derivatives) 및 시나메이트(cinnamates) 등의 유기 화합물과 UV-A를 차단하는 디벤조일메탄(dibenzoylmethane), 안드라니레이트(anthranilate), 벤조페논(benzophenone), 트리아졸(triazole) 등이 혼합된 형태로 주로 이용되지만, 피부 독성, 알레르기 및 변색 등이 발생한다는 단점이 있다. Organic sunscreens exhibit UV-blocking effects mainly by absorbing UV light, and there is a conjugation bond that can absorb UV light in the molecular structure of the sunscreen, and organic sunscreens include PABA (para-aminobenzoic acid) and PABA. Organic compounds such as esters (PABA esters), salicylates, camphor derivatives and cinnamates, and dibenzoylmethane, anthranilate and benzo, which block UV-A. Phenone (benzophenone), triazole (triazole) is mainly used in a mixed form, but there are disadvantages such as skin toxicity, allergies and discoloration occurs.
이에 따라 최근에는 무기계 자외선 차단제를 주로 사용하는 추세이다. 무기계 자외선 차단제는 주로 자외선을 반사 및 산란함으로써 자외선 차단 효과를 나타내는데, 이산화티탄(TiO2), 산화아연(ZnO), 산화세륨(CeO2), 산화알루미늄(Al2O3) 또는 산화지르코늄(ZrO) 등의 금속 산화물과 염화철(ferric chloride), 탈크(talc), 카오린(kaolin) 및 이크탐몰(ichthammol : Ichthyol) 등이 주로 사용되고 있다. Accordingly, in recent years, an inorganic sunscreen is mainly used. Inorganic sunscreens exhibit an ultraviolet-blocking effect mainly by reflecting and scattering ultraviolet light, including titanium dioxide (TiO 2 ), zinc oxide (ZnO), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), or zirconium oxide (ZrO). Metal oxides such as c), ferric chloride, talc, kaolin, and ichthymol (ichthyol) are mainly used.
무기계 자외선 차단제는 일반적으로 주성분인 무기계 입자의 크기가 작을수록 자외선 차단 효과가 크지만, 나노입자 크기의 무기계 입자는 동물 실험 연구를 통해 인체에 유독성이 있다고 알려져 있다. 이에 따라 미국 국립 직업 안전 건강연구소(NIOSH)에서는 나노입자 크기의 무기계 입자의 복용 허용치를 0.1mg/ m2로 제한하고 있으며, 우리나라 식품의약품 안전처에서는 100 nm이하의 나노물질을 함유하는 화장품에 대해 나노물질을 사용하였음을 표기하고, 인체에 무해하다는 안전성 입증 자료를 구비할 것을 요구하고 있다. Inorganic sunscreens generally have a larger UV protection effect as the size of inorganic particles, the main component of which is a major component, is known to be toxic to humans through animal experiments. Accordingly, the National Institute for Occupational Safety and Health (NIOSH), and the tolerance and limit the taking of the inorganic particles in the nanoparticle size to 0.1mg / m 2, the Korean KFDA for cosmetics containing nanomaterials of 100 nm or less It indicates that nanomaterials are used and requires that safety proof data be provided that they are harmless to humans.
하지만 안전성 확보를 위해 자외선 차단제에 사용되는 금속산화물의 크기를 증가시키게 되면 자외선 차단 효과가 떨어지고, 이에 따라 동일한 자외선 차단 효과를 확보하기 위해서는 사용되는 금속산화물의 사용량이 많아져야만 된다는 문제점이 있다. 동시에 금속산화물 크기가 증가하게 되면 거친 느낌 등이 생겨 사용감(발림성 등)이 나빠지고, 얼굴이나 몸에 도포하면 흰빛을 띠는 백탁 현상이 심해진다.However, when the size of the metal oxide used in the sunscreen is increased to ensure safety, there is a problem in that the sunscreen effect is lowered, and accordingly, the amount of the metal oxide used must be increased in order to secure the same sunscreen effect. At the same time, when the metal oxide size increases, a feeling of roughness is generated, and the feeling of use (applicability, etc.) worsens, and when applied to the face or body, a white-white cloudy phenomenon occurs.
상기와 같은 기존의 유기계 및 무기계 자외선 차단제의 문제점을 해결하기 위해 유기계 자외선 차단제와 금속이온의 킬레이트를 포함하는 안정하면서도 자외선 차단 성능이 향상된 자외선 차단제 조성물(일본 공개특허 제2010-510170호)이 제시된 바 있으며, 자외선 차단제의 함량은 감소시키면서 동일한 함량의 차단제에 대해 보호 지수를 증가시킬 수 있는 새로운 제형 시스템으로, 하나 이상의 음이온성 계면활성제로 안정화된 두 개의 비혼화성 상과 음이온성 계면활성제 및 양이온성 또는 쯔비터이온성 친양쪽성 화합물을 추가로 포함하는 화장용 조성물(대한민국 공개특허 제2001-0023743호)이 제시된 바 있다.In order to solve the problems of the conventional organic and inorganic sunscreens as described above, a stable sunscreen composition including an organic sunscreen and a chelate of metal ions and improved sunscreen performance (Japanese Patent Publication No. 2010-510170) has been proposed. And a new formulation system that can increase the protection index for the same amount of sunscreen while reducing the amount of sunscreen, including two immiscible phases stabilized with one or more anionic surfactants and anionic surfactants and cationic or A cosmetic composition (Korean Patent Publication No. 2001-0023743) further comprising a zwitterionic amphiphilic compound has been presented.
하지만, 여전히 높은 안전성과 우수한 자외선 차단 효과를 유지하면서, 백탁 현상 등이 발생하지 않는 우수한 자외선 차단제 및 이를 포함하는 화장품에 대한 시장의 요구가 절실한 상황이다.However, there is still an urgent need for a market for excellent sunscreens and cosmetics including the same, while maintaining high safety and excellent sunscreen effect, which does not occur cloudiness.
발명의 요약Summary of the Invention
본 발명은 상기와 같은 기존의 문제점을 해결하고자, 기존 무기계 나노입자를 포함하는 자외선 차단제가 가지는 우수한 자외선 차단효과를 유지하면서, 작은 입자 크기로 인한 안전성 문제가 발생하지 않는 신규 자외선 차단제 및 그 제조방법을 제공하는 것을 목적으로 한다. The present invention is to solve the existing problems as described above, while maintaining the excellent ultraviolet protection effect of the existing sunscreen containing an inorganic nanoparticles, a new sunscreen and a method of manufacturing the same does not occur safety problems due to small particle size The purpose is to provide.
본 발명의 다른 목적은 본 발명에 따른 신규 자외선 차단제를 포함하는 화장료 조성물 및 그 제조방법을 제공하는 것이다.Another object of the present invention is to provide a cosmetic composition comprising the novel sunscreen according to the present invention and a method for producing the same.
상기 목적을 달성하기 위하여, 본 발명은 이산화티탄 미립자와 유기물이 공유결합으로 결합된 유/무기 하이브리드 이산화티탄 복합체 및 이를 포함하는 자외선 차단용 화장료 조성물을 제공한다. In order to achieve the above object, the present invention provides an organic / inorganic hybrid titanium dioxide composite and a sunscreen cosmetic composition comprising the same covalently bonded to titanium dioxide fine particles and organic matter.
상기 이산화티탄 미립자는 바람직하게는 유기물과 공유결합할 수 있는 하나 이상의 작용기를 가지도록 표면개질된 것을 특징으로 하며, 유/무기 하이브리드 이산화티탄 복합체에 포함되는 유기물은 표면개질된 이산화티탄 미립자의 작용기와 반응할 수 있는 활성 사이트를 하나 이상 포함하는 것을 특징으로 한다.The titanium dioxide fine particles are preferably surface-modified to have at least one functional group that can be covalently bonded to an organic material, and the organic material contained in the organic / inorganic hybrid titanium dioxide composite is a functional group of the surface-modified titanium dioxide fine particles. It is characterized in that it comprises at least one active site capable of reacting.
본 발명은 또한, (a) 하나 이상의 작용기가 표면에 도입되도록 이산화티탄 미립자를 표면개질하는 단계; 및 (b) 표면개질된 이산화티탄 미립자 표면의 작용기와 결합할 수 있는 하나 이상의 활성 사이트를 가지는 유기물을 혼합하는 단계;를 포함하는 유/무기 하이브리드 이산화티탄 복합체의 제조 방법을 제공한다.The present invention also provides a method for preparing a titanium dioxide particle, comprising the steps of: (a) surface modifying the titanium dioxide fine particles so that at least one functional group is introduced to the surface; And (b) mixing an organic material having at least one active site capable of bonding with a functional group on the surface-modified titanium dioxide fine particle surface.
발명의 상세한 설명 및 구체적인 구현예Detailed Description of the Invention and Specific Embodiments
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 통상의 기술자에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 또한, 일반적으로 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, the nomenclature used herein is generally well known and commonly used in the art.
본 발명은 일 관점에서, 이산화티탄 미립자와 유기물로 이루어진 유/무기 하이브리드 이산화티탄 복합체를 제공한다. 본 발명에서 '유/무기 하이브리드 이산화티탄 복합체'는 이산화티탄 미립자와 유기물이 화합결합, 바람직하게는 공유결합으로 결합된 물질 또는 그러한 물질의 응집체를 의미한다.In one aspect, the present invention provides an organic / inorganic hybrid titanium dioxide composite composed of titanium dioxide fine particles and an organic material. In the present invention, the 'organic / inorganic hybrid titanium dioxide composite' means a substance or aggregate of such substances in which titanium dioxide fine particles and an organic substance are combined by a covalent bond, preferably covalently.
본 발명에서 상기 이산화티탄 미립자는 유기물과의 결합을 위한 작용기(기능기: functional group)가 표면에 도입되도록 표면개질된 것을 특징으로 한다. 상기 작용기를 도입하기 위해서는 비닐트리메톡시실란(Vinyltrimethoxysilane), 비닐트리에톡시실란(Vinyltriethoxysilane), 2-(3,4 에폭시사이클로헥실)에틸트리메톡시실란(2-(3,4 epoxycyclohexyl) ethyltrimethoxysilane), 3-글리시독시프로필트리메톡시실란(3-Glycidoxypropyl trimethoxysilane), 3-글리시독시프로필메틸디에톡시실란(3-Glycidoxypropyl methyldiethoxysilane), 3-글리시독시프로필트리에톡시실란(3-Glycidoxypropyl triethoxysilane), 3-아크릴록시프로필트리메톡시실란(3-Acryloxypropyl trimethoxysilane), N-2-(아미노에틸)-3-아미노프로필메틸다이메톡시실란(N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane), 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane) 및 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane) 등의 3-아미노프로필트리알콕시실란(3-Aminopropyltrialkoxysilane), 3-트리에톡시실릴-N-(1,3 디메틸부틸리덴)프로필아민의 부분 가수분해물(Partially hydrolysates of 3-Triethoxysilyl-N-(1,3 dimethyl-butylidene)propylamine), N-페닐-3-아미노프로필트리메톡시실란(N-Phenyl-3-aminopropyltrimethoxysilane), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드의 가수분해물(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-우레이도프로필트리에톡시실란(3-Ureidopropyltriethoxysilane) 및 3-이소시아테이트프로필트리에톡시실란(3-Isocyanatepropyltriethoxysilane)로 이루어진 군에서 선택된 하나 이상의 실란커플링제가 이용될 수 있으나 이에 한정되는 것은 아니다. In the present invention, the titanium dioxide fine particles are surface-modified to introduce a functional group (functional group) for bonding with an organic material to the surface. In order to introduce the functional group, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane) 3-Glycidoxypropyl trimethoxysilane, 3-Glycidoxypropyl methyldiethoxysilane, 3-Glycidoxypropyl triethoxysilane, 3-Glycidoxypropyl triethoxysilane ), 3-Acryloxypropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-Aminopropyltrialkoxysilane, 3-triethoxysilyl-N, such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane -(1,3 dimethyl Partially hydrolysates of 3-Triethoxysilyl-N- (1,3 dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane (N-Phenyl-3-aminopropyltrimethoxysilane ), N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride), N- (vinylbenzyl) -2- Hydrolysates of aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-ureidopropyltriethoxysilane and One or more silane coupling agents selected from the group consisting of 3-isocyanatepropyltriethoxysilane may be used, but is not limited thereto.
상기 실란 커플링제에 의해 표면개질된 이산화티탄 미립자는 표면에 하나 이상의 아민기, 비닐기, 에폭시기, 아크릴옥시기, 아미노기, 우레이드(ureide)기 및 이소시아네이트기로 구성된 그룹에서 선택되는 하나 이상의 작용기를 포함할 수 있다. The titanium dioxide fine particles surface-modified by the silane coupling agent include at least one functional group selected from the group consisting of at least one amine group, vinyl group, epoxy group, acryloxy group, amino group, ureide group and isocyanate group on the surface. can do.
특히, 이산화티탄 미립자의 표면개질을 위해서 아미노실란이 이용되는 것이 바람직하며, 이에 따라 본 발명에 따른 표면개질된 이산화티탄 미립자는 표면에 식(1)과 같은 구조를 가지는 작용기가 도입되는 것이 바람직하지만, 이에 한정되는 것은 아니며, 유기물과의 결합이 가능한 작용기가 도입될 수 있는 어떠한 물질이라도 표면개질에 이용될 수 있으며, 이에 따라 유기물과의 결합이 가능한 어떠한 작용기라도 이산화티탄 미립자 표면에 도입될 수 있음은 통상의 기술자에게는 자명한 것이다. In particular, it is preferable that aminosilane is used for surface modification of the titanium dioxide fine particles. Accordingly, the surface-modified titanium dioxide fine particles according to the present invention is preferably introduced with a functional group having a structure such as formula (1) on the surface thereof. However, the present invention is not limited thereto, and any material capable of introducing a functional group capable of binding to an organic material may be used for surface modification, and thus, any functional group capable of binding to an organic material may be introduced to the surface of the titanium dioxide fine particles. Is obvious to the skilled person.
식 1Equation 1
Figure PCTKR2014009051-appb-I000001
Figure PCTKR2014009051-appb-I000001
상기 식 (1)에서 R1은 탄소수 1 내지 10, 바람직하게는 탄소수 1 내지 6의 알킬기, 또는 탄소수 6 내지 20, 바람직하게는 탄소수 6 내지 12의 아릴기를 의미하며, R2는 수소, 탄소수 1 내지 10, 바람직하게는 탄소수 1 내지 6의 알킬기, 또는 탄소수 6 내지 20, 바람직하게는 탄소수 6 내지 12의 아릴기를 의미한다.In Formula (1), R 1 represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and R 2 represents hydrogen or 1 carbon atom. 10 to 10, preferably an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
특히 이러한 표면개질에 의해 이산화티탄 미립자 표면에 하나 이상의 작용기가 도입됨에 따라 표면개질된 이산화티탄 미립자는 하나 이상의 유기물과의 복합체 형성이 가능하다. 본 발명의 하나의 구체예로서, 본 발명에서 사용될 수 있는 아미노실란은, N-2-(아미노에틸)-3-아미노프로필메틸다이메톡시실란(N-(2-Aminoethyl)-3-aminopropylmethyldimethoxysilane), N-2-(아미노에틸)-3-아미노프로필트리메톡시실란(N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane), 바람직하게는 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane) 및 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane) 등의 3-아미노프로필트리알콕시실란(3-aminopropyltrialkoxysilane), N-페닐-3-아미노프로필트리메톡시실란(N-Phenyl-3-aminopropyltrimethoxysilane) 및 N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane HCl) 또는 그 가수분해물(hydrolysates) 등에서 선택되는 것이 바람직하지만 이에 한정되는 것은 아니다. 본 발명에서의 상기 유기물은 이산화티탄 미립자 표면의 작용기와 화학결합할 수 있는 활성 사이트를 포함하는 것을 특징으로 한다. 상기 활성사이트로는 카르복실산(carboxylic acid), 아실 할라이드(acyl halide), 알데하이드 아민(aldehyde, amine), 카르복실레이트 시아네이트(carboxylate, cyanate), 에스테르(ester), 이민(imine), 설포닉산(sulfonic acid), 설폭사이드(sulfoxide), 티올(thiol), 알코올(alcohol), 이소시아네이트(isocyanate) 등이 있으며, 예를 들어 아미노실란으로 표면개질되어 상기 식 (1)과 같은 구조를 갖는 작용기를 표면에 가지는 이산화티탄 미립자가 이용될 경우, 상기 유기물의 활성 사이트로는 -COOH 또는 -COOR 등이 사용될 수 있다. 상기 -COOR에서, R은 할로겐(halogen), C1-5 알킬, C6-12 아릴, 알칼리금속, 알칼리 토금속, 또는 -NCO 등이 예시될 수 있지만 이에 한정되는 것은 아니다. 특히 상기, 알칼리금속 또는 알칼리 토금속은 Na, K, Mg 등에서 선택되는 것이 바람직하지만, 이에 한정되는 것은 아니다. In particular, as the surface modification introduces one or more functional groups on the surface of the titanium dioxide fine particles, the surface-modified titanium dioxide fine particles can form a complex with one or more organic substances. As an embodiment of the present invention, the aminosilane that may be used in the present invention is N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N- (2-Aminoethyl) -3-aminopropylmethyldimethoxysilane) , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane), preferably 3-aminopropyltrimethoxysilane and 3 3-aminopropyltrialkoxysilane, such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-Phenyl-3-aminopropyltrimethoxysilane -(Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane HCl) or its hydrolysates, etc. It is not limited to this. The organic material in the present invention is characterized in that it comprises an active site capable of chemically bonding with the functional groups on the surface of the titanium dioxide fine particles. The active site is a carboxylic acid, acyl halide, aldehyde, amine, carboxylate cyanate, ester, imine, sulfo Sulfonic acid, sulfoxide, thiol, alcohol, isocyanate, etc., for example, a surface-modified functional group with aminosilane When titanium dioxide fine particles having a surface are used, -COOH or -COOR or the like can be used as the active site of the organic material. In the above-COOR, R may be exemplified by halogen, C 1-5 alkyl, C 6-12 aryl, alkali metal, alkaline earth metal, or -NCO, but is not limited thereto. In particular, the alkali metal or alkaline earth metal is preferably selected from Na, K, Mg, but is not limited thereto.
본 발명에서 사용될 수 있는 유기물로는 폴리아크릴산(Polyacrylic acid(PAA)), 소듐아크릴레이트(Sodium Polyacrylate), 헥사노익산(Hexanoic acid), 폴리메틸렌폴리페닐폴리이소시아네이트(Polymethylene polyphenyl polyisocyanate), 옥살산(oxalic acid), 말로닉산(malonic acid), 숙신산(succinic acid), 글루타릭산(glutaric acid), 아디픽산(adipic acid), 피메릭산(pimelic acid), 수베릭산(suberic, acid), 아제라익산(azelaic acid), 세배식산(sebacic acid), 언데카네이오익산(undecanedioic acid), 프타릭산(phthalic acid), 말레익산(maleic acid), 푸마릭산(fumaric acid), 글루타코닉산(glutaconic acid), 트라우마틱산(traumatic acid), 무코닉산(muconic acid), 폴리(에틸렌글리콜)-비스(카르복시메틸)에테르(poly(ethyleneglycol)bis(carboxymethyl)ether), 무수숙신산(succinic anhydride), 무수말레익산(maleic anhydride), 구연산(citric acid), 아코니틱산(aconitic acid), 트리카르발릭산(tricarballylic acid), 트리메식산(trimesic acid), 2-포스포노부탄-1,2,3-트리카르복실산(2-Phosphonobutane-1,2,4-tricarboxylic acid), 1,4-(디이소시아네이트부탄(1,4-diisocyanatobutane), 페닐렌디이소시아네이트(phenylene diisocyanate) 및 자일렌디이소시아네이트(xylene diisocyanate)로 구성된 군에서 선택된 하나 이상의 물질이 사용될 수 있지만, 이에 한정되는 것은 아니며, 본 발명이 목적에 부합하는 한, 어떠한 유기물이라도 이용할 수 있음은 통상의 기술자에게는 자명한 것이다. Organic materials that can be used in the present invention are polyacrylic acid (Polyacrylic acid (PAA)), sodium acrylate (Sodium Polyacrylate), hexanoic acid (Hexanoic acid), polymethylene polyphenyl polyisocyanate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic, acid, azelaic acid acid, sebacic acid, undecanedioic acid, phthalic acid, maleic acid, fumaric acid, glutaconic acid, trauma Traumatic acid, muconic acid, poly (ethyleneglycol) -bis (carboxymethyl) ether, poly (ethyleneglycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride anhydride, citric acid, aconitic acid, Tricarballylic acid, trimesic acid, 2-phosphonobutane-1,2,3-tricarboxylic acid, 1,4 One or more materials selected from the group consisting of 1,4-diisocyanatobutane, phenylene diisocyanate, and xylene diisocyanate may be used, but the present invention is not limited thereto. As long as the purpose is met, any organic substance can be used.
상기 표면개질된 이산화티탄 미립자 표면의 작용기와 유기물에 존재하는 활성사이트 (active site) 간의 화학결합을 통해 복합체가 형성되게 된다.A complex is formed through a chemical bond between a functional group on the surface-modified titanium dioxide particulate surface and an active site present in the organic material.
본 발명에서 상기 유/무기 하이브리드 이산화티탄 복합체에서의 이산화티탄의 함량은 복합체 총 중량 대비 60 내지 99.5 중량%인 것이 바람직하다. 이산화티탄의 함량이 60 중량% 이하이면 이산화티탄 함량이 너무 적어서 자외선 차단 효과가 감소하게 되며, 99.5 중량% 이상이면 유기물 함량이 적어 사용감이 저하되고 백탁 현상이 발생할 우려가 있다. In the present invention, the content of titanium dioxide in the organic / inorganic hybrid titanium dioxide composite is preferably 60 to 99.5 wt% based on the total weight of the composite. If the content of titanium dioxide is less than 60% by weight, the titanium dioxide content is too small to reduce the sunscreen effect. If the content of more than 99.5% by weight of organic matter is less, there is a possibility that the feeling of use is lowered and cloudiness occurs.
본 발명에서 상기 유/무기 하이브리드 이산화티탄 복합체의 평균입자 크기(Dv50)는 0.1~50 ㎛, 바람직하게는 0.5~30 ㎛, 가장 바람직하게는 1~20 ㎛ 인 것을 특징으로 한다. 이러한 본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체의 평균입자 크기는 작은 크기의 나노입자 (100 nm 이하) 사용으로 인해 발생할 수 있는 인체 유해성 등의 안전성 문제를 원천적으로 해결하면서, 유/무기 하이브리드 이산화티탄 복합체 내부에는 나노 크기의 무기물, 즉 금속산화물이 포함되어 있으므로, 기존의 나노 크기의 무기물을 사용하는 자외선 차단제와 동등하거나 오히려 향상된 성능을 나타낼 수 있다는 장점이 있다. In the present invention, the average particle size (Dv50) of the organic / inorganic hybrid titanium dioxide composite is 0.1 to 50 μm, preferably 0.5 to 30 μm, and most preferably 1 to 20 μm. The average particle size of the organic / inorganic hybrid titanium dioxide composite according to the present invention, while solving the safety problems such as human hazards that may occur due to the use of small size nanoparticles (100 nm or less), organic / inorganic hybrid dioxide Since the titanium composite contains nano-sized inorganic material, that is, metal oxide, there is an advantage that the titanium composite can exhibit the same or improved performance as the sunscreen using the nano-sized inorganic material.
본 발명은 다른 관점에서 상기 유/무기 하이브리드 이산화티탄 복합체의 제조방법을 제공한다. The present invention provides a method for producing the organic / inorganic hybrid titanium dioxide composite in another aspect.
본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체의 제조방법은, The method for producing an organic / inorganic hybrid titanium dioxide composite according to the present invention,
(a) 하나 이상의 작용기가 표면에 도입되도록 이산화티탄 미립자를 표면개질하는 단계; 및(a) surface modifying the titanium dioxide fine particles so that one or more functional groups are introduced to the surface; And
(b) 표면개질된 이산화티탄 미립자 표면의 작용기와 결합할 수 있는 하나 이상의 활성 사이트를 가지는 유기물을 혼합하는 단계;(b) mixing an organic material having at least one active site capable of binding to functional groups on the surface-modified titanium dioxide particulate surface;
를 포함하는 것을 특징으로 한다. Characterized in that it comprises a.
본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체 제조방법에 있어서, 이산화티탄 미립자의 표면개질에 이용되는 물질, 특성, 크기, 그리고 유기물의 종류, 특성은 앞서 유/무기 하이브리드 이산화티탄 복합체에서 설명한 바와 동일하며, 또한 제조된 유/무기 하이브리드 이산화티탄 복합체에서의 이산화티탄의 함량, 복합체의 크기 역시 앞서 유/무기 하이브리드 이산화티탄 복합체에서 설명한 바와 동일하다. In the method for producing an organic / inorganic hybrid titanium dioxide composite according to the present invention, the materials, properties, sizes, and types and properties of organic materials used for surface modification of titanium dioxide fine particles are the same as described in the organic / inorganic hybrid titanium dioxide composite. In addition, the content of the titanium dioxide in the prepared organic / inorganic hybrid titanium dioxide composite, the size of the composite is also the same as described in the organic / inorganic hybrid titanium dioxide composite.
상기 (a) 단계에 따른 이산화티탄 미립자의 표면개질은 증류수, 에탄올이나 메탄올 등의 알코올 등에서 선택된 하나 이상의 용액에 이산화티탄 입자(미립자)를 혼합하여 5~120분, 바람직하게는 10~60분, 더욱 바람직하게는 20~40분 동안 교반하고, 에탄올이나 메탄올 등의 용매에 용해된 아미노실란을 첨가하여 0.5~6 시간, 바람직하게는 1~5 시간, 더욱 바람직하게는 2~4 시간 동안 교반함으로써 달성될 수 있다. 표면개질에 사용되는 이산화티탄 미립자는 10~70 nm, 바람직하게는 20~50 nm 크기가 적절하다. 또한, 이산화티탄 미립자를 증류수와 알코올등에서 선택된 하나 이상의 용액에 혼합하여 교반한 후, 암모니아수를 첨가하여 교반하는 단계가 추가적으로 포함될 수 있다. 이어 여과, 알코올 및/또는 증류수로 세정 및 건조 단계를 추가적으로 거쳐 아미노실란으로 표면개질된 이산화티탄 미립자를 수득할 수 있다. 상기 교반은 모두 10~50℃, 바람직하게는 15~40℃, 더욱 바람직하게는 20~30℃의 온도에서 수행될 수 있다. 본 발명에서의 ‘상온’은 20~30℃, 특히 25℃를 의미한다.Surface modification of the titanium dioxide fine particles according to the step (a) is 5 to 120 minutes, preferably 10 to 60 minutes by mixing titanium dioxide particles (particulates) in one or more solutions selected from distilled water, alcohol, such as ethanol or methanol, More preferably, the mixture is stirred for 20 to 40 minutes, by adding aminosilane dissolved in a solvent such as ethanol or methanol, and stirred for 0.5 to 6 hours, preferably 1 to 5 hours, and more preferably 2 to 4 hours. Can be achieved. The titanium dioxide fine particles used for the surface modification are suitably in the size of 10 to 70 nm, preferably 20 to 50 nm. In addition, after the titanium dioxide fine particles are mixed and stirred in distilled water and one or more solutions selected from alcohols, and the like, the method may further include adding and stirring ammonia water. Subsequent filtration, washing with alcohol and / or distilled water, and drying may additionally give fine particles of titanium dioxide surface-modified with aminosilane. All the stirring may be performed at a temperature of 10 to 50 ℃, preferably 15 ~ 40 ℃, more preferably 20 ~ 30 ℃. "Room temperature" in the present invention means 20 ~ 30 ℃, especially 25 ℃.
또한 상기 (b) 단계는 유/무기 하이브리드 이산화티탄 복합체를 제조하는 단계로서, 유기용매에 유기물을 첨가하고 40~80℃, 바람직하게는 50~70℃에서 5~120분, 바람직하게는 10~60분, 더욱 바람직하게는 20~40분 동안 교반하여 유기물 용액을 제조하고, 이를 상기 (a) 단계에서 수득된 이산화티탄 미립자가 분산되어 있는 유기용매에 혼합하고, 첨가하고 모두 10~50℃, 바람직하게는 15~40℃, 더욱 바람직하게는 20~30℃에서 4~40 시간, 바람직하게는 10~30 시간, 더욱 바람직하게는 12~20 시간 동안 교반하는 단계를 포함하여 이루어질 수 있다. In addition, the step (b) is to prepare an organic / inorganic hybrid titanium dioxide composite, the organic material is added to the organic solvent and 5 to 120 minutes at 40 to 80 ℃, preferably 50 to 70 ℃, preferably 10 ~ 60 minutes, more preferably, 20 to 40 minutes of stirring to prepare an organic solution, which is mixed with an organic solvent in which the titanium dioxide fine particles obtained in step (a) are dispersed, added, and all are 10 to 50 ° C., Preferably 15 to 40 ℃, more preferably 20 to 30 ℃ 4 to 40 hours, preferably 10 to 30 hours, more preferably 12 to 20 hours it can be made, including the step of stirring.
상기 유기물을 용해하기 위한 유기용매로는 DMF(N,N-Dimethylformamide), NMP(N-Methtylpyrrolidone), 헥산(hexane), 클로로포름(chloroform), 사이클로헥산(cyclohexane), 벤젠(benzene), 톨루엔(toluene), 디옥산(dioxane), 클로로포름디에틸에테르(chloroform, diethyl ether), 디클로로메탄(dichloromethane), 테트라하이드로퓨란(tetrahydrofuran), 에틸아세테이트(ethyl acetate), 아세톤(acetone), 디에틸에테르(diethylether), 디메틸포름아마이드(dimethylformamide), 아세토나이트릴(acetonitrile), 디메틸설폭사이드(dimethyl sulfoxide), 프로필렌카보네이트(propylene carbonate), 메탄올(methanol), 에탄올(ethanol), 프로판올(proranol), 부탄올(butanol), 아세트산(acetic acid) 및 니트로메탄(nitromethane)으로 구성된 군에서 선택된 하나 이상의 용매가 사용될 수 있지만, 이에 제한되는 것은 아니며, 본 발명의 목적에 부합하는 한 어떠한 유기용매라도 사용될 수 있다. 특히, a) 단계에서 제조된 표면개질된 이산화티탄 미립자는 NMP(N-Methtylpyrrolidone)에 분산되는 것이 바람직하지만 이에 한정되는 것은 아니다. The organic solvent for dissolving the organic material is DMF (N, N-dimethylformamide), NMP (N-Methtylpyrrolidone), hexane (hexane), chloroform (chloroform), cyclohexane, benzene (benzene), toluene ), Dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, diethylether , Dimethylformamide, acetonitrile, dimethyl sulfoxide, propylene carbonate, methanol, methanol, ethanol, proranol, butanol, One or more solvents selected from the group consisting of acetic acid and nitromethane may be used, but is not limited thereto, and any organic solvent may be used as long as it is suitable for the purpose of the present invention. Even it can be used. In particular, the surface-modified titanium dioxide fine particles prepared in step a) is preferably dispersed in NMP (N-Methtylpyrrolidone), but is not limited thereto.
표면개질된 이산화티탄 미립자가 분산되어 있는 유기용매와 유기물 용액을 혼합하여 교반이 완료된 후, 반응물을 HCl, 증류수, 아세톤, 알코올 등에서 선택된 하나 이상을 사용하여 수회 세척 및 여과하고 최종 건조하여 유/무기 하이브리드 이산화티탄 복합체를 수득할 수 있다. After stirring is completed by mixing the organic solvent and the organic solution in which the surface-modified titanium dioxide fine particles are dispersed, the reaction is washed several times with one or more selected from HCl, distilled water, acetone, alcohol, etc. Hybrid titanium dioxide composites can be obtained.
본 발명은 다른 관점에서, 유/무기 하이브리드 이산화티탄 복합체를 포함하는 자외선 차단용 화장료 조성물을 제공한다. In another aspect, the present invention provides a sunscreen cosmetic composition comprising an organic / inorganic hybrid titanium dioxide composite.
본 발명에서의 유/무기 하이브리드 이산화티탄 복합체를 포함하는 자외선 차단용 화장료 조성물은 통상적인 O/W 크림베이스 조성물과 유/무기 하이브리드 이산화티탄 복합체를 혼합하여 제조할 수 있지만, 이에 한정되는 것은 아니며, 본 발명이 속하는 기술분야에서 통상적으로 사용되는 화장료 조성물에 함유되는 성분들이 이용될 수 있음은 통상의 기술자에게는 자명한 것이다. The sunscreen cosmetic composition including the organic / inorganic hybrid titanium dioxide composite in the present invention may be prepared by mixing a conventional O / W cream base composition and an organic / inorganic hybrid titanium dioxide composite, but are not limited thereto. It will be apparent to those skilled in the art that the components contained in the cosmetic composition commonly used in the art can be used.
본 발명에 따른 자외선 차단용 화장료 조성물에는 유/무기 하이브리드 이산화티탄 복합체가 약 0.1~30 중량%, 바람직하게는 0.5~25 중량%, 가장 바람직하게는 1~20 중량% 함유되는 것이 바람직하며, 추가적으로 마이크로크리스탈린 왁스(Microcrystalline Wax), 비즈 왁스(Bees Wax), 카르보머(Carbomer), 옥틸메톡시시나메이트(Octyl Methoxycinnamate), 비스-에틸헥실로페놀메톡시페닐트리아진(Bis-Etylhexyloxyphenol Methoxyphenyl Triazine), 이소아밀-p-메톡시시나메이트(Isoamyl-p-methoxycinnamate), 디소듐 EDTA(Disodium EDTA), 페녹시에탄올(Phenoxyethanol), 메틸-p-하이드록시벤조에이트(Methyl-p-hydroxybenzoate), 프로필-p-하이드록시벤조에이트(Propyl-p-hydroxybenzoate), 부틸렌글리콜(Butylene glycol), 폴리글리세릴-3-메틸글루코스 디스테아레이트(Polyglyceryl-3-Methylglucose Distearate), 세티아릴 알코올(Cetearyl Alcohol), 글리세릴 스테아레이트(Glyceryl Stearate), PEG-100 스테아레이트(Stearate), 페닐트리메티콘(Phenyl Trimethicone), 데카메틸 사이클로펜타실록산(Decamethyl Cyclopentasiloxane), 폴리아크릴레이트-13(Polyacrylate-13), 폴리이소부텐(Polyisobutene), 폴리소르베이트(Polysorbate) 트리에탄올아민 디솔빈(Triethanolamine Dissolvine) Na2-S, 프로필렌글리콜(Propylene Glycol), 핀솔브(Finsolv) TN, 프로타켐(Protachem) SMO, 에스카롤(Escalol) 557, 옥티노세이트(Octinoxate), 에스카롤(Escalol) 567, 옥시벤존(Oxybenzone), 에스카롤(Escalol) 587, 크로다포스(Crodafos) CES, 세테아릴 알코올(Ceterayl Alcohol) 50/50, 크로다포스 C320 산(Crodafos C320 Acid), 액상 게르몰 플러스(Liquid Germall Plus), 프랑그랑스(Frangrance), 및 TEA 99% 에서 선택된 하나 이상의 물질이 포함될 수 있지만 이에 한정되는 것은 아니다.The sunscreen cosmetic composition according to the present invention preferably contains about 0.1 to 30% by weight, preferably 0.5 to 25% by weight, and most preferably 1 to 20% by weight of the organic / inorganic hybrid titanium dioxide composite. Microcrystalline Wax, Bead Wax, Carbomer, Octyl Methoxycinnamate, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine , Isoamyl-p-methoxycinnamate, disodium EDTA, phenoxyethanol, methyl-p-hydroxybenzoate, propyl -p-hydroxybenzoate, butylene glycol, polyglyceryl-3-methylglucose distearate, cetiaryl alcohol , Glee Glyceryl Stearate, PEG-100 Stearate, Phenyl Trimethicone, Decamethyl Cyclopentasiloxane, Polyacrylate-13, Polyisobutene (Polyisobutene), Polysorbate Triethanolamine Dissolvine Na2-S, Propylene Glycol, Finsolv TN, Protachem SMO, Escalol 557, Octinoxate, Escalol 567, Oxybenzone, Escalol 587, Crodafos CES, Cetearyl Alcohol 50/50, Crodafoss One or more materials selected from C320af Acid (Crodafos C320 Acid), Liquid Germall Plus, Francrance, and TEA 99% may be included, but are not limited thereto.
또한, 본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체를 포함하는 자외선 차단용 화장료 조성물에는 추가적으로 양이온성 유/무기 하이브리드 입자와 음이온성 고분자의 응집체가 포함될 수 있다. 이때, 자외선 차단용 화장료 조성물에는 유/무기 하이브리드 이산화티탄 복합체와, 양이온성 유/무기 하이브리드 입자와 음이온성 고분자의 응집체가 중량비로 0.01 : 99.99 내지 20 : 80의 비율, 바람직하게는 0.1 : 99.9 내지 10 : 90의 비율로 혼합되는 것이 바람직하다. In addition, the cosmetic composition for sunscreen comprising an organic / inorganic hybrid titanium dioxide composite according to the present invention may additionally include aggregates of cationic organic / inorganic hybrid particles and anionic polymer. At this time, the cosmetic composition for sunscreen is an organic / inorganic hybrid titanium dioxide composite, the aggregate of the cationic organic / inorganic hybrid particles and the anionic polymer in a weight ratio of 0.01: 99.99 to 20: 80, preferably 0.1: 99.9 to It is preferable to mix in the ratio of 10:90.
상기 "양이온성 유/무기 하이브리드 입자"는 양이온성 작용기(기능기, functional group)를 가지도록 표면이 개질(modified)된 금속산화물 등의 무기물, 또는 금속산화물 등의 무기물과 양전하를 가지도록 하는 전하조절제(Charge Control Agent, CCA)의 혼합물을 의미하며, "양이온성 유/무기 하이브리드 입자"는무기물, 바람직하게는 금속산화물의 표면을 양이온성 작용기를 가지도록 개질하거나, 금속산화물 등의 무기물과 양전하를 가지도록 하는 양전하성 전하조절제를 혼합하여 제조함으로써 수득될 수 있다. The "cationic organic / inorganic hybrid particles" are charged to have positive charges with inorganic materials such as metal oxides or surfaces such as metal oxides whose surfaces are modified to have cationic functional groups (functional groups). Means a mixture of a charge control agent (CCA), "cationic organic / inorganic hybrid particles" is to modify the surface of the inorganic, preferably metal oxide to have a cationic functional group, or positive charge with inorganic materials such as metal oxide It can be obtained by mixing a positively charged charge control agent to have a.
상기 양이온성 유/무기 하이브리드 입자 표면에 양이온성 작용기를 가지도록 개질하는 방법으로는, 금속산화물 등의 무기물 표면에 양이온성 작용기를 도입시킬 수 있는 물질, 바람직하게는 아미노실란으로 표면개질하는 방법, 또는 음이온성 작용기를 가지도록 금속산화물 등의 무기물 표면을 개질한 후 폴리양이온성(polycationic) 작용기를 갖는 물질을 반응시키는 방법 등이 바람직하지만 이에 한정되는 것은 아니다As a method of modifying the surface of the cationic organic / inorganic hybrid particles to have a cationic functional group, a method of introducing a cationic functional group to the surface of an inorganic material such as a metal oxide, preferably a surface modification with an aminosilane, Alternatively, a method of modifying the surface of an inorganic material such as a metal oxide to have an anionic functional group and then reacting a material having a polycationic functional group is preferable, but is not limited thereto.
상기 양이온성 유/무기 하이브리드 입자에 사용될 수 있는 무기물은 금속산화물이 바람직하지만, 이에 한정되는 것은 아니며, 본 발명의 목적을 달성할 수 있는 어떠한 무기물이라도 사용가능함은 통상의 기술자에게는 자명한 것이다. 본 발명에서 사용될 수 있는 금속산화물은 이산화티탄(TiO2), 산화아연(ZnO), 산화세륨(CeO2), 산화알루미늄(Al2O3) 및 산화지르코늄(ZrO)으로 이루어진 군에서 선택된 하나 이상일 수 있으며, 이산화티탄 또는 산화아연이 바람직하다. The inorganic material that can be used for the cationic organic / inorganic hybrid particles is preferably a metal oxide, but is not limited thereto. It will be apparent to those skilled in the art that any inorganic material that can achieve the object of the present invention can be used. The metal oxide that can be used in the present invention is at least one selected from the group consisting of titanium dioxide (TiO 2 ), zinc oxide (ZnO), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ) and zirconium oxide (ZrO). Titanium dioxide or zinc oxide is preferred.
본 발명에서의 무기물, 바람직하게는 금속산화물 표면에 도입될 수 있는 양이온성 작용기는 상기 식(1) 또는 식 (2)와 같은 구조를 갖는 것이 바람직하지만 이에 한정되는 것은 아니다.The inorganic material in the present invention, preferably cationic functional groups that can be introduced to the surface of the metal oxide preferably has a structure such as formula (1) or formula (2), but is not limited thereto.
금속산화물 등의 무기물이 아미노실란으로 표면개질될 경우, 양이온성 유/무기 하이브리드 입자 표면에 하나 이상의 제1차, 제2차, 또는 제3차 아민이 도입되어 양이온성을 나타내게 되는데, 본 발명의 하나의 구체예로서, 본 발명에서 무기물, 바람직하게는 금속산화물의 표면개질을 위해 사용될 수 있는 아미노실란은 N-2-(아미노에틸)-3-아미노프로필메틸다이메톡시실란(N-(2-Aminoethyl)-3-aminopropylmethyldimethoxysilane), N-2-(아미노에틸)-3-아미노프로필트리메톡시실란(N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane), 바람직하게는 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane) 및 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane) 등의 3-아미노프로필트리알콕시실란(3-aminopropyltrialkoxysilane), N-페닐-3-아미노프로필트리메톡시실란(N-Phenyl-3-aminopropyltrimethoxysilane), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란하이드로클로라이드(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane HCl) 또는 그 가수분해물(hydrolysates) 등이 바람직하지만 이에 한정되는 것은 아니다. When inorganic substances such as metal oxides are surface-modified with aminosilane, one or more primary, secondary, or tertiary amines are introduced to the surface of the cationic organic / inorganic hybrid particle to exhibit cationicity. In one embodiment, the aminosilanes that may be used for surface modification of inorganics, preferably metal oxides, in the present invention are N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane), preferably 3-aminopropyltrimethoxy 3-aminopropyltrialkoxysilane, N-phenyl-3-aminopropyltrimethoxysilane (N-, such as 3-Aminopropyltrimethoxysilane) and 3-Aminopropyltriethoxysilane Phenyl-3-aminopropyltrimethoxysilane), N -(Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilanehydrochloride (N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane HCl) or its hydrolysates and the like are preferred, but not limited thereto. It doesn't happen.
금속산화물 등의 무기물을 음이온성 작용기를 가지도록 표면개질한 후 폴리양이온성(polycationic) 작용기를 갖는 물질과 반응시킴으로써 입자 표면에 양이온성 작용기를 가지도록 개질하는 방법으로는 아미노실란 등으로 표면개질되어 양이온성을 띄는 유/무기 하이브리드 입자를 폴리음이온성(polyanionic) 작용기를 갖는 물질과 반응시켜 그 표면을 음이온성 작용기를 가지도록 개질한 후, 다시 폴리양이온성 작용기를 갖는 물질과 반응시키는 방법, 또는 직접 음이온성 작용기를 가지도록 폴리음이온성 작용기를 갖는 물질로 금속산화물 표면을 개질한 후, 다시 폴리양이온성 작용기를 갖는 물질과 반응시키는 방법 등이 사용될 수 있다. 상기 음이온성 작용기의 예로서는 카르복실산기, 인산기, 황산기, 설페이트기 등이 예시될 수 있지만, 이에 한정되는 것은 아니다.Surface-modified inorganic materials such as metal oxides to have anionic functional groups and then reacted with a material having a polycationic functional group to modify them to have cationic functional groups on the surface of the particles, such as aminosilane, Reacting a cationic organic / inorganic hybrid particle with a material having a polyanionic functional group and modifying its surface to have an anionic functional group, and then reacting with a material having a polycationic functional group, or A method of modifying a metal oxide surface with a material having a polyanionic functional group to have a direct anionic functional group, and then reacting with a material having a polycationic functional group may be used. Examples of the anionic functional group include, but are not limited to, carboxylic acid groups, phosphoric acid groups, sulfuric acid groups, sulfate groups, and the like.
상기 폴리양이온성 작용기를 갖는 물질은 폴리아민(polyamine), 바람직하게는 에틸렌다이아민, 1,2-디아미노프로판, 1,3-디아미노프로판, N-메틸에틸렌디아민, 1,4-디아미노부탄, 3-(메틸아미노)프로필아민, N,N'-디메틸에틸렌디아민,N,N-디메틸에틸렌디아민, 트리메틸렌테트라아민, 트리에틸렌테트라아민, 페닐렌디아민, 헥사메틸렌테트라아민, 디아미노사이클로헥산, 아미노벤질아민 및 테트라에틸렌펜타아민으로 구성된 군에서 선택된 하나 이상의 물질이 사용될 수 있지만, 이에 한정되는 것은 아니다. The material having a polycationic functional group is a polyamine, preferably ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, N-methylethylenediamine, 1,4-diaminobutane , 3- (methylamino) propylamine, N, N'-dimethylethylenediamine, N, N-dimethylethylenediamine, trimethylenetetraamine, triethylenetetraamine, phenylenediamine, hexamethylenetetraamine, diaminocyclohexane One or more materials selected from the group consisting of, aminobenzylamine and tetraethylenepentaamine can be used, but are not limited thereto.
상기 폴리음이온성(polyanionic) 작용기를 갖는 물질로는 폴리산(polyacid) 또는 폴리산 유도체(polyacid derivatives) 또는 폴리산의 무수화합물 등을 사용할 수 있으며, 구체적으로 옥살산(oxalic acid), 말로닉산(malonic acid), 숙신산(succinic acid), 글루타릭산(glutaric acid), 아디픽산(adipic acid), 피메릭산(pimelic acid), 수베릭산(suberic, acid), 아제라익산(azelaic acid), 세배식산(sebacic acid), 언데카네이오익산(undecanedioic acid), 프타릭산(phthalic acid), 말레익산(maleic acid), 푸마릭산(fumaric acid), 글루타코닉산(glutaconic acid), 트라우마틱산(traumatic acid), 무코닉산(muconic acid), 폴리(에틸렌글리콜)-비스(카르복시메틸)에테르poly(ethylene glycol)bis(carboxymethyl)ether, 무수숙신산(succinic anhydride), 무수말레익산(maleic anhydride), 구연산(citric acid), 아코니틱산(aconitic acid), 트리카르발릭산(tricarballylic acid), 트리메식산(trimesic acid), 2-포스포노부탄-1,2,3-트리카르복실산(2-Phosphonobutane-1,2,4-tricarboxylic acid), 폴리아크릴산(polyacrylic acid), 소듐폴리아크릴레이트(sodium polyacrylate) 등이 사용될 수 있지만 이에 한정되는 것은 아니다. As the material having a polyanionic functional group, polyacid, polyacid derivatives, or anhydrous compounds of polyacid may be used, and specifically, oxalic acid and malonic acid. acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic, acid, azelaic acid, sebacic acid acid), undecanedioic acid, phthalic acid, maleic acid, fumaric acid, glutaconic acid, traumatic acid, no radish Muconic acid, poly (ethylene glycol) -bis (carboxymethyl) ether poly (ethylene glycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride, citric acid , Aconitic acid, tricarballylic acid, tree Trimesic acid, 2-Phosphonobutane-1,2,3-tricarboxylic acid, polyacrylic acid, sodium polyacrylate polyacrylate) and the like may be used, but is not limited thereto.
양전하를 가지도록 하는 양전하성 전하조절제는 암모늄염, 특히 4급 암모늄염(quaternary ammonium salt) 계열의 물질이 사용되는 것이 바람직한데, 이는 4급 암모늄 염은 흰색의 분말 형태이므로, 최종적으로 제조되는 입자의 색에 영향을 끼치지 않는다는 장점이 있기 때문이다. 양전하성 전하조절제의 구체적인 예로서는 Oriental Corp.의 N-시리즈나 P-시리즈, 바람직하게는 Bontron P51이나 Bontron P53 등의 상용화된 물질(http://www.orient-usa.com/index.php?link=bontron 참조)이 사용될 수 있다. A positively charged charge control agent that has a positive charge is preferably used ammonium salts, especially quaternary ammonium salts, which are quaternary ammonium salts. This is because it does not affect the advantage. Specific examples of positively charged charge regulators include Oriental Corp. N-series and P-series, preferably commercialized materials such as Bontron P51 or Bontron P53 ( http://www.orient-usa.com/index.php?link = bontron ) can be used.
상기 양전하성 전하조절제의 사용량이 지나치게 적은 경우 제조된 유/무기 하이브리드 입자의 이온성이 나타나지 않으므로 제조되는 최종 입자의 중량 대비 0.5 중량% 이상, 바람직하게는 1 중량% 이상 포함될 수 있으며, 약 40 중량% 이하로 사용되는 것이 바람직하다.When the amount of the positively charged charge control agent is too small, since the ionicity of the organic / inorganic hybrid particles produced is not present, 0.5 wt% or more, preferably 1 wt% or more, may be included relative to the weight of the final particles to be manufactured, and about 40 wt% It is preferably used in% or less.
또한, 상기 응집체에 있어, 음이온성 고분자는 양이온성 유/무기 하이브리드 입자(hybrid particle)와 이온성 상호작용(ionic interaction)을 통해 응집체를 형성할 수 있는 것이라면 어떠한 것이라도 제한없이 사용가능하며, 비닐피롤리돈-아크릴산 공중합체(vinylpyrrolidone-acrylic acid copolymer), 메틸 메타크릴레이트-아크릴산 공중합체(Methyl Methacrylate-acrylic acid copolymer), 메틸 메타크릴레이트-메타크릴산 공중합체 (Methyl Methacrylate-methacrylic acid copolymer), 폴리아크릴산(polyacrylic acid: PAA), 폴리메타아크릴산(polymethacrylic acid) 및 카르복시메틸셀룰로오스(carboxymethylcellolulose)로 구성된 군에서 선택된 하나 이상인 것이 바람직하며, 폴리아크릴산이 가장 바람직하다.In addition, in the aggregate, the anionic polymer may be used without limitation as long as it can form an aggregate through ionic interaction with the cationic organic / inorganic hybrid particles. Pyrrolidone-acrylic acid copolymer, Methyl methacrylate-acrylic acid copolymer, Methyl methacrylate-methacrylic acid copolymer , Polyacrylic acid (PAA), polymethacrylic acid (polymethacrylic acid) and carboxymethyl cellulose (carboxymethylcellolulose) is preferably at least one selected from the group consisting of, polyacrylic acid is most preferred.
본 발명에 따른 화장료 조성물은 다양한 화장품 형태로 제조될 수 있다. 예를 들어, 크림, 로션, 스틱, 파운데이션, 에멀젼, 왁스, 오일, 스프레이, 에어로졸, 화장수, 에센스, 팩, 파우더, 젤 등의 형태로 제조될 수 있지만, 이에 한정되는 것은 아니며, 본 발명이 속하는 기술분야에서 통상적으로 사용되는 어떠한 형태라도 사용가능함은 통상의 기술자에게는 자명한 것이다. Cosmetic compositions according to the invention can be prepared in various cosmetic forms. For example, it may be prepared in the form of cream, lotion, stick, foundation, emulsion, wax, oil, spray, aerosol, lotion, essence, pack, powder, gel and the like, but is not limited thereto. It will be apparent to those skilled in the art that any form commonly used in the art can be used.
본 발명은 다른 관점에서, 유/무기 하이브리드 이산화티탄 복합체, 또는 유/무기 하이브리드 이산화티탄 복합체 및 양이온성 작용기를 가지도록 표면개질된 이산화티탄 미립자와 음이온성 고분자의 응집체를 포함하는 자외선 차단용 화장료 조성물 및 화장품의 제조방법을 제공한다. In another aspect, the present invention, an organic / inorganic hybrid titanium dioxide complex, or an organic / inorganic hybrid titanium dioxide complex and a sunscreen cosmetic composition comprising an aggregate of an anionic polymer with titanium dioxide fine particles surface-modified to have a cationic functional group And it provides a method of manufacturing cosmetics.
본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체, 또는 유/무기 하이브리드 이산화티탄 복합체 및 양이온성 작용기를 가지도록 표면개질된 이산화티탄 미립자와 음이온성 고분자의 응집체를 포함하는 자외선 차단용 화장료 조성물의 제조방법은 유/무기 하이브리드 이산화티탄 복합체, 또는 유/무기 하이브리드 이산화티탄 복합체 및 양이온성 작용기를 가지도록 표면개질된 이산화티탄 미립자와 음이온성 고분자의 응집체를 적절한 화장료 조성물 원료와 혼합하는 것을 특징으로 하며,Organic / Inorganic Hybrid Titanium Dioxide Complex or Organic / Inorganic Hybrid Titanium Dioxide Complex and Method for Producing Cosmetic Composition for UV Protection Comprising Aggregate of Titanium Dioxide Fine Particles Modified to Have Cationic Functionality and Anionic Polymer The silver / inorganic hybrid titanium dioxide complex, or the aggregate of the organic / inorganic hybrid titanium dioxide complex and the surface-modified titanium dioxide fine particles and anionic polymer to have a cationic functional group is mixed with a suitable cosmetic composition raw material,
본 발명에 따른 자외선 차단용 화장품의 제조방법은 상기 제조된 화장료 조성물을 크림, 로션, 스틱, 파운데이션, 에멀젼, 왁스, 오일, 스프레이, 에어로졸 화장수, 에센스, 팩, 파우더, 젤 등의 제품 형태에 따라 적절한 부형제, 분산제, 유화제, 안료, 유분, 보습제 및 계면활성제 등을 혼합하여 제형화하여 제조할 수 있다.The manufacturing method of the sunscreen cosmetics according to the present invention according to the product form of the cosmetic composition, such as cream, lotion, stick, foundation, emulsion, wax, oil, spray, aerosol lotion, essence, pack, powder, gel, etc. Suitable excipients, dispersants, emulsifiers, pigments, oils, humectants, surfactants and the like may be mixed and formulated.
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 통상의 기술자에는 자명한 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not interpreted to be limited by these examples.
실시예Example
실시예 1: 유/무기 하이브리드 이산화티탄 복합체 제조Example 1 Preparation of Organic / Inorganic Hybrid Titanium Dioxide Complex
실시예 1-1: 유/무기 하이브리드 이산화티탄 복합체의 제조예 1Example 1-1 Preparation Example 1 of Organic / Inorganic Hybrid Titanium Dioxide Composite
(A) 아미노실란으로 표면개질된 이산화티탄 미립자의 제조(A) Preparation of Titanium Dioxide Fine Particles Surface-Modified with Aminosilane
증류수 409.0g과 에탄올(삼전화학) 45.0 g의 혼합 용액에 평균입자 직경 40nm인 이산화티탄 미립자(TiO2) (VK-T25, Xuancheng Jingrui New Material Co., Ltd.) 100.0을 혼합하여 상온에서 30분간 교반하였다. 그 후, 35% 암모니아수 10.0g을 첨가하여 30분간 교반하였다. 그 후에 에탄올 90.0g에 용해시킨 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane) (Aldrich) 3.0g을 30분간 첨가한 후, 상온에서 3시간 동안 교반하였다. 반응 종료 후 여과, 에탄올 세정 및 건조하여 아미노실란 처리된 이산화티탄 미립자 98.1g을 얻었다. 제조한 아미노실란 처리된 이산화티탄 미립자를 동적광산란법 측정장비인 ZEN-3690 (Malvern Instruments Ltd)으로 측정한 결과 평균 입자 직경이 130 nm임을 확인하였다.Titanium dioxide fine particles (TiO 2 ) (VK-T25, Xuancheng Jingrui New Material Co., Ltd.) 100.0 with an average particle diameter of 40 nm were mixed with 409.0 g of distilled water and 45.0 g of ethanol (Samjeon Chemical) for 30 minutes at room temperature. Stirred. Then, 10.0 g of 35% ammonia water was added, followed by stirring for 30 minutes. Thereafter, 3.0 g of 3-aminopropyltriethoxysilane (Aldrich) dissolved in 90.0 g of ethanol was added for 30 minutes, followed by stirring at room temperature for 3 hours. Filtration, ethanol washing, and drying after the completion of the reaction gave 98.1 g of aminosilane-treated titanium dioxide fine particles. The prepared aminosilane-treated titanium dioxide fine particles were measured by ZEN-3690 (Malvern Instruments Ltd), a dynamic light scattering method, and the average particle diameter was 130 nm.
(B) 유/무기 하이브리드 이산화티탄 복합체의 제조(B) Preparation of Organic / Inorganic Hybrid Titanium Dioxide Composite
DMF(N,N-Dimethylformamide, 삼전화학) 40.0g에 폴리아크릴산 (Carbopol 981, Lubrizol, Mw 1,250,000) 0.1 g을 혼합하여 60℃에서 30분간 교반시킨 후, DCC(N,N'-Dicyclohexylcarbodiimide, 삼전화학) 0.1g을 투입하고 30분간 교반하였다. 상기 혼합용액을 아미노실란 처리된 이산화티탄 미립자 20.0 g을 NMP(N-Methtylpyrrolidone, 삼전순약) 80.0 g에 분산시킨 용액에 첨가하고 상온에서 16시간 동안 교반하였다. 그 후 반응물을 1M HCl 수용액, 증류수, 아세톤으로 여과/세척하고 건조하여 유/무기 하이브리드 이산화티탄 복합체 18.7 g을 얻었다. 제조한 유/무기 하이브리드 이산화티탄 복합체를 Microtrac S3000 (Microtrac Inc.)으로 측정한 결과 평균 입자 직경이 9.1 ㎛ 임을 확인하였다.0.1 g of polyacrylic acid (Carbopol 981, Lubrizol, Mw 1,250,000) was mixed with 40.0 g of DMF (N, N-Dimethylformamide, Samjeon Chemical), stirred at 60 ° C for 30 minutes, and then DCC (N, N'-Dicyclohexylcarbodiimide, Samjeon Chemical) ) 0.1g was added and stirred for 30 minutes. 20.0 g of aminosilane-treated titanium dioxide fine particles were added to a solution of 80.0 g of NMP (N-Methtylpyrrolidone), and the mixture was stirred at room temperature for 16 hours. The reaction was then filtered / washed with 1M aqueous HCl solution, distilled water and acetone and dried to obtain 18.7 g of an organic / inorganic hybrid titanium dioxide composite. The resulting organic / inorganic hybrid titanium dioxide composite was measured by Microtrac S3000 (Microtrac Inc.), and the average particle diameter was found to be 9.1 μm.
실시예 1-2: 유/무기 하이브리드 이산화티탄 복합체의 제조예 2Example 1-2 Preparation Example 2 of Organic / Inorganic Hybrid Titanium Dioxide Composite
폴리아크릴산 0.1g 대신 12.0g을 사용한 것 이외에는 실시예 1-1에서의 제조 방법과 동일하게 유/무기 하이브리드 이산화티탄 복합체를 제조하였다. 평균 입자 직경은 19.3㎛임을 확인하였다.An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in the production method of Example 1-1, except that 12.0 g was used instead of 0.1 g of polyacrylic acid. It was confirmed that the average particle diameter was 19.3 μm.
실시예 1-3: 유/무기 하이브리드 이산화티탄 복합체의 제조예 3Example 1-3 Preparation Example 3 of Organic / Inorganic Hybrid Titanium Dioxide Composite
폴리아크릴산 0.1g 대신 0.04g을 사용한 것 이외에는 실시예 1-1과 동일하게 유/무기 하이브리드 이산화티탄 복합체를 제조하였다. 평균 입자 직경은 5.1㎛ 임을 확인하였다.An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 0.04 g instead of 0.1 g of polyacrylic acid was used. It was confirmed that the average particle diameter was 5.1 μm.
실시예 1-4: 유/무기 하이브리드 이산화티탄 복합체의 제조예 4Example 1-4 Preparation Example 4 of Organic / Inorganic Hybrid Titanium Dioxide Composite
폴리아크릴산 0.1g 대신 16.0g을 사용한 것 이외에는 실시예 1-1과 동일하게 유/무기 하이브리드 이산화티탄 복합체를 제조하였다. 평균 입자 직경은 23.2㎛ 임을 확인하였다.An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 16.0 g instead of 0.1 g of polyacrylic acid was used. It was confirmed that the average particle diameter was 23.2 μm.
실시예 1-5: 유/무기 하이브리드 이산화티탄 복합체의 제조예 5Example 1-5 Preparation of Organic / Inorganic Hybrid Titanium Dioxide Composite 5
폴리아크릴산 0.1g 대신 폴리아크릴산나트륨(Aldrich, Mw123,000)을 사용한 것 이외에는 실시예 1-1과 동일하게 유/무기 하이브리드 이산화티탄 복합체를 제조하였다. 평균 입자 직경은 8.1㎛임을 확인하였다.An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that sodium polyacrylate (Aldrich, Mw123,000) was used instead of 0.1 g of polyacrylic acid. It was confirmed that the average particle diameter was 8.1 mu m.
실시예 1-6: 유/무기 하이브리드 이산화티탄 복합체의 제조예 6Example 1-6 Preparation Example 6 of Organic / Inorganic Hybrid Titanium Dioxide Composite
폴리아크릴산 0.1g 대신 헥사노익산(Aldrich) 0.05g과 폴리아크릴산 0.05g을 사용한 것 이외에는 실시예 1-1과 동일하게 유/무기 하이브리드 이산화티탄 복합체를 제조하였다. 평균 입자 직경은 6.3㎛ 임을 확인하였다.An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 0.05 g of hexanoic acid (Aldrich) and 0.05 g of polyacrylic acid were used instead of 0.1 g of polyacrylic acid. It was confirmed that the average particle diameter was 6.3 μm.
실시예 1-7: 유/무기 하이브리드 이산화티탄 복합체의 제조예 7Example 1-7 Preparation Example 7 of Organic / Inorganic Hybrid Titanium Dioxide Composite
폴리아크릴산 0.1g 대신 폴리메틸렌 폴리페닐 폴리이소시아네이트 (Polymethylene polyphenyl polyisocyanate, Aldrich, Mw 400) 0.1g을 사용하고 DCC를 사용하지 않은 것 이외에는 실시예 1-1과 동일하게 유/무기 하이브리드 이산화티탄 복합체를 제조하였다. 평균 입자 직경은 4.3 ㎛ 임을 확인하였다.An organic / inorganic hybrid titanium dioxide composite was prepared in the same manner as in Example 1-1 except that 0.1 g of polymethylene polyphenyl polyisocyanate (Aldrich, Mw 400) was used instead of 0.1 g of polyacrylic acid, and DCC was not used. It was. The average particle diameter was found to be 4.3 μm.
표 1에 상기 실시예 1-1 내지 1-7에 따른 유/무기 하이브리드 이산화티탄 복합체의 특성을 나타내었다.Table 1 shows the properties of the organic / inorganic hybrid titanium dioxide composite according to Examples 1-1 to 1-7.
표 1
Figure PCTKR2014009051-appb-T000001
 Table 1
Figure PCTKR2014009051-appb-T000001
실시예 1-8: 아미노실란으로 표면개질된 이산화티탄 미립자와 폴리아크릴산의 응집체 제조Example 1-8 Preparation of Aggregates of Titanium Dioxide Fine Particles Modified with Aminosilane and Polyacrylic Acid
유/무기 하이브리드 이산화티탄 복합체와의 혼합 사용을 위해 실시예 1-1 (a) 에서 제조된 아미노실란으로 표면개질된 이산화티탄 미립자 10g을 증류수 80g에 투입하고 호모게나이저(IKA T25)로 10,000 rpm으로 5분간 교반하여 제조한 분산액과 증류수에 1% 용액으로 제조한 폴리아크릴산 (Carbopol 981, Lubrizol, Mw 1,250,000) 용액 10 g을 혼합하여 500rpm으로 30분간 교반하여 아미노실란으로 표면개질된 이산화티탄 미립자와 폴리아크릴산의 응집체 및 이를 포함하는 분산액을 제조하였다.10 g of titanium dioxide fine particles surface-modified with aminosilane prepared in Example 1-1 (a) were added to 80 g of distilled water and mixed with an organic / inorganic hybrid titanium dioxide composite, and 10,000 rpm with a homogenizer (IKA T25). 10 g of a solution of polyacrylic acid (Carbopol 981, Lubrizol, Mw 1,250,000) prepared as a 1% solution in distilled water and a dispersion prepared by stirring for 5 minutes and stirred for 30 minutes at 500rpm and the titanium dioxide fine particles surface-modified with aminosilane Aggregates of polyacrylic acid and dispersions containing the same were prepared.
제조된 아미노실란으로 표면개질된 이산화티탄 미립자와 폴리아크릴산의 응집체의 D50은 7.8 ㎛였으며, 이산화티탄 대비 함량은 1.0 wt.% 이었다.The D50 of the aggregate of titanium dioxide fine particles and polyacrylic acid surface-modified with the prepared aminosilane was 7.8 μm, and the content was 1.0 wt.% Relative to titanium dioxide.
실시예 2: 유/무기 하이브리드 이산화티탄 복합체를 포함하는 화장료 조성물 제조Example 2 Preparation of Cosmetic Composition Comprising Organic / Inorganic Hybrid Titanium Dioxide Complex
상기 실시예 1-1 내지 1-7에 따라 제조된 유/무기 하이브리드 이산화티탄 복합체 및 실시예 1-8에 따라 제조된 응집체를 수중유형(O/W) 크림베이스 조성물과 혼합하여 자외선 차단 크림을 제조하였다. 각 성분들을 첨가한 후, 최종적으로 100 g이 되도록 물을 첨가하였다. 비교예는 나노 이산화티탄(Parsol TX, DSM)를 사용하였다. 구체적인 조성은 하기 표 2에 나타낸 바와 같다. 실시예 2-8에서는 실시예 1-8에서 제조된 응집체를 10 중량% 포함하는 분산액을 사용하였다.The sunscreen cream was prepared by mixing the organic / inorganic hybrid titanium dioxide composite prepared according to Examples 1-1 to 1-7 and the aggregate prepared according to Example 1-8 with an oil-in-water type (O / W) cream base composition. Prepared. After each component was added, water was finally added to 100 g. Comparative Example used nano titanium dioxide (Parsol TX, DSM). Specific compositions are as shown in Table 2 below. In Example 2-8, a dispersion containing 10% by weight of the aggregate prepared in Example 1-8 was used.
표 2
Figure PCTKR2014009051-appb-T000002
 TABLE 2
Figure PCTKR2014009051-appb-T000002
시험예 1: 자외선 차단 지수 측정Test Example 1 UV Protection Index Measurement
상기 실시예와 비교예에서 제조된 크림 제형을 이용하여 각각 자외선 차단 효과의 경향을 확인하고자 in-vitro 자외선 차단지수(SPF) 테스트(모델명: SPF 290S, 제조사: Optometrics사)를 실시하였다. 트랜스포어 테이프(transpore tape)에 1㎎/㎠ 수준으로 도포하고, 15분 건조 후 SPF290 분석기(Optometrics, USA)로 스캔 측정을 12번 진행하여 측정하고, 3회 반복 측정하여 얻은 평균값으로 나타내었다.In order to confirm the trend of the sunscreen effect using the cream formulations prepared in Examples and Comparative Examples, the in-vitro sunscreen index (SPF) test (model: SPF 290S, manufacturer: Optometrics) was carried out. 1 mg / cm 2 was applied to a transpore tape, and after 15 minutes of drying, the scan measurement was performed 12 times with an SPF290 analyzer (Optometrics, USA), and the average value was obtained by repeating the measurement three times.
시험예 2: 사용감 평가 실험Test Example 2: Feeling Evaluation Experiment
20~30세 여성 20명을 대상으로 하여 사용시의 피부 감촉, 피부 부착성 등을 2회에 걸쳐 5점 척도법으로 평가하고, 그 평균값으로 나타내었다. 이때 관능평가는 매우 우수(5점), 우수(4점), 보통(3점), 나쁨(2점), 매우나쁨(1점)의 기준에 의거하여 수행하고, 평가 수치가 클수록 피부 감촉 및 피부 부착성이 우수함을 나타낸다.Twenty women aged 20 to 30 years were evaluated by the five-point scale twice, using the skin texture and skin adhesion at the time of use. The sensory evaluation was performed based on the criteria of very good (5 points), good (4 points), normal (3 points), bad (2 points), very bad (1 point), and the larger the evaluation value, the more skin texture and It shows excellent skin adhesion.
시험예 3: 백탁 평가 실험Test Example 3: Whitening Evaluation Experiment
팔의 상박의 2×2㎠의 직사각형 6곳의 맨피부에 대해서 먼저 colorimeter(Minolta CR-200)를 이용하여 L값을 측정한 후, 각각의 장소에 샘플 각각 0.1g를 정확히 칭량하여 손가락으로 30번 문지른 후 5분 후에 colorimeter로 측정하여 맨피부 L 값과 측정된 L값 사이의 차이를 평가하였다. 상기 L값의 차이가 클수록 백탁도가 큰 것을 나타내고, L값의 차이가 작을수록 백탁도가 작은 것을 나타낸다.Measure the L value using six colorimeters (Minolta CR-200) for six bare skins of 2 × 2cm2 of the upper arm of the arm. Five minutes after rubbing, a colorimeter was used to evaluate the difference between the bare skin L value and the measured L value. The larger the difference between the L values, the larger the turbidity. The smaller the difference between the L values, the smaller the turbidity.
표 3
Figure PCTKR2014009051-appb-T000003
 TABLE 3
Figure PCTKR2014009051-appb-T000003
표 3에 기재된 바와 같이 본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체를 포함하는 자외선 차단제(실시예 2-1, 2-2, 2-5, 2-6, 2-7, 2-8)는 나노 이산화티탄을 포함한 자외선 차단제(비교예 1)와 비교하여 동등하거나 우수한 자외선 차단 성능을 나타냈으며, 사용감이 크게 개선되었고 백탁도도 낮아진 것을 확인할 수 있다. 또한, 실시예 2-3의 사용감 평가 결과 및 2-4의 자외선 차단 성능 측정 결과로 미루어 볼 때, 유/무기 하이브리드 이산화티탄 복합체에서 이산화티탄의 함량은 상기 복합체 중량 대비 60 내지 99.5% 인 것이 바람직하다.As shown in Table 3, the sunscreen (Examples 2-1, 2-2, 2-5, 2-6, 2-7, 2-8) containing the organic / inorganic hybrid titanium dioxide composite according to the present invention is Compared with the sunscreen agent containing nano titanium dioxide (Comparative Example 1) showed the same or better sunscreen performance, the feeling of use is greatly improved and the turbidity is also lowered. In addition, considering the usability evaluation results of Example 2-3 and UV-blocking performance measurement results of 2-4, the content of titanium dioxide in the organic / inorganic hybrid titanium dioxide composite is preferably 60 to 99.5% by weight of the composite. Do.
본 발명에 따른 유/무기 하이브리드 이산화티탄 복합체는 안전하면서도 매우 우수한 자외선 차단 효과를 가지고 있으며, 균질하면서도 매우 얇은 막을 형성할 수 있어 사용감과 백탁 현상이 크게 개선되는 효과가 있으므로 자외선 차단제로서 매우 유용하게 사용될 수 있다.The organic / inorganic hybrid titanium dioxide composite according to the present invention has a safe and very excellent UV blocking effect, and can form a homogeneous and very thin film, so that the feeling of use and cloudiness are greatly improved. Can be.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 통상의 기술자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.Having described specific parts of the present invention in detail, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (18)

  1. 하나 이상의 작용기가 표면에 도입되도록 표면개질된 이산화티탄 미립자와 상기 이산화티탄의 표면의 작용기와 결합할 수 있는 하나 이상의 활성 사이트를 가지는 유기물이 화학결합에 의해 결합된 유/무기 하이브리드 이산화티탄 복합체.An organic / inorganic hybrid titanium dioxide complex in which titanium dioxide particles surface-modified so that one or more functional groups are introduced to a surface, and an organic material having one or more active sites capable of bonding with functional groups on the surface of the titanium dioxide are bonded by chemical bonding.
  2. 제1항에 있어서,The method of claim 1,
    이산화티탄 미립자의 표면개질은 비닐트리메톡시실란(Vinyltrimethoxysilane), 비닐트리에톡시실란(Vinyltriethoxysilane), 2-(3,4 에폭시사이클로헥실)에틸트리메톡시실란(2-(3,4 epoxycyclohexyl) ethyltrimethoxysilane), 3-글리시독시프로필트리메톡시실란(3-Glycidoxypropyl trimethoxysilane), 3-글리시독시프로필메틸디에톡시실란(3-Glycidoxypropyl methyldiethoxysilane), 3-글리시독시프로필트리에톡시실란(3-Glycidoxypropyl triethoxysilane), 3-아크릴록시프로필트리메톡시실란(3-Acryloxypropyl trimethoxysilane), N-2-(아미노에틸)-3-아미노프로필메틸다이메톡시실란(N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane), 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane), 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane), 3-트리에톡시실릴-N-(1,3 디메틸부틸리덴)프로필아민의 부분 가수분해물(Partially hydrolysates of 3-Triethoxysilyl-N-(1,3 dimethyl-butylidene)propylamine), N-페닐-3-아미노프로필트리메톡시실란(N-Phenyl-3-aminopropyltrimethoxysilane), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드의 가수분해물(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-우레이도프로필트리에톡시실란(3-Ureidopropyltriethoxysilane) 및 3-이소시아테이트프로필트리에톡시실란(3-Isocyanatepropyltriethoxysilane)으로 구성된 군에서 선택된 하나 이상의 실란 커플링제에 의해 이루어지는 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체.The surface modification of the titanium dioxide fine particles is vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane ), 3-Glycidoxypropyl trimethoxysilane, 3-Glycidoxypropyl methyldiethoxysilane, 3-Glycidoxypropyl triethoxysilane (3-Glycidoxypropyl triethoxysilane), 3-Acryloxypropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N-2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane) , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 dimethylbutylidene) propylamine Partially hydrolysates of 3-Tr iethoxysilyl-N- (1,3 dimethyl-butylidene) propylamine), N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3 N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride Hydrolysates (N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-ureidopropyltriethoxysilane and 3-Isocyanatepropyltriethoxysilane (3-Isocyanatepropyltriethoxysilane) Organic / inorganic hybrid titanium dioxide composite, characterized in that made by at least one silane coupling agent selected from the group consisting of.
  3. 제1항에 있어,The method of claim 1,
    상기 실란 커플링제에 의해 표면개질된 이산화티탄 미립자는 표면에 하나 이상의 아민기, 비닐기, 에폭시기, 아크릴옥시기, 아미노기, 우레이드(ureide)기 및 이소시아네이트기로 구성된 그룹에서 선택되는 하나 이상의 작용기를 포함하는 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체.The titanium dioxide fine particles surface-modified by the silane coupling agent include at least one functional group selected from the group consisting of at least one amine group, vinyl group, epoxy group, acryloxy group, amino group, ureide group and isocyanate group on the surface. Organic / inorganic hybrid titanium dioxide composite, characterized in that.
  4. 제1항에 있어서,The method of claim 1,
    상기 유기물의 활성 사이트는 -COOH 또는 -COOR 이며, 상기 R은 할로겐 또는 C1-5 알킬, C6-12 아릴, 알칼리 금속, 알칼리토금속 또는 -NCO에서 선택되는 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체.The active site of the organic material is -COOH or -COOR, wherein R is selected from halogen or C 1-5 alkyl, C 6-12 aryl, alkali metal, alkaline earth metal or -NCO. Titanium complex.
  5. 제1항에 있어서,The method of claim 1,
    상기 유기물은 폴리아크릴산(Polyacrylic acid(PAA)), 소듐아크릴레이트(Sodium Polyacrylate), 헥사노익산(Hexanoic acid), 폴리메틸렌폴리페닐폴리이소시아네이트(Polymethylene polyphenyl polyisocyanate), 옥살산(oxalic acid), 말로닉산(malonic acid), 숙신산(succinic acid), 글루타릭산(glutaric acid), 아디픽산(adipic acid), 피메릭산(pimelic acid), 수베릭산(suberic, acid), 아제라익산(azelaic acid), 세배식산(sebacic acid), 언데카네이오익산(undecanedioic acid), 프타릭산(phthalic acid), 말레익산(maleic acid), 푸마릭산(fumaric acid), 글루타코닉산(glutaconic acid), 트라우마틱산(traumatic acid), 무코닉산(muconic acid), 폴리(에틸렌글리콜)-비스(카르복시메틸)에테르(poly(ethyleneglycol)bis(carboxymethyl)ether), 무수숙신산(succinic anhydride), 무수말레익산(maleic anhydride), 구연산(citric acid), 아코니틱산(aconitic acid), 트리카르발릭산(tricarballylic acid), 트리메식산(trimesic acid), 2-포스포노부탄-1,2,3-트리카르복실산(2-Phosphonobutane-1,2,4-tricarboxylic acid), 1,4-(디이소시아네이트부탄(1,4-diisocyanatobutane) 페닐렌디이소시아네이트(phenylene diisocyanate) 및 자일렌디이소시아네이트(xylene diisocyanate)로 이루어진 그룹에서 선택된 하나 이상의 물질임을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체.The organic material may be polyacrylic acid (PAA), sodium acrylate (Sodium Polyacrylate), hexanoic acid (Hexanoic acid), polymethylene polyphenyl polyisocyanate, oxalic acid, malonic acid ( malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic, acid, azelaic acid, triglyceride ( sebacic acid, undecanedioic acid, phthalic acid, maleic acid, fumaric acid, glutaconic acid, glutaconic acid, traumatic acid, Muconic acid, poly (ethyleneglycol) -bis (carboxymethyl) ether (poly (ethyleneglycol) bis (carboxymethyl) ether), succinic anhydride, maleic anhydride, citric acid acid, aconitic acid, tricarballylic acid, trimesic acid, 2-Phosphonobutane-1,2,4-tricarboxylic acid, 1,4- (isocyanate butane) (1,4-diisocyanatobutane) Organic / inorganic hybrid titanium dioxide composite, characterized in that at least one material selected from the group consisting of phenylene diisocyanate and xylene diisocyanate.
  6. 제1항에 있어서,The method of claim 1,
    상기 이산화티탄의 함량은 상기 복합체의 총 중량 대비 60 내지 99.5 중량%인 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체.The content of the titanium dioxide is an organic / inorganic hybrid titanium dioxide composite, characterized in that 60 to 99.5% by weight relative to the total weight of the composite.
  7. 제1항에 있어서,The method of claim 1,
    유/무기 하이브리드 이산화티탄 복합체의 평균입자 크기는 1~20 ㎛ 임을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체.Organic / inorganic hybrid titanium dioxide composite is an average particle size of 1 ~ 20 ㎛ organic / inorganic hybrid titanium dioxide composite.
  8. (a) 하나 이상의 작용기가 표면에 도입되도록 이산화티탄 미립자를 표면개질하는 단계; 및(a) surface modifying the titanium dioxide fine particles so that one or more functional groups are introduced to the surface; And
    (b) 표면개질된 이산화티탄 미립자 표면의 작용기와 결합할 수 있는 하나 이상의 활성 사이트를 가지는 유기물을 혼합하는 단계;(b) mixing an organic material having at least one active site capable of binding to functional groups on the surface-modified titanium dioxide particulate surface;
    를 포함하는 유/무기 하이브리드 이산화티탄 복합체의 제조 방법.Method for producing an organic / inorganic hybrid titanium dioxide composite comprising a.
  9. 제8항에 있어서,The method of claim 8,
    (a) 단계의 이산화티탄 미립자는 비닐트리메톡시실란(Vinyltrimethoxysilane), 비닐트리에톡시실란(Vinyltriethoxysilane), 2-(3,4 에폭시사이클로헥실)에틸트리메톡시실란(2-(3,4 epoxycyclohexyl) ethyltrimethoxysilane), 3-글리시독시프로필트리메톡시실란(3-Glycidoxypropyl trimethoxysilane), 3-글리시독시프로필메틸디에톡시실란(3-Glycidoxypropyl methyldiethoxysilane), 3-글리시독시프로필트리에톡시실란(3-Glycidoxypropyl triethoxysilane), 3-아크릴록시프로필트리메톡시실란(3-Acryloxypropyl trimethoxysilane), N-2-(아미노에틸)-3-아미노프로필메틸다이메톡시실란(N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane), 3-아미노프로필트리메톡시실란(3-Aminopropyltrimethoxysilane), 3-아미노프로필트리에톡시실란(3-Aminopropyltriethoxysilane), 3-트리에톡시실릴-N-(1,3 디메틸부틸리덴)프로필아민의 부분 가수분해물(Partially hydrolysates of 3-Triethoxysilyl-N-(1,3 dimethyl-butylidene)propylamine), N-페닐-3-아미노프로필트리메톡시실란(N-Phenyl-3-aminopropyltrimethoxysilane), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride), N-(비닐벤질)-2-아미노에틸-3-아미노프로필트리메톡시실란 하이드로클로라이드의 가수분해물(N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-우레이도프로필트리에톡시실란(3-Ureidopropyltriethoxysilane) 및 3-이소시아테이트프로필트리에톡시실란(3-Isocyanatepropyltriethoxysilane)로 이루어진 군에서 선택되는 하나 이상의 실란 커플링제에 의해 표면개질된 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체의 제조 방법.The titanium dioxide fine particles of step (a) include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4 epoxycyclohexyl) ) ethyltrimethoxysilane), 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane (3 -Glycidoxypropyl triethoxysilane, 3-Acryloxypropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane-3-N-2- (Aminoethyl) -3- aminopropylmethyldimethoxysilane), 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 dimethylbutylidene) propyl Partially hydrolysates of 3-Trie thoxysilyl-N- (1,3 dimethyl-butylidene) propylamine), N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3 N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride Hydrolysates (N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, hydrolysate), 3-ureidopropyltriethoxysilane and 3-Isocyanatepropyltriethoxysilane (3-Isocyanatepropyltriethoxysilane) Method of producing an organic / inorganic hybrid titanium dioxide composite, characterized in that the surface-modified by at least one silane coupling agent selected from the group consisting of.
  10. 제8항에 있어서,The method of claim 8,
    (b) 단계에서의 유기물의 활성 사이트는 -COOH 또는 -COOR 이며, 상기 R은 할로겐 또는 C1-5 알킬, C6-12 아릴, 알칼리금속, 알칼리토금속 또는 -NCO에서 선택되는 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체의 제조방법.The active site of the organic material in step (b) is -COOH or -COOR, wherein R is selected from halogen or C 1-5 alkyl, C 6-12 aryl, alkali metal, alkaline earth metal or -NCO Method for preparing organic / inorganic hybrid titanium dioxide composite.
  11. 제8항에 있어서,The method of claim 8,
    (b) 단계의 유기물은 폴리아크릴산(Polyacrylic acid(PAA)), 소듐아크릴레이트(Sodium Polyacrylate), 헥사노익산(Hexanoic acid), 폴리메틸렌폴리페닐폴리이소시아네이트(Polymethylene polyphenyl polyisocyanate), 옥살산(oxalic acid), 말로닉산(malonic acid), 숙신산(succinic acid), 글루타릭산(glutaric acid), 아디픽산(adipic acid), 피메릭산(pimelic acid), 수베릭산(suberic, acid), 아제라익산(azelaic acid), 세배식산(sebacic acid), 언데카네이오익산(undecanedioic acid), 프타릭산(phthalic acid), 말레익산(maleic acid), 푸마릭산(fumaric acid), 글루타코닉산(glutaconic acid), 트라우마틱산(traumatic acid), 무코닉산(muconic acid), 폴리(에틸렌글리콜)-비스(카르복시메틸)에테르poly(ethyleneglycol)bis(carboxymethyl)ether, 무수숙신산(succinic anhydride), 무수말레익산(maleic anhydride), 구연산(citric acid), 아코니틱산(aconitic acid), 트리카르발릭산(tricarballylic acid), 트리메식산(trimesic acid), 2-포스포노부탄-1,2,3-트리카르복실산(2-Phosphonobutane-1,2,4-tricarboxylic acid), 1,4-(디이소시아네이트부탄(1,4-diisocyanatobutane) 페닐렌디이소시아네이트(phenylene diisocyanate) 및 자일렌디이소시아네이트(xylene diisocyanate)로 구성된 군에서 선택되는 하나 이상의 물질인 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체의 제조 방법.Organic matter of step (b) is polyacrylic acid (PAA), sodium acrylate (Sodium Polyacrylate), hexanoic acid (Hexanoic acid), polymethylene polyphenyl polyisocyanate, oxalic acid , Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic, acid, azelaic acid , Sebacic acid, undecanedioic acid, phthalic acid, maleic acid, fumaric acid, glutaconic acid, glutaconic acid, traumatic acid ( traumatic acid, muconic acid, poly (ethylene glycol) -bis (carboxymethyl) ether poly (ethyleneglycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride, citric acid (citric acid), aconitic acid, tricarballic acid (tricarball) ylic acid, trimesic acid, 2-phosphonobutane-1,2,3-tricarboxylic acid, 1,4- (isocyanate) Butane (1,4-diisocyanatobutane) phenylene diisocyanate and xylene diisocyanate is a method for producing an organic / inorganic hybrid titanium dioxide composite, characterized in that at least one material selected from the group consisting of.
  12. 제8항에 있어서,The method of claim 8,
    상기 이산화티탄의 함량은 상기 복합체의 총 중량 대비 60 내지 99.5 중량%인 것을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체의 제조 방법.The content of the titanium dioxide is a method for producing an organic / inorganic hybrid titanium dioxide composite, characterized in that 60 to 99.5% by weight relative to the total weight of the composite.
  13. 제8항에 있어서,The method of claim 8,
    유/무기 하이브리드 이산화티탄 복합체의 평균입자 크기는 1~20 ㎛ 임을 특징으로 하는 유/무기 하이브리드 이산화티탄 복합체의 제조 방법.Method for producing an organic / inorganic hybrid titanium dioxide composite, characterized in that the average particle size of the organic / inorganic hybrid titanium dioxide composite is 1 ~ 20 ㎛.
  14. 제1항 내지 제7항 중 어느 한 항에 따른 유/무기 하이브리드 이산화티탄 복합체를 포함하는 자외선 차단용 화장료 조성물.A cosmetic composition for sunscreen comprising an organic / inorganic hybrid titanium dioxide composite according to any one of claims 1 to 7.
  15. 제14항에 있어서,The method of claim 14,
    양이온성 유/무기 하이브리드 입자와 음이온성 고분자의 응집체를 추가적으로 포함하는 자외선 차단용 화장료 조성물.A sunscreen cosmetic composition further comprising agglomerates of cationic organic / inorganic hybrid particles and anionic polymers.
  16. 제14항에 있어서,The method of claim 14,
    유/무기 하이브리드 이산화티탄 복합체가 0.1~20 중량% 포함된 것을 특징으로 하는 자외선 차단용 화장료 조성물.Organic / inorganic hybrid titanium dioxide composite is a sunscreen cosmetic composition, characterized in that containing 0.1 to 20% by weight.
  17. 제14항에 따른 화장료 조성물을 포함하는 자외선 차단용 화장품.A sunscreen cosmetic comprising a cosmetic composition according to claim 14.
  18. 제17항에 있어서, 크림, 로션, 스틱, 파운데이션, 에멀젼, 왁스, 오일, 스프레이, 에어로졸, 화장수, 에센스, 팩, 파우더 및 젤에서 선택된 어느 하나의 제형을 갖는 것을 특징으로 하는 자외선 차단용 화장품.18. The sunscreen cosmetic according to claim 17, having any one of a cream, lotion, stick, foundation, emulsion, wax, oil, spray, aerosol, lotion, essence, pack, powder and gel.
PCT/KR2014/009051 2013-09-27 2014-09-26 Organic/inorganic hybrid tio2 complex, cosmetic composition containing same, and method for manufacturing same WO2015046968A1 (en)

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KR101997870B1 (en) 2017-12-06 2019-07-09 주식회사 세라수 Organic-inorganic complex, Manufacturing method thereof and UV blocking agents using the same
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KR102158010B1 (en) 2020-04-27 2020-09-21 한국콜마주식회사 Titaniumdioxide-melanoidine composite for uv screening, manufacturing method thereof, and uv screening cosmetic composition comprising the same
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