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WO2024088297A1 - Procédé de traitement d'une poudre inorganique en vue de l'obtention d'une surface organique faisant appel à un polymère de phosphorylcholine - Google Patents

Procédé de traitement d'une poudre inorganique en vue de l'obtention d'une surface organique faisant appel à un polymère de phosphorylcholine Download PDF

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Publication number
WO2024088297A1
WO2024088297A1 PCT/CN2023/126416 CN2023126416W WO2024088297A1 WO 2024088297 A1 WO2024088297 A1 WO 2024088297A1 CN 2023126416 W CN2023126416 W CN 2023126416W WO 2024088297 A1 WO2024088297 A1 WO 2024088297A1
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Prior art keywords
titanium dioxide
inorganic powder
slurry
surface treatment
modified
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PCT/CN2023/126416
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English (en)
Chinese (zh)
Inventor
李小虎
陆一仁
程伟峰
胡永明
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Jiangsu Oji Biotech Co Ltd
Shanghai Olin Material Technology Co Ltd
Original Assignee
Jiangsu Oji Biotech Co Ltd
Shanghai Olin Material Technology Co Ltd
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Publication of WO2024088297A1 publication Critical patent/WO2024088297A1/fr
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the invention relates to the field of cosmetic raw materials, in particular to a method for organic surface treatment of inorganic powder by a phosphorylcholine polymer, and further to a method for organic surface treatment of titanium dioxide by a phosphorylcholine polymer.
  • Inorganic powder, especially titanium dioxide is widely used in cosmetics and is often used as a colorant, concealing agent and sunscreen.
  • the role of inorganic powder, especially titanium dioxide is usually determined by its particle size distribution range.
  • inorganic powder, especially titanium dioxide used in the field of cosmetic raw materials is subjected to organic surface treatment.
  • inorganic powders such as titanium dioxide with a particle size distribution range of more than 200nm and iron oxide color powder are used as colorants or concealing agents, and titanium dioxide with a particle size distribution range of less than 200nm and zinc oxide are used as sunscreens.
  • Powder surface treatment technology, surface treatment agent, surface properties, different surface treatment agents and treatment amounts, and even different treatment methods will have different degrees of influence on the properties of the powder base (dispersibility, weather resistance, oil absorption, gloss, hiding power, surface area, makeup durability, skin feel, rheology, storage stability, etc.), among which dispersibility, sunscreen ability, formula stability, skin feel, makeup durability and other properties are particularly important.
  • the performance of the powder base depends mainly on the surface treatment agent used and the completeness of the surface treatment. Therefore, the selection of the surface treatment agent is a prerequisite for achieving high-performance powder bases.
  • Surface treatment agents are divided into two categories: inorganic and organic.
  • inorganic surface treatment agents are mainly aluminum, silicon, etc.
  • organic surface treatments mostly use polydimethylsiloxane, triethoxyoctylsilane, stearate, titanate coupling agent, lecithin, perfluorophosphate, etc.
  • the phosphorylcholine polymer used in the present invention to perform organic surface treatment on inorganic powder, especially titanium dioxide, is a unique technology in the field of cosmetic raw materials.
  • phosphorylcholine polymers have emerged as a biomimetic biomaterial with good biocompatibility.
  • This high-end medical biomimetic material has high biocompatibility and is mainly used in the fields of biomedicine and medical devices. It has also been used as a moisturizing ingredient in high-end cosmetics.
  • NOF Corporation developed a series of biomimetic phosphorylcholine products. Due to its extremely high moisturizing and breathable properties and its extremely similar composition and properties to human cell membranes, it is known as an artificial cell membrane.
  • phosphorylcholine polymers artificial cell membranes represented by polyquaternium-51 have gradually come into people's view.
  • phosphorylcholine polymer as a colorant (covering agent) and an organic surface treatment agent for inorganic powder, especially titanium dioxide, to coat the surface of inorganic powder, especially titanium dioxide, can make the inorganic powder, especially titanium dioxide, have the advantages of phosphorylcholine polymer, and the dispersibility, formula stability, skin feel and makeup durability of the inorganic powder, especially titanium dioxide are all improved.
  • the purpose of the present invention is to provide an inorganic powder modified with a phosphorylcholine polymer with high dispersity.
  • a further object of the present invention is to provide a highly dispersed phosphorylcholine polymer-modified titanium dioxide.
  • the first aspect of the present invention provides a phosphorylcholine polymer modified inorganic powder, wherein the inorganic powder is selected from at least one of zinc oxide, iron oxide or titanium dioxide powder; the phosphorylcholine polymer is selected from the following group: polyquaternium-51, polyquaternium-61, polyquaternium-64, polyquaternium-65, or a combination thereof;
  • the particle size D50 of the modified inorganic powder is 50-450nm.
  • the particle size D50 of the modified inorganic powder is 50-200 nm.
  • the main chain is selected from the following group:
  • the phosphorylcholine polymer is selected from: 2-methacryloyloxyethyl phosphorylcholine homopolymer, 2-methacryloyloxyethyl phosphorylcholine, polyphosphorylcholine glycol acrylate, polyphosphorylcholine n-butyl methacrylate, or a combination thereof.
  • the second aspect of the present invention provides a method for preparing the phosphorylcholine polymer modified inorganic powder according to the first aspect of the present invention, wherein the method is selected from any one of the following:
  • Method (I) is a dry preparation method, comprising the following steps:
  • Method (II) is a wet preparation method, comprising the following steps:
  • (C) Dispersion premixing premixing the inorganic powder with a dispersant to obtain an inorganic powder dispersion slurry
  • step (D) the first solvent is mixed with the inorganic powder dispersion slurry by a constant flow pump under ultra-high speed stirring.
  • the first solvent is selected from the following group: water, C1-C6 alcohol solvents, C2-C6 ketone solvents, or a combination thereof.
  • the first solvent is selected from the following group: water, ethanol, isopropanol, polyethylene glycol, isopropyl ketone, or a combination thereof.
  • step (D) the stirring temperature is controlled below 55°C.
  • step (E) the moisture content of the dried filter cake is less than 0.3%; preferably, less than 0.2%.
  • the amount of the phosphorylcholine polymer is 0.01-3 wt %; preferably, 0.1-1 wt %, based on the mass of the modified inorganic powder.
  • the amount of the dispersant is 0.1-0.8 wt %; preferably, 0.1-0.6 wt %, based on the mass of the modified inorganic powder.
  • the inorganic powder before dispersion, is optionally subjected to a treatment comprising the following steps:
  • (z1) beating and dispersing the inorganic powder is beaten with water, a dispersant is added, and the pH value is adjusted to 9.0-11.0 to obtain a slurry, wherein the dispersant is selected from the group consisting of sodium hexametaphosphate, sodium silicate, sodium polyacrylate, monoethanolamine, polyether polyol, or a combination thereof;
  • step (z3) Inorganic surface treatment: heating the slurry described in step (z2) to 70-75° C., adding an alkaline inorganic surface treatment agent, adjusting the pH value of the system to 9.0-10.0 with an alkali solution, cooling to 60-65° C., adding an acidic inorganic surface treatment agent, and adjusting the pH value to 6.5-7.5 to obtain a second slurry;
  • the alkaline inorganic surface treatment agent is selected from the following group: sodium aluminate, sodium silicate, sodium hydroxide, or a combination thereof.
  • the acidic inorganic surface treatment agent is selected from the following group: aluminum sulfate, dilute sulfuric acid, or a combination thereof.
  • the alkali solution is selected from the following group: potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, triethanolamine aqueous solution, arginine solution, or a combination thereof.
  • step (z3) the slurry is heated to 60-90°C, preferably 70°C.
  • the moisture content of the dried filter cake is less than 0.5%, preferably, less than 0.3%.
  • the inorganic surface treatment agent is selected from the following group: aluminum-containing compounds, silicon-containing compounds, or a combination thereof.
  • the aluminum-containing compound is selected from the following group: aluminum hydroxide, aluminum oxide, or a combination thereof.
  • the third invention of the present invention provides a dispersion liquid, comprising: the modified inorganic powder as described in the first aspect of the present invention and a dispersion medium.
  • the fourth aspect of the present invention provides an emulsion comprising the following components:
  • 0.1-25 parts by weight of the modified inorganic powder as described in the first aspect of the present invention 0.1-5 parts by weight of an emulsifier, 1-40 parts by weight of silicone oil, 1-30 parts by weight of an emollient, 1-60 parts by weight of deionized water, 1-15 parts by weight of a humectant, and 0.1-2 parts by weight of a preservative, wherein the particle size D50 of the modified inorganic powder is 50-450 nm.
  • the emulsifier is selected from the following group: polyglycerol esters, sorbitan fatty acid ester series, sorbitan cocoate, sucrose fatty acid esters, alkyl glycosides, hydrogenated lecithin, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyethers, glycerol caprylate/caprate, or a combination thereof.
  • the silicone oil is selected from the following group: cyclopentasiloxane, polydimethylsiloxane, phenyl trimethicone, or a combination thereof.
  • the emollient is selected from the following group: isotridecyl isononanoate, tridecyl trimellitate, caprylic capric triglyceride, tocopheryl acetate, isononyl isononanoate, isodecyl neopentanoate, squalane, jojoba oil, ethylhexyl methoxycinnamate, or a combination thereof.
  • the moisturizing agent is selected from the following group: glycerin, butylene glycol, propylene glycol, polyethylene glycol, polysaccharides, panthenol, sodium hyaluronate, or a combination thereof.
  • the preservative is selected from the following group: caprylyl glycol, phenoxyethanol, ethylhexylglycerin, hexylene glycol, pentylene glycol, or a combination thereof.
  • a fifth aspect of the present invention provides a sunscreen product, comprising the modified inorganic powder according to the first aspect of the present invention, wherein the particle size D50 of the modified inorganic powder is 50-200 nm.
  • the sixth aspect of the present invention provides a cosmetic comprising the modified inorganic powder according to the first aspect of the present invention.
  • a phosphorylcholine polymer-modified titanium dioxide wherein the titanium dioxide is titanium dioxide Powder; the phosphorylcholine polymer is selected from the group consisting of polyquaternium-51, polyquaternium-61, polyquaternium-64, polyquaternium-65, or a combination thereof;
  • the particle size D50 of the modified titanium dioxide is 100-400nm.
  • the particle size D50 of the modified titanium dioxide is 100-200 nm.
  • the main chain is selected from the following group:
  • the phosphorylcholine polymer is selected from: 2-methacryloyloxyethyl phosphorylcholine homopolymer, 2-methacryloyloxyethyl phosphorylcholine, polyphosphorylcholine glycol acrylate, polyphosphorylcholine n-butyl methacrylate, or a combination thereof.
  • a method for preparing the phosphorylcholine polymer modified titanium dioxide according to the seventh aspect of the present invention is provided, wherein the method is (i) a dry preparation method, comprising the following steps:
  • the method is (ii) a wet preparation method, comprising the following steps:
  • step (d) the first solvent is mixed with the titanium dioxide dispersion slurry by a constant flow pump under ultra-high speed stirring.
  • the first solvent is selected from the following group: water, C1-C6 alcohol solvents, C2-C6 ketone solvents, or a combination thereof.
  • the first solvent is selected from the following group: water, ethanol, isopropanol, polyethylene glycol, isopropyl ketone, or a combination thereof.
  • step (d) the stirring temperature is controlled below 55°C.
  • the moisture content of the dried filter cake is less than 0.3%; preferably, less than 0.2%.
  • the amount of the phosphorylcholine polymer is 0.01-3wt%; preferably, 0.1-1wt%, The mass of titanium dioxide after sexualization.
  • the amount of the dispersant is 0.1-0.8 wt %; preferably, 0.1-0.6 wt %, based on the mass of the modified titanium dioxide.
  • the titanium dioxide powder before dispersion, is optionally treated by the following steps:
  • the titanium dioxide primary product is slurried with water, a dispersant is added, and the pH value is adjusted to 9.0-11.0 to obtain a slurry, wherein the dispersant is selected from the following group: sodium hexametaphosphate, sodium silicate, sodium polyacrylate, monoethanolamine, polyether polyol, or a combination thereof;
  • (Z2) fine grinding and screening fine grinding the slurry to obtain titanium dioxide slurry with a specific particle size by screening
  • step (Z3) Inorganic surface treatment: heating the slurry described in step (Z2) to 70-75° C., adding an alkaline inorganic surface treatment agent, adjusting the pH value of the system to 9.0-10.0 with an alkali solution, cooling to 60-65° C., adding an acidic inorganic surface treatment agent, and adjusting the pH value to 6.5-7.5 to obtain a second slurry;
  • the alkaline inorganic surface treatment agent is selected from the following group: sodium aluminate, sodium silicate, sodium hydroxide, or a combination thereof.
  • the acidic inorganic surface treatment agent is selected from the following group: aluminum sulfate, dilute sulfuric acid, or a combination thereof.
  • the alkali solution is selected from the following group: potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, triethanolamine aqueous solution, arginine solution, or a combination thereof.
  • step (Z3) the slurry is heated to 60-90°C, preferably 70°C.
  • the moisture content of the dried filter cake is less than 0.5%, preferably, less than 0.3%.
  • the inorganic surface treatment agent is selected from the following group: aluminum-containing compounds, silicon-containing compounds, or a combination thereof.
  • the aluminum-containing compound is selected from the following group: aluminum hydroxide, aluminum oxide, or a combination thereof.
  • the ninth invention of the present invention provides a dispersion comprising: the modified titanium dioxide as described in the seventh aspect of the present invention and a dispersion medium.
  • the dispersion medium is selected from the following group: water, silicone oil, or a combination thereof.
  • the tenth aspect of the present invention provides an emulsion comprising the following components:
  • 0.1-25 parts by mass of the titanium dioxide as described in the seventh aspect of the present invention 0.1-5 parts by mass of an emulsifier, 1-40 parts by mass of silicone oil, 1-30 parts by mass of an emollient, 1-60 parts by mass of deionized water, 1-15 parts by mass of a humectant, and 0.1-2 parts by mass of a preservative, wherein the particle size D50 of the titanium dioxide is 100-400 nm.
  • the emulsifier is selected from the following group: polyglycerol esters, sorbitan fatty acid ester series, sorbitan cocoate, sucrose fatty acid esters, alkyl glycosides, hydrogenated lecithin, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyethers, glycerol caprylate/caprate, or a combination thereof.
  • the silicone oil is selected from the following group: cyclopentasiloxane, polydimethylsiloxane, phenyl trimethicone, or a combination thereof.
  • the emollient is selected from the following group: isotridecyl isononanoate, tridecyl trimellitate, caprylic capric triglyceride, tocopheryl acetate, isononyl isononanoate, isodecyl neopentanoate, squalane, jojoba oil, ethylhexyl methoxycinnamate, or a combination thereof.
  • the moisturizing agent is selected from the following group: glycerin, butylene glycol, propylene glycol, polyethylene glycol, polysaccharides, panthenol, sodium hyaluronate, or a combination thereof.
  • the preservative is selected from the following group: caprylyl glycol, phenoxyethanol, ethylhexylglycerin, hexylene glycol, pentylene glycol, or a combination thereof.
  • a sunscreen product comprising the modified titanium dioxide according to the seventh aspect of the present invention, wherein the particle size D50 of the titanium dioxide is 100-200 nm.
  • the twelfth aspect of the present invention provides a cosmetic comprising the modified titanium dioxide described in the seventh aspect of the present invention.
  • FIG. 1 is a particle size distribution diagram of crude titanium dioxide measured by laser diffraction.
  • FIG. 2 is a particle size distribution diagram of the phosphorylcholine polymer modified titanium dioxide prepared in Example 1.
  • FIG. 3 is a particle size distribution diagram of the phosphorylcholine polymer modified titanium dioxide prepared in Example 2.
  • the inventors have developed a titanium dioxide organically modified with a phosphorylcholine polymer for the first time after extensive and in-depth research and a large number of experiments.
  • the titanium dioxide of the present invention has a simple preparation method, high dispersibility, water-oil affinity, and high emulsification stability. Depending on the size of the titanium dioxide, it can be used as a sunscreen and/or lotion and other cosmetics. On this basis, the present invention is completed.
  • colorant is a material that provides color to cosmetics.
  • concealing agent is a substance that provides covering ability to cosmetics, so that the cosmetics have the function of covering blemishes or spots on the skin surface.
  • sunscreen is the ability to provide sun protection for cosmetics, so that the cosmetics have the functions of absorbing, reflecting, and scattering ultraviolet rays, protecting the skin from sunburn, etc.
  • high and low temperature cycle test a test to observe the stability of the sample by placing the test sample in a variable temperature constant temperature and humidity test box equipment, with high temperature (about 40-60°C) to low temperature (-25-0°C) and then to high temperature (about 40-60°C) as a cycle.
  • emulsifiers are organic molecules with a hydrophilic group at one end and a lipophilic group at the other end. Molecules with this structure can connect oil and water to form a relatively stable system, so they are called emulsifiers.
  • the phosphorylcholine polymer contains (a) a hydrophilic group and (b) a hydrophobic group.
  • the hydrophilic group contains a branched structure represented by Formula II:
  • R 1 , R 2 and R 3 are independently selected from: H, C1-C4 alkyl, C3-C4 cycloalkyl.
  • the main chain unit of the phosphorylcholine polymer is selected from the following group:
  • the phosphorylcholine group shown in formula II is connected to the main chain through -CO-O-CH 2 -CH 2 -, -CO-O-CH 2 -CH 2 -O-, and/or -CO-O-(CH 2 )m-CH 2 -, wherein m is a positive integer of 2-17.
  • the main chain is selected from the following group:
  • the phosphorylcholine polymer is selected from: 2-methacryloyloxyethyl phosphorylcholine homopolymer, a copolymer of 2-methacryloyloxyethyl phosphorylcholine and other hydrophilic and/or hydrophobic monomers or a combination thereof, polyphosphorylcholine glycol acrylate, polyphosphorylcholine n-butyl methacrylate, or a combination thereof.
  • the present invention also aims to provide a method for preparing phosphorylcholine polymer modified inorganic powder.
  • the phosphorylcholine polymer-modified inorganic powder of the present invention can be prepared by the following method, however, the conditions of the method, such as reactants, solvents, bases, amounts of the compounds used, reaction temperature, time required for the reaction, etc. are not limited to the following explanations.
  • the preparation method provided by the present invention comprises the steps of:
  • (I) is a dry preparation method, comprising the following steps:
  • (II) is a wet preparation method, comprising the following steps:
  • (C) Dispersion premixing premixing the inorganic powder with a dispersant to obtain an inorganic powder dispersion slurry
  • the first solvent is mixed with the inorganic powder dispersion slurry by a constant flow pump under ultra-high speed stirring.
  • the first solvent is selected from the group consisting of water, C1-C6 alcohol solvents, C2-C6 ketone solvents, or a combination thereof.
  • the first solvent is selected from the group consisting of water, ethanol, isopropanol, polyethylene glycol, isopropyl ketone, or a combination thereof.
  • step (D) the stirring temperature is controlled below 55°C.
  • step (E) the moisture content of the dried filter cake is less than 0.3%; preferably, less than 0.2%.
  • the amount of the phosphorylcholine polymer is 0.01-3 wt %; preferably, 0.1-1 wt %, based on the mass of the modified inorganic powder.
  • the amount of the dispersant is 0.1-0.8 wt %; preferably, 0.1-0.6 wt %, based on the mass of the modified inorganic powder.
  • the inorganic powder before dispersion, is optionally subjected to a treatment comprising the following steps:
  • (z1) beating and dispersing the inorganic powder is beaten with water, a dispersant is added, and the pH value is adjusted to 9.0-11.0 to obtain a slurry, wherein the dispersant is selected from the group consisting of sodium hexametaphosphate, sodium silicate, sodium polyacrylate, monoethanolamine, polyether polyol, or a combination thereof;
  • step (z3) Inorganic surface treatment: heating the slurry described in step (z2) to 70-75° C., adding an alkaline inorganic surface treatment agent, adjusting the pH value of the system to 9.0-10.0 with an alkali solution, cooling to 60-65° C., adding an acidic inorganic surface treatment agent, and adjusting the pH value to 6.5-7.5 to obtain a second slurry;
  • the alkaline inorganic surface treatment agent is selected from the following group: sodium aluminate, sodium silicate, sodium hydroxide, or a combination thereof.
  • the acidic inorganic surface treatment agent is selected from the following group: aluminum sulfate, dilute sulfuric acid, or a combination thereof.
  • the alkali solution is selected from the group consisting of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, triethanolamine aqueous solution, arginine solution, or a combination thereof.
  • step (z3) the slurry is heated to 60-90°C, preferably 70°C.
  • the moisture content of the dried filter cake is less than 0.5%, preferably, less than 0.3%.
  • the inorganic surface treatment agent is selected from the following group: aluminum-containing compounds, silicon-containing compounds, or a combination thereof.
  • the aluminum-containing compound is selected from the group consisting of aluminum hydroxide, aluminum oxide, or a combination thereof.
  • the present invention also aims to provide a method for preparing phosphorylcholine polymer modified titanium dioxide.
  • the phosphorylcholine polymer modified titanium dioxide of the present invention can be prepared by the following method, however, the conditions of the method, such as reactants, solvents, bases, amounts of the compounds used, reaction temperature, time required for the reaction, etc. are not limited to the following explanation.
  • the preparation method provided by the present invention comprises the steps of:
  • a dry preparation method comprising the following steps:
  • step (d) the first solvent is mixed with the titanium dioxide dispersion slurry by a constant flow pump under ultra-high speed stirring.
  • the first solvent is selected from the following group: water, C1-C6 alcohol solvents, C2-C6 ketone solvents, or a combination thereof; preferably, the first solvent is selected from the following group: water, ethanol, isopropanol, polyethylene glycol, isopropyl ketone, or a combination thereof.
  • step (d) the stirring temperature is controlled below 55°C.
  • the moisture content of the dried filter cake is less than 0.3%; preferably, less than 0.2%.
  • the amount of the phosphorylcholine polymer is 0.01-3 wt %; preferably, 0.1-1 wt %, based on the mass of the modified titanium dioxide.
  • the amount of the dispersant is 0.1-0.8 wt %; preferably, 0.1-0.6 wt %, based on the mass of the modified titanium dioxide.
  • the titanium dioxide powder before dispersion, is optionally treated by the following steps:
  • the titanium dioxide primary product is slurried with water, a dispersant is added, and the pH value is adjusted to 9.0-11.0 to obtain a slurry, wherein the dispersant is selected from the following group: sodium hexametaphosphate, sodium silicate, sodium polyacrylate, monoethanolamine, polyether polyol, or a combination thereof;
  • (Z2) fine grinding and screening fine grinding the slurry to obtain titanium dioxide slurry with a specific particle size by screening
  • step (Z3) Inorganic surface treatment: heating the slurry described in step (Z2) to 70-75° C., adding an alkaline inorganic surface treatment agent, adjusting the pH value of the system to 9.0-10.0 with an alkali solution, cooling to 60-65° C., adding an acidic inorganic surface treatment agent, and adjusting the pH value to 6.5-7.5 to obtain a second slurry;
  • the alkaline inorganic surface treatment agent is selected from the following group: sodium aluminate, sodium silicate, sodium hydroxide, or a combination thereof.
  • the acidic inorganic surface treatment agent is selected from the following group: aluminum sulfate, dilute sulfuric acid, or a combination thereof.
  • the alkali solution is selected from the group consisting of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, triethanolamine aqueous solution, arginine solution, or a combination thereof.
  • step (Z3) the slurry is heated to 60-90°C, preferably 70°C.
  • the moisture content of the dried filter cake is less than 0.5%, preferably, less than 0.3%.
  • the inorganic surface treatment agent is selected from the following group: aluminum-containing compounds, silicon-containing compounds, or a combination thereof.
  • the aluminum-containing compound is selected from the group consisting of aluminum hydroxide, aluminum oxide, or a combination thereof.
  • Example 1 Operation process of dry organic surface treatment
  • (a) Dispersing titanium dioxide powder 99.7 parts by weight of crude titanium dioxide is slurried with water to form a 300-600 g/L aqueous solution, and then 0.15% wt (based on the mass of titanium dioxide) of sodium hexametaphosphate is added, and the slurry after slurrying is further finely ground to obtain titanium dioxide slurry with a particle size of less than 45 ⁇ m; wherein the crude titanium dioxide is in granular or powdery form, slightly yellow in color, and agglomerated.
  • step (b) Organic surface treatment: 0.3 parts by mass of phosphorylcholine polymer is dissolved in a solvent prepared by mixing water, ethanol and isopropanol in a mass ratio of 1:1:0.2, and the solvent is added to the titanium dioxide dispersion obtained in step (a) by a constant flow pump under ultra-high-speed stirring, and stirred continuously to obtain a first slurry;
  • Example 3 Referring to the steps in Example 2 and the amounts used refer to Table 1, phosphorylcholine polymer modified titanium dioxide was obtained.
  • Example 4 Operation process of inorganic surface treatment
  • step (c) Inorganic surface treatment: The slurry described in step (b) is heated to about 70°C, sodium aluminate, an alkaline inorganic surface treatment agent, is added, the pH value of the system is adjusted to 9.0-10.0 with an aqueous sodium hydroxide solution, stirred evenly, and then cooled to about 60°C. Aluminum sulfate was added, the pH value was maintained at 5.0-6.0, and the pH value was adjusted to 6.5-7.5 after stirring evenly to obtain a second slurry;
  • a scraper fineness meter was used as a tool, and titanium dioxide with a solid content of 15% was prepared with different dispersion media (deionized water and silicone oil). After being dispersed using a fixed process, a dispersibility test was performed.
  • the results show that compared with the control example, the titanium dioxide group treated with phosphorylcholine polymer organic surface has a significant improvement in fineness results; at the same time, the higher the amount of phosphorylcholine polymer added, the greater the fineness of the titanium dioxide, and the better the dispersibility.
  • dry organic surface treatment and wet organic surface treatment have little effect on the fineness results of titanium dioxide.
  • titanium dioxide treated with aluminum hydroxide inorganic surface has a slight improvement in fineness results.
  • titanium dioxide treated with phosphorylcholine polymer organic surface has better dispersibility.
  • the results show that the phosphorylcholine polymer itself has no sun protection ability.
  • the sun protection index of titanium dioxide is significantly improved after the organic surface treatment of phosphorylcholine polymer, with an average increase of nearly 25%; at the same time, the higher the amount of phosphorylcholine polymer added, the higher the sun protection index.
  • dry organic surface treatment and wet organic surface treatment have little effect on the sun protection effect of titanium dioxide.
  • the titanium dioxide treated with wet organic surface has an increase of about 2-3% in sun protection index.
  • the organic surface modification of phosphorylcholine polymer can improve the sun protection ability of titanium dioxide.
  • emulsions were prepared using the modified titanium dioxide prepared in Examples 1-6 and Comparative Examples 1-2, and stability tests and skin feel tests were performed.
  • the prepared emulsion was subjected to a high and low temperature cycle test at -20°C to 55°C to observe how many cycles it takes for the emulsion to produce oil or break.
  • the results show that compared with the control example, the titanium dioxide group with organic surface treatment of phosphorylcholine polymer has a significant improvement in stability.
  • the titanium dioxide with wet organic surface treatment has a slight improvement in stability test results compared with the titanium dioxide with dry organic surface treatment; at the same time, compared with the titanium dioxide without inorganic surface treatment, the stability of the titanium dioxide group with inorganic surface treatment of aluminum hydroxide is slightly improved.
  • titanium dioxide with organic surface treatment of phosphorylcholine polymer can improve the stability of cosmetics in practical applications.
  • the lotion was distributed to 10 test volunteers, and their skin feel was scored on a scale of 1-10, with 1 being the worst and 10 being the best.
  • the results show that compared with the control group, the titanium dioxide group treated with the organic surface of phosphorylcholine polymer has a significant improvement in skin feel.
  • the higher the amount of phosphorylcholine polymer added the better the skin feel of the product.
  • dry organic surface treatment and wet organic surface treatment have little effect on the skin feel of titanium dioxide.
  • the skin feel of the titanium dioxide group treated with aluminum hydroxide inorganic surface treatment is slightly improved.
  • titanium dioxide treated with the organic surface of phosphorylcholine polymer can improve the skin feel of cosmetics in practical applications.
  • the various evaluation results of the titanium dioxide prepared in Examples 1-6 are better than those of the corresponding Comparative Examples 1 and 2. It can be seen that, compared with the titanium dioxide that has not been organically surface treated with the phosphorylcholine polymer, the titanium dioxide that has been organically surface treated with the phosphorylcholine polymer (whether by a wet process or a dry process), whether or not it has been inorganically surface treated, has better dispersibility and sunscreen ability, better stability in the formula, and better skin feel, and as the content of the phosphorylcholine polymer increases, various parameters are improved.

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Abstract

La présente invention concerne un procédé de traitement d'une poudre inorganique en vue de l'obtention d'une surface organique faisant appel à un polymère de phosphorylcholine. Plus précisément, la présente invention concerne une poudre inorganique modifiée par un polymère de phosphorylcholine et son procédé de préparation, concerne un dioxyde de titane modifié par un polymère de phosphorylcholine et son procédé de préparation, et concerne également des dispersions, des émulsions, des écrans solaires et des produits cosmétiques contenant la poudre inorganique modifiée par un polymère de phosphorylcholine ou le dioxyde de titane modifié par un polymère de phosphorylcholine. Grâce au procédé de traitement d'une poudre inorganique en vue de l'obtention d'une surface organique faisant appel à un polymère de phosphorylcholine selon la présente invention, une poudre inorganique ou du dioxyde de titane ayant été traité en vue de l'obtention d'une surface organique à l'aide du polymère de phosphorylcholine présente de meilleures performances de dispersion, une meilleure capacité de protection solaire et une meilleure stabilité, et présente également une meilleure sensation cutanée.
PCT/CN2023/126416 2022-10-26 2023-10-25 Procédé de traitement d'une poudre inorganique en vue de l'obtention d'une surface organique faisant appel à un polymère de phosphorylcholine Ceased WO2024088297A1 (fr)

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CN116492231B (zh) * 2023-04-04 2024-10-29 广东工业大学 一种可自转变的改性片状氧化锌及其制备方法和应用
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