KR102151419B1 - Manufacturing method of organic-inorganic composite materials having function high efficiency loading and controlled release - Google Patents

Abstract

The present invention relates to a method of manufacturing an organic-inorganic composite material having a high-efficiency supporting function and a release control function, wherein the material reacts a surfactant and a silica precursor to prepare mesoporous silica through hydrothermal synthesis, and a positively charged polymer and a negatively charged polymer It is prepared by coating. The organic-inorganic composite material prepared by the above method can support a large amount of whitening substances such as niacinamide and various drugs, and has excellent release control function, so that it can be easily used as a raw material for cosmetics, pharmaceutical compositions, and the like.

Description

Manufacturing method of organic-inorganic composite materials having function high efficiency loading and controlled release}

The present invention relates to a method of manufacturing an organic-inorganic composite material having a high-efficiency loading function and emission control function.

Porous materials using high surface area and pore properties are widely applied as catalysts or carriers for functional materials, drugs, and environments. To this end, the mesoporous silica manufacturing method used in the past requires a process of stirring a mixed solution of surfactant and water in an acidic atmosphere and then transferring it to a high temperature/high pressure steel bomb and aging it in a closed system. There was a problem of being produced in small quantities. The acidic atmosphere incurs a lot of additional costs, such as additional costs for treating the generated acid after repeating washing several times, environmental pollution, and cost for the Teflon coating or acid-resistant coating of equipment to react to acidic conditions, making it difficult to manufacture in large volumes. have. In addition, even if the mesoporous silica is prepared in this way, the controlled release and loading efficiency of the material by itself is not better than the intended purpose, so various methods of preparing silica to overcome this have been studied.

Therefore, in order to overcome the disadvantages of this method, the present inventors prepared mesoporous silica under a neutral condition, and sequentially coated the silica with a positively charged material and a negatively charged material to prepare a porous silica having novel properties, and the silica is highly efficient. The present invention was finally completed by confirming that it can be used as an organic-inorganic composite material having a supporting function and an emission control function.

Republic of Korea Patent Registration No. 10-1540587 (Name of the invention: Wet-molded color cosmetics containing organic sunscreen supported on hydrophobically treated porous silica and its manufacturing method, Applicant: Kolmar Korea, Registration: July 24, 2015 ) Republic of Korea Patent Registration No. 10-1141983 (Name of the invention: Boron nitride powder for cosmetics with a nanoporous silicified phospholipid membrane layer capable of supporting a physiologically active substance and its manufacturing method, Applicant: Kolmar Korea, Registration date: 2012 April 25)

It is an object of the present invention to provide a method for manufacturing an organic-inorganic composite material having a high-efficiency supporting function and an emission control function.

The present invention relates to a method of manufacturing an organic-inorganic composite material having a high-efficiency loading function and emission control function.

The organic-inorganic composite material is characterized in that it is manufactured through the following method.

That is, (1st step) preparing mesoporous silica through hydrothermal synthesis by reacting a surfactant and a silica precursor;

(Second step) coating a positively charged polymer on mesoporous silica; And,

(3rd step) coating a negatively charged polymer on the mesoporous silica coated with a positively charged polymer;

It characterized in that it is manufactured, including.

As the surfactant, a poly(alkylene oxide) block copolymer may be used.

It is preferable to use tetraethyl orthosilicate as the silica precursor.

It is appropriate to use polyacrylic acid as the negatively charged polymer.

Chitosan may be used as the positively charged polymer.

The present invention can provide a cosmetic composition comprising the organic-inorganic composite material prepared by the above method. The cosmetic composition is characterized by having a whitening effect. In addition, the cosmetic composition is characterized in that it supports niacinamide.

The cosmetic composition is skin lotion, skin softener, skin toner, astringent, lotion, milk lotion, moisture lotion, nutrition lotion, massage cream, nutrition cream, moisture cream, hand cream, foundation, essence, nutrition essence, pack, soap, cleansing It is characterized by having a formulation selected from the group consisting of foam, cleansing lotion, cleansing cream, body lotion and body cleanser.

In another aspect, the present invention can provide a pharmaceutical formulation comprising the organic-inorganic composite material prepared by the above method. The pharmaceutical preparation may include one or more selected from the group consisting of an anti-cancer agent, a cardio-cerebrovascular disease therapeutic agent, a wrinkle improving agent, a whitening agent, an antioxidant, an anti-inflammatory agent, an anti-inflammatory agent, a hair growth agent, an allergy inhibitor, and an atopic inhibitor.

Hereinafter, the present invention will be described in more detail.

In the production method of the present invention, the mesoporous silica is characterized in that it reacts in neutral, not acidic conditions.

In addition, in the manufacturing method of the present invention, the reaction temperature in the step of reacting the surfactant and the silica precursor is preferably 30 ~ 50 ℃.

Mesoporous silica used in the present invention comprises the steps of preparing a mixed solution in which a poly(alkylene oxide) block copolymer and water are mixed; Adding and mixing tetraethylortho silicate to the mixed solution; And aging, drying, and sintering the mixed solution to which the tetraethyl orthosilicate is added.

The mesoporous silica material undergoes hydration and condensation (sol-gel process of Hyderlysis / condensation) of silica through a hydrothermal synthesis method in which water is used as a solvent to react at a high temperature, and in particular, a surfactant and a silica precursor. By performing the step of reacting in a large-capacity equipment, a mesoporous silica material is formed that is environmentally safe and does not incur additional costs.

The mesoporous silica material is a material having a high specific surface area and has an average specific surface area of 350 m ² /g to 750 m ² /g, and preferably 600 m ² /g or more.

The preparation of the mesoporous silica material proceeds by mixing a surfactant with water and then adding a silica precursor. The surfactant and water are carried out under stirring at 30 to 50 °C, preferably 35 to 45 °C so that the surfactant is dissolved. It is carried out under stirring for 24 to 48 hours, preferably 36 to 48 hours so that the mixing can be performed well. Thereafter, a silica precursor is added to allow hydrolysis of the surfactant and the silica precursor, and the reaction of the silica precursor is performed at 30 to 50°C, preferably 35 to 45°C, for 24 hours under stirring. Then, by stopping the stirring and aging under heated and pressurized conditions, a mesoporous silica material may be formed. That is, the aging step under heated and pressurized conditions is to make the outer wall of silica more uniform in the hydrothermal synthesis reaction, and can make the material stable. In this regard, according to a preferred embodiment of the present invention, it is particularly preferable that the aging process is performed by sealing the inside using a 100 L-class large-capacity equipment, and the pressure is naturally increased during the heating process. The aging temperature is preferably about 110 to 130°C, particularly preferably about 120°C. This aging process corresponds to the hydrothermal synthesis process.

Representative examples of surfactants that can be used for the production of mesoporous silica materials are poly(alkylene oxide) block copolymers, such as polyethylline oxide-block-(polypropylene oxide)-polyethylene oxide, and BASF's product name Pluronic P123 can be used. In addition, various silica precursors widely known in the art may be used as the silica precursor, but it is preferable to use tetraethyl orthosilicate (TEOS).

On the other hand, for the synthesis of mesoporous silica material, it is sufficient if the concentration of the surfactant is dissolved in an aqueous solution to form micelles, that is, a concentration equal to or higher than the critical micelle concentration (CMC). In consideration of these conditions, the silica precursor may be used in a ratio of about 0.01 to 0.02 mol (particularly, about 0.017 mol) with respect to 1 mol of the surfactant when preparing the mesoporous silica material in the present invention.

After passing through the aging step, a conventional subsequent treatment process, that is, washing (including filtration)-drying-calcination step is sequentially performed. The conditions of this subsequent process are not limited to a specific range, but typically, in the case of the drying process, it is carried out at about 25 to 30°C for about 24 to 36 hours, and the calcination process is performed at about 550°C for about 6 to 8 hours. It is enough to practice.

In the present invention, when performing organic-inorganic coating on the mesoporous silica material, it is preferable to sequentially coat a positively charged polymer and a negatively charged polymer. It is appropriate to use polyacrylic acid as the negatively charged polymer. In addition, chitosan may be used as the positively charged polymer. In this case, it is preferable to coat the positively charged polymer 1 to 3 times and the negatively charged polymer 1 to 3 times. Most preferably, it is better to coat once or twice, and most preferably, it is best to coat twice.

This coating process can be performed through the following process.

Preferably, 2 to 10 parts by weight of mesoporous silica is added to the chitosan solution prepared by adding 0.1 to 2 parts by weight of chitosan based on 100 parts by weight of an aqueous 0.5 to 2% (w/v) acetic acid solution, followed by stirring for 1 to 3 hours. The silica can be separated from the solution and dried to coat the positively charged polymer. In addition, the positively charged polymer-coated silica was added to the poly(acrylic) acid solution prepared by adding 0.1 to 2 parts by weight of poly(acrylic) acid based on 100 parts by weight of water, and stirred for 1 to 3 hours, and the silica was removed from the solution. It can be separated and dried to coat a negatively charged polymer.

The cosmetic composition of the present invention has a whitening effect and can be used as a skin whitening composition capable of preventing, improving, and alleviating various pigmentation of the skin caused by skin aging or UV exposure. As the cosmetic composition, various cosmetic raw materials may be supported, and as an example, niacinamide may be supported. Niacinamide may be supported by adding 1 g of a mesoporous silica material coated with a positive/negatively charged polymer material to 5-20 ml of a 4-40 mM niacinamide ethanol solution, and stirring for 12 to 48 hours. have. After stirring, only the mesoporous silica material coated with the positively charged/negatively charged polymer material is separated from the niacinamide ethanol solution and dried before use.

The cosmetic composition prepared through the method of the present invention may contain 0.001 to 5% by weight in the cosmetic formulation.

The formulation of the cosmetic composition is not particularly limited, but preferably, skin lotion, skin softener, skin toner, astringent, lotion, milk lotion, moisture lotion, nutrition lotion, massage cream, nutrition cream, moisture cream, hand cream, foundation, It can be selected from the group consisting of essence, nutritional essence, pack, soap, cleansing foam, cleansing lotion, cleansing cream, body lotion, and body cleanser.

The cosmetic composition of the present invention may further include a component selected from the group consisting of water-soluble vitamins, oil-soluble vitamins, polymer peptides, polymer polysaccharides, sphingo lipids, and seaweed extract.

The water-soluble vitamin may be any one that can be blended in cosmetics, but preferably vitamin B1, vitamin B2, vitamin B6, pyridoxine, pyridoxine hydrochloride, vitamin B12, pantothenic acid, nicotinic acid, nicotinic acid amide, folic acid, vitamin C, vitamin H, etc. And their salts (thiamine hydrochloride, sodium ascorbate, etc.) and derivatives (ascorbic acid-2-phosphate sodium salt, ascorbic acid-2-magnesium salt, etc.) are also included in the water-soluble vitamins that can be used in the present invention. Included. Water-soluble vitamins can be obtained by conventional methods such as a microbial transformation method, a purification method from a culture of microorganisms, an enzyme method or a chemical synthesis method.

The oil-soluble vitamin may be any one that can be blended into a cosmetic, but preferably vitamin A, carotene, vitamin D2, vitamin D3, vitamin E (d1-alpha tocopherol, D-alpha tocopherol, D-alpha tocopherol), and the like. , Their derivatives (ascorbine palmitate, ascorbine stearate, ascorbine dipalmitate, DL-alpha tocopherol acetate, DL-alpha tocopherol nicotinic acid, vitamin E, DL-pantothenyl alcohol, D-pantotenyl alcohol, pantotenyl ethyl Ether, etc.) are also included in the oil-soluble vitamin used in the present invention. Oil-soluble vitamins can be obtained by conventional methods such as a microbial transformation method, a purification method from a microorganism culture, an enzyme or a chemical synthesis method.

The polymer peptide may be any one as long as it can be blended into a cosmetic, but preferably, collagen, hydrolyzed collagen, gelatin, elastin, hydrolyzed elastin, keratin, and the like are exemplified. The polymeric peptide can be purified and obtained by a conventional method such as a purification method from a culture medium of a microorganism, an enzyme method, or a chemical synthesis method, or it can be used after being purified from natural products such as dermis of pigs and cattle, silk fibers of silkworms.

The polymer polysaccharide may be any one as long as it can be blended in the cosmetic composition, but preferably, hydroxyethyl cellulose, xanthan gum, sodium hyaluronate, chondroitin sulfuric acid or a salt thereof (sodium salt, etc.) may be mentioned. For example, chondroitin sulfate or a salt thereof can be used after being purified from mammals or fish.

The sphingo lipid may be any one as long as it can be blended into the cosmetic composition, and ceramide, phytosphingosine, sphingoglycolipid, and the like are preferably mentioned. Sphingo lipids are usually purified from mammals, fish, shellfish, yeast, plants, etc. by a conventional method, or can be obtained by chemical synthesis.

The seaweed extract may be anything as long as it can be blended into the cosmetic composition, but preferably brown algae extract, red algae extract, green algae extract, etc. are exemplified, and carrageenan, arginic acid, sodium arginate purified from these seaweed extracts And potassium arginate are also included in the seaweed extract used in the present invention. Seaweed extract can be obtained by purifying from seaweed by a conventional method.

In the cosmetic composition of the present invention, other ingredients to be blended in conventional cosmetics may also be blended.

Other ingredients that may be added include fats and oils, moisturizers, emollients, surfactants, organic and inorganic pigments, organic powders, ultraviolet absorbers, preservatives, fungicides, antioxidants, plant extracts, pH adjusters, alcohols, pigments, fragrances, Blood circulation accelerators, cold sensation agents, restrictors, and purified water.

Examples of oil and fat components include ester oils and fats, hydrocarbon oils, silicone oils, fluorine oils, animal oils and vegetable oils.

Examples of ester oils include glyceryl tri2-ethylhexanoate, cetyl 2-ethylhexanoate, isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl stearate, octyl palmitate, isocetyl isostearate, stearic acid. Butyl, ethyl linoleate, isopropyl linoleate, ethyl oleate, isocetyl myristate, isostearyl myristate, isostearyl palmitate, octyldodecyl myristate, isocetyl isostearate, diethyl sebacate, adipine Diisopropyl acid, isoalkyl neopentanoate, tri(capryl, capric acid) glyceryl, tri2-ethylhexanoate trimethylolpropane, triisostearate trimethylolpropane, tetra2-ethylhexanoate pentaelisitol , Cetyl caprylate, decyl laurate, hexyl laurate, decyl myristic acid, myristic myristic acid, cetyl myristate, stearyl stearate, decyl oleate, cetyl ricinooleate, isostea laurate Reel, isotridecyl myristate, isocetyl palmitate, octyl stearate, isocetyl stearate, isodecyl oleate, octyldodecyl oleate, octyldodecyl linoleate, isopropyl isostearate, 2-ethylhexanoate cetoste Aryl, 2-ethylhexanoate stearyl, isostearate hexyl, dioctanoate ethylene glycol, dioleate ethylene glycol, dicaprylic acid propylene glycol, dicaprylic acid propylene glycol, dicaprylic acid propylene glycol, dica Neopentyl glycol prinate, neopentyl glycol dioctanoate, glyceryl tricaprylate, glyceryl triundecylate, glyceryl triisopalmitate, glyceryl triisostearate, octyldodecyl neopentanoate, isostearyl octanoate , Octyl isononanoate, hexyldecyl neodecanoate, octyldodecyl neodecanoate, isocetyl isostearate, isostearyl isostearate, octyldecyl isostearate, polyglycerololeic acid ester, polyglycerin isostearate, Triisocetyl citrate, triisoalkyl citrate, triisooctyl citrate, lauryl lactate, myristyl lactate, cetyl lactate, octyldecyl lactate, triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, trioctyl citrate, di malic acid Isostearyl, 2-ethylhexyl hydroxystearate, di2-ethylhexyl succinate, diisobutyl adipate, diisopropyl sebacate, dioctyl sebacate, Cholesteryl stearate, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl oleate, dihydrocholesteryl oleate, pitsteryl isostearate, pitsteryl oleate, 12-stealoyl And esters such as isocetyl hydroxystearate, stearyl 12-stealoylhydroxystearate, and isostearyl 12-stealoylhydroxystearate.

Examples of hydrocarbon-based fats and oils include hydrocarbon-based fats such as squalene, liquid paraffin, alpha-olefin oligomer, isoparaffin, ceresin, paraffin, liquid isoparaffin, polybuden, microcrystalline wax, and petrolatum.

Silicone-based fats and oils include polymethylsilicone, methylphenylsilicone, methylcyclopolysiloxane, octamethylpolysiloxane, decamethylpolysiloxane, dodecamethylcyclosiloxane, dimethylsiloxane/methylcetyloxysiloxane copolymer, dimethylsiloxane/methylsteaoxysiloxane copolymer, alkyl And modified silicone oil and amino-modified silicone oil.

As fluorine-based fats and oils, perfluoropolyether, etc. are mentioned.

Animal or vegetable oils include avocado oil, almond oil, olive oil, sesame oil, rice bran oil, new flower oil, soybean oil, corn oil, rapeseed oil, almond oil, palm kernel oil, palm oil, castor oil, sunflower oil, grape seed oil. , Cottonseed Oil, Palm Oil, Cucuine Nut Oil, Wheat Germ Oil, Rice Germ Oil, Shea Butter, Walnut Colostrum Oil, Marker Demi Anut Oil, Meadow Home Oil, Egg Yolk Oil, Tallow Oil, Horse Oil, Mink Oil, Orange Rape Oil, Jojoba Oil , Animal or plant fats such as canderry wax, carnauba wax, liquid lanolin, and hydrogenated castor oil.

Examples of the moisturizing agent include a water-soluble low-molecular moisturizer, a fat-soluble molecular moisturizer, a water-soluble polymer, and a fat-soluble polymer.

Water-soluble low molecular weight moisturizers include serine, glutamine, sorbitol, mannitol, pyrrolidone-sodium carboxylate, glycerin, propylene glycol, 1,3-butylene glycol, ethylene glycol, polyethylene glycol B (polymerization degree n = 2 or more), polypropylene Glycol (polymerization degree n = 2 or more), polyglycerin B (polymerization degree n = 2 or more), lactic acid, lactate, and the like.

As a fat-soluble low molecular weight moisturizer, cholesterol, cholesterol ester, etc. are mentioned.

Examples of the water-soluble polymer include carboxyvinyl polymer, polyaspartic acid salt, tragacanth, xanthan gum, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, water-soluble chitin, chitosan, dextrin, and the like. I can.

Examples of the oil-soluble polymer include polyvinylpyrrolidone/eicosene copolymer, polyvinylpyrrolidone/hexadecene copolymer, nitrocellulose, dextrin fatty acid ester, and polymer silicone.

Examples of the emollient agent include long-chain acyl glutamate cholesteryl ester, hydroxystearate cholesteryl, 12-hydroxystearic acid, stearic acid, rosin acid, and lanolin fatty acid cholesteryl ester.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

Nonionic surfactants include self-emulsifying glycerin monostearate, propylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerol fatty acid ester, sorbitan fatty acid ester, POE (polyoxyethylene) sorbitan fatty acid ester, POE sorbit fatty acid ester, POE Glycerin fatty acid ester, POE alkyl ether, POE fatty acid ester, POE hydrogenated castor oil, POE castor oil, POE·POP (polyoxyethylene·polyoxypropylene) copolymer, POE·POP alkyl ether, polyether-modified silicone, lauric acid Alkanolamides, alkylamine oxides, hydrogenated soybean phospholipids, and the like.

As anionic surfactants, fatty acid soap, alpha-acyl sulfonate, alkyl sulfonate, alkyl allyl sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, POE alkyl ether sulfate, alkylamide sulfate, alkyl phosphate, POE alkyl phosphate, alkyl amide Phosphate, alkyloylalkyltaurine salt, N-acylamino acid salt, POE alkylether carboxylate, alkyl sulfosuccinate, sodium alkylsulfoacetate, acylated hydrolyzed collagen peptide salt, perfluoroalkyl phosphate, and the like. have.

Cationic surfactants include alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, cetostearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyldimethylbenzyl ammonium chloride, behenyl trimethyl ammonium bromide, and chloride. Benzalkonium, diethylaminoethyl amide stearate, dimethylaminopropyl amide stearate, lanolin derivative quaternary ammonium salt, and the like.

Examples of amphoteric surfactants include carboxybetaine type, amidebetaine type, sulfobetaine type, hydroxysulfobetaine type, amide sulfobetaine type, phosphobetaine type, aminocarboxylate type, imidazoline derivative type, amideamine type, etc. Amphoteric surfactants, and the like.

As organic and inorganic pigments, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, bengala, clay, bentonite, titanium coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, aluminum oxide , Inorganic pigments such as calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, iron oxide, ultramarine, chromium oxide, chromium hydroxide, calamine, and complexes thereof; Polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene-styrene copolymer, Organic pigments, such as silk powder, cellulose, CI pigment yellow, and CI pigment orange, and complex pigments of these inorganic pigments and organic pigments, etc. are mentioned.

Examples of the organic powder include metal soaps such as calcium stearate; Alkyl phosphate metal salts, such as sodium zinc cetylate, a zinc laurylate, and calcium laurylate; Acylamino acid polyvalent metal salts such as N-lauroyl-beta-alanine calcium, N-lauroyl-beta-alanine zinc, and N-lauroyl glycine calcium; Amide sulfonic acid polyvalent metal salts such as N-lauroyl-taurine calcium and N-palmitoyl-taurine calcium; N, such as N-epsilon-lauroyl-L-lysine, N-epsilon-palmitoyl lizine, N-alpha-paritoylolnitine, N-alpha-lauroylarginine, N-alpha-hardened tallow fatty acid acylarginine, etc. -Acyl basic amino acid; N-acyl polypeptides such as N-lauroylglycylglycine; Alpha-amino fatty acids such as alpha-aminocaprylic acid and alpha-aminolauric acid; Polyethylene, polypropylene, nylon, polymethyl methacrylate, polystyrene, divinylbenzene/styrene copolymer, ethylene tetrafluoride, and the like.

UV absorbers include paraaminobenzoic acid, ethyl paraaminobenzoate, amyl paraaminobenzoate, octyl paraaminobenzoate, ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicate, butyl phenyl salicylate, homomentyl salicylate, benzyl cinnamate , Paramethoxycinnamic acid-2-ethoxyethyl, paramethoxycinnamic acid octyl, diparamethoxycinnamic acid mono-2-ethylhexane glyceryl, paramethoxycinnamic acid isopropyl, diisopropyl·diisopropyl cinnamic acid ester mixture, right Cannic acid, ethyl urocanate, hydroxymethoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and salts thereof, dihydroxymethoxybenzophenone, sodium dihydroxymethoxybenzophenone disulfonate, dihydroxybenzophenone , Tetrahydroxybenzophenone, 4-tert-butyl-4'-methoxydibenzoylmethane, 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)-1 ,3,5-triazine, 2-(2-hydroxy-5-methylphenyl)benzotriazole, etc. are mentioned.

As a disinfectant, hinokitiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, phenoxyethanol, resorcin, isopropylmethylphenol, azulene, salicylic acid, zinphylithione, benzalkonium chloride, photosensitization Sono No. 301, mononitroguarous sodium, undecylenic acid, and the like.

Examples of the antioxidant include butylhydroxyanisole, propyl gallic acid, and elisorbic acid.

Examples of the pH adjuster include citric acid, sodium citrate, malic acid, sodium malate, pmalic acid, sodium pmarate, succinic acid, sodium succinate, sodium hydroxide, sodium monohydrogen phosphate, and the like.

Examples of alcohol include higher alcohols such as cetyl alcohol.

In addition, the blending ingredients that may be added are not limited thereto, and any of the above ingredients can be blended within a range that does not impair the object and effect of the present invention, but preferably 0.01 to 5% by weight, more preferably, based on the total weight. May be blended in 0.01-3% by weight.

The cosmetic composition of the present invention may take the shape of a solution, an emulsion, a viscous mixture, or the like.

Ingredients included in the cosmetic composition of the present invention may include ingredients commonly used in cosmetics in addition to the extract as an active ingredient. For example, conventional adjuvants such as stabilizers, solubilizers, vitamins, pigments and fragrances, and It includes a carrier.

When the cosmetic composition formulation of the present invention is a paste, cream, or gel, animal fibers, plant fibers, wax, paraffin, starch, tracant, cellulose derivatives, polyethylene glycol, silicone, bentonite, silica, talc, or zinc oxide, etc. are used as carrier components. Can be used.

When the cosmetic composition formulation of the present invention is a powder or spray, lactose, talc, silica, aluminum hydroxide, calcium silicate, or polyamide powder may be used as a carrier component. In particular, in the case of a spray, additional chlorofluorohydrocarbons , Propane/butane or a propellant such as dimethyl ether.

When the cosmetic composition formulation of the present invention is a solution or emulsion, a solvent, solvating agent or emulsifying agent is used as a carrier component, such as water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol , 1,3-butylglycol oil, glycerol aliphatic ester, polyethylene glycol or fatty acid ester of sorbitan.

When the cosmetic composition formulation of the present invention is a suspension, as a carrier component, a liquid diluent such as water, ethanol or propylene glycol, an ethoxylated isostearyl alcohol, a suspending agent such as polyoxyethylene sorbitol ester and polyoxyethylene sorbitan ester, Crystalline cellulose, aluminum metahydroxide, bentonite, agar or tracant, and the like may be used.

When the cosmetic composition formulation of the present invention is a surfactant containing cleansing, as carrier components, aliphatic alcohol sulfate, aliphatic alcohol ether sulfate, sulfosuccinic acid monoester, isethionate, imidazolinium derivative, methyltaurate, sarcosinate, Fatty acid amide ether sulfates, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable oils, linoline derivatives, or ethoxylated glycerol fatty acid esters may be used.

In another aspect, the present invention can provide a pharmaceutical formulation comprising the organic-inorganic composite material prepared by the above method. The pharmaceutical preparation may include one or more selected from the group consisting of an anti-cancer agent, a cardio-cerebrovascular disease therapeutic agent, a wrinkle improving agent, a whitening agent, an antioxidant, an anti-inflammatory agent, an anti-inflammatory agent, a hair growth agent, an allergy inhibitor, and an atopic inhibitor. In addition, the target material may be a natural compound, a natural extract, a powder of a natural product, a synthetic compound, a natural peptide, a recombinant peptide, a microorganism or a culture solution thereof, a mineral, and the like. In this case, especially as a wrinkle improving agent, as a substance that inhibits MMP-1, an extracellular matrix (ECM) proteolytic enzyme, silicic acid, N-Methyl-L-serine , Isoflavonoids, Dehydroepiendrosteron, Paoniflorin, etc. can be selected. Benzastatin is a substance that prevents skin aging by removing free radicals that promote the breakdown of ECM. (Benzastatins), Coenzyme Q10, etc. can be used.In addition, adenosine, ascorbyl glucoside, kinetin, auxin, peptides, which are known for various wrinkle improvement effects, etc. (peptide), retinol (retinol), retinyl palmitate (retinyl palmitate), polyethoxylated retinamide (Polyethoxylated Retinamide), alpha-hydroxy acid (alpha hydroxyl acid) and the like can be used. As the whitening agent, the whitening agent is arbutin, niacinamide, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl acid-2-glucoside. , Japanese oak extract, ethyl ascorbyl ether, oil-soluble licorice extract, etc. In addition, collagen, various vitamins, etc. may be added as the drug, promoting epidermal cell proliferation and having a moisturizing effect. Oxyproline and the like may be included.

Each of the pharmaceutical preparations can be formulated in the form of oral dosage forms such as powders, granules, tablets, capsules, suspensions, emulsions, syrups, aerosols, etc., external preparations, suppositories, and sterile injectable solutions according to conventional methods. Carriers, excipients and diluents that may be included in the pharmaceutical preparation include lactose, dextrose, sucrose, sorbitol, mannitol, xylitol, erythritol, maltitol, starch, gum acacia, alginate, gelatin, calcium phosphate, calcium silicate, Cellulose, methyl cellulose, microcrystalline cellulose, polyvinyl pyrrolidone, water, methylhydroxybenzoate, propylhydroxybenzoate, talc, magnesium stearate, and mineral oils. In the case of formulation, it is prepared using diluents or excipients such as fillers, extenders, binders, wetting agents, disintegrants, and surfactants that are usually used. Solid preparations for oral administration include tablets, pills, powders, granules, capsules, and the like, and these solid preparations are at least one excipient, such as starch, calcium carbonate, sucrose, or It is prepared by mixing lactose and gelatin. In addition to simple excipients, lubricants such as magnesium stearate and talc are also used. Liquid preparations for oral use include suspensions, liquid solutions, emulsions, syrups, etc. In addition to water and liquid paraffin, which are commonly used simple diluents, various excipients such as wetting agents, sweetening agents, fragrances, and preservatives may be included. . Preparations for parenteral administration include sterile aqueous solutions, non-aqueous solutions, suspensions, emulsions, lyophilized preparations, and suppositories. As the non-aqueous solvent and suspending agent, propylene glycol, polyethylene glycol, vegetable oil such as olive oil, and injectable ester such as ethyl oleate may be used. As a base for suppositories, witepsol, macrogol, tween 61, cacao butter, laurin, glycerogelatin, and the like may be used.

The present invention relates to a method of manufacturing an organic-inorganic composite material having a high-efficiency supporting function and a release control function, wherein the material reacts a surfactant and a silica precursor to prepare mesoporous silica through hydrothermal synthesis, and a positively charged polymer and a negatively charged polymer It is prepared by coating. The organic-inorganic composite material prepared by the above method can support a large amount of whitening substances such as niacinamide and various drugs, and has excellent release control function, so that it can be easily used as a raw material for cosmetics, pharmaceutical compositions, and the like.

1 shows the measurement results of BET (BET Surface Area Analysis) of the mesoporous silica material of Example 1.
FIG. 2 shows the results of scanning electron microscope (SEM) images of the mesoporous silica material of Example 1. FIG.
3 is a flow chart schematically showing a process of manufacturing the material of Example 2 by coating an organic-inorganic material on the mesoporous silica material of Example 1 by a layer-by-layer technique.
4 shows the results of SEM image capture of mesoporous silica powder coated with the organic-inorganic material of Example 2.
5 shows the results of FT-IR analysis of mesoporous silica powder coated with the organic-inorganic material of Example 2.
6 shows the surface potential value of the mesoporous silica powder coated with the organic-inorganic material of Example 2.
7 shows the chemical structural formula of niacinamide.
8 shows a standard calibration curve for confirming the amount of niacinamide released.
9 is a graph showing the release rate of the powder of Example 2 on which niacinamide is supported.

Hereinafter, a preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, it is provided to sufficiently convey the spirit of the present invention to those skilled in the art so that the contents introduced herein are thorough and complete.

<Example 1. Preparation of mesoporous silica >

Pluronic P123 (PEO-PPO-PEO block copolymer) 2,135 g and 80 L of water were mixed and stirred at about 40 ℃ for about 48 hours, then tetraethylorthosilicate (TEOS) was added and stirred at 40 ℃ for about 24 hours I did. Silica particles are generated to become an opaque solution. Stirring of the opaque mesoporous silica material mixed solution was stopped, heated to 120° C., and aged for 8 hours. The aged mesoporous silica material was naturally cooled to room temperature, washed with water, and the washed mesoporous silica material was dried in a dryer for 24 hours and then calcined at 550° C. for 6 hours to prepare a mesoporous silica material having a high surface area.

In order to evaluate the properties of the silica material thus prepared, the analysis was carried out as follows. First, BET was measured to confirm the specific surface area and pore size, and SEM was performed to observe the surface shape of the particles.

The results of measuring BET (BET Surface Area Analysis) are shown in Fig. 1 and Table 1. Looking at the adsorption/desorption isotherm graph, a material having meso properties was manufactured, the specific surface area was 768.95 m ² /g, and the pore size was 6.65 It can be seen that it has a characteristic of nm.

sample Specific surface area [m ² /g] Pore volume [cm ³ /g] Pore size [nm] Preparation Example 1 Sample 768.95 1.21 6.65

In addition, as a result of observing a scanning electron microscope (SEM) image, as shown in FIG. 2, a material having a particle size of 2 μm or less was manufactured, and it can be seen that the shape of the particle is slightly spherical.

<Example 2. Preparation of mesoporous silica powder coated with organic/inorganic materials>

Using the Layer-by-Layer technique, Chitosan, a positively charged polymer material, was adsorbed once on the mesoporous silica powder of Example 1 having a negative surface charge, and once using a negatively charged polymer material, Poly(acrylic) acid. Mesoporous silica powder (APP) coated with organic/inorganic materials was prepared in an adsorption manner. At this time, the number of adsorption of the polymer was adjusted three times to analyze the surface potential according to the coating, the shape of the particles, and the components.

For coating, first, 3 mL of acetic acid was mixed with 300 mL of distilled water as a solvent, and then 2 g of the positively charged polymer Chitosan was dissolved using this solvent. After dissolving for about 30 minutes, 10 g of mesoporous silica prepared in Example 1 was added. And reacted for 2 hours. After completion of the reaction for 2 hours, the sample was centrifuged at 4000 rpm for 5 minutes to separate the solution and the sample, and the separated sample was lyophilized. Up to this point, the positively charged polymer was coated, and after drying it for 24 hours, 2 g of the negatively charged polymer, Poly(acrylic) acid, was dissolved in 300 mL of distilled water and reacted for 2 hours. After the reaction for 2 hours, the sample was dried to obtain a powder coated with a positively charged polymer and a negatively charged polymer in sequence, and the same process was added once and twice, respectively, to sequentially coat the positively charged polymer and the negatively charged polymer until the third time. One powder was obtained. Of the obtained samples, only the positively charged polymer was additionally coated, and only the positively charged polymer was immediately overcoated without performing the negatively charged polymer coating process.

In addition, in order to carry out the experiment under the comparative conditions, the order of coating the positively charged polymer and the negatively charged polymer was changed to prepare a sample coated with a negatively charged polymer and then sequentially coated with a positively charged polymer twice. The silica powder of Example 1 was set as a control sample.

This process is schematically shown in FIG. 3, and this layer-by-layer technique is a method of manufacturing by continuously adsorbing substances of opposite attraction by using attraction of materials such as electrostatic attraction, hydrogen bonding, and covalent bonding. to be.

The coating/adsorption state of each sample is shown in Table 2 below.

Sample Sample name Example 1 One-time coating of a positively charged polymer on silica L1 Example 1 After coating a positively charged polymer on silica, a negatively charged polymer coating process was performed once in total L1PAA Example 1 Coating of a positively charged polymer twice on silica L2 Example 1 After coating the positively charged polymer on silica, the negatively charged polymer coating process was performed twice in total L2PAA Example 1 Coating of a positively charged polymer 3 times on silica L3 Example 1 After coating the positively charged polymer on silica, the negatively charged polymer coating process was performed three times. L3PAA Example 1 After negatively charged polymer coating on silica, positively charged polymer coating process was performed twice in total NP2 Example 1 silica S

<Experimental Example 1. Physicochemical analysis of mesoporous silica powder coated with organic/inorganic materials>

The physicochemical analysis of mesoporous silica powder (APP) coated with organic/inorganic materials confirms the component evaluation (FT-IR) according to the coating of the polymer material, the surface potential value of the polymer material and the inorganic material silica, and the shape of the particles. The results were confirmed through a possible SEM.

Referring to FIG. 4, the shape of the particles according to the number of coatings of the polymer and the inorganic material silica can be confirmed by SEM images, but the change in the shape of the particles according to the number of applications of the polymer was not largely distinguished by the naked eye.

The results of FT-IR (Fourier Transform Infrared Spectroscopy) analysis according to the number of coatings are shown in FIG. 5, which is for component confirmation through polymer coating, and the C-H band of the polymer and the Si-O band of silica can be confirmed.

Zeta potential for confirming the change in the surface potential value according to the number of coatings of the positive/negatively charged material and the porous silica material is shown in FIG. 6.

According to FIG. 6, the silica material has a surface potential value of 0.597 mV according to the number of coatings of the positive/negative material, and is 0.597 mV when positive and negative charges are coated once, respectively, and -10.5 mV is applied to the positive/negative charge coating. Accordingly, it can be seen that the positive and negative characteristics change and appear. In the case of a porous silica material, it can be seen that the surface potential value tends to increase due to the positive charge compared to the general surface potential value of about -25mV, and the difference in the surface potential value appears due to coating with a negative charge.

<Experimental Example 2. Application of whitening material loading and release control of mesoporous silica powder coated with organic/inorganic material>

An experiment was conducted to confirm the loading efficiency characteristics of the mesoporous silica powder coated with the organic-inorganic material prepared in Example 2.

First, the loading efficiency was evaluated using niacinamide, which is widely known as a whitening material. Niacinamide has the structure shown in Fig. 7, and is called nicotinic acid and niacin, and refers to the physiologically active amide of niacin (Vitamin B3/Niancin) as a vitamin B complex. It is notified as a whitening ingredient that can have a whitening effect on the skin.

To 10 ml of a 10 mM niacinamide ethanol solution, 1 g of the material of Example 2, coated with a positive/negatively charged polymer material 1 to 3 times, was added and stirred for 12 hours to allow niacin amide to be supported. Thereafter, the material of Example 2 was taken from the solution, dried, and 10 mg of the dried material was added to 1.5 ml of PBS (Phosphate buffer saline) pH 7.4, and the release behavior was confirmed at 37°C. The amount of niacinamide released was confirmed based on the calibration curve of FIG. 8.

As a result, as shown in FIG. 9, it can be seen that the composition in which niacinamide is supported on the material of Example 2 continuously releases niacinamide, which is a functional material, compared to short-time release, and the release effect is that the positively charged/negatively charged polymer material is 2 It can be seen that the ash-coated one (L2PAA) is the best.

On the other hand, although not shown in FIG. 9, the sample (NP2) or Example 1 silica (S) prepared by performing a total of two times of coating a positively charged polymer after coating a negatively charged polymer on silica in Example 1 did not release niacinamide, and thus was not supported. It was found that it was not in a state of being (we did not experiment on coating only positively charged polymers 1 to 3 times).

<Cosmetic formulation example 1. Preparation of sun cream>

As shown in the composition of Table 3 below, niacinamide was supported on the silica powder prepared in Example 2, and a sunscreen (100g) containing the same was prepared according to a conventional method.

Raw material Content (g) Powder of Example 2 on which niacinamide is supported 0.5 Sitosterol 4.0 Polyglyceryl 2-oleate 3.0 Ceramide 0.7 Ceteares-4 2.0 cholesterol 3.0 Dicetyl phosphate 0.4 Concentrated glycerin 5.0 Sunflower Oil 22.0 Carboxyvinyl polymer 0.5 Triethanolamine 0.5 antiseptic a very small amount Spices a very small amount Purified water Balance

<Cosmetic formulation example 2. Preparation of foundation>

As shown in the composition of Table 4 below, niacinamide was supported on the silica powder prepared in Example 2, and a foundation (100 g) containing the same was prepared according to a conventional method.

Raw material Content (g) Powder of Example 2 on which niacinamide is supported 0.5 Beeswax 2.0 Cyclomethicone 2.0 Floating paraffin 5.0 Squalane 5.0 Stearic acid 2.0 Lipophilic glycerin monostearate 3.0 Caprylic/Capric Triglyceride 4.0 glycerin 4.0 Propylene glycol 3.0 Butylene glycol 3.0 Triethanolamine 1.0 Aluminum Magnesium Silicate 0.5 Pigment 12.0 antiseptic a very small amount Spices a very small amount Purified water Balance

Claims (11)

(First step) preparing mesoporous silica through hydrothermal synthesis by reacting a poly(alkylene oxide) block copolymer and tetraethylorthosilicate;
(2nd step) coating chitosan on mesoporous silica; And,
(3rd step) obtaining an organic-inorganic composite material by coating polyacrylic acid on chitosan-coated mesoporous silica;
Including,
To the organic-inorganic composite material obtained in the third step, a step of performing the chitosan coating step of the second step and the polyacrylic acid coating step of the third step by the same method was added, so that it has a high-efficiency loading function and a release control function. Method for manufacturing organic-inorganic composite material. delete delete delete delete A cosmetic composition comprising the organic-inorganic composite material prepared by the method of claim 1. The method of claim 6,
The cosmetic composition is a cosmetic composition, characterized in that the whitening effect. The method of claim 6,
The cosmetic composition is a cosmetic composition, characterized in that supporting niacinamide. The method of claim 6,
The formulation of the cosmetic composition is skin lotion, skin softener, skin toner, astringent, lotion, milk lotion, moisture lotion, nutrition lotion, massage cream, nutrition cream, moisture cream, hand cream, foundation, essence, nutrition essence, pack, soap , Cleansing foam, cleansing lotion, cleansing cream, body lotion, and a cosmetic composition, characterized in that selected from the group consisting of a body cleanser. A pharmaceutical formulation comprising an organic-inorganic composite material prepared by the method of claim 1. The method of claim 10,
The pharmaceutical preparation is a target drug, characterized in that it comprises at least one selected from the group consisting of anticancer agents, cardiovascular disease therapeutics, anti-wrinkle agents, whitening agents, antioxidants, anti-inflammatory agents, anti-inflammatory agents, hair growth agents, allergy inhibitors, and atopic inhibitors. Pharmaceutical formulations.

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