KR101522722B1 - Aggregates Comprising Ionic Organic/Inorganic Hybrid Particle, Cosmetic Composition Comprising the Aggregates, and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to an organic / inorganic hybrid particle aggregate aggregated by ionic interaction between a cationic organic / inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer, The organic / inorganic hybrid particle agglomerate according to the present invention has a safe and highly excellent ultraviolet shielding effect and can be very useful as an ultraviolet screening agent.
The present invention also relates to a process for producing the above aggregate of organic / inorganic hybrid particles, a cosmetic composition comprising the aggregate and a process for producing the same.

Description

TECHNICAL FIELD The present invention relates to an agglomerate containing ionic organic / inorganic hybrid particles, a cosmetic composition containing the same, and a method for preparing the same. [0002]

The present invention relates to an organic / inorganic hybrid particle aggregate aggregated by ionic interaction between a cationic organic / inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer, The organic / inorganic hybrid particle agglomerate according to the present invention has a safe and highly excellent ultraviolet shielding effect and can be very useful as an ultraviolet screening agent.

The present invention also relates to a process for producing the above aggregate of organic / inorganic hybrid particles, a cosmetic composition comprising the aggregate and a process for producing the same.

In recent years, there has been a growing interest in cosmetics, and as the population of outdoor activities, especially outdoors, increases, the sunscreen effect to prevent skin damage and burns such as erythema caused by ultraviolet rays The demand for various products is continuously increasing.

The UV protection effect of cosmetics is generally expressed in terms of SPF (Sun Protection Factor) and PA (Protection Grade of UV-A). The SPF index is a numerical value developed to show how well the product protects skin from ultraviolet rays If the SPF index is 30, it means that it will increase the time it takes for the skin to get reddish (erythema formation) 30 times after being exposed to the sun. If it is 20 minutes (PA + PA +++ PA +++) is a measure of the degree of blocking of UVA (UVA), which means that it protects skin from ultraviolet rays for 600 minutes (10 hours) And PA +++ is the most effective UV blocking agent.

In general, the ultraviolet screening agents used for cosmetic purposes are classified into organic ultraviolet screening agents and inorganic ultraviolet screening agents.

Organic ultraviolet screening agents exhibit ultraviolet ray blocking effect mainly by absorbing ultraviolet rays. The organic ultraviolet screening agents have characteristics of presence of conjugation bonds capable of absorbing ultraviolet rays in the molecular structure of ultraviolet screening agent. Examples of organic ultraviolet screening agents include para-aminobenzoic acid (PABA) Organic compounds such as PABA esters, salicylates, camphor derivatives and cinnamates and dibenzoylmethane, anthranilate, benzoate blocking UV-A, Benzophenone, triazole and the like are mixed, but they have a disadvantage of causing skin toxicity, allergy and discoloration.

Accordingly, recently, inorganic sunscreen agents have been mainly used. The inorganic ultraviolet screening agent mainly exhibits an ultraviolet shielding effect by reflecting and scattering ultraviolet rays. Examples of the ultraviolet screening agent include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), or zirconium oxide ) And metal oxides such as ferric chloride, talc, kaolin and ichthammol (Ichthyol) are mainly used. Titanium dioxide exhibits strong blocking ability against ultraviolet ray B, but shows a relatively weak blocking ability against ultraviolet ray A region. Zinc oxide has excellent blocking ability against ultraviolet ray A region, but blocking ability against ultraviolet ray B region There is a drawback that it is low.

Inorganic UV blocking agents generally have a greater UV blocking effect when the size of the main inorganic particles is smaller, but nanoparticle size inorganic particles are known to be toxic to humans through animal experimental studies. Accordingly, the National Institute of Occupational Safety and Health (NIOSH) limits the use of nanoparticle-sized inorganic particles to 0.1 mg / m ^{2. In} Korea, the Korea Food and Drug Administration It states that the use of nanomaterials is indicated and requires that the material be proven to be harmless to the human body. However, if the size of the metal oxide used in the ultraviolet screening agent is increased to secure safety, the ultraviolet screening effect is lowered, and accordingly, the amount of the metal oxide used must be increased in order to secure the same ultraviolet screening effect. At the same time, when the size of the metal oxide is increased, rough feeling and the like are generated, and the feeling of use (such as wettability) is deteriorated, and when applied to the face or body,

In order to solve the problems of the conventional organic and inorganic ultraviolet screening agents as described above, there has been proposed a UV screening composition (JP-A No. 2010-510170) which contains an organic ultraviolet screening agent and a chelate of a metal ion and has improved ultraviolet screening performance , A new formulation system that can reduce the content of sunscreen agents and increase the protection index against the same amount of blocking agents, comprising two immiscible and anionic surfactants stabilized with one or more anionic surfactants, A cosmetic composition (Korean Patent Laid-Open No. 2001-0023743) which further contains a zwitterionic ampholytic compound has been proposed.

However, there is still a need for an excellent sunscreen agent that does not cause opacity and cosmetics containing the same, while still maintaining high safety and excellent ultraviolet shielding effect.

Disclosure of the Invention The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a novel ultraviolet screening agent which completely solves the safety problem due to small particle size while maintaining the excellent ultraviolet screening effect of the ultraviolet screening agent comprising the inorganic nano- And a method thereof.

Another object of the present invention is to provide a cosmetic composition comprising the novel ultraviolet screening agent and a process for producing the same.

In order to accomplish the above object, the present invention provides an organic / inorganic hybrid material in which a cationic organic / inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer are aggregated by ionic interaction, Inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer in an appropriate ratio, wherein the cationic organic / inorganic hybrid particle and the anionic organic / inorganic hybrid particle or the anionic polymer are mixed in an appropriate ratio.

The present invention also provides a cosmetic composition comprising the oil / inorganic hybrid particle agglomerates and a method for producing the same.

The organic / inorganic hybrid particle agglomerates according to the present invention are safe and excellent, and have a blocking effect against a wide range of ultraviolet rays, and can form a homogeneous and thin film, Can be very useful.

Unless otherwise defined, 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 in this specification is generally well known and commonly used in the art.

The present invention, in one aspect, provides an oil / inorganic hybrid particle aggregate.

The 'oil / inorganic hybrid particle agglomerates' in the present invention are obtained by aggregating cationic organic / inorganic hybrid particles and anionic organic / inorganic hybrid particles or anionic polymers by ionic interaction And it is preferable to have a spherical form, but the present invention is not limited thereto.

The "cationic organic / inorganic hybrid particle" among the constituents of the organic / inorganic hybrid particle aggregate is an inorganic substance such as a metal oxide whose surface has been modified to have a cationic functional group (functional group) (Charge Control Agent, CCA), which has a positive charge and an inorganic substance,

The "cationic organic / inorganic hybrid particle" is obtained by modifying the surface of an inorganic material, preferably a metal oxide, to have a cationic functional group, or by mixing a positive charge control agent to have a positive charge with an inorganic substance such as a metal oxide .

Examples of the method for modifying the surface of the cationic organic / inorganic hybrid particle to have a cationic functional group include a method of modifying the surface with an aminosilane, preferably a substance capable of introducing a cationic functional group onto the surface of an inorganic substance such as a metal oxide, Or a method of modifying the surface of an inorganic substance such as a metal oxide so as to have an anionic functional group and then reacting a substance having a polycationic functional group, but the present invention is not limited thereto

The inorganic material that can be used for the cationic organic / inorganic hybrid particles is preferably a metal oxide. However, the present invention is not limited thereto, and any inorganic material capable of achieving 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 And titanium dioxide or zinc oxide is preferable.

The cationic functional group which can be introduced into the surface of the inorganic substance, preferably the metal oxide, in the present invention preferably has a structure represented by the following formula (1), but is not limited thereto.

식 (1)

Equation (1)

In the 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, 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.

When an inorganic substance such as a metal oxide is surface-modified with aminosilane, one or more primary, secondary, or tertiary amines are introduced into the surface of the cationic organic / inorganic hybrid particle to exhibit cationicity. In one embodiment, the aminosilane that can be used in the present invention for the surface modification of an inorganic, preferably metal oxide, is N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N- 3-aminopropyltrimethoxysilane), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrialkoxysilane such as 3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrialkoxysilane, -aminopropyltrimethoxysilane, and N- (vinylbenzyl) (Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane HCl) or a hydrolyzate thereof is used as the material But is not limited thereto.

A method of modifying an inorganic substance such as a metal oxide to have an anionic functional group and then modifying the surface of the inorganic substance to have a cationic functional group by reacting with a substance having a polycationic functional group is surface modified with aminosilane or the like A method wherein a cationic organic / inorganic hybrid particle is reacted with a substance having a polyanionic functional group to modify the surface thereof to have an anionic functional group and then reacted with a substance having a polyionic functional group, or A method in which the metal oxide surface is modified with a substance having a polyanionic functional group so as to have a direct anionic functional group and then reacted with a substance having a polycationic functional group can be used. Examples of the anionic functional groups include, but are not limited to, a carboxylic acid group, a phosphoric acid group, a sulfuric acid group, and a sulfate group.

The material having the polycationic functional group may be a polyamine, preferably ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, N-methylethylenediamine, 1,4-diaminobutane, But are not limited to, N, N-dimethylethylenediamine, N, N-dimethylethylenediamine, trimethylenetetramine, triethylenetetramine, phenylenediamine, hexamethylenetetramine, diaminocyclohexane, Aminobenzylamine, tetraethylene pentaamine, and the like can be used, but are not limited thereto.

As the polyanionic functional group-containing substance, polyacid or polyacid derivatives or an anhydride of polyacid may be used. Specific examples thereof include oxalic acid, malonic acid, acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acid, citric acid, undecanedioic acid, phthalic acid, maleic acid, fumaric acid, glutaconic acid, traumatic acid, (Poly (ethyleneglycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride, citric acid (citric acid) ), Aconitic acid, tricarballylic acid, tri Trimesic acid, trimesic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, polyacrylic acid, or sodium polyacrylate sodium polyacrylate), and the like may be used, but the present invention is not limited thereto.

The positively chargeable charge control agent having a positive charge is preferably an ammonium salt, particularly a quaternary ammonium salt, because the quaternary ammonium salt is in the form of a white powder, Because it has the advantage of not affecting. Specific examples of positively chargeable charge control agents include commercially available materials such as N-series or P-series of Oriental Corp., preferably Bontron P51 or Bontron P53 ( http://www.orient-usa.com/index.php?link = bontron ) can be used.

If the amount of the positively charge-controlling agent is too small, the produced organic / inorganic hybrid particles do not exhibit ionic properties. Therefore, the amount of the organic / inorganic hybrid particles may be 0.5 wt% or more, preferably 1 wt% % Or less.

The "anionic organic / inorganic hybrid particle" of the constituent components of the organic / inorganic hybrid particle aggregate is an inorganic material such as a metal oxide whose surface is modified so as to have an anionic functional group or a negative charge Refers to a mixture of a charge control agent and can be obtained by preparing an inorganic material, preferably a metal oxide, by modifying the surface thereof to have an anionic functional group, or by mixing a charge control agent having a negative charge with a metal oxide.

Among the inorganic materials that can be used for the anionic organic / inorganic hybrid particles, metal oxides include titanium oxide (TiO ₂ ), zinc oxide (ZnO), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), and zirconium oxide ), And titanium dioxide or zinc oxide is preferable.

As a method for modifying the anionic organic / inorganic hybrid particle surface to have an anionic functional group, a method of modifying an inorganic substance, preferably a metal oxide surface, as a substance capable of imparting an anionic functional group, A method of modifying the surface of an inorganic substance such as a metal oxide with a substance capable of imparting a functional group, preferably aminosilane, to introduce a cationic functional group and then reacting with a substance having a polyanionic functional group to modify the surface anionically Can be used.

Examples of the anionic functional groups include, but are not limited to, a carboxylic acid group, a phosphoric acid group, a sulfuric acid group, and a sulfate group.

The cationic functional group which can be used in the production of the anionic organic / inorganic hybrid particles preferably has the structure of the formula (1).

More specifically, the aminosilane which can be used in the present invention to impart a cationic functional group is N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 3-aminopropyltrialkoxysilane such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N- ( Vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane HCl). .

Examples of the substance having a polyanionic functional group include a polyacid or a polyacid derivative or an anhydride of a polyacid, and more specifically, oxalic acid, malonic acid, succinic acid, It is also possible to use glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid ), Phthalic acid, maleic acid, fumaric acid, glutaconic acid, traumatic acid, muconic acid, poly (ethylene Poly (ethyleneglycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride, citric acid, aconitic acid, Tricarballylic acid, trimesic acid, 2-phosphonobutane (2-Phosphonobutane-1,2,4-tricarboxylic acid), polyacrylic acid, or sodium polyacrylate may be used. It is not.

The negative charge control agent having a negative charge is preferable because the charge control agent of the tert-butyl salicycic acid metal salt series does not affect the color of the finally produced particles. Chromium, aluminum, zinc, calcium boron, and acetylboron are mainly used as the central metal of the negative charge control agent of the tert-butylsalicylic acid metal salt series. Such a center metal controls the ionic properties of the particles. Specific examples of anionic charge control agents include commercially available materials such as E-series, F-series or S-series of Oriental Corp., preferably Bontron E8 ( http://www.orient-usa.com/index.php? link = bontron ) can be used.

As shown in the positive charge control agent, the negatively chargeable charge control agent is used in an amount of not less than 0.5% by weight, preferably not less than 1% by weight, based on the weight of the final particles produced, Or more, and it is preferable to use about 40 wt% or less.

Among the constituents of the oil / inorganic hybrid particle agglomerates The anionic polymer can be used without limitation as long as it can form an aggregate through ionic interaction with cationic organic / inorganic hybrid particles. The vinylpyrrolidone-acrylic acid copolymer acrylic acid copolymer, a vinylpyrrolidone-acrylic acid copolymer, a methyl methacrylate-acrylic acid copolymer, a methyl methacrylate-methacrylic acid copolymer, a polyacrylic acid- PAA, polymethacrylic acid, and carboxymethylcellulose. Polyacrylic acid is most preferable, but is not limited thereto.

The organic / inorganic hybrid particle aggregate according to the present invention is formed by aggregating cationic organic / inorganic hybrid particles and anionic organic / inorganic hybrid particles or anionic polymer such as salpin by ionic interaction , Preferably distilled water, alcohol, or the like, mixed in a single solution or mixed solution to form an aggregate by forming ionic bonds between the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles or the anionic polymer.

The aggregation of the organic / inorganic hybrid particles according to the present invention can be suitably selected depending on the type and mixing ratio of the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles or the anionic polymer used and the net charge of the agglomerate, Can be adjusted.

The cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles may be mixed in a weight ratio of 5:95 to 95: 5, preferably 7: 3 to 3: 7, and the cationic oil / The inorganic hybrid particles and the anionic polymer may be mixed in a weight ratio of 99.9: 0.01 to 50:50, preferably 99.95: 0.05 to 80:20.

The average particle size (Dv50) of the aggregate of the organic / inorganic hybrid particles provided in the present invention is 0.1 to 50 占 퐉, preferably 0.5 to 30 占 퐉, and most preferably 1 to 20 占 퐉. The average particle size of the aggregate of the organic / inorganic hybrid particles according to the present invention is advantageous in solving the safety problem such as the human hazard which may occur due to the use of the small size nanoparticles (less than 100 nm) Since inorganic nanoparticles, i.e., metal oxides, are contained in the inorganic hybrid particle aggregate, they can exhibit equivalent or superior performance to those of the conventional nano-sized inorganic materials.

In addition, the cationic or anionic organic / inorganic hybrid particles constituting the aggregate of the organic / inorganic hybrid particles according to the present invention may be prepared by mixing various inorganic materials, preferably metal oxides, and the ultraviolet blocking region of each metal oxide There is an advantage that the ultraviolet blocking range can be widened.

For example, since titanium dioxide and zinc oxide are different from each other in ultraviolet ray shielding region, cationic organic / inorganic hybrid particles are prepared using titanium dioxide, and anionic organic / inorganic hybrid particles are prepared using zinc oxide, Inorganic hybrid particle agglomerates are prepared by mixing titanium dioxide and zinc oxide when preparing the cationic or anionic organic / inorganic hybrid particles, and when the organic / inorganic hybrid particle agglomerates are prepared from the mixture, titanium dioxide And the ultraviolet shielding regions that each of zinc oxide can block.

Furthermore, the organic / inorganic hybrid particle agglomerates according to the present invention are more stable because the penetration of nanomaterials into the skin is limited by the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles or the anionic polymer. .

In another aspect, the present invention provides a method for producing the aggregate of organic / inorganic hybrid particles.

A method for producing an aggregate of organic / inorganic hybrid particles according to the present invention comprises:

(a) providing a cationic organic / inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer;

(b) mixing the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles or the anionic polymer to produce an organic / inorganic hybrid particle aggregate; And a control unit.

In the method for producing an organic / inorganic hybrid particle aggregate according to the present invention, the materials, characteristics, and sizes used in the production of the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles or the anionic polymer, Hybrid particle agglomerate, and the mixing ratio of the cationic organic / inorganic hybrid particle and the anionic organic / inorganic hybrid particle or the anionic polymer is the same as that described above in the organic / inorganic hybrid particle agglomerate.

The cationic organic / inorganic hybrid particles in the step (a) may be modified to have a cationic functional group (functional group) on the surface of an inorganic substance, preferably a metal oxide, or a metal oxide and a positive charge (Charge Control Agent, CCA), which is a compound of the present invention.

Examples of the method of preparing the cationic organic / inorganic hybrid particles by surface modification to have an amine group among the cationic functional groups include distillation water, titanium dioxide, zinc oxide and the like in at least one solution selected from alcohols such as ethanol and methanol And the mixture is stirred for 5 to 120 minutes, preferably 10 to 60 minutes, more preferably 20 to 40 minutes, and aminosilane dissolved in an alcohol such as ethanol or methanol is added to the mixture to obtain 0.5 To 6 hours, preferably 1 to 5 hours, more preferably 2 to 4 hours. The titanium dioxide or zinc oxide fine particles to be used are preferably 10 to 70 nm, preferably 20 to 50 nm in size. Furthermore, mixing the titanium dioxide or zinc oxide fine particles with at least one solution selected from distilled water and alcohol, stirring the mixture, adding ammonia water and stirring the mixture may be further included. Followed by washing and drying with alcohol, and / or distilled water, to obtain aminosilane-modified cationic organic / inorganic hybrid particles. The stirring may be carried out at a temperature of 10 to 50 ° C, preferably 15 to 40 ° C, more preferably 20 to 30 ° C. The 'room temperature' in the present invention means 20 to 30 ° C, particularly 25 ° C.

When a method of modifying a metal oxide to have a cationic functional group on the surface of a cationic organic / inorganic hybrid particle by reacting the metal oxide with a substance having a polycationic functional group after the surface modification to have an anionic functional group is used, Dispersing the cationic organic / inorganic hybrid particles obtained by the method of surface modification with silane in an organic solvent, adding thereto polyacid such as anhydrous succinic acid dissolved in an organic solvent for 0.5 to 6 hours, The mixture is stirred for 1 to 5 hours, more preferably 2 to 4 hours to obtain a surface-modified metal oxide having an anionic functional group. Thereafter, a polyamine dissolved in an organic solvent, preferably triethylenetetraamine And stirring for 4 to 40 hours, preferably 10 to 30 hours, more preferably 12 to 20 hours. Can. The stirring may be carried out at a temperature of 10 to 50 ° C, preferably 15 to 40 ° C, more preferably 20 to 30 ° C.

Examples of the organic solvent that can be used in the present invention include N, N-dimethylformamide, N-methylpyrrolidone, hexane, chloroform, cyclohexane, benzene, toluene ), Dioxane, chloroform, diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, Acetonitrile, dimethyl sulfoxide, propylene carbonate, methanol, ethanol, propanol, butanol, acetic acid, and nitro And nitromethane may be suitably used according to the object, but the present invention is not limited thereto. Any organic solvent may be used as long as the object of the present invention is met. Can.

In the case of producing cationic organic / inorganic hybrid particles using a metal oxide and a positive charge control agent, a resin is dissolved in an organic solvent, a metal oxide and a charge control agent are added thereto, and a beads mill, To obtain a dispersion, mixing the resin with a solvent insoluble in the resin to form particles, removing the solvent under reduced pressure, and drying the dispersion.

Specifically, a polyester resin, preferably a polyester, polystyrene, a styrene acrylic resin or the like is dissolved in an organic solvent, preferably methyl ethyl ketone, and then a charge control agent, preferably, , Bontron P51 is added and dispersion is carried out using a beads mill at non-affinity for 5 to 18 hours, preferably 8 to 15 hours, more preferably 11 to 13 hours. The dispersion is added to n-hexane under stirring at room temperature and stirred to prepare a mixed solution. The mixed solution is diluted with n-hexane after removing the solvent under reduced pressure, and centrifuged to dry the slurry to obtain organic / inorganic hybrid particles.

The anionic organic / inorganic hybrid particles in the step (a) may be obtained by modifying the surface of an inorganic material, preferably a metal oxide, so as to have an anionic functional group, or by mixing a charge control agent having a negative charge with a metal oxide .

The method of modifying the surface of the anionic organic / inorganic hybrid particle so as to have an anionic functional group includes a method of modifying the surface of a metal oxide with a substance capable of imparting an anionic functional group, The surface of the metal oxide is modified with aminosilane to introduce a cationic functional group, for example, a cationic functional group such as the formula (1), and then reacted with a substance having a polyanionic functional group to have an anionic functional group A method of modifying the surface, and the like can be used.

A method of preparing anionic organic / inorganic hybrid particles by modifying the surface with a substance having a cationic property to introduce a cationic functional group and then reacting the substance with a substance having a polyanionic functional group to have an anionic functional group, As an example of introducing a cationic functional group into silane, the cationic organic / inorganic hybrid particles surface-modified with aminosilane obtained by the above-described method are dispersed in an organic solvent, and then an organic solvent Dissolved anhydrous succinic acid, and the like, and the mixture is stirred for 0.5 to 6 hours, preferably 1 to 5 hours, more preferably 2 to 4 hours, to obtain anionic organic / inorganic hybrid particles.

In addition, when anionic organic / inorganic hybrid particles are prepared using a negative charge control agent, a resin, preferably a polyester, a polystyrene, or a styrene acrylic resin, After the ester resin is dissolved in an organic solvent, a metal oxide and a charge control agent are added thereto and dispersed by using a beads mill or the like to obtain a dispersion. The resin is mixed with a solvent insoluble in the resin to form particles, And then drying it.

In the step (b), an organic / inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer provided in the step (a) are mixed to prepare an organic / inorganic hybrid particle aggregate, Inorganic hybrid particle dispersions each dispersed in an alcohol and an anionic organic / inorganic hybrid particle dispersion or an anionic polymer solution are mixed and stirred.

In the step of preparing each of the dispersions of the cationic and anionic organic / inorganic hybrid particles, ultrasonic treatment may be carried out. In the case of mixing and stirring the dispersions of cationic and anionic organic / inorganic hybrid particles, a homogenizer ) Can be used.

In another aspect, the present invention provides a cosmetic composition for ultraviolet shielding comprising the above aggregate of organic / inorganic hybrid particles.

The cosmetic composition for UV screening comprising the organic / inorganic hybrid particle agglomerates in the present invention can be prepared by mixing a conventional O / W cream base composition and an organic / inorganic hybrid particle agglomerate, but not limited thereto, It will be apparent to those skilled in the art that the ingredients contained in the cosmetic compositions commonly used in the art may be used.

The cosmetic composition for protecting ultraviolet rays 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 an organic / inorganic hybrid particle aggregate, But are not limited to, microcrystalline wax, bees wax, carbomer, octyl methoxycinnamate, bis-ethylhexyloxyphenol methoxyphenyl triazine, But are not limited to, isoamyl-p-methoxycinnamate, disodium EDTA, phenoxyethanol, methyl-p-hydroxybenzoate, propyl-p-hydroxybenzoate, butylene glycol, polyglyceryl-3-methylglucose distearate, Cetearyl Alcohol, Glyceryls PEG-100 stearate, Phenyl Trimethicone, Decamethyl Cyclopentasiloxane, Polyacrylate-13, Polyisobutene, and the like. Polyisobutene, Polysorbate 20, Triethanolamine Dissolvine Na2-S, Propylene Glycol, Finsolv TN, Protachem SMO, Escalol 557 Octinoxate, Escalol 567, Oxybenzone, Escalol 587, Crodafos CES, Cetearyl Alcohol 50/50, Croda But are not limited to, one or more materials selected from the group consisting of Coddose C320 Acid, Liquid Germall Plus, Frangrance, and TEA 99%.

The cosmetic composition according to the present invention can be produced in various cosmetic forms. For example, it can be manufactured in the form of cream, lotion, stick, foundation, emulsion, wax, oil, spray, aerosol, lotion, essence, pack, powder, gel, It will be apparent to those of ordinary skill in the art that any form of use commonly used in the art may be used.

In another aspect, the present invention provides a cosmetic composition for protecting ultraviolet rays containing an aggregate of organic / inorganic hybrid particles and a process for producing cosmetics.

The method for producing a cosmetic composition for protecting ultraviolet rays comprising an organic / inorganic hybrid particle agglomerate according to the present invention is characterized by mixing an organic / inorganic hybrid particle agglomerate and a suitable cosmetic composition raw material, The preparation method may be carried out by mixing the prepared cosmetic composition with a suitable excipient, a dispersing agent, an emulsifying agent, a pigment, a preservative, an emulsifier, Oils, moisturizers, surfactants and the like may be mixed and formulated.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are for illustrating the present invention only, and it is apparent to those skilled in the art that the scope of the present invention is not construed as being limited by these embodiments.

[Example]

Example  One: Cationic  Weapons / weapons hybrid  Particle manufacturing

Example  1-1: Aminosilane  Titanium dioxide used On surface modification  by Cationic  Preparation of organic / inorganic hybrid particles

100 g of TiO ₂ (VK-T25, Xuancheng Jingrui New Material Co., Ltd.) having an average particle diameter of 40 nm was mixed with a mixed solution of 410 g of distilled water and 45 g of ethanol (Samgan Chemical Co., Ltd.), and the mixture was stirred at room temperature for 30 minutes. Thereafter, 10 g of 35% ammonia water was added, and the mixture was stirred for 30 minutes. After that, 3 g of 3-aminopropyltriethoxysilane (Aldrich) dissolved in 90 g of ethanol was added for 30 minutes, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was filtered, washed with ethanol and dried to obtain 98 g of cationic organic / inorganic hybrid particles. The average particle diameter and surface charge (Zeta-Potential) of the prepared cationic organic / inorganic hybrid particles were measured with a dynamic light scattering method measuring instrument ZEN-3690 (Malvern Instruments Ltd).

Example  1-2: Anionic  To have a functional group Surface modified  Titanium dioxide and Polyamine  By reaction Cationic  Weapons / weapons hybrid  Manufacturing of particles

1 g of triethylenetetramine (Aldrich) was mixed with 40 g of DMF (N, N-Dimethylformamide, Samcheon Chemical), and the mixture was stirred at 60 ° C for 30 minutes. Then, DCC (N, N'-Dicyclohexylcarbodiimide, And the mixture was stirred for 30 minutes. The mixed solution was added to a solution prepared by dispersing 20 g of the organic / inorganic hybrid particles prepared in Example 2-1 in 80 g of NMP (N-methypyrrolidone), followed by stirring at room temperature for 16 hours. Thereafter, the reaction product was filtered / washed with 1 M aqueous HCl solution, distilled water, acetone, and dried to obtain 19 g of cationic organic / inorganic hybrid particles. The average particle diameter and surface charge (Zeta-Potential) of the prepared cationic organic / inorganic hybrid particles were measured with a dynamic light scattering method measuring instrument ZEN-3690 (Malvern Instruments Ltd).

Example 1-3: Preparation of cationic organic / inorganic hybrid particles by surface modification of titanium dioxide using (+) CCA and resin 60 g of polyester resin (ET-6000, SK Chemical) was dissolved in methyl ethyl ketone ), 60 g of TiO ₂ and 1.2 g of charge control agent Bontron P51 (Orient Corp.) were added and dispersed at room temperature for 12 hours using a beads mill. The dispersion was added to 1000 g of n-hexane under stirring at 100 rpm at a rate of 50 ml / min at room temperature and stirred for 10 minutes. After removing the solvent under reduced pressure, the mixture was diluted with n-hexane and centrifuged to dry the slurry to prepare organic / inorganic hybrid particles.

Example  1-4: Aminosilane  Used zinc oxide On surface modification  by Cationic  Weapons / weapons hybrid  Manufacturing of particles

Cationic organic / inorganic hybrid particles were prepared in the same manner as in Example 1, except that 100 g of zinc oxide (MZ-500, Tayca Corp.) having a size of 20 nm was used instead of TiO ₂ .

Example  2: Anionic  Weapons / weapons hybrid  Particle manufacturing

Example  2-1: With aminosilane Surface modified  Titanium dioxide and succinic anhydride ( succinic  anhydride Anionic  Weapons / weapons hybrid  Manufacturing of particles

80 g of the cationic organic / inorganic hybrid particles prepared in Example 1-1 was dispersed in 800 g of NMP (1-Methyl-2-pyrrolidone) (Samcheon Chemical Co., Ltd.), 10 ml of pyridine And stirred at room temperature. 3 g of succinic anhydride (Samcheon Chemical) dissolved in 80 g of NMP was added to the solution for 30 minutes, followed by stirring at room temperature for 3 hours. After completion of the reaction, the reaction mixture was washed with ethanol, filtered and dried to obtain 70 g of anionic organic / inorganic hybrid particles. The average diameter and surface charge (Zeta-Potential) of the prepared anionic organic / inorganic hybrid particles were measured with a dynamic light scattering method measuring instrument ZEN-3690 (Malvern Instruments Ltd).

Example  2-2: With aminosilane Surface modified  Titanium dioxide and polyacid ( polyacid ) ≪ / RTI > Anionic  Weapons / weapons hybrid  Manufacturing of particles

6 g of 2-Phosphonobutane-1,2,4-tricarboxylic acid (Shanghai Sunwise Chemical Co. Ltd) was used instead of succinic anhydride Anionic organic / inorganic hybrid particles were prepared in the same manner as in Example 2-1.

Example  2-3: (-) CCA  And Titanium Dioxide with Resin On surface modification  by Anionic  Weapons / weapons hybrid  Manufacturing of particles

Anionic organic / inorganic hybrid particles were prepared in the same manner as in Example 1-3, except that Bontron E8 (Orient corp.) Was used instead of the charge control agent Bontron P51.

Example  2-4: With aminosilane Surface modified  Anionic oil / weapon by reaction of zinc oxide with succinic acid hybrid  Manufacturing of particles

Except that the cationic organic / inorganic hybrid particles prepared in Example 1-4 were used in place of the cationic organic / inorganic hybrid particles prepared in Example 1-1, anionic organic / inorganic hybrid particles Particles were prepared.

Example  3: Ionic oil / weapon hybrid  Agglomerate production of particles

Example  3-1-: Cationic  And Anionic  Weapons / weapons hybrid  Characteristics of particles

Table 1 shows the size and charge characteristics of the cationic and anionic organic / inorganic hybrid particles prepared according to each example.

bracket Weapons / weapons hybrid  Measurement results of particle size and charge characteristics division Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 Size (nm) 130 143 230 128 80 102 246 92 Zeta potential (Zeta-
potential)
(mV) +38.7 +40.6 +23.4 +47.2 -20.3 -25.1 -17.2 -10.1

Example  3-2: Ionic Oil / Weapon hybrid  Aggregate of particles Manufacturing example  One

To 225 g of distilled water was added 35 g of the cationic organic / inorganic hybrid particles prepared in Example 1-1 and ultrasonicated (40 kHz) for 5 minutes. To 225 g of distilled water was added the anionic oil / (IKA T25 digital) with stirring for 10 minutes while applying a solution prepared by mixing 15 g of the hybrid particles and ultrasonication (40 kHz) for 5 minutes, and the mixture was stirred for 10 minutes to obtain an ionic organic / inorganic hybrid Agglomerates and dispersions of the particles were prepared.

Example  3-3: Ionic Oil / Weapon hybrid  Aggregate of particles Manufacturing example  2

In the same manner as in Example 3-2, except that 25 g of the cationic organic / inorganic hybrid particles prepared in Example 1-1 and 25 g of the anionic organic / inorganic hybrid particles prepared in Example 2-1 were used, / Inorganic hybrid particles were prepared.

Example  3-4: Ionic oil / weapon hybrid  Aggregate of particles Manufacturing example  3

In the same manner as in Example 3-2, except that 15 g of the cationic organic / inorganic hybrid particles prepared in Example 1-1 and 35 g of the anionic organic / inorganic hybrid particles prepared in Example 2-1 were used, / Inorganic hybrid particles were prepared.

Example  3-5: Ionic oil / weapon hybrid  Aggregate of particles Manufacturing example  4

Except that 7.5 g of each of the cationic organic / inorganic hybrid particles prepared in Examples 1-1 and 1-2 and 17.5 of the anionic organic / inorganic hybrid particles prepared in Examples 2-1 and 2-2 were used, respectively, Aggregates and dispersions of ionic organic / inorganic hybrid particles were prepared in the same manner as in the method of 3-2.

Example  3-6: Ionic Oil / Weapon hybrid  Aggregate of particles Manufacturing example  5

The procedure of Example 3-2 was repeated except that 7.5 g of each of the cationic organic / inorganic hybrid particles prepared in Examples 1-1 and 1-2 and 35 g of the anionic organic / inorganic hybrid particles prepared in Example 2-3 were used. , Agglomerates and dispersions of ionic organic / inorganic hybrid particles were prepared.

Example  3-7: Ionic oil / weapon hybrid  Aggregate of particles Manufacturing example  6

15 g of each of the cationic organic / inorganic hybrid particles prepared in Example 1-3 and 17.5 g of the anionic organic / inorganic hybrid particles prepared in Examples 2-1 and 2-2 were used, , Agglomerates and dispersions of ionic organic / inorganic hybrid particles were prepared.

Example  3-8: Ionic Oil / Weapon hybrid  Aggregate of particles Manufacturing example  7

In the same manner as in Example 3-2, except that 15 g of the cationic organic / inorganic hybrid particles prepared in Example 1-1 and 35 g of the anionic organic / inorganic hybrid particles prepared in Example 2-4 were used, / Inorganic hybrid particles were prepared.

Example  3-9: Ionic Oil / Weapon hybrid  Aggregate of particles Manufacturing example  8

In the same manner as in Example 3-2, except that 15 g of the cationic organic / inorganic hybrid particles prepared in Example 1-4 and 35 g of the anionic organic / inorganic hybrid particles prepared in Example 2-1 were used, / Inorganic hybrid particles were prepared.

Example  3-10: Ionic Oil / Weapon hybrid  Aggregate of particles Manufacturing example  9

10 g of the cationic organic / inorganic hybrid particles prepared in Example 1-1 was added to 80 g of distilled water, and the mixture was dispersed by a homogenizer (IKA T25) at 10,000 rpm for 5 minutes, 10 g of a solution of acrylic acid (Carbopol 981, Lubrizol, Mw 1,250,000) was mixed and stirred at 500 rpm for 30 minutes to prepare an aggregate dispersion of the ionic organic / inorganic hybrid particles and organic matter.

Example  3-11: Manufactured oil / weapon hybrid  Characteristics of aggregates

The characteristics of the oil / inorganic hybrid agglomerates prepared according to Examples 3-2 to 3-10 are shown in Table 2. Aggregates prepared according to Examples 3-2 to 3-9 were measured for diameters and surface charge of aggregates using ZEN-3690 (Malvern Instruments Ltd), a dynamic light scattering method measuring apparatus, The resulting aggregates were measured for their diameter using a Microtrac S3000 (Microtrac Inc.).

Example  4: Ionic oil / weapon hybrid  Including particle agglomerates Cosmetics  Composition manufacturing

The test cream was prepared by mixing the ionic organic / inorganic hybrid particle agglomerates prepared in Examples 3-2 to 3-10 with an underwater type (O / W) cream base composition. After addition of the ingredients, water was added to a final weight of 100 g. Comparative examples were prepared using nanosized titanium dioxide (Parsol TX, DSM) and zinc nano-oxide (MZ-500, Tayca Corp.). (Table 3).

Ionic oil / weapon hybrid  Containing agglomerates of particles Cosmetics  Composition manufacturing ingredient Example (g) Comparative Example 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 One 2 3 3-2 aggregate dispersion 50 - - - - - - - - - - 3-3 Aggregate dispersion - 50 - - - - - - - - - 3-4 Aggregate dispersion - - 50 - - - - - - - - 3-5 agglomerate dispersion - - - 50 - - - - - - - 3-6 agglomerate dispersion - - - - 50 - - - - - - 3-7 agglomerate dispersion - - - - - 50 - - - - - 3-8 agglomerate dispersion - - - - - - - 50 - - - 3-10 aggregate dispersion - - - - - - 50 - - - - Nano titanium dioxide - - - - - - - - 5.0 3.5 - Nano zinc oxide - - - - - - - - - 1.5 - Octyl Methoxycinnamate 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 Bis-Etylhexyloxyphenol Methoxyphenyl Triazine 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Isoamyl-p-methoxycinnamate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Disodium EDTA 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Phenoxyethanol 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Methyl-p-hydroxybenzoate 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Propyl-p-hydroxybenzoate 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Butylene glycol 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 Polyglyceryl-3-Methylglucose Distearate 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 Cetearyl Alcohol 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Glyceryl Stearate and PEG-100 Stearate 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 1.10 Phenyl Trimethicone 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Decamethyl Cyclopentasiloxane 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 Polyacrylate-13 & Polyisobutene & Polysorbate 20 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Triethanolamine 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Water To
100 To
100 To
100 To
100 To
100 To
100 To
100 To
100 To
100 To
100 To
100

Test Example  1: Measurement of ultraviolet shielding index

The SPF (Sun Protection Factor) and PFA (Protection Factor of UVA) of the composition were measured using an optical device measuring instrument (model name : SPF 290S, manufactured by Optometrics). The coating was applied to a transpore tape at a level of 1 mg / cm 2, dried for 15 minutes, and then scanned 12 times using an SPF290 analyzer (Optometrics, USA). The measurement was repeated three times.

Test Example  2: Feeling  Evaluation experiment

Twenty women aged 20 to 30 years were used to evaluate the skin texture and skin adhesion at the time of use by using the five point scale method, and the average value was expressed. The sensory evaluation was performed based on the criteria of excellent (5 points), excellent (4 points), normal (3 points), poor (2 points) and very poor (1 point). Indicating excellent skin adhesion.

Test Example  3: Cloudiness  Evaluation experiment

L values were measured using a colorimeter (Minolta CR-200) on 6 rectangles of 2 × 2 cm square on the upper arm. Weigh accurately 0.1 g of each sample in each place, Five minutes after rubbing once, the colorimeter was measured to evaluate the difference between the bare skin L value and the measured L value. The larger the difference between the L values, the greater the degree of whiteness. The smaller the difference in the L value, the smaller the whiteness. The results of Test Examples 1 to 3 are shown in Table 4.

Sun Protection Factor ( SPF , PFA ), Feeling  And Cloudiness  Evaluation test result
Example Comparative Example 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 One 2 3 SPF 42 40 41 42 41 40 42 39 37 35 20 PFA - - - - - - - 12 - 10 6 Feeling 3.8 3.7 3.7 4.0 4.0 3.9 4.0 3.8 3.5 3.2 - Cloudiness 4.0 3.8 4.2 3.9 3.9 4.2 4.2 4.1 4.9 4.8 -

As shown in Table 4, the ultraviolet screening agent using the ionic organic / inorganic hybrid particle aggregates (Examples 4-1 to 4-8) of the present invention was found to be at least equivalent to the ultraviolet screening agent (Comparative Example 1) using the titanium dioxide nanoparticles UV protection performance and feeling of use, and the whiteness is equivalent. In comparison with Comparative Example 3 in which an inorganic UV-blocking agent was not used, the cosmetic composition for UV-blocking using the ionic organic / inorganic hybrid particle agglomerates of the present invention showed a high ultraviolet shielding performance.

Further, the ultraviolet screening agent (Example 4-8) using aggregates of ionic organic / inorganic hybrid particles made of titanium dioxide and zinc oxide was compared with the ultraviolet screening agent (Comparative Example 2) made of titanium dioxide nanoparticles and nano zinc oxide (SPF, PFA) and turbidity generation level, and the use feeling was greatly improved.

Claims (28)

Organic / inorganic hybrid particle aggregates aggregated by ionic interaction between cationic organic / inorganic hybrid particles and anionic organic / inorganic hybrid particles or anionic polymers.
The method according to claim 1,
The cationic organic / inorganic hybrid particles may be prepared by modifying the surface of a metal oxide to have a cationic functional group or by mixing a metal oxide with a positive charge control agent (CCA) Wherein the organic / inorganic hybrid particle agglomerates have a particle size of not more than 100 nm.
3. The method of claim 2,
Wherein the metal oxide 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 2) Inorganic hybrid particle aggregates.
3. The method of claim 2,
(1), R ₁ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ₂ represents hydrogen, an alkyl group having 1 to 10 carbon atoms To 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Equation (1)
3. The method of claim 2,
Inorganic hybrid particle aggregate characterized in that the surface of the metal oxide having the cationic functional group is modified by aminosilane.
6. The method of claim 5,
Wherein the aminosilane is selected from the group consisting of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrialkoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- ) And N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane HCl) Organic / inorganic hybrid particle aggregates.
3. The method of claim 2,
The modification of the surface of the metal oxide having a cationic functional group is carried out by reacting a substance having a polycationic functional group after surface modification of the metal oxide to have an anionic functional group. .
8. The method of claim 7,
Wherein the material having a polycationic functional group is a polyamine.
9. The method of claim 8,
The polyamine may be selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, N-methylethylenediamine, 1,4-diaminobutane, 3- (methylamino) N, N-dimethylethylenediamine, N, N-dimethylethylenediamine, trimethylenetetramine, triethylenetetramine, phenylenediamine, hexamethylenetetramine, diaminocyclohexane, aminobenzylamine and tetra Ethylene pentaamine, and ethylene pentaamine. 10. The organic / inorganic hybrid particle aggregate according to claim 1,
3. The method of claim 2,
Wherein the positive charge control agent is an ammonium salt.
11. The method of claim 10,
Wherein the positive charge control agent is contained in an amount of 0.5 to 40% by weight based on the weight of the final cationic hybrid particles.
The method according to claim 1,
Wherein the anionic organic / inorganic hybrid particles are prepared by modifying a surface of a metal oxide having an anionic functional group, or by mixing a metal oxide with a negative charge control agent.
13. The method of claim 12,
Wherein the metal oxide 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 2) / Inorganic hybrid particle aggregates.
13. The method of claim 12,
Wherein the anionic functional group is selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a sulfate group, and a sulfate group.
13. The method of claim 12,
Characterized in that the modification of the surface of the metal oxide having an anionic functional group is carried out by reacting a cationically surface-modified metal oxide with a substance having a polyanionic functional group by using aminosilane / Inorganic hybrid particle aggregates.
16. The method of claim 15,
The polyanionic functional group-containing substance may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, acid, sebacic acid, undecanedioic acid, phthalic acid, maleic acid, fumaric acid, succinic acid, succinic acid, succinic acid, such as fumaric acid, glutaconic acid, traumatic acid, muconic acid, poly (ethyleneglycol) -bis (carboxymethyl) ether (poly (ethyleneglycol) bis (carboxymethyl) ether, succinic anhydride, maleic anhydride, citric acid, aconitic acid, tricarballylic acid, trimesic acid, 2 2-Phosphonobutane-1,2,4-tricarboxylic acid, polyacrylic acid, And sodium polyacrylate. 10. The organic / inorganic hybrid particle aggregate according to claim 1, wherein the inorganic particles are at least one selected from the group consisting of sodium polyacrylate and sodium polyacrylate.
13. The method of claim 12,
Wherein the negative charge control agent is a metal salt of tert-butyl salicycic acid.
18. The method of claim 17,
Wherein the central metal of the metal salt of the tert-butylsalicylic acid is selected from the group consisting of chromium, aluminum, zinc, calcium, boron and acetylboron. 18. The method of claim 17,
Wherein the negative charge control agent is contained in an amount of 0.5 to 40% by weight based on the weight of the final anionic hybrid particles.
The method according to claim 1,
The anionic polymer may be selected from the group consisting of a vinylpyrrolidone-acrylic acid copolymer, a methyl methacrylate-acrylic acid copolymer, a methyl methacrylate-methacrylic acid copolymer Inorganic hybrid particle aggregate characterized in that it is at least one selected from the group consisting of methacrylate-methacrylic acid copolymer, polyacrylic acid (PAA), polymethacrylic acid, and carboxymethylcellulose.
The method according to claim 1,
Wherein the agglomerate has an average particle size of 0.1 to 50 占 퐉. The method according to claim 1,
Wherein the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles are mixed in a weight ratio of 95: 5 to 5: 95.
The method according to claim 1,
Wherein the cationic organic / inorganic hybrid particles and the anionic polymer are mixed in a weight ratio of 99.9: 0.01 to 50:50.
(a) providing a cationic organic / inorganic hybrid particle and an anionic organic / inorganic hybrid particle or an anionic polymer;
(b) mixing the cationic organic / inorganic hybrid particles and the anionic organic / inorganic hybrid particles or the anionic polymer to produce an organic / inorganic hybrid particle aggregate;
By weight based on the total weight of the organic / inorganic hybrid particles.
23. A UV-blocking cosmetic composition comprising the organic / inorganic hybrid particle aggregate according to any one of claims 1 to 23.
26. The cosmetic composition for protecting ultraviolet rays according to claim 25, wherein 0.1 to 20% by weight of an oil / inorganic hybrid particle aggregate is contained.
26. A UV-blocking cosmetic comprising the cosmetic composition according to claim 26.
28. The UV-blocking cosmetic product according to claim 27, which has any one of formulations selected from creams, lotions, sticks, foundations, emulsions, waxes, oils, sprays, aerosols, lotions, essences, packs, powders and gels.