Modified titanium dioxide and its preparation method and application

Abstract

The invention discloses a modified titanium dioxide and a preparation method and application thereof, belonging to the technical field of cosmetics, comprising the following components in percentage by mass: 60-77.5% of titanium dioxide powder, 1-3% of polydimethylsiloxane, 1.5-4% of a wetting agent, 18-26% of a surface treatment agent, and 2-7% of tetrahydroxypropylethylenediamine. The invention adopts polydimethylsiloxane, a wetting agent, a surface treatment agent, and tetrahydroxypropylethylenediamine to modify the titanium dioxide powder, thereby obtaining the modified titanium dioxide with high solid content, high density, good dispersibility, excellent stability, and storage resistance (storing for two years at room temperature and away from light in a sealed manner without precipitation, without obvious secondary polymerization, without volatilization of the dispersant, and without obvious weight change). The modified titanium dioxide of the invention is applied to cosmetics, has excellent dispersibility and color development performance, and when applied to sunscreen cosmetics, can effectively improve the SPF value, and has broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of cosmetics, and in particular to modified titanium dioxide and a preparation method and application thereof. Background Art

[0002] On February 18, 2020, the European Union published an official delegated regulation classifying titanium dioxide as a suspected carcinogen by inhalation, in accordance with European Regulation (EC) No 1272 / 2008 on the classification, labelling and packaging (CLP) of substances and mixtures.

[0003] Titanium dioxide has excellent sun protection, whitening, blemish concealing and oil control effects and is widely used in cosmetics. In the prior art, titanium dioxide is directly added to cosmetics. However, directly adding titanium dioxide to cosmetics has the following disadvantages: ① The production process generates serious dust, which is prone to inhalation by operators; ② The powder has a low bulk density, and commercially available products are generally between 0.5-0.8g / mL, which takes up a lot of space for transportation and storage. Making titanium dioxide powder into titanium dioxide slurry that is not prone to dust is not only environmentally friendly and beneficial to workers' health, but also greatly improves dispersibility.

[0004] CN102228412A discloses a nano titanium dioxide oil phase dispersion sunscreen concentrate and its preparation method and application, which is composed of the following substances by weight: (a) 35-60% nano titanium dioxide; (b) 30-62% organic solvent, the organic solvent is one or more selected from dimethyl polysiloxane, cyclopentasiloxane, alkyl benzoate, caprylic triglyceride and capric triglyceride; and (c) 1-10% dispersing aid. It improves the dispersibility of titanium dioxide by adding a large amount of organic solvent and dispersing aid, but the amount of organic solvent added is too large, resulting in insufficient storage stability, easy separation and oiling between titanium dioxide and organic solvent, which limits its application.

[0005] CN 112603838 A discloses a nano titanium dioxide oil slurry and a preparation method and application thereof. Titanium dioxide is modified by PEG-9 polydimethylsiloxyethyl polydimethylsiloxane and triethoxyoctylsilane, and then the modified nano titanium dioxide is mixed with PEG-9 polydimethylsiloxyethyl polydimethylsiloxane and polydimethylsiloxane for sand grinding to obtain the nano titanium dioxide oil slurry. However, the effective content of titanium dioxide is low, which is only 40% to 55% (actually lower than 40% to 55%), resulting in a low solid content. At the same time, more than 40% of polydimethylsiloxane is added to the oil slurry, resulting in insufficient storage stability, and easy separation and oiling between titanium dioxide and organic solvent.

[0006] In view of this, this application is filed. Summary of the invention

[0007] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a modified titanium dioxide and a preparation method and application thereof. The modified titanium dioxide has high solid content, high density, good dispersibility, excellent stability, storage resistance, excellent dispersibility and color development properties. When used in sunscreen cosmetics, it can effectively improve the SPF value and has broad application prospects.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] A modified titanium dioxide comprises the following components in percentage by weight: 60-77.5% titanium dioxide powder, 1-3% polydimethylsiloxane, 1.5-4% wetting agent, 18-26% surface treatment agent, and 2-7% tetrahydroxypropylethylenediamine;

[0010] The surface treatment agent includes at least one of polyglyceryl-2 triisostearate, polyglyceryl-2 diisostearate, polyglyceryl-2 tetraisostearate, polyglyceryl-2 isostearate, polyglyceryl-3 isostearate, polyglyceryl-3 diisostearate, and polyglyceryl-4 isostearate.

[0011] As a preferred embodiment of the present invention, the modified titanium dioxide comprises the following components in percentage by mass: 64-72.5% titanium dioxide powder, 2-2.5% polydimethylsiloxane, 2.5-3.5% wetting agent, 20-25% surface treatment agent, and 3-5% tetrahydroxypropylethylenediamine.

[0012] As a preferred embodiment of the present invention, the wetting agent includes at least one of trisiloxane and trimethylpentaphenyltrisiloxane.

[0013] As a preferred embodiment of the present invention, the kinematic viscosity of the polydimethylsiloxane at 25° C. is 50 to 1000 cst.

[0014] As a preferred embodiment of the present invention, the kinematic viscosity of the polydimethylsiloxane at 25° C. is 200 to 500 cst.

[0015] As a preferred embodiment of the present invention, the mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the A and B satisfy: A <B。

[0016] As a preferred embodiment of the present invention, the mass percentage of the surface treatment agent is C, and A, B, and C satisfy: 3.5≤C / (A+B)≤5.2.

[0017] As a preferred embodiment of the present invention, A, B, and C satisfy: 3.5≤C / (A+B)≤4.5.

[0018] The present invention also provides a method for preparing modified titanium dioxide, comprising the following steps:

[0019] The titanium dioxide powder and polydimethylsiloxane are uniformly mixed, ground, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0020] The polydimethylsiloxane-coated titanium dioxide and the surface treatment agent are mixed evenly, and then a wetting agent and tetrahydroxypropylethylenediamine are added, mixed evenly, and ground to obtain modified titanium dioxide.

[0021] The present invention also provides an application of the modified titanium dioxide in the preparation of cosmetics.

[0022] The beneficial effects of the present invention are as follows: the present invention adopts polydimethylsiloxane, a wetting agent, a surface treatment agent, and tetrahydroxypropylethylenediamine to modify titanium dioxide powder, thereby obtaining modified titanium dioxide with high solid content, high density, good dispersibility, excellent stability, and storage resistance (storage at room temperature and light-proof for two years without precipitation, no obvious secondary polymerization, no volatilization of the dispersant, and no obvious change in weight). The modified titanium dioxide of the present invention is applied to cosmetics, has excellent dispersibility and color development performance, and when applied to sunscreen cosmetics, can effectively improve the SPF value, and has broad application prospects. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0024] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0025] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0026] Unless otherwise specified, the components, raw materials or instruments used in the embodiments and comparative examples of the present invention are all commercially available raw materials or instruments, and the components and raw materials used in each parallel experiment are all of the same type, and the grinding and stirring methods in the preparation process of titanium dioxide are the same.

[0027] The titanium dioxide powder of the present invention was purchased from Tayca Company.

[0028] 50cst polydimethylsiloxane, 200cst polydimethylsiloxane, 500cst polydimethylsiloxane and 1000cst polydimethylsiloxane are all from DOWSIL (Dow Chemical).

[0029] Trisiloxane comes from Dow Corning (Guangzhou Wanlu Chemical Agent), XIAMETER TM PMX-200 / 1CS.

[0030] Polyglyceryl-2 triisostearate comes from NISSHIN OILLIO.

[0031] The embodiment of the present application provides a modified titanium dioxide, comprising the following components in percentage by weight: 60-77.5% titanium dioxide powder, 1-3% polydimethylsiloxane, 1.5-4% wetting agent, 18-26% surface treatment agent, and 2-7% tetrahydroxypropyl ethylenediamine;

[0032] The surface treatment agent includes at least one of polyglyceryl-2 triisostearate, polyglyceryl-2 diisostearate, polyglyceryl-2 tetraisostearate, polyglyceryl-2 isostearate, polyglyceryl-3 isostearate, polyglyceryl-3 diisostearate, and polyglyceryl-4 isostearate.

[0033] The present invention creatively adopts polydimethylsiloxane, a wetting agent, a surface treatment agent, and tetrahydroxypropylethylenediamine to modify titanium dioxide powder, thereby obtaining modified titanium dioxide with high solid content, high density, good dispersibility, excellent stability, and storage resistance (storage at room temperature and light-proof for two years without precipitation, no obvious secondary polymerization, no volatilization of the dispersant, and no obvious change in weight). The modified titanium dioxide of the present invention is applied to cosmetics, has excellent dispersibility and color development performance, and when applied to sunscreen cosmetics, can effectively improve the SPF value, and has broad application prospects.

[0034] The polydimethylsiloxane of the present invention has a physical covering effect on the polar groups on the surface of titanium dioxide, and can reduce its surface activity. Since the amount of polydimethylsiloxane used in the present invention is 1-3%, part of the titanium dioxide is not completely wrapped, and the exposed surface of the titanium dioxide that is not completely covered has a negative charge. Tetrahydroxypropylethylenediamine has multiple hydroxyl and amino groups, and is a positively charged molecule with high steric hindrance. When adsorbed on the exposed surface of titanium dioxide, it gives the titanium dioxide the same positive charge, and prevents powder aggregation through charge repulsion. Therefore, the present invention controls the amount of polydimethylsiloxane and tetrahydroxypropylethylenediamine, so that part of the titanium dioxide is physically covered by polydimethylsiloxane, and another part of the titanium dioxide is adsorbed by tetrahydroxypropylethylenediamine. The two work together to effectively reduce its surface activity, and prevent powder aggregation through charge repulsion, effectively improve the dispersibility and stability of titanium dioxide, and prevent it from agglomerating. The surface treatment agent has isostearic acid chains and polyglycerol chains, and the isostearic acid chains have excellent compatibility with the polydimethylsiloxane coated on the surface of titanium dioxide. The polyglycerol chain has excellent compatibility with the hydroxyl group of tetrahydroxypropylethylenediamine, forming a better coating effect on titanium dioxide particles, further improving the dispersibility and stability of titanium dioxide. The wetting agent has excellent surface wetting and viscosity reduction effects, which can make the material viscosity lower, the uniformity lower, and the surface more glossy. The present invention effectively improves the dispersibility and stability of titanium dioxide through the joint action of polydimethylsiloxane, wetting agent, surface treatment agent, and tetrahydroxypropylethylenediamine, significantly improves the storage resistance and color development performance, and can effectively improve the SPF value.

[0035] The inventors explored the dosage of each raw material. Based on the complex mechanism of action of the present invention and the high addition amount of titanium dioxide (60-77.5%), the dosage of each raw material has a great influence on the dispersibility, stability and color development performance of titanium dioxide. If the dosage of titanium dioxide powder is too low (less than 60%), the solid content is too low and the storage resistance is reduced. If the dosage of titanium dioxide powder is too high (greater than 77.5%), the sample is rough, the dispersibility is reduced, and it is easy to agglomerate. If the dosage of polydimethylsiloxane is too low, the surface activity of titanium dioxide cannot be effectively improved, and titanium dioxide is not Stable and easy to stratify. If the dosage of polydimethylsiloxane is too high, it is easy to produce oil and stratify; if the dosage of the wetting agent is too low, the consistency of the material is too high and it is difficult to obtain effective grinding. If the dosage of the wetting agent is too high, the modified titanium dioxide will be rough, stratified, and oily; if the dosage of the surface treatment agent is too low, the sample will be rough, too thick, and have poor dispersibility. If the dosage is too high, it will cause oil and stratification; if the dosage of tetrahydroxypropylethylenediamine is too low, the sample will be rough and the powder will agglomerate. If the dosage of tetrahydroxypropylethylenediamine is too high, the sample will be rough, agglomerated, and oily. Therefore, in the present invention, it is necessary to strictly control the dosage of each raw material.

[0036] Among them, the titanium dioxide in the present invention is the conventional titanium dioxide in the art, and the representative ones are MT-100TV, MT-100Z, MT-10EX, and MT-700Z of Tayca Corporation.

[0037] The average particle size of the titanium dioxide is 10-100 nm.

[0038] Among them, trisiloxane is included in the "List of Names of Cosmetic Ingredients in Use (2021 Edition)", with the serial number 05751 and the CAS number 107-51-7.

[0039] In one of the embodiments, the modified titanium dioxide comprises the following components in mass percentage: 64-72.5% titanium dioxide powder, 2-2.5% polydimethylsiloxane, 2.5-3.5% wetting agent, 20-25% surface treatment agent, 3-5% tetra-hydroxypropyl ethylenediamine. Especially when the dosage of each raw material is within this range, the dispersibility, stability and color development performance are better.

[0040] In one of the embodiments, the wetting agent comprises at least one of trisiloxane and trimethylpentaphenyltrisiloxane. By adopting such a wetting agent, the surface of the powder can be effectively wetted, playing an excellent viscosity reduction role, reducing the viscosity of the system, improving the uniformity of titanium dioxide, and making its surface more shiny.

[0041] In one of the embodiments, the kinematic viscosity of the polydimethylsiloxane at 25°C is 50-1000 cst. Using polydimethylsiloxane with 50-1000 cst has better fluidity, and the prepared modified titanium dioxide is more stable and has better dispersibility.

[0042] It should be noted that the polydimethylsiloxane of the present invention can be sourced from Dow Corning Corporation or Merck & Co., Inc.

[0043] Among them, 50 cst polydimethylsiloxane represents polydimethylsiloxane with a kinematic viscosity of 50 cst at 25°C, and other data can be inferred by analogy.

[0044] In one of the embodiments, the kinematic viscosity of the polydimethylsiloxane at 25°C is 200-500 cst.

[0045] In one of the embodiments, the mass percentage of the polydimethylsiloxane is A, and the mass percentage of the tetra-hydroxypropyl ethylenediamine is B, and A and B satisfy: A < B. In the present invention, by controlling the dosage of polydimethylsiloxane to be less than that of tetra-hydroxypropyl ethylenediamine, the physical coating amount of polydimethylsiloxane and the adsorption amount of tetra-hydroxypropyl ethylenediamine on titanium dioxide are controlled, so as to obtain modified titanium dioxide with better dispersibility, color development performance and stability.

[0046] In one embodiment, the mass percentage of the surface treatment agent is C, and A, B, and C satisfy: 2.6≤C / (A+B)≤5. The present invention controls the amount of polydimethylsiloxane, the amount of tetrahydroxypropylethylenediamine, and the amount of the surface treatment agent to satisfy this relationship, so that the isostearic acid chain of the surface treatment agent and the polydimethylsiloxane coated on the surface of titanium dioxide have better compatibility, and the polyglycerol chain and the hydroxyl group of tetrahydroxypropylethylenediamine have better compatibility, so that the system has better compatibility, can be better coated, and improve the intermolecular force, thereby further improving the dispersibility, color development performance and stability.

[0047] In one embodiment, A, B, and C satisfy: 3.5≤C / (A+B)≤4.5. Especially when controlled within this range, the dispersibility, color development performance, and stability are better.

[0048] An embodiment of the present application provides a method for preparing modified titanium dioxide, comprising the following steps:

[0049] The titanium dioxide powder and polydimethylsiloxane are uniformly mixed, ground, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0050] The polydimethylsiloxane-coated titanium dioxide and the surface treatment agent are mixed evenly, and then a wetting agent and tetrahydroxypropylethylenediamine are added, mixed evenly, and ground to obtain modified titanium dioxide.

[0051] It should be noted that the grinding mentioned in the present invention adopts three-roll mill grinding.

[0052] One embodiment of the present application provides an application of modified titanium dioxide in the preparation of cosmetics.

[0053] In one embodiment, the cosmetic is in the form of an aqueous solution, emulsion, cream, gel or mask.

[0054] In one embodiment, the cosmetic may contain excipients acceptable in the cosmetic field.

[0055] In one embodiment, the cosmetically acceptable excipients include, but are not limited to, at least one of moisturizers, emollients, emulsifiers, preservatives, antioxidants, pH adjusters, penetration enhancers, chelating agents, surfactants, flavors, and pigments.

[0056] In one embodiment, suitable moisturizers include, but are not limited to, at least one of sodium hyaluronate, panthenol, hydroxyethyl urea, polyethylene glycol, xylitol, maltose, sodium polyglutamate, erythritol, sorbitol, mannitol, glucose, lactose, betaine, inositol, trehalose, and hydrogenated starch hydrolysate.

[0057] In one embodiment, suitable emollients include, but are not limited to, at least one of isododecane, isohexadecane, caprylic / capric triglyceride, pentaerythrityl tetraisostearate, isononyl isononanoate, diisostearyl malate, phytosterols, macadamia oil, squalane, hexyl laurate, castor oil, hydrogenated polyisobutene, octyldodecanol, shea butter, dicaprylyl carbonate, jojoba oil, lanolin, sweet almond oil, dicaprylyl adipate, and coconut oil-caprylate / caprate.

[0058] In one embodiment, suitable emulsifiers include, but are not limited to, at least one of glyceryl stearate, polyglyceryl-10 stearate, polyglyceryl-10 laurate, polyglyceryl-10 myristate, polyglyceryl-5 trioleate, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PPG-13-decyltetradeceth-24, sodium stearoyl glutamate, steareth-2, steareth-21, and hydrogenated lecithin.

[0059] In one embodiment, suitable antioxidants include, but are not limited to, at least one of carotenoids, ascorbic acid and its derivatives, resveratrol, pentaerythritol tetra(di-tert-butylhydroxyhydrocinnamate), arbutin, tocopherol (vitamin E), and sodium metabisulfite.

[0060] In one embodiment, suitable pH adjusters include, but are not limited to, at least one of arginine, tromethamine, aminomethyl propanol, tetrahydroxypropyl ethylenediamine, triethanolamine, citric acid, sodium citrate, sodium hydroxide, and potassium hydroxide.

[0061] In one embodiment, suitable colorants include, but are not limited to, at least one of white, black, yellow, blue, green, pink, red, orange, purple, indigo, brown, and the like.

[0062] In one embodiment, suitable preservatives include, but are not limited to, at least one of p-hydroxyacetophenone, 1,2-hexanediol, 1,2-pentanediol, isopentyl glycol, ethylhexylglycerin, caprylyl glycol, chlorphenesin, methylparaben, potassium sorbate, sodium benzoate, phenoxyethanol, caprylhydroxamic acid, glyceryl caprylate, cetylpyridinium chloride, and cetrimide chloride.

[0063] The following examples are provided to facilitate understanding of the present invention. These examples are not provided to limit the scope of the claims.

[0064] Example 1

[0065] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 2.2% 200cst polydimethylsiloxane, 3% trisiloxane, 23.2% polyglycerol-2 triisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0066] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0067] In this embodiment, A <B,C / (A+B)=4。

[0068] The preparation method of the modified titanium dioxide comprises the following steps:

[0069] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0070] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0071] Example 2

[0072] A modified titanium dioxide comprises the following components in percentage by mass: 67% titanium dioxide powder, 2.1% 200cst polydimethylsiloxane, 3.3% trisiloxane, 24.3% polyglyceryl-2 triisostearate, and 3.3% tetrahydroxypropyl ethylenediamine.

[0073] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0074] In this embodiment, A <B,C / (A+B)=4.5。

[0075] The preparation method of the modified titanium dioxide comprises the following steps:

[0076] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0077] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0078] Example 3

[0079] A modified titanium dioxide comprises the following components in percentage by mass: 68.4% titanium dioxide powder, 2.4% 200cst polydimethylsiloxane, 2.8% trisiloxane, 22.4% polyglycerol-2 triisostearate, and 4% tetrahydroxypropyl ethylenediamine.

[0080] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0081] In this embodiment, A <B,C / (A+B)=3.5。

[0082] The preparation method of the modified titanium dioxide comprises the following steps:

[0083] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0084] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0085] Example 4

[0086] A modified titanium dioxide comprises the following components in percentage by mass: 67.5% titanium dioxide powder, 2% 200cst polydimethylsiloxane, 2.5% trisiloxane, 25% polyglyceryl-2 triisostearate, and 3% tetrahydroxypropyl ethylenediamine.

[0087] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0088] In this embodiment, A <B,C / (A+B)=5。

[0089] The preparation method of the modified titanium dioxide comprises the following steps:

[0090] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0091] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0092] Example 5

[0093] A modified titanium dioxide comprises the following components in percentage by mass: 69% titanium dioxide powder, 2.5% 200cst polydimethylsiloxane, 3.5% trisiloxane, 20% polyglyceryl-2 triisostearate, and 5% tetrahydroxypropyl ethylenediamine.

[0094] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0095] In this embodiment, A <B,C / (A+B)=2.67。

[0096] The preparation method of the modified titanium dioxide comprises the following steps:

[0097] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0098] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0099] Example 6

[0100] A modified titanium dioxide comprises the following components in percentage by mass: 77.5% titanium dioxide powder, 1% 200cst polydimethylsiloxane, 1.5% trisiloxane, 18% polyglyceryl-2 triisostearate, and 2% tetrahydroxypropyl ethylenediamine.

[0101] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0102] In this embodiment, A <B,C / (A+B)=6。

[0103] The preparation method of the modified titanium dioxide comprises the following steps:

[0104] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0105] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0106] Example 7

[0107] A modified titanium dioxide comprises the following components in percentage by mass: 65% titanium dioxide powder, 3% 200cst polydimethylsiloxane, 4% trisiloxane, 21% polyglyceryl-2 triisostearate, and 7% tetrahydroxypropyl ethylenediamine.

[0108] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0109] In this embodiment, A <B,C / (A+B)=2.1。

[0110] The preparation method of the modified titanium dioxide comprises the following steps:

[0111] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0112] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0113] Example 8

[0114] A modified titanium dioxide comprises the following components in percentage by mass: 65.4% titanium dioxide powder, 3% 200cst polydimethylsiloxane, 3.6% trisiloxane, 26% polyglyceryl-2 triisostearate, and 2% tetrahydroxypropyl ethylenediamine.

[0115] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0116] In this embodiment, B <A,C / (A+B)=5.2。

[0117] The preparation method of the modified titanium dioxide comprises the following steps:

[0118] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0119] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0120] Example 9

[0121] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 2.2% 500cst polydimethylsiloxane, 3% trisiloxane, 23.2% polyglyceryl-2 triisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0122] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0123] In this embodiment, A <B,C / (A+B)=4。

[0124] The preparation method of the modified titanium dioxide comprises the following steps:

[0125] The titanium dioxide powder and 500 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0126] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0127] Example 10

[0128] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 2.2% 50cst polydimethylsiloxane, 3% trisiloxane, 23.2% polyglycerol-2 triisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0129] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0130] In this embodiment, A <B,C / (A+B)=4。

[0131] The preparation method of the modified titanium dioxide comprises the following steps:

[0132] The titanium dioxide powder and 50 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0133] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0134] Embodiment 11

[0135] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 2.2% 1000cst polydimethylsiloxane, 3% trisiloxane, 23.2% polyglycerol-2 triisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0136] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 triisostearate is C.

[0137] In this embodiment, A <B,C / (A+B)=4。

[0138] The preparation method of the modified titanium dioxide comprises the following steps:

[0139] The titanium dioxide powder and 1000 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0140] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0141] Example 12

[0142] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 2.2% 200cst polydimethylsiloxane, 3% trisiloxane, 23.2% polyglyceryl-2 diisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0143] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the polyglyceryl-2 diisostearate is C.

[0144] In this embodiment, A <B,C / (A+B)=4。

[0145] The preparation method of the modified titanium dioxide comprises the following steps:

[0146] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0147] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 diisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0148] Comparative Example 1

[0149] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not contain polydimethylsiloxane, and the other contents are the same.

[0150] A modified titanium dioxide comprises the following components in percentage by mass: 70.2% titanium dioxide powder, 3% trisiloxane, 23.2% polyglycerol-2 triisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0151] The preparation method of the modified titanium dioxide comprises the following steps:

[0152] The titanium dioxide powder and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine are added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0153] Comparative Example 2

[0154] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 does not contain tetrahydroxypropylethylenediamine, and the other contents are the same.

[0155] A modified titanium dioxide comprises the following components in percentage by mass: 71.6% titanium dioxide powder, 2.2% 200cst polydimethylsiloxane, 3% trisiloxane, and 23.2% polyglycerol-2 triisostearate.

[0156] The preparation method of the modified titanium dioxide comprises the following steps:

[0157] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0158] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane is added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0159] Comparative Example 3

[0160] The difference between Comparative Example 3 and Example 1 is that Comparative Example 3 does not contain polydimethylsiloxane, and an equal amount of tetrahydroxypropylethylenediamine is used to replace polydimethylsiloxane, and the other contents are the same.

[0161] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 3% trisiloxane, 23.2% polyglycerol-2 triisostearate, and 5.8% tetrahydroxypropyl ethylenediamine.

[0162] The preparation method of the modified titanium dioxide comprises the following steps:

[0163] Titanium dioxide powder, 200 cst and polyglyceryl-2 triisostearate were mixed evenly, and then trisiloxane and tetrahydroxypropyl ethylenediamine were added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0164] Comparative Example 4

[0165] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 does not contain tetrahydroxypropylethylenediamine, and an equal amount of polydimethylsiloxane is used to replace tetrahydroxypropylethylenediamine, and the other contents are the same.

[0166] A modified titanium dioxide comprises the following components in percentage by mass: 68% titanium dioxide powder, 5.8% 200cst polydimethylsiloxane, 3% trisiloxane, and 23.2% polyglycerol-2 triisostearate.

[0167] The preparation method of the modified titanium dioxide comprises the following steps:

[0168] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0169] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then trisiloxane is added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0170] Comparative Example 5

[0171] The difference between Comparative Example 5 and Example 1 is that Comparative Example 5 does not contain trisiloxane, and the other contents are the same.

[0172] A modified titanium dioxide comprises the following components in percentage by mass: 71% titanium dioxide powder, 2.2% 200cst polydimethylsiloxane, 23.2% polyglycerol-2 triisostearate, and 3.6% tetrahydroxypropyl ethylenediamine.

[0173] The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the surface treatment agent is C.

[0174] In this embodiment, A <B,C / (A+B)=4。

[0175] The preparation method of the modified titanium dioxide comprises the following steps:

[0176] The titanium dioxide powder and 200 cst polydimethylsiloxane were mixed evenly, ground evenly with a three-roll mill, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder;

[0177] The polydimethylsiloxane-coated titanium dioxide and polyglyceryl-2 triisostearate are mixed evenly, and then tetrahydroxypropyl ethylenediamine is added, mixed evenly, and ground evenly with a three-roll mill to obtain modified titanium dioxide.

[0178] Comparative Example 6

[0179] The difference between Comparative Example 6 and Example 1 is that Comparative Example 6 uses an equal amount of glycerol glucoside (polyhydroxy compound) to replace tetrahydroxypropylethylenediamine, and the other parts are the same.

[0180] Comparative Example 7

[0181] The difference between Comparative Example 7 and Example 1 is that Comparative Example 7 uses an equal amount of polyhydroxystearic acid to replace polyglyceryl-2 triisostearate, and the other contents are the same.

[0182] Comparative Example 8

[0183] The difference between Comparative Example 8 and Example 1 is that the amount of raw materials used in Comparative Example 8 is different from that in Example 1, and the others are the same.

[0184] A modified titanium dioxide comprises the following components in percentage by mass: 81.7% titanium dioxide powder, 0.8% 200cst polydimethylsiloxane, 1% trisiloxane, 15% polyglyceryl-2 triisostearate, and 1.5% tetrahydroxypropyl ethylenediamine.

[0185] Comparative Example 9

[0186] The difference between Comparative Example 9 and Example 1 is that the amount of raw materials used in Comparative Example 9 is different from that in Example 1, and the others are the same.

[0187] A modified titanium dioxide comprises the following components in percentage by mass: 55% titanium dioxide powder, 4% 200cst polydimethylsiloxane, 5% trisiloxane, 28% polyglyceryl-2 triisostearate, and 8% tetrahydroxypropyl ethylenediamine.

[0188] Test Case

[0189] Test 1. Centrifugation experiment

[0190] The samples were centrifuged to simulate gravity settling over time at 5000 RPM for 5 hours.

[0191] Test 2. Comparative experiment on dispersibility of cosmetics (SPF parameter test)

[0192] Sample preparation: Based on titanium dioxide, take an appropriate amount of the prepared slurry to prepare a sunscreen with a titanium dioxide solid content of 16% as the sample to be tested;

[0193] According to standard ISO 24443, the instrument selected is: UV-2000S, brand: Labsphere Optics.

[0194] 1. Operation method

[0195] 1.1 Turn on the power and allow the instrument to preheat for 20 minutes.

[0196] 1.2 Use a pipette to weigh an appropriate amount of the sample to be tested, and apply it evenly on the PMMA substrate with a seamless powder-free finger cot. Let it stand in a dark room for 15-20 minutes until the material solidifies.

[0197] 1.3 Push the sample to be tested into the optical path and test five points on the PMMA substrate. The average SPF value of the five points is the SPF value of the test sample.

[0198] Table 1

[0199] Centrifuge test SPF value Example 1 No stratification 52.2 Example 2 No stratification 51.7 Example 3 No stratification 48.9 Example 4 No stratification 45.5 Example 5 No stratification 43.7 Example 6 No stratification 39.7 Example 7 No stratification 38.2 Example 8 No stratification 37.1 Example 9 No stratification 48.3 Example 10 No stratification 43.1 Embodiment 11 No stratification 43.6 Example 12 No stratification 42.4 Comparative Example 1 Layering 24.6 Comparative Example 2 Layering 25.8 Comparative Example 3 Layering 27.7 Comparative Example 4 Layering 28.1 Comparative Example 5 Slightly delaminated 26.7 Comparative Example 6 Layering 26.6 Comparative Example 7 Slightly delaminated 25.2 Comparative Example 8 Slightly delaminated 19.3 Comparative Example 9 Severe stratification 20.7

[0200] It can be seen from Table 1 that the modified titanium dioxide described in the present invention has high solid content, high density, good dispersibility, excellent stability, storage resistance, excellent dispersibility and color development performance. When applied to sunscreen cosmetics, it can effectively improve the SPF value and has broad application prospects.

[0201] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A modified titanium dioxide, characterized in that: The invention comprises the following components in percentage by weight: 60-77.5% titanium dioxide powder, 1-3% polydimethylsiloxane, 1.5-4% wetting agent, 18-26% surface treatment agent, and 2-7% tetrahydroxypropylethylenediamine; wherein a part of the titanium dioxide is physically covered by the polydimethylsiloxane, and another part of the titanium dioxide is adsorbed by the tetrahydroxypropylethylenediamine; The surface treatment agent includes at least one of polyglyceryl-2 triisostearate, polyglyceryl-2 diisostearate, polyglyceryl-2 tetraisostearate, polyglyceryl-2 isostearate, polyglyceryl-3 isostearate, polyglyceryl-3 diisostearate, and polyglyceryl-4 isostearate; The mass percentage of the polydimethylsiloxane is A, the mass percentage of the tetrahydroxypropylethylenediamine is B, and the mass percentage of the surface treatment agent is C. A, B, and C satisfy: 2.6≤C / (A+B)≤5.

2. The modified titanium dioxide according to claim 1, characterized in that The invention comprises the following components in percentage by weight: 64-72.5% titanium dioxide powder, 2-2.5% polydimethylsiloxane, 2.5-3.5% wetting agent, 20-25% surface treatment agent and 3-5% tetrahydroxypropyl ethylenediamine.

3. The modified titanium dioxide according to claim 1, characterized in that The wetting agent includes at least one of trisiloxane and trimethylpentaphenyltrisiloxane.

4. The modified titanium dioxide according to claim 1, characterized in that The kinematic viscosity of the polydimethylsiloxane at 25° C. is 50-1000 cst.

5. The modified titanium dioxide according to claim 4, characterized in that The kinematic viscosity of the polydimethylsiloxane at 25° C. is 200-500 cst.

6. The modified titanium dioxide according to claim 1, characterized in that A and B satisfy: <B。 7. The modified titanium dioxide according to claim 6, characterized in that A, B, and C satisfy: 3.5≤C / (A+B)≤4.

5.

8. The method for preparing modified titanium dioxide according to any one of claims 1 to 7, characterized in that: The following steps are involved: The titanium dioxide powder and polydimethylsiloxane are uniformly mixed, ground, and dried to obtain polydimethylsiloxane-coated titanium dioxide powder; The polydimethylsiloxane-coated titanium dioxide and the surface treatment agent are mixed evenly, and then a wetting agent and tetrahydroxypropylethylenediamine are added, mixed evenly, and ground to obtain modified titanium dioxide.

9. Use of the modified titanium dioxide according to any one of claims 1 to 7 in the preparation of cosmetics.