Ultraviolet blocking titanium dioxide composite, and ultraviolet blocking titanium dioxide dispersion and cosmetic composition that comprise same

Abstract

The present invention relates to an ultraviolet blocking titanium dioxide composite, and an ultraviolet blocking titanium dioxide dispersion and a cosmetic composition that comprise same. According to one aspect of the present invention, the ultraviolet blocking titanium dioxide composite comprises titanium dioxide and a polymer bonded to the surface of the titanium dioxide, wherein the polymer comprises an acrylate group at the end thereof.

Description

Titanium dioxide complex for UV protection, titanium dioxide dispersion for UV protection and cosmetic composition containing the same

[0001] The present invention relates to a titanium dioxide complex for blocking ultraviolet rays, a titanium dioxide dispersion for blocking ultraviolet rays and a cosmetic composition containing the same, and more specifically, to a titanium dioxide complex for blocking ultraviolet rays having excellent ultraviolet ray blocking ability, a titanium dioxide dispersion for blocking ultraviolet rays and a cosmetic composition containing the same.

[0002] UV-blocking cosmetics are products containing functional compositions that block ultraviolet rays and thereby prevent skin aging (e.g., erythema, edema, freckles, or skin cancer) caused by ultraviolet rays. There are inorganic UV-blocking cosmetics based on inorganic substances such as titanium dioxide and zinc oxide, and organic UV-blocking cosmetics based on organic substances such as ethylhexyl methoxycinnamate, ethylhexyl salicylate, octocrylene, ethylhexyl triazone, and benzophenone-3 (oxybenzone).

[0003] Inorganic UV-blocking cosmetics have the advantage of not causing skin problems as much as organic UV-blocking cosmetics, but they have the problem of causing a white cast when applied and having a lower sun protection factor (SPF) than organic UV-blocking cosmetics.

[0004] Recently, active research has been conducted on inorganic UV-blocking compositions that maximize UV-blocking effectiveness while minimizing whitening by manufacturing ultrafine titanium dioxide particles. Specifically, dispersing an appropriate amount of ultrafine titanium dioxide rod-shaped particles measuring several nanometers to several hundred nanometers in diameter can improve transparency and maximize UV-blocking efficacy.

[0005] However, titanium dioxide has a high photocatalytic activity, and due to the photocatalytic action, it generates active oxygen radicals, which can cause deterioration or oxidation of other raw materials in the formulation, and attack the cell membrane and nucleus of skin cells, causing DNA damage and skin aging.

[0006] To solve these problems, a technology has been developed to improve the stability of photocatalysts by surface-treating titanium dioxide to suppress photocatalysis, and generally, a technology has been introduced to modify the surface of titanium dioxide with inorganic substances such as alumina or silica, or with fatty acid or silicone oil.

[0007] However, as titanium dioxide particles become ultrafine, it can be difficult to completely coat the surface of the titanium dioxide. Meanwhile, increasing the particle size of the titanium dioxide facilitates surface modification, potentially improving photocatalytic stability. However, this can lead to a lower UV protection factor or increased cloudiness.

[0008] In addition, if the surface of titanium dioxide is not perfectly coated, electrons may be generated due to photocatalytic action in the functional group portion that has not been surface-modified, and these electrons may lower the function of the water-soluble thickener used in the oil-in-water formulation, thereby causing a problem of lowering the emulsion stability. In this case, aggregation of titanium dioxide particles and the water-soluble thickener may occur, which may lower the marketability of the UV-blocking cosmetic product in the oil-in-water formulation.

[0009] To improve these problems, water-in-oil or silicone-in-water formulations of UV-blocking cosmetic compositions can be used, but these formulations have the disadvantage of giving a heavy and sticky feeling and causing skin irritation.

[0010] Accordingly, there is a need for the development of a titanium dioxide dispersion and cosmetic composition technology for UV protection that maintains an excellent UV protection index while simultaneously improving photocatalytic stability and exhibiting excellent formulation stability even in oil-in-water formulations.

[0011] Meanwhile, the background technology described above is technical information that the inventor possessed for the purpose of deriving the present invention or acquired during the process of deriving the present invention, and cannot necessarily be said to be publicly known technology disclosed to the general public prior to the application for the present invention.

[0012] One embodiment of the present invention aims to provide a titanium dioxide complex for blocking ultraviolet rays while maintaining an excellent ultraviolet blocking index and at the same time having excellent photocatalytic stability, and a method for producing the same.

[0013] One embodiment of the present invention aims to provide a cosmetic composition for blocking ultraviolet rays that maintains an excellent ultraviolet ray blocking index while simultaneously having excellent photocatalytic stability.

[0014] Another object of one embodiment of the present invention is to provide a cosmetic composition for blocking ultraviolet rays that does not cause a decrease in the function of a water-soluble thickener and has excellent oil-in-water formulation stability.

[0015] As a technical means for achieving the above-described technical task, according to one aspect of the present invention, a titanium dioxide complex for blocking ultraviolet rays comprises titanium dioxide and a polymer bonded to the surface of the titanium dioxide, wherein the polymer comprises an acrylate group at a terminal.

[0016] According to another aspect of the present invention, the polymer may further include a beta-ketoester group capable of bonding to the surface of the titanium dioxide.

[0017] According to another aspect of the present invention, the polymer may further include at least one ester group in the middle or side of the chain.

[0018] According to another aspect of the present invention, the polymer can be formed by polymerization of different (meth)acrylate monomers.

[0019] According to another aspect of the present invention, the polymer comprises a first monomer comprising any one selected from among 2-(acetoacetoxy)methylmethacrylate, 2-(acetoacetoxy)ethyl acrylate, 2-(acetoacetoxy)ethyl ethylacrylate, and 2-(acetoacetoxy)ethyl methacrylate, and isobutyl methacrylate, butyl methacrylate, ethylhexyl acrylate, methyl methacrylate, butyl acrylate, and ethyl acrylate. Acrylate) can be formed from a second monomer comprising any one selected from the group consisting of:

[0020] According to another aspect of the present invention, the first monomer and the second monomer can be polymerized in a ratio of 1:9 to 7:3.

[0021] According to another aspect of the present invention, the titanium dioxide composite may have a photocatalytic stability of % or more according to the KS L ISO 10678 photocatalytic test method.

[0022] According to another aspect of the present invention, the titanium dioxide particles may have an average particle diameter of 10 to 100 nm.

[0023] According to another aspect of the present invention, the polymer can coat the titanium dioxide particles to a thickness of less than 10 nm.

[0024] According to another aspect of the present invention, the titanium dioxide particles may be particles coated with an inorganic or organic material.

[0025] As a technical means for achieving the above-described technical task, according to another aspect of the present invention, a titanium dioxide dispersion for blocking ultraviolet rays comprises a titanium dioxide complex including titanium dioxide particles coated with a high molecular weight polymer having an acrylate group at the terminal, and a dispersion stabilizer.

[0026] According to another aspect of the present invention, at least a portion of the surface of the titanium dioxide particles may be coated with an inorganic or organic material different from the polymer.

[0027] According to another aspect of the present invention, the dispersion stabilizer may include at least one of hydrogenated lecithin, cetearyl alcohol, behenyl alcohol, glyceryl stearate, polyhydroxystearic acid, PEG-10 dimethicone, and polyglyceryl-6-polyricinoleate.

[0028] As a technical means for achieving the above-described technical task, according to another aspect of the present invention, a cosmetic composition for blocking ultraviolet rays comprises an aqueous phase, a water-soluble thickener, an oil phase, and a titanium dioxide dispersion for blocking ultraviolet rays, wherein the titanium dioxide dispersion for blocking ultraviolet rays comprises a titanium dioxide complex including titanium dioxide particles coated with a high molecular weight polymer having an acrylate group at a terminal, and a dispersion stabilizer.

[0029] According to another aspect of the present invention, the water-soluble thickener may include at least one of carbomer, acrylate / C10-30 acrylate crosspolymer, hydroxyethylcellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, ethylcellulose, xanthan gum, gellan gum, guar gum, and Arabic gum.

[0030] According to any one of the above-described means for solving the problem of the present invention, the titanium dioxide complex for blocking ultraviolet rays, the titanium dioxide dispersion for blocking ultraviolet rays and the cosmetic composition containing the same are surface-modified with a polymer bonded to the surface of titanium dioxide and having an acrylate group at the terminal, so that they have the advantage of maintaining an excellent ultraviolet ray blocking index while simultaneously improving the photocatalytic stability.

[0031] In addition, the cosmetic composition for sunscreen of the present invention does not reduce the function of a water-soluble thickener, and thus, when formulated in the form of an oil-in-water, it has excellent emulsion stability, and thus, can provide an excellent feeling of use.

[0032] The effects that can be obtained from the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by a person having ordinary skill in the art to which the present invention belongs from the description below.

[0033] FIG. 1 is a flow chart illustrating a method for manufacturing a titanium dioxide complex for blocking ultraviolet rays according to one embodiment of the present invention.

[0034] Figure 2 is a graph showing the photocatalytic stability of titanium dioxide complexes for blocking ultraviolet rays according to embodiments of the present invention.

[0035] Figures 3a to 3h are graphs showing the UV blocking rate by wavelength of titanium dioxide complexes for UV blocking according to embodiments of the present invention and titanium dioxide complexes for UV blocking according to comparative examples.

[0036] Figure 4 is a comparative graph for explaining the excellent photocatalytic stability of a titanium dioxide dispersion for blocking ultraviolet rays according to one embodiment of the present invention.

[0037] FIG. 5 is a comparative experimental photograph to explain the excellent oil-in-water formulation stability of a titanium dioxide dispersion for UV protection according to one embodiment of the present invention.

[0038] Figure 6 is a comparative experimental photograph illustrating the excellent stability over time of a titanium dioxide dispersion for blocking ultraviolet rays according to one embodiment of the present invention.

[0039] Below, with reference to the attached drawings, embodiments of the present invention are described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein. In the drawings, irrelevant parts have been omitted for clarity of description, and similar reference numerals have been used throughout the specification to indicate similar elements.

[0040] Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with other elements or components intervening between them. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather includes other components, unless otherwise specifically stated.

[0041] The present invention will be described in detail with reference to the attached drawings below.

[0042] The titanium dioxide complex for blocking ultraviolet rays of the present invention comprises titanium dioxide and a polymer bonded to the surface of titanium dioxide.

[0043] Titanium dioxide is a substance composed of a combination of titanium atoms and oxygen atoms, and has excellent reflectivity for UVB and UVA rays.

[0044] Titanium dioxide may be used in any one of the anatase phase, rutile phase, and brookite phase, but the rutile phase is preferably used.

[0045] The titanium dioxide of the present invention may have an average particle diameter of 10 to 100 nm. In addition, the titanium dioxide of the present invention may be composed of rod-type particles, and may have an average axial ratio of 1.2 to 5.0. The titanium dioxide described above may be composed of rod-type particles alone or in a form in which the rod-type particles are aggregated together.

[0046] In some embodiments, the titanium dioxide may be a coated particle. For example, the titanium dioxide may have a surface coated with silicon oxide (SiO x ), aluminum oxide (Al x O y ) may be particles coated with inorganic substances such as stearic acid, glycerin, trimethoxycaprylylsilane, dimethicone, simethicone, etc., and may be particles coated with organic substances such as stearic acid, glycerin, trimethoxycaprylylsilane, dimethicone, simethicone, etc. Preferably, the particles may be particles coated with alumina (Al2O3) on the surface of titanium dioxide.

[0047] The polymer of the present invention is a material that coats the surface of titanium dioxide, and may be a polymer formed through a polymerization reaction of two or more monomers.

[0048] The polymer contains a beta-ketoester group. The beta-ketoester functional group of the polymer can be coordinated to the titanium dioxide surface. Specifically, the ketone functional group and the ester functional group of the beta-ketoester group can be coordinated to the titanium dioxide surface, thereby uniformly coating the titanium dioxide surface in the form of ultrafine particles.

[0049] Additionally, the polymer includes an acrylate group at the terminal. Specifically, a (meth)acrylate functional group is positioned at the terminal of the polymer. The (meth)acrylate functional group at the terminal of the polymer can be formed by a polymerization reaction of the monomer containing the above-described beta-ketoester group and a (meth)acrylate monomer.

[0050] Additionally, the polymer comprises at least one ester group, wherein the ester group may be generated during the process of polymerizing two or more monomers with each other.

[0051] For example, the polymer described above can be expressed by the following [chemical formula 1].

[0052]

[0053] Here R 1 may be an alkyl group having 1 to 10 carbon atoms.

[0054] The polymer can coat the surface of titanium dioxide particles to a thickness of less than 10 nm. When the polymer is coated to a thickness exceeding 10 nm, photocatalytic stability may be improved, but the large coating thickness may reduce the UV-blocking ability of the titanium dioxide.

[0055] The polymer of the present invention can be formed through a copolymerization reaction of two or more monomers. For example, the polymer can be formed through a copolymerization reaction of a first monomer and a second monomer.

[0056] The first monomer is a monomer having a beta-ketoester group and is involved in surface modification of titanium dioxide particles. The first monomer may be, for example, any one selected from among 2-(acetoacetoxy)methylmethacrylate (2-(acetoacetoxy)2-(acetoacetoxy)methylmethacrylate), 2-(acetoacetoxy)ethyl acrylate (2-(acetoacetoxy)ethyl ethylacrylate), and 2-(acetoacetoxy)ethyl methacrylate (2-(acetoacetoxy)ethyl methacrylate). Preferably, the first monomer may be 2-(acetoacetoxy)ethyl methacrylate (AAEMA).

[0057] The second monomer is a monomer that polymerizes with the first monomer to form an acrylate functional group at the terminal, and may be a monomer of an acrylate series different from the first monomer. For example, the second monomer may be any one selected from isobutyl methacrylate, butyl methacrylate, ethylhexyl acrylate, methyl methacrylate, butyl acrylate, and ethyl acrylate. Preferably, the second monomer may be any one of isobutyl methacrylate, butyl methacrylate, ethylhexyl acrylate, and methyl methacrylate.

[0058] The first monomer and the second monomer can be polymerized at an appropriate ratio within the range of 1:9 to 7:3 of the first monomer:second monomer. When the titanium dioxide particles are surface-modified by the polymer formed within the above-described range, the titanium dioxide complex can maintain an excellent UV protection factor. If the ratio of the first monomer:second monomer exceeds 7:3, the UV protection factor of the titanium dioxide complex may decrease, and the functionality as a UV protection cosmetic may be degraded. In addition, when the ratio of the first monomer:second monomer is less than 1:9, the titanium dioxide particles may not be sufficiently surface-modified, which may deteriorate the photocatalytic stability, which is not preferable.

[0059] Surface modification of titanium dioxide particles by the first monomer and the second monomer can proceed in the following order: surface modification by the first monomer is induced by coordination bonding through the beta-ketoester functional group of the first monomer, followed by a copolymerization reaction between the terminal of the first monomer coordinated with the second monomer. For a detailed description thereof, see Fig. 1.

[0060] FIG. 1 is a flow chart illustrating a method for manufacturing a titanium dioxide complex for blocking ultraviolet rays according to one embodiment of the present invention.

[0061] Referring to FIG. 1, the method for manufacturing a titanium dioxide complex for blocking ultraviolet rays of the present invention first introduces titanium dioxide particles into a first monomer solution (S110).

[0062] The first monomer solution can be prepared by dispersing the first monomer in a solvent.

[0063] As described above, the first monomer may be an acrylate monomer having a beta-ketoester group.

[0064] The solvent is not particularly limited as a solvent capable of promoting the coordination bond of the first monomer. For example, it may be a polar protic solvent, a non-polar solvent, or a mixed solvent thereof, and examples thereof include water, a glycol solvent, a glycol ether solvent, an alcohol solvent, a ketone solvent, an ester solvent, an amide solvent, a sulfoxide or sulfone solvent, a phenolic solvent, or a mixed solvent thereof. At this time, the glycol solvent may include ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, polyethylene glycol, ethoxydiglycol, dipropylene glycol, or a combination thereof, the glycol ether solvent may include methyl glycol ether, ethyl glycol ether, isopropyl glycol ether, or a combination thereof, the alcohol solvent may include methanol, ethanol, n-propanol, isopropanol, butanol, or a combination thereof, the ketone solvent may include acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof, the ester solvent may include ethyl acetate, butyl acetate, diethylene glycol ether acetate, methoxypropyl acetate, ethylene carbonate, propylene carbonate, or a combination thereof, the amide solvent may include dimethylformamide, dimethylacetamide, The organic solvent may include, but is not limited to, dimethylcaprylic / capric fatty acid amide, N-alkylpyrrolidone, or a combination thereof, and the sulfoxide or sulfone solvent may include, but is not limited to, dimethylsulfoxide (DMSO) or sulfolane, and the phenolic solvent may include, but is not limited to, toluene or xylene. As a specific example, the organic solvent may be, but is not limited to, toluene.

[0065] Afterwards, titanium dioxide particles are added to the first monomer solution.

[0066] In this case, the titanium dioxide particles may be introduced in a dosage set so that the content of the first monomer is 50 to 500 parts by weight, preferably 100 to 300 parts by weight, based on 100 parts by weight of the titanium dioxide particles.

[0067] Additionally, the titanium dioxide particles may be introduced so that the solvent content is 300 to 800 parts by weight, preferably 400 to 500 parts by weight, based on 100 parts by weight of the titanium dioxide particles.

[0068] By adding titanium dioxide particles to the first monomer solution so that the content of the first monomer and the solvent is the weight parts described above based on the weight parts of the titanium dioxide particles, the surface of the titanium dioxide particles can be uniformly modified by the first monomer.

[0069] After this, the method for manufacturing a titanium dioxide complex for blocking ultraviolet rays of the present invention manufactures a primary complex by coordinating a first monomer to the surface of titanium dioxide particles (S120).

[0070] Specifically, by introducing titanium dioxide particles into a first monomer solution and then applying ultrasound, a coordination bond between the first monomer and the titanium dioxide particles can be induced. In this case, the ultrasound application can be freely applied for a period ranging from 5 to 30 minutes, and can be performed at room temperature. However, the process for inducing a coordination bond between the first monomer and the titanium dioxide particles is not limited to the above example, and known processes capable of inducing a coordination bond of a beta-ketoester group can be freely used.

[0071] After this, the method for manufacturing a titanium dioxide complex for blocking ultraviolet rays of the present invention involves adding a second monomer of an acrylate series different from the first monomer (S130).

[0072] The second monomer is an acrylate series monomer, and as described above, may be any one selected from among isobutyl methacrylate, butyl methacrylate, ethylhexyl acrylate, methyl methacrylate, butyl acrylate, and ethyl acrylate.

[0073] The second monomer may be introduced singly into the mixed solution of titanium dioxide particles and the first monomer, or may be introduced in the form of a solution dispersed in a separate solvent. In this case, the solvent into which the second monomer is introduced may be the same solvent as the solvent of the first monomer solution described above.

[0074] The second monomer may be introduced so that the ratio of the first monomer to the second monomer is 1:9 to 7:3. The above-described ratio is a coating ratio of the first monomer and the second monomer, and may correspond to the concentration ratio of the first monomer and the second monomer.

[0075] After this, the method for manufacturing a titanium dioxide complex for blocking ultraviolet rays of the present invention polymerizes a second monomer on the surface of the first complex (S140).

[0076] Specifically, the second monomer copolymerizes with a functional group present on the surface of the primary complex, thereby secondarily modifying the surface of the primary complex. As the second monomer modifies the surface of the primary complex, a titanium dioxide complex is obtained.

[0077] Copolymerization of the second monomer can be induced by a general copolymerization reaction of acrylate-based monomers, and the copolymerization reaction can be induced, for example, by heat or light. In this case, an initiator for initiating the copolymerization reaction can be added during the second monomer addition process.

[0078] As the surface of the primary complex is secondarily modified by the second monomer, the titanium dioxide complex includes a polymer coordinated to the surface of the titanium dioxide inorganic particle via a beta-ketoester functional group. In this case, the terminal of the polymer has an acrylate functional group provided by the second monomer, and the middle or side chain of the polymer has at least one ester functional group generated by copolymerization of the second monomer with the surface of the primary complex.

[0079] Meanwhile, the coating layer in the titanium dioxide composite can have a thickness of less than 10 nm.

[0080] In some embodiments, after the copolymerization reaction of the second monomer has been induced, a further purification step may be performed to obtain a titanium dioxide composite. Specifically, the titanium dioxide composite may be purified from the solvent through centrifugation. Subsequently, a titanium dioxide composite powder may be obtained through drying and milling.

[0081] The titanium dioxide composite of the present invention is composed of ultrafine titanium dioxide particles of 10 to 100 nm in size, and each titanium dioxide particle has its surface uniformly modified by a polymer, thereby exhibiting excellent photocatalytic stability. In addition, the titanium dioxide composite undergoes a second surface modification, and is secondarily modified with a second monomer of an acrylate series different from the first monomer, so that an acrylate group can be positioned at the polymer terminal. Accordingly, the titanium dioxide composite of the present invention can exhibit excellent photocatalytic stability while simultaneously maintaining an excellent UV blocking index.

[0082] The titanium dioxide complex of the present invention described above can be manufactured in the form of a dispersion by being dispersed in a solvent.

[0083] That is, the titanium dioxide dispersion of the present invention may include a titanium dioxide complex, a solvent, and a dispersion stabilizer.

[0084] The titanium dioxide complex is as described above, and any redundant description will be omitted.

[0085] The solvent may be an aqueous solvent containing water or an oily solvent containing oil.

[0086] The aqueous solvent may be, for example, water, a polar protic solvent, a ketone solvent, or a combination thereof. The polar protic solvent may be, for example, an alcohol solvent or a glycol solvent, and examples thereof include, but are not limited to, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol (PEG), or a combination thereof. The ketone solvent may include, but is not limited to, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), or a combination thereof.

[0087] In the case of oil, it may be an oil used in a food, medical composition or cosmetic composition, and may be, for example, a hydrocarbon-based oil, an ester-based oil, a vegetable oil or a silicone-based oil, and is not particularly limited, but a non-silicone-based oil may be suitable.

[0088] The dispersion stabilizer is a composition for improving the dispersibility of the titanium dioxide complex in a solvent and minimizing aggregation of the titanium dioxide complex, and may include, for example, at least one of hydrogenated lecithin, cetearyl alcohol, behenyl alcohol, glyceryl stearate, polyhydroxystearic acid, PEG-10 dimethicone, and polyglyceryl-6-polyricinoleate. Preferably, at least one of polyhydroxystearic acid and polyglyceryl-6-polyricinoleate may be included.

[0089] The above-described dispersion stabilizer may be included in an amount of 5 wt% or less based on the total weight of the titanium dioxide dispersion. If the amount of the dispersion stabilizer exceeds 5 wt%, dispersibility may be improved, but the amount of the titanium dioxide complex may be relatively reduced due to an unnecessarily high amount of the dispersion stabilizer, which is undesirable.

[0090] The titanium dioxide dispersion of the present invention can be formulated in various forms, such as an oil-in-water formulation or a water-in-oil formulation. In particular, the titanium dioxide dispersion of the present invention can be formulated in an oil-in-water formulation and has excellent formulation stability.

[0091] Specifically, the cosmetic composition of the present invention in the form of an oil-in-water formulation comprises an aqueous phase, a water-soluble thickener, an oil phase, and a titanium dioxide dispersion for UV protection.

[0092] Since the titanium dioxide dispersion for UV protection has been described above, a duplicate description will be omitted.

[0093] The aqueous phase is a solvent containing water, and may have the same composition as the aqueous solvent described above.

[0094] The oil phase is a hydrophobic solvent containing oil, and may have the same composition as the oily solvent described above.

[0095] The water-soluble thickener controls the viscosity so that the cosmetic composition is implemented with an appropriate viscosity, and is a component that allows the titanium dioxide complex to be dispersed rather than settled within the formulation, and may include, for example, at least one of carbomer, acrylate / C10-30 acrylate crosspolymer, hydroxyethylcellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, ethylcellulose, xanthan gum, gellan gum, guar gum, and Arabic gum.

[0096] The water-soluble thickener may be included in an amount optimized to increase the viscosity of the cosmetic composition to a specific viscosity. For example, the thickener may be included in an amount of 1 wt% or less based on the total weight of the cosmetic composition, but is not limited thereto.

[0097] In some embodiments, the cosmetic composition of the present invention may further include a neutralizing agent. The neutralizing agent is configured to neutralize changes in the pH of the cosmetic composition, and examples thereof include, but are not limited to, tromethamine, triethanolamine (TEA), potassium hydroxide (KOH), and sodium hydroxide (NaOH).

[0098] The titanium dioxide dispersion of the present invention and the cosmetic composition comprising the same comprise ultrafine titanium dioxide particles having a size of 10 to 100 nm, and each titanium dioxide particle has its surface uniformly modified with a polymer, thereby exhibiting excellent photocatalytic stability. In addition, the surface modification described above may be performed in a two-stage surface modification process. In this case, the titanium dioxide particles may be first surface-modified with a first monomer, and then second surface-modified with a second monomer of an acrylate series different from the first monomer. As a result, the titanium dioxide particles may be uniformly surface-modified with a polymer having an acrylate group at its terminal. The titanium dioxide dispersion of the present invention and the cosmetic composition comprising a titanium dioxide complex having such characteristics may exhibit excellent photocatalytic stability while simultaneously maintaining an excellent UV protection factor.

[0099] In addition, the titanium dioxide dispersion and cosmetic composition of the present invention have almost no photocatalytic activity, and can minimize the deterioration of the function of a water-soluble thickener by uniform surface modification of titanium dioxide particles, thereby improving the stability of oil-in-water formulations.

[0100] Hereinafter, the above-described advantages of the present invention will be described in detail through the following experimental examples.

[0101] (Manufacturing Example 1, Manufacturing of titanium dioxide complex)

[0102] First, a titanium dioxide complex for blocking ultraviolet rays was manufactured according to the method for manufacturing a titanium dioxide complex for blocking ultraviolet rays of the present invention.

[0103] Titanium dioxide composites according to the examples were manufactured by surface-modifying needle-shaped titanium dioxide powder (average particle size 25 nm, average axis ratio 3.5) with the materials shown in [Table 1] below.

[0104] Classification 1 Monomer system 2 Monomer ratio (Note) Manufacturing example 1-1 AAEMA (Acetoacetoxy Ethylmethacrylate) IMA (Isobutyl Methacrylate) 5:5 Manufacturing example 1-2 AAEMABMA (Butyl Methacrylate) 5:5 Manufacturing example 1-3 AAEMAEHA (Ethylhexyl Acrylate) 5:5 Manufacturing example 1-4 AAEMAMMA (Methyl Methacrylate) 5:5 Manufacturing example 1-5 AAEMABA (Butyl Acrylate) 5:5 Manufacturing example 1-6 AAEMAEA (Ethyl Acrylate) 5:5 Manufacturing example 1-7 AAEMA-1:0 Comparative example 1-1 Alumina Stearic acid Tayca Corporation

[0105]

[0106] Meanwhile, as comparative example 1, the MT100TV product from Tayca Corporation was obtained and used.

[0107]

[0108] (Experimental Example 1: Measurement of photocatalytic stability of titanium dioxide complex)

[0109] The photocatalytic stability of the titanium dioxide complexes of Examples 1-1 to 1-7 described above and the titanium dioxide complex according to Comparative Example 1 was measured.

[0110] Photocatalytic stability was performed according to KS L ISO 10678 photocatalytic test method, specifically, ① 0.02 g of methylene blue was added to 1 L of ethanol and stirred to prepare a 20 ppm methylene blue solution, ② 0.01 g of the titanium dioxide complexes of Examples 1-1 to 1-7 and the titanium dioxide complex of Comparative Example 1 and 50 g of methylene blue solution were added to a graduated cylinder and stirred, and the standard sample was wrapped with foil to block UV. After that, ③ a UV lamp was installed at the center of a multi-magnetic stirrer, and the graduated cylinders were installed at equal distances and stirred at 500 rpm for 1 hour. After that, ④ a test sample at a level where absorbance can be measured was taken, and the solid phase was separated from the liquid phase through centrifugation. After that, ⑤ the absorbance of the standard sample and the test sample was measured at 655 nm using a spectrophotometer. Afterwards, ⑥ the photocatalyst stability is calculated by [Mathematical Formula 1] below.

[0111]

[0112] But here, MB UV is the absorbance of the sample for UV irradiation test after 1 hour of reaction, MB NUV is the absorbance of the UV-irradiated test sample after N hours of reaction.

[0113] The results of the photocatalyst stability measured by the above-described method are shown in Fig. 2.

[0114] Figure 2 is a graph showing the photocatalytic stability of a titanium dioxide complex for blocking ultraviolet rays according to embodiments of the present invention.

[0115] Additionally, the result values ​​of Fig. 2 are as shown in [Table 2] below.

[0116] Time (min) Photocatalytic stability (%) 0 1 5 3 0 4 5 6 0 Manufacturing example 1-1 (AAEMA: IMA) 10.98 4 0.97 2 0.94 2 0.93 2 9 3.2 0 Manufacturing example 1-2 (AAEMA: BMA) 10.99 9 4 0.99 0.97 8 9 7.8 0 Manufacturing example 1-3 (AAEMA: EHA) 10.99 9 4 0.99 4 0.99 2 9 20 Manufacturing example 1-4 (AAEMA: MMA) 10.99 9 4 0.99 2 0.95 4 9 5.4 0 Manufacturing example 1-5 (AAEMA: BA) 10.99 8 0.92 1 0.85 4 0.85 2 8 5.2 0 Manufacturing example 1-6(AAEMA:EA)10.9970.9480.9020.84084.00 Manufacturing Example 1-7(AAEMA)10.9990.9980.9970.99799.70 Comparative Example 1(Alumina: Stearic acid)10.9400.9200.9100.86586.50

[0117] As can be seen with reference to the above [Table 2] and Fig. 2, in the case of Preparation Examples 1-1 to 1-6 regarding the titanium dioxide complex surface-modified with the first monomer and the second monomer, it can be seen that it has an excellent photocatalytic stability of 84% or more. In particular, in the case of Preparation Examples 1-1 to 1-4, it has an excellent photocatalytic stability of 90% or more, which is considered to be superior to the titanium dioxide complex of Comparative Example 1.

[0118]

[0119] (Experimental Example 2: Measurement of UV protection factor for titanium dioxide complex)

[0120] The titanium dioxide complexes of the above-described Manufacturing Examples 1-1 to 1-7 and Comparative Example 1 were diluted in mineral oil, and then the ultraviolet protection factor (SPF) and ultraviolet A index (PFA) were measured.

[0121] Specifically, the titanium dioxide complexes of Manufacturing Examples 1-1 to 1-7 and Comparative Example 1 were diluted to a concentration of 8%, and SPF was measured according to ISO 24444, and PFA was measured according to ISO 24442. The measurement results are as shown in [Table 3] and FIGS. 3a to 3h below.

[0122] Figures 3a to 3h are graphs showing the UV blocking rate by wavelength of titanium dioxide complexes for UV blocking according to embodiments of the present invention and titanium dioxide complexes for UV blocking according to comparative examples.

[0123] Classification SPFPFA Manufacturing Example 1-1 (AAEMA:IMA) 20.567.72 Manufacturing Example 1-2 (AAEMA:BMA) 24.649.22 Manufacturing Example 1-3 (AAEMA:EHA) 19.698.01 Manufacturing Example 1-4 (AAEMA:MMA) 23.238.38 Manufacturing Example 1-5 (AAEMA:BA) 10.384.22 Manufacturing Example 1-6 (AAEMA:EA) 15.465.87 Manufacturing Example 1-7 (AAEMA) 7.924.21 Comparative Example 1 (Alumina:Stearic acid) 8.313.52

[0124]

[0125] Referring to the above [Table 3] and FIGS. 3a to 3h, it can be seen that the titanium dioxide complexes of Manufacturing Examples 1-1 to 1-6 have superior SPF and PFA compared to the titanium dioxide complex of Comparative Example 1. In particular, it can be seen that Manufacturing Examples 1-1, 1-2, and 1-4 have SPF and PFA that are more than twice that of Comparative Example 1.

[0126] Meanwhile, it can be seen that the titanium dioxide complexes of Manufacturing Examples 1-1 to 1-6 have superior SPF and PFA compared to Manufacturing Example 1-7. This is thought to be because aggregation between titanium dioxide complexes is suppressed and the uniformity of surface modification is further increased by secondary surface modification with a second monomer after surface modification with a first monomer.

[0127] In addition, as can be seen with reference to FIGS. 3a to 3h, the titanium dioxide complexes of Preparation Examples 1-1 to 1-6 can be confirmed to have relatively high absorption capacities for UVA and UVB compared to Preparation Example 1-7 and Comparative Example 1. In particular, in the case of Preparation Examples 1-2 and 1-4, it can be seen that the absorption capacities for UVA are about twice as high.

[0128] (Manufacturing Example 2, Manufacturing of titanium dioxide complex)

[0129] Meanwhile, the inventors of the present invention prepared a titanium dioxide composite as shown in [Table 4] below to test the degree of SPF and PFA improvement according to the first monomer and second monomer coating ratio of the titanium dioxide composite.

[0130] ClassificationTiO2 concentration(%)First monomer concentration(%)Second monomer concentration(%)Coating ratioAAEMA:IMAManufacturing example 2-1802181:9Manufacturing example 2-2806143:7Manufacturing example 2-38010105:5Manufacturing example 2-4801467:3Manufacturing example 2-5801829:1AAEMA:BMAManufacturing example 2-6802181:9Manufacturing example 2-7806143:7Manufacturing example 2-88010105:5Manufacturing example 2-9801467:3Manufacturing example 2-10801829:1 AAEMA:EHA Manufacturing Example 2-11802181:9 Manufacturing Example 2-12806143:7 Manufacturing Example 2-138010105:5 Manufacturing Example 2-14801467:3 Manufacturing Example 2-15801829:1 AAEMA:MMA Manufacturing Example 2-16802181:9 Manufacturing Example 2-17806143:7 Manufacturing Example 2-188010105:5 Manufacturing Example 2-19801467:3 Manufacturing Example 2-20801829:1

[0131]

[0132] (Experimental Example 3: Measurement of UV protection factor for titanium dioxide complex)

[0133] The titanium dioxide complexes of the above-described manufacturing examples 2-1 to 2-20 were diluted in mineral oil, and then the ultraviolet protection factor (SPF) and ultraviolet A index (PFA) were measured.

[0134] Specifically, the titanium dioxide complexes of Manufacturing Examples 2-1 to 2-20 were diluted to a concentration of 8%, and SPF was measured according to ISO 24444, and PFA was measured according to ISO 24442. The measurement results are as shown in [Table 5] below.

[0135] ClassificationSPFPFAAAEMA:IMA Manufacturing Example 2-1 (9:1) 3.48 1.74 Manufacturing Example 2-2 (7:3) 19.42 6.05 Manufacturing Example 2-3 (5:5) 20.56 7.72 Manufacturing Example 2-4 (3:7) 20.73 8.88 Manufacturing Example 2-5 (1:9) 24.52 9.05 AAEMA:BMA Manufacturing Example 2-6 (9:1) 3.28 1.82 Manufacturing Example 2-7 (7:3) 15.8 7.58 Manufacturing Example 2-8 (5:5) 25.18 8.81 Manufacturing Example 2-9 (3:7) 26.52 10.01 Manufacturing Example 2-10 (1:9) 29.44 11.59 AAEMA:EHA Manufacturing Example 2-11 (9:1)4.831.54 Manufacturing Example 2-12 (7:3)11.426.84 Manufacturing Example 2-13 (5:5)16.678.01 Manufacturing Example 2-14 (3:7)21.448.91 Manufacturing Example 2-15 (1:9)26.729.81 AAEMA:MMA Manufacturing Example 2-16 (9:1)5.412.14 Manufacturing Example 2-17 (7:3)16.45.43 Manufacturing Example 2-18 (5:5)23.238.38 Manufacturing Example 2-19 (3:7)27.849.54 Manufacturing Example 2-20 (1:9)28.5510.38

[0136] As can be seen from the above [Table 5], the higher the concentration ratio of the second monomer, the higher the SPF and PFA. In particular, when the concentration ratio of the first monomer to the second monomer is 1:9 to 7:3, the SPF is maintained at 15 or higher, and the PFA is also high at 7 or higher.

[0137]

[0138] (Manufacturing Example 3: Manufacturing of titanium dioxide dispersion)

[0139] In order to confirm the excellent ultraviolet ray blocking performance of the titanium dioxide dispersion prepared from the titanium dioxide composite of the present invention, the titanium dioxide dispersion was prepared by the following method.

[0140] First, a titanium dioxide complex was manufactured using the same method as in Manufacturing Example 2-18 described above.

[0141] Specifically, a titanium dioxide composite was manufactured by first surface-modifying needle-shaped titanium dioxide powder (average particle size 25 nm, average axis ratio 3.5) with AAEMA and then second surface-modifying with MMA. In this case, the coating ratio of AAEMA:MMA was 5:5, and the purity of the titanium dioxide particles was 35%.

[0142] Thereafter, a titanium dioxide complex was dispersed in a solvent according to the composition shown in [Table 6] below to prepare a dispersion (Example 3). Specifically, C12-15 alkyl benzonate was used as the solvent, and polyhydroxystearic acid and polyglyceryl-6 polyricinoleate were used as dispersion stabilizers.

[0143] No.IngredientsWeight (%)1Titanium dioxide composite(AAEMA, MMA surface treated)50.02C12-15 Alkyl benzonate46.53polyhydroxystearic acid2.54polyglyceryl-6-polyricinoleate1.0Total100

[0144]

[0145] Meanwhile, as a comparative example, a commercially available titanium dioxide complex (Comparative Example 1) was dispersed in the composition shown in [Table 7] below to prepare dispersions of Comparative Examples 2 to 4.

[0146] In each dispersion, the solvent and dispersion stabilizer were selected appropriately depending on the type of titanium dioxide complex.

[0147] No.ingredientsWeight (%)Comparative example 21titanium dioxide(alumina, stearic acid surface treated)50.02cyclopentasiloxane31.33PEG-10 dimethicone8.24hexyl laurate10.0Total100titanium dioxide purity40%Comparative example 31Titanium dioxide(alumina, hydrogen dimethicone surface treated)502cyclopentasiloxane31.73PEG-10 dimethicone8.34hexyl laurate10Total100titanium dioxide purity40%Comparative example 41Titanium dioxide(alumina, silica surface treated)52.52water453glycerin24caprylyl glycol0.5Total100titanium dioxide purity37%

[0148]

[0149] (Experimental Example 4: Measurement of photocatalytic stability of titanium dioxide dispersion)

[0150] The photocatalytic stability of the dispersions of the above-described manufacturing example 3 and comparative examples 2 to 4 was measured.

[0151] The photocatalytic stability was performed according to the KS L ISO 10678 photocatalytic test method, as described in Experimental Example 1 above.

[0152] The results of the photocatalyst stability measured by the above-described method are shown in Fig. 4.

[0153] Figure 4 is a comparative graph for explaining the excellent photocatalytic stability of a titanium dioxide dispersion for blocking ultraviolet rays according to one embodiment of the present invention.

[0154] Additionally, the result values ​​of Fig. 4 are as shown in [Table 8] below.

[0155] Time (min) Photocatalyst stability015304560Comparative example 210.9990.9870.9640.9520.952Comparative example 310.9330.9310.9210.9080.908Comparative example 410.9820.9450.9310.9250.925Example 310.9990.9940.9920.9900.990

[0156]

[0157] As can be seen from the above [Table 8] and FIG. 4, the titanium dioxide dispersion of the present invention (example 3) has excellent photocatalytic stability (over 99%) compared to other dispersions (comparative examples 2 to 4). This shows that the titanium dioxide complex of the titanium dioxide dispersion of the present invention has undergone almost complete surface modification.

[0158]

[0159] (Experimental Example 5: Measurement of UV protection factor for titanium dioxide dispersion)

[0160] The dispersion of the above-described manufacturing example 3 was diluted in the same solvent to concentrations of 10%, 20%, and 30% to manufacture examples 3-1 to 3-3.

[0161] Similarly, each of the dispersions of Comparative Examples 2 to 4 was diluted with the same solvent as each solvent to concentrations of 10%, 20%, and 30% to prepare Comparative Examples 2-1 to 4-3.

[0162] Afterwards, the ultraviolet protection factor (SPF) and ultraviolet A index (PFA) were measured for Manufacturing Example 3-1 to Comparative Example 4-3. Specifically, SPF was measured according to ISO 24444, and PFA was measured according to ISO 24442.

[0163] In addition, the SPF of the titanium dioxide complex of each sample was compared and analyzed by converting the UV protection factor per 1% of titanium dioxide purity based on Example 3-1, Comparative Example 2-1, Comparative Example 3-1, and Comparative Example 4-1, which were diluted to a concentration of 10%.

[0164] The measurement results are as shown in [Table 9] below.

[0165] ClassificationConcentrationSPFPFATiO21% per SPPFExample 3-110%6.902.801.97Example 3-220%23.317.87Example 3-330%42.3314.54Comparative example 2-110%6.232.851.02Comparative example 2-220%11.944.78Comparative example 2-330%19.516.75Comparative example 3-110%4.061.941.57Comparative example 3-220%8.383.19Comparative example 3-330%15.445.36Comparative example 4-110%5.712.951.54Comparative example 4-220%12.56.05Comparative example 4-330%22.7411.35

[0166]

[0167] Referring to the above [Table 9], it can be seen that the titanium dioxide dispersions according to the embodiments of the present invention (example 3-1 to example 3-3) have superior SPF and PFA compared to the titanium dioxide dispersions according to the comparative examples (comparative example 2-1 to comparative example 4-3). In particular, it can be seen that when used at a concentration of 20% or more, they have SPF and PFA that are approximately twice as high as the titanium dioxide dispersions according to the comparative examples.

[0168] In addition, even when looking at the SPF value per 1% of the titanium dioxide complex, it can be seen that the titanium dioxide dispersion according to the embodiment of the present invention (example 3-1) is superior by 0.4 or more to the titanium dioxide dispersions according to the comparative examples (comparative examples 2-1, 3-1, and 4-1).

[0169] This is because the titanium dioxide complexes of the titanium dioxide dispersion according to the embodiments of the present invention undergo secondary surface modification by a second monomer after surface modification by a first monomer, so that the uniformity of surface modification is excellent, and as a result, aggregation between titanium dioxide complexes is suppressed, so that the effect of ultraviolet reflection (or scattering) by titanium dioxide is maximized.

[0170]

[0171] (Manufacturing Example 4: Manufacturing of a UV-blocking cosmetic composition in an oil-in-water formulation)

[0172] Meanwhile, in order to evaluate the stability of the titanium dioxide dispersion of the present invention in an oil-in-water formulation, the inventors prepared a cosmetic composition for UV protection in an oil-in-water formulation with a composition as shown in [Table 10].

[0173] Classification Ingredients Composition 1 Composition 2 Composition 3 Water phase Water to 100 to 100 to 100 Butylene glycol 0.5 0.5 0.5 Glycerin 1.0 1.0 1.0 1,2-hexanediol 2.0 2.0 2.0 Water-soluble thickener Carbomer 0.2 -- xanthan gum -- 0.4-hydroxyethyl cellulose -- 0.4 Oil phase Polysorbate 60 0.7 0.7 0.7 Sorbitan sesquioleate 0.5 0.5 0.5 Hydrogenated polydecene 10.0 10.0 10.0 Dimethicone 0.6 0.6 0.6 Caprylic / capric triglyceride 10.0 10.0 10.0 Dispersion Preparation Examples 3 to Comparative Examples 5 Dispersion 20.0 20.0 20.0 Neutralizer Tromethamine Amount Amount Amount Amount

[0174] In the above [Table 10], the dispersions used were the dispersion manufactured in the above-described manufacturing example 3 (example 3) and the dispersions of comparative examples 2 to 4 (comparative examples 2 to 4).

[0175] As can be seen from the above [Table 10], carbomer was used as a water-soluble thickener in composition 1, xanthan gum was used as a water-soluble thickener in composition 2, and hydroxyethylcellulose was used as a water-soluble thickener in composition 3.

[0176] Therefore, 12 types of cosmetic compositions were manufactured by combining three types of water-soluble thickeners and four types of dispersions.

[0177] (Experimental Example 6: Formulation Stability Evaluation)

[0178] The emulsion stability of 12 types of UV-blocking cosmetic compositions of Manufacturing Example 4 described above was evaluated. Emulsion stability was assessed by uniformly applying each cosmetic composition to glass and visually observing whether coagulation occurred or whether the water phase and oil phase separated and water leaked out onto the surface of the coating. The results are shown in Fig. 5.

[0179] FIG. 5 is a comparative experimental photograph to explain the excellent oil-in-water formulation stability of a titanium dioxide dispersion for UV protection according to one embodiment of the present invention.

[0180] As can be seen with reference to FIG. 5, cosmetic compositions manufactured using the titanium dioxide dispersion of the present invention (example 3) showed no separation of the oil phase and the water phase regardless of the type of water-soluble thickener, and maintained the applied shape, showing excellent emulsion stability.

[0181] On the other hand, it can be seen that the cosmetic compositions of comparative examples 2 to 4 exhibit coagulation and separation of the oil phase and the water phase when a water-soluble thickener is used. In particular, it can be seen that the dispersions of comparative examples 2 to 4 in composition 1 using carbomer as a water-soluble thickener and composition 3 using hydroxyethylcellulose as a water-soluble thickener both exhibit poor emulsion stability.

[0182] Meanwhile, since it was confirmed that the dispersions of comparative example 4 and example 3 in composition 2 using xanthan gum as a water-soluble thickener had relatively excellent emulsion stability, the stability over time of comparative example 4 and example 3 was additionally evaluated.

[0183] (Experimental Example 7: Evaluation of stability over time)

[0184] As described above, the stability over time of the dispersion of comparative example 4 and the dispersion of example 3 in composition 2 using xanthan gum as a water-soluble thickener was evaluated.

[0185] Stability was assessed visually by exposing each cosmetic composition to a high-temperature environment of 50°C for three days and then evaluating emulsion stability. The results are shown in Figure 6.

[0186] Figure 6 is a comparative experimental photograph illustrating the excellent stability over time of a titanium dioxide dispersion for blocking ultraviolet rays according to one embodiment of the present invention.

[0187] As can be seen with reference to FIG. 6, the titanium dioxide dispersion of the present invention (example 3) has superior stability over time compared to the dispersion of comparative example 4. That is, when exposed to a high temperature environment of 50°C for 3 days, the titanium dioxide dispersion of the present invention (example 3) is found to be evenly applied to glass without agglomeration, while the dispersion of comparative example 4 shows agglomeration, and it can be easily confirmed with the naked eye that separation of the oil phase and the water phase occurs during application.

[0188] The above-described advantages are believed to be due to the fact that, in the case of the titanium dioxide dispersion of the present invention, the titanium dioxide particles undergo two-stage surface modification using different first and second monomers of the acrylate series, thereby improving the photocatalytic stability to 99% or more. That is, in the case of the titanium dioxide dispersions according to the comparative examples, the surface modification is not uniform, so electron generation is induced in the functional group portion that has not been surface modified, and the electrons thus generated inhibit the function of the water-soluble thickener, thereby lowering the emulsion stability in the oil-in-water formulation.

[0189] In addition, as verified in Experimental Example 5 above, the titanium dioxide dispersion of the present invention has the advantage of excellent emulsion stability and an excellent UV protection factor. This is understood to be because, as described above, due to surface modification by the first and second monomers of different acrylate series, aggregation between titanium dioxide complexes is minimized, thereby maximizing the UV reflection effect by the titanium dioxide particles.

[0190] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0191] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

[0192] The present invention can be applied to various daily necessities. For example, the present invention can be added to various daily necessities for skin and hair, such as cosmetics, soap, shampoo, and toothpaste, and can provide excellent UV protection.

Claims

1. Titanium dioxide; and Comprising a polymer bonded to the surface of the titanium dioxide, The above polymer is a titanium dioxide complex for blocking ultraviolet rays, containing an acrylate group at the terminal.

2. In paragraph 1, A titanium dioxide complex for blocking ultraviolet rays, wherein the polymer further comprises a beta-ketoester group capable of bonding to the titanium dioxide surface.

3. In paragraph 2, A titanium dioxide complex for blocking ultraviolet rays, wherein the polymer further comprises at least one ester group in the middle or side of the chain.

4. In paragraph 1, The above polymer is a titanium dioxide complex for blocking ultraviolet rays, formed by polymerization of different (meth)acrylate monomers.

5. In paragraph 4, The polymer comprises a first monomer selected from among 2-(acetoacetoxy)methylmethacrylate, 2-(acetoacetoxy)ethyl acrylate, 2-(acetoacetoxy)ethyl ethylacrylate, and 2-(acetoacetoxy)ethyl methacrylate; and A titanium dioxide complex for blocking ultraviolet rays, formed from a second monomer comprising any one selected from the group consisting of isobutyl methacrylate, butyl methacrylate, ethylhexyl acrylate, methyl methacrylate, butyl acrylate, and ethyl acrylate.

6. In paragraph 5, A titanium dioxide complex for blocking ultraviolet rays, wherein the first monomer and the second monomer are polymerized in a ratio of 1:9 to 7:

3.

7. In paragraph 1, A titanium dioxide complex for blocking ultraviolet rays, wherein the above polymer coats the titanium dioxide particles with a thickness of less than 10 nm.

8. In paragraph 1, A titanium dioxide complex for blocking ultraviolet rays, wherein the titanium dioxide particles have an average particle diameter of 10 to 100 nm.

9. In paragraph 1, The above titanium dioxide complex is, Titanium dioxide complex for blocking ultraviolet rays, having a photocatalytic stability of 90% or higher according to the KS L ISO 10678 photocatalytic test method.

10. In paragraph 1, The above titanium dioxide particles are titanium dioxide complexes for blocking ultraviolet rays, which are particles coated with inorganic or organic substances.

11. A titanium dioxide composite comprising titanium dioxide particles coated with a high molecular weight polymer having an acrylate group at the terminal; and A titanium dioxide dispersion for blocking ultraviolet rays, comprising a dispersion stabilizer.

12. In paragraph 11, A titanium dioxide dispersion for blocking ultraviolet rays, wherein at least a portion of the surface of the titanium dioxide particles is coated with an inorganic or organic material different from the high molecular weight polymer.

13. In paragraph 11, The above dispersion stabilizer is, A titanium dioxide dispersion for sunscreen comprising at least one of hydrogenated lecithin, cetearyl alcohol, behenyl alcohol, glyceryl stearate, polyhydroxystearic acid, PEG-10 dimethicone, and polyglyceryl-6-polyricinoleate.

14. Awards; water soluble thickener; Paid portion; and Containing titanium dioxide dispersion for ultraviolet protection, The above titanium dioxide dispersion for blocking ultraviolet rays is, A titanium dioxide composite comprising titanium dioxide particles coated with a high molecular weight polymer having acrylate groups at the terminals; and A cosmetic composition for blocking ultraviolet rays, comprising a dispersion stabilizer.

15. In paragraph 14, The above water-soluble thickener is, A cosmetic composition for sunscreen comprising at least one of carbomer, acrylate / C10-30 acrylate crosspolymer, hydroxyethylcellulose, hydroxypropyl methylcellulose, carboxymethylcellulose, ethylcellulose, xanthan gum, gellan gum, guar gum, and Arabic gum.

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