Polymers and their applications

Abstract

The present invention relates to a polymer compound that can be chemically bonded to the surface of an inorganic nanopowder to modify the surface, and applications thereof. More specifically, the present invention relates to a polymer compound that can be easily and quickly chemically bonded to the surface of an inorganic nanoparticle powder to modify the surface of the inorganic nanoparticles and form a polymer coating layer, and that can be produced economically and efficiently, and applications thereof.

Description

[Technical field]

[0001] The present invention relates to a polymer compound that can chemically bond to the surface of an inorganic nanopowder to modify the surface, and applications thereof. More specifically, the present invention relates to a polymer compound that can easily and quickly undergo a chemical bonding reaction with the surface of an inorganic nanoparticle powder to modify the surface of the inorganic nanoparticles and form a polymer coating layer, and that can be produced economically and efficiently, and applications thereof. [Background technology]

[0002] Inorganic nanoparticle powders commonly used in the cosmetics industry are mainly titanium dioxide (TiO2) or zinc oxide (ZnO). These inorganic nanoparticle powders are mainly used as pigments in tone-up cream formulations to brighten skin tone, and as inorganic sunscreens in the formulation of sunscreen products. Especially in recent years, global warming due to ozone layer destruction and skin exposure to ultraviolet rays have increased rapidly. To protect the skin from such increasing ultraviolet rays, the market for sunscreen products has been growing rapidly by more than 10% annually. Sunscreen products use dispersion formulation systems based on inorganic nanoparticles and organic ultraviolet absorbers to protect the skin from ultraviolet rays. In addition, such sunscreen products are required to have effective ultraviolet blocking function while also having a light feel, smooth application, and a clean finish. However, inorganic nanoparticle powders, which have high density and strong interactions between particles, are important materials with ultraviolet scattering ability, but have a negative effect on all other performance. Therefore, attempts have been made to improve skin stability and dispersibility and enhance product performance by modifying the surface properties of inorganic nanoparticle powders. Although efforts have been made to improve dispersion instability by organic coating and silica coating, the fundamental problem has not been solved. In order to improve the essential properties of inorganic materials, new coating technologies based on organic materials are necessary, but no coating technology that satisfies both productivity and product performance has yet been developed.

[0003] For the surface coating of inorganic nano powders (TiO2, ZnO) commonly used in conventional cosmetic preparations, approaches using materials such as fatty acids, silicones, amino acids, and fluorine compounds have been attempted, but these materials have the following problems in use. In the case of fatty acid coating, oil resistance against sebum is reduced, causing shine and discoloration, and in the case of silicone coating, it feels dry and rough. In the case of amino acid coating, water resistance and oil resistance are reduced, making it feel heavy, and in the case of fluorine compound coating, the cosmetics become steamy or look unnatural, and moldability is reduced. In order to improve such drawbacks of low skin compatibility, attempts are being made to develop new inorganic nano powder coating technologies.

[0004] In particular, a technique for uniformly forming a thin layer of biocompatible molecules on the surface of inorganic nanopowder has been reported in order to improve favorable usability such as adhesion to the skin, moisturizing properties, and adhesiveness (e.g., Patent Document 1; Non-Patent Document 1). However, the polymerization method for the inorganic nanopowder surface coating molecules used in the above technique is a surface growth polymerization method and a surface deposition polymerization method, so there is a limit to strengthening the thickness of the surface thin film of the inorganic nanopowder, and a surface initiator linker is required, which not only results in low polymerization efficiency but also limits the introduction of hydrophobic monomers into the polymer structure to improve skin adhesiveness. In addition, the production requires an expensive multi-step process, and there are various disadvantages such as reduced productivity, making development difficult. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent No. 10-1767207 [Non-patent literature]

[0006] [Non-Patent Document 1] Polymer, 54 (21), 2013, 5609-5614 Summary of the Invention [Problem to be solved by the invention]

[0007] The object of the present invention is to provide a polymer compound which can easily and quickly undergo a chemical bonding reaction with the surface of inorganic nanoparticle powder used in cosmetic preparations, thereby modifying the surface of the inorganic nanoparticles and forming a polymer coating layer, and which can be produced economically and efficiently, and applications thereof. [Means for solving the problem]

[0008] In order to achieve the above object, the present invention provides a compound represented by the following formula (1): [ka] (In the formula, R' may be the same or different and each independently represents a hydrogen atom or a methyl group; R1 is a group containing a phosphorylcholine-like phospholipid structure, R2 is independently hydrogen; an alkoxy group; an amino group; an epoxy group; or a C1-C20 aliphatic hydrocarbon group or a C6-C20 aromatic hydrocarbon group which is unsubstituted or substituted with one or more functional groups; R3 is independently an alkyl group, an alkoxy group, an epoxy group, a hydroxyl group, or a C1 to C20 aliphatic hydrocarbon group or a C6 to C20 aromatic hydrocarbon group which is substituted or unsubstituted with an acid functional group; R4 is a C1 to C10 aliphatic hydrocarbon group, R5, R6 and R7 are the same or different and each independently represents hydrogen; or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkyl group, an alkoxy group, an epoxy group, a hydroxyl group or an acid functional group; R8 and R9 are the same or different and each independently represent hydrogen; or a group containing a hydroxy, carboxylic acid, or alkoxy functional group, provided that at least one of R8 and R9 contains a hydroxy, carboxylic acid, or alkoxy functional group; W, X, Y, and Z are the mole fractions of the corresponding repeating units and are each independently 0 to 1, with the proviso that at least one of W and X is greater than 0, and W+X+Y+Z=1.

[0009] According to another aspect of the present invention, there is provided an inorganic nanopowder having a surface to which the polymer compound of the present invention is chemically bonded.

[0010] According to yet another aspect of the present invention, there is provided a powder formulation comprising the inorganic nanopowder of the present invention. Effect of the Invention

[0011] The polymer compound of the present invention can easily and quickly undergo a chemical bonding reaction with the surface of inorganic nanoparticle powder used in cosmetic preparations to modify the inorganic nanoparticle surface and form a polymer coating layer. The polymer production process does not require expensive processes or complex multi-stage production processes, making it very economical and contributing to improved productivity. [Brief description of the drawings]

[0012] [Figure 1] FIG. 2 is an HR-TEM image of the inorganic nanopowder produced in Coating Example 21 of the present invention, showing the formation of a polymer layer on the TiO2 surface coated with polymer compound 1. [Diagram 2] FIG. 2 shows the XPS analysis results of the inorganic nanopowder prepared in coating Example 21 of the present invention, which shows the difference in the bond energy (O1S, Ti2p) values ​​of the TiO2 surface before and after coating, proving that the chemical bond between the polymer compound and the TiO2 surface is well established. [Diagram 3] 3 shows HR-TEM images of inorganic nanopowders produced in Coating Examples 21 to 28 of the present invention and Comparative Examples 1 and 2. BEST MODE FOR CARRYING OUT THEINVENTION

[0013] The present invention will now be described in more detail.

[0014] The polymer compound of the present invention is represented by the following formula (1): [ka] (In the formula, R' may be the same or different and each independently represents a hydrogen atom or a methyl group, R1 is a group containing a phosphorylcholine-like phospholipid structure, R2 is independently hydrogen; an alkoxy group; an amino group; an epoxy group; or a C1-C20 aliphatic hydrocarbon group or a C6-C20 aromatic hydrocarbon group which is unsubstituted or substituted with one or more functional groups; R3 is independently an alkyl group, an alkoxy group, an epoxy group, a hydroxyl group, or a C1 to C20 aliphatic hydrocarbon group or a C6 to C20 aromatic hydrocarbon group which is substituted or unsubstituted with an acid functional group; R4 is a C1 to C10 aliphatic hydrocarbon group, R5, R6 and R7 are the same or different and each independently represents hydrogen; or an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which is substituted or unsubstituted with an alkyl group, an alkoxy group, an epoxy group, a hydroxyl group or an acid functional group; R8 and R9 are the same or different and each independently represent hydrogen; or a group containing a hydroxy, carboxylic acid, or alkoxy functional group, provided that at least one of R8 and R9 contains a hydroxy, carboxylic acid, or alkoxy functional group; W, X, Y, and Z are the mole fractions of the corresponding repeating units, and each is independently 0 to 1, provided that at least one of W and X is greater than 0, and W+X+Y+Z=1.

[0015] In one embodiment, in the formula (1), R1 is represented by the following formula (2): [ka] (In the formula, a is an integer of 0 to 2, b is an integer from 2 to 4; R 10 , R 11 and R 12 are the same or different and each independently represents a hydrogen atom, a C1-C6 hydrocarbon group, or -(CH2) n It represents an —OH group, where n is an integer of 1 to 6. It may also be a group containing a phosphorylcholine-like phospholipid structure represented by the following formula:

[0016] In one embodiment, in the formula (1), the alkyl group may be a C1 to C20 alkyl group or a C3 to C20 cycloalkyl group, the alkoxy group may be a C1 to C20 alkoxy group or a C3 to C20 cycloalkoxy group, the acid functional group may be a carboxylic acid group, and the aliphatic hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group.

[0017] In one embodiment, in the formula (1), the functional group substituted on the C1 to C20 aliphatic hydrocarbon group or the C6 to C20 aromatic hydrocarbon group may be an alkoxy group, an aryloxy group, an ether group, a halogen group, an isocyanate group, a lactone group, a hydroxy group, or an acid functional group.

[0018] In the formula (1), W is 0 to 1, and more specifically, it may be 0.01 or more, 0.05 or more, or 0.1 or more, and may be 1 or less, 0.99 or less, 0.95 or less, 0.9 or less, 0.85 or less, or 0.8 or less, but is not limited thereto.

[0019] In the formula (1), X is 0 to 1, and more specifically, X may be 0.01 or more, 0.05 or more, or 0.1 or more, and may be 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less, but is not limited thereto.

[0020] In the formula (1), Y is 0 to 1, and more specifically, Y may be 0.01 or more, 0.05 or more, or 0.1 or more, and may be 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, or 0.8 or less, but is not limited thereto.

[0021] In the formula (1), Z is 0 to 1, and more specifically, Z may be 0.01 or more, 0.02 or more, or 0.05 or more, and may be 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less, but is not limited thereto.

[0022] In one embodiment, the unsaturated phospholipid monomer providing the repeating unit represented by the molar fraction W in the formula (1) is, for example, 2-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 3-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 7-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 8-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 9-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 10-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 11-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 12-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 13-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 14-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 15-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 16-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 17-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)butyl-2 '-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(p-vinylbenzyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(p-vinyl benzoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(styryloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(p-vinylbenzyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(acryloylamino)ethyl-2'-(trimethylammonio)ethyl phosphate,2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(buteroyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(crotonoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, ethyl-(2'-trimethylammonioethylphosphorylethyl) fumarate, butyrate The compound may be one or more selected from the group consisting of ethyl-(2'-trimethylammonioethyl phosphorylethyl) fumarate, hydroxyethyl-(2'-trimethylammonioethyl phosphorylethyl) fumarate, ethyl-(2'-trimethylammonioethyl phosphorylethyl) fumarate, butyl-(2'-trimethylammonioethyl phosphorylethyl) fumarate, and hydroxyethyl-(2'-trimethylammonioethyl phosphorylethyl) fumarate.

[0023] In one embodiment, in the formula (1), R2 is, for example, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, lauryl, tetradecyl, hexadecyl, isobornyl, dicyclopentanyl, dicyclopentenyl, benzyl, 2-methoxyethyl, 2-ethoxyethyl, succinyl, monoalkyl succinate, monoalkyl fumarate, glycidyl, 3,4-epoxybutyl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexylmethyl, 3-methyloxetane-3-methyl, 3-ethyloxetane-3-methyl, NH2, NHCH3, allyl, 2-hydroxyethyl, 3-oxypropylmethyldimethoxysilane, tetrahydrofurfuryl, ethylene glycol disilane, ethylene glycol diphenyl ether ... clopentenyl ether, 2-ethyl-2-methyl-1,3-dioxoreynylmethyl, 2-isocyanatoethyl, 4-morpholine, phenyl glycidyl ether, phenoxydiethylene glycol, methoxypolyethylene glycol, 2-[4-(-1 methyl-1-phenylethyl)-phenoxy]ethyl, t-butyl, 2-oxypropyl hexahydrophthalate, gamma-butyrolactone, propoxyethyl, n-isobutoxymethyl, 2-oxyethyl phthalate, 1,1,1,3,3,3-hexafluoroisopropyl, octafluoropentyl, tetrafluoropropyl, heptadecafluorodecyl, and tribromophenyl.

[0024] In one embodiment, in formula (1), R3 may be, for example, independently selected from the group consisting of phenyl, p-methylphenyl, and p-acetoxyphenyl.

[0025] In one embodiment, in formula (1), R4 may be, for example, a methylene group or an ethylene group.

[0026] In one embodiment, in the formula (1), R5, R6 and R7 are, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl, vinyl, methacryloxymethyl, 2-methacryloxyethyl, 3-methacryloxypropyl, 3-methacryloxypropyl, 3-methacryloxypropyl, acryloxymethyl, 2-acryloxyethyl, 3-acryloxypropyl, 3-acryloxypropyl, 3-acryloxypropyl, 3-glycidyloxypropyl, 2-epoxycyclohexylethyl, 3-epoxycyclohexylpropyl, and OR. 12 (where R 12 is hydrogen, methyl, ethyl or propyl.

[0027] The polymer compound of the present invention can be produced by any one of known polymerization methods such as radical polymerization, cationic polymerization, anionic polymerization, and condensation polymerization, but it is preferable to use radical polymerization from the viewpoint of ease of production of the polymer compound and economical aspects. It can also be produced by mixing the monomer with a polymerization solvent, heating to an appropriate temperature depending on the half-life temperature of the thermal initiator used, and then removing oxygen under a nitrogen atmosphere.

[0028] Polymerization conditions for polymer compounds may vary in polymerization time and temperature depending on the type of thermal initiator used. The radical polymerization initiator may be a commonly known thermal initiator, more specifically, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1'-bis-(bis-t-butylperoxy)cyclohexane, 1,1'-azobis(cyclohexane-1-carbonitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) ) propionamide, 2,2'-azobis(N-butyl-2-methylpropionamide, 2,2'-azobis[2-(2-imidazolinyl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolinyl)propane, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and the like may be used alone or in combination of two or more.

[0029] In one embodiment, a commonly known chain transfer agent may be used to adjust the weight average molecular weight (Mw) of the polymer during the preparation of the polymer compound. More specifically, 1-dodecanethiol, octadecanethiol, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyroethyl)-1,3,5-triazine-2,4,6-trione, thioglycolic acid, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyldiethoxysilane, 2-mercaptopropionic acid, 3-mercaptopropionic acid, etc. may be used.

[0030] In one embodiment, the weight average molecular weight (Mw, g / mol) of the polymer compound of the present invention may be 1,000 to 200,000 g / mol, and the polydispersity (PDI) may be 1.0 to 20, more specifically, the weight average molecular weight (Mw) may be 5,000 to 100,000 g / mol, and the polydispersity (PDI) may be 1.0 to 10, more specifically, the weight average molecular weight (Mw) may be 10,000 to 50,000 g / mol, and the polydispersity (PDI) may be 1.0 to 5.0, but is not limited thereto. In addition, the polymer compound of the present invention may be a homopolymer or a random copolymer not limited by the sequence of each polymer unit, but is not limited thereto.

[0031] For polymer polymerization, a suitable solvent can be used in consideration of the ease of use with the monomer, initiator, chain transfer agent, and other additives. For example, alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- Ketones such as 2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, and 2-heptanol; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;2-Alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-propionate and methyl 2-oxy-2-propionate, and monooxymonocarboxylic acid alkyl esters of methyl alkyl 2-alkoxy-2-propionates such as methyl methyl 2-methoxy-2-propionate and methyl ethyl 2-ethoxy-2-propionate; ethyl 2-hydroxypropionate, methyl ethyl 2-hydroxy-2-propionate, ethyl hydroxyacetate, and 2-hydroxy-3-methylbutanoic acid esters such as methyl; ketone acid esters such as ethyl pyruvate; and a single solvent selected from N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., or a mixed solvent of two or more of them may be used.

[0032] The polymer compound of the present invention easily and quickly undergoes a chemical bonding reaction with the surface of inorganic nanoparticle powder used in cosmetic preparations, and can therefore modify the surface of the inorganic nanoparticle powder and form a polymer coating layer.

[0033] Therefore, according to another aspect of the present invention, there is provided an inorganic nanopowder having a surface to which the polymer compound of the present invention is chemically bonded. In one embodiment, the inorganic nanopowder may be an inorganic nanomaterial (e.g., titanium dioxide, zinc oxide, mica, sericite, kaolin, silicic acid anhydride, boron nitride, or talc having an average particle size of 100 nm or less) having a coating layer of the polymer compound of the present invention on its surface.

[0034] According to yet another aspect of the present invention, there is provided a powder formulation comprising the inorganic nanopowder of the present invention.

[0035] In one embodiment, the powder formulation may be, but is not limited to, a powder for blocking ultraviolet rays, a powder for cosmetics, or a powder for color toning.

[0036] The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereby in any way.

[0037] Working Example Examples 1 to 20 <Polymerization of polymer compounds> Polymerization was carried out using monomers A to E of the types and ratios shown in Table 1 below, and thermal initiators and chain transfer inhibitors of the types and amounts (parts by weight relative to a total of 100 parts by weight of monomers) shown in Table 1 below. As polymerization conditions, a three-neck round-bottom flask was used, anhydrous ethanol was used as the polymerization solvent, and the mixture was dissolved so that the solid content was 35 parts by weight in total, and polymerization was carried out by applying heat. After the polymerization was completed, 100 ppm of t-butylhydroquinone (t-BHQ) was added as a polymerization inhibitor to prevent further polymerization. The weight average molecular weight (Mw) and polydispersity (PDI) at the end of the polymerization are shown in Table 1 below. At this time, the weight average molecular weight (Mw) and polydispersity (PDI) were controlled using a chain transfer agent.

[0038] [Ingredients used] A: 2-methacryloyloxyethyl phosphorylcholine B: 3-trimethoxypropyl methacrylate C: tert-butyl methacrylate D: Methyl methacrylate E: Allyltriethoxysilane F: 2,2'-azobisisobutyronitrile G: 4,4'-azobis(4-cyanovaleric acid) H: 3-mercaptopropyltrimethoxysilane I: 1-dodecanethiol

[0039] [Table 1]

[0040] Examples 21 to 28 <Evaluation of TiO2 coating using polymer compounds> Using each of the polymer compounds 1, 2, 6, 7, 9, 12, 15 and 17 in Table 1 prepared as described above, the surface of titanium dioxide was coated under the conditions shown in Table 2 below. Titanium dioxide was purchased from a commercial source and used. After coating, HR-TEM resolution analysis was performed to confirm whether a polymer compound layer was formed on the titanium dioxide surface, and XPS analysis was performed to confirm the transfer of binding energy values. The results are shown in Table 2 below.

[0041] Comparative Examples 1-2 The surface of titania was coated with each of the polymer compounds of the following formulas (3) and (4), and the results were evaluated in the same manner. The results are shown in Table 2 below. [ka] TiO2 surface coating and cleaning test The TiO2 surface coating and washing process was carried out as follows. First, in the coating process, 97g of TiO2 was placed in a beaker, 100g of anhydrous ethanol solvent was added, and the mixture was homogenized by high-speed stirring with a homodisperse at room temperature. Next, 3g of polymer compound was added in 4 batches while stirring with a homodisperse. The mixture was homogenized by stirring for 10 minutes at room temperature, and the product was dried on aluminum foil at 100°C for 12 hours, then crushed with a hammer mill and filtered with a 60 mesh. After the coating process was completed, in the washing process, 30g of TiO2 coated with 200mL of PET sample was added to 120g of ionized water in a bottle, stirred at high speed for 1 hour, and then centrifuged (3000 rpm, 10 minutes) to precipitate inorganic powder. Then, the transparent upper layer solution was removed, and the lower solid precipitate was transferred to aluminum foil and dried at 100°C for 12 hours, and the dried TiO2 powder was finely crushed in a bowl and stored.

[0042] Confirmation of the formation of a polymer compound coating layer on the TiO2 surface (TEM image confirmation) In order to confirm whether the coating of the polymer compound on the inorganic nanopowder (TiO2) surface after the coating and cleaning processes had progressed well, measurements were taken using an HR-TEM device. On the other hand, cases in which a polymer layer was formed and observed in the TEM image even after the strong cleaning treatment were indicated with an "O", and cases in which the polymer layer was not formed and was washed away, resulting in no polymer layer being observed, were indicated with an "X".

[0043] Confirmation of the presence or absence of chemical bonds of polymer compounds on the TiO2 surface (confirmation by XPS analysis) XPS analysis was used to confirm whether the produced polymer compound was chemically well bonded to the TiO2 surface through chemical reaction. X-ray photoelectron spectroscopy (XPS) is one of the most widely used analytical techniques in surface analysis. The binding energy measured using XPS is an element-specific energy, so the elements of the analysis sample can be analyzed, and since the binding energy changes depending on the chemical bonding state, information on the chemical bonding state can be obtained. The binding energy of the O1S level of TiO2 and the binding energy of the Ti2p level were confirmed. The change in surface modification due to chemical bonding is expressed as a shift in the binding energy value of each level, and the presence or absence of surface coating can be confirmed. In the case of binding energy values, a shift of 0.3 eV or more is considered to be a significant shift. The cases where a shift in the binding energy value was observed are indicated by "○", and the cases where no shift was observed are indicated by "X".

[0044] [Table 2]

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R' may be the same or different and each independently represents a hydrogen atom or a methyl group; R 1 is a group containing a phosphorylcholine-like phospholipid structure, R 2 are independently hydrogen; an alkoxy group; an amino group; an epoxy group; or a C1-C20 aliphatic hydrocarbon group or a C6-C20 aromatic hydrocarbon group which is unsubstituted or substituted with one or more functional groups; R 3 are independently an alkyl group, an alkoxy group, an epoxy group, a hydroxyl group, or a C1-C20 aliphatic hydrocarbon group or a C6-C20 aromatic hydrocarbon group, which is substituted or unsubstituted with an acid functional group; R 4 is a C1 to C10 aliphatic hydrocarbon group, R 5 , R 6 and R 7 are the same or different and each independently represent hydrogen; or a C1-C20 aliphatic hydrocarbon group or a C6-C20 aromatic hydrocarbon group which is substituted or unsubstituted with an alkyl group, an alkoxy group, an epoxy group, a hydroxy group, or an acid functional group, R 8 and R 9 are the same or different and are each independently hydrogen; or a group containing a hydroxy, carboxylic acid, or alkoxy functional group, with the proviso that R 8 and R 9 at least one of contains a hydroxy group, a carboxylic acid group, or an alkoxy functional group; W, X, Y, and Z are mole fractions of the corresponding repeating units and are each independently 0 to 1, with the proviso that at least one of W and X is greater than 0, and W+X+Y+Z=1.

2. R 1 is expressed by the following formula (2): 【Chemistry 2】 (In the formula, a is an integer from 0 to 2, b is an integer from 2 to 4, R 10 , R 11 and R 12 are the same or different and each independently represents a hydrogen atom, a C1 to C6 hydrocarbon group, or -(CH 2 ) n 2. The polymer compound according to claim 1, wherein n is an integer of 1 to 6, and n is a group containing a phosphorylcholine-like phospholipid structure represented by the formula:

3. The polymer compound according to claim 1, wherein the unsaturated phospholipid monomer providing the repeating unit represented by the molar fraction W is one or more selected from the group consisting of: 2-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 3-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(p-vinylbenzyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(p-vinylbenzoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(styryloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(p-vinylbenzyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(acryloylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(buteroyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(crotonoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, Ethyl-(2'-trimethylammonioethylphosphorylethyl) fumarate, butyl-(2'-trimethylammonioethylphosphorylethyl) fumarate, Hydroxyethyl-(2'-trimethylammonioethylphosphorylethyl) fumarate, Ethyl-(2'-trimethylammonioethylphosphorylethyl) fumarate, butyl-(2'-trimethylammonioethylphosphorylethyl) fumarate, and Hydroxyethyl-(2'-trimethylammonioethylphosphorylethyl) fumarate

4. R 2 is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, lauryl, tetradecyl, hexadecyl, isobornyl, dicyclopentanyl, dicyclopentenyl, benzyl, 2-methoxyethyl, 2-ethoxyethyl, succinyl, monoalkyl succinate, monoalkyl fumarate, glycidyl, 3,4-epoxybutyl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexylmethyl, 3-methyloxetane-3-methyl, 3-ethyloxetane-3-methyl, NH 2 , N.H.H. 3 , allyl, 2-hydroxyethyl, 3-oxypropylmethyldimethoxysilane, tetrahydrofurfuryl, ethylene glycol dicyclopentenyl ether, 2-ethyl-2-methyl-1,3-dioxoreynylmethyl, 2-isocyanatoethyl, 4-morpholine, phenyl glycidyl ether, phenoxydiethylene glycol, methoxypolyethylene glycol, 2-[4-(-1-methyl-1-phenylethyl)-phenoxy]ethyl, t-butyl, 2-oxypropylhexahydrophthalate, γ-butyrolactone, propoxyethyl, n-isobutoxymethyl, 2-oxyethylphthalate, 1,1,1,3,3,3-hexafluoroisopropyl, octafluoropentyl, tetrafluoropropyl, heptadecafluorodecyl, and tribromophenyl.

5. R 3 The polymeric compound according to claim 1, wherein is independently selected from the group consisting of phenyl, p-methylphenyl, and p-acetoxyphenyl.

6. R 4 The polymer compound according to claim 1 , wherein is a methylene group or an ethylene group.

7. R 5 , R 6 and R 7 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl, vinyl, methacryloxymethyl, 2-methacryloxyethyl, 3-methacryloxypropyl, 3-methacryloxypropyl, 3-methacryloxypropyl, acryloxymethyl, 2-acryloxyethyl, 3-acryloxypropyl, 3-acryloxypropyl, 3-acryloxypropyl, 3-glycidyloxypropyl, 2-epoxycyclohexylethyl, 3-epoxycyclohexylpropyl, and O-R 12 (Here, R 12 The polymer compound according to claim 1 , wherein each of the groups is independently selected from the group consisting of hydrogen, methyl, ethyl, or propyl.

8. 8. An inorganic nanopowder having a surface to which the polymer compound according to claim 1 is chemically bonded.

9. A powder formulation comprising the inorganic nanopowder according to claim 8.

10. 10. The powder preparation according to claim 9, which is a powder for blocking ultraviolet rays, a powder for cosmetics, or a powder for color toning.

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