Modified titanium dioxide for cosmetics and preparation method thereof

Abstract

The invention relates to the technical field of daily chemicals, in particular to modified titanium dioxide for cosmetics and a preparation method of the modified titanium dioxide. The modified titanium dioxide is prepared from the following raw materials: sodium stearoyl glutamate, titanium isopropoxide triisostearate, silica and titanium dioxide; the mass ratio of the sodium stearoyl glutamate to the titanium isopropoxide triisostearate to the silica to the titanium dioxide is (2-4): (0.2-1): (1-3): (93-97). Through synergistic modification of sodium acyl glutamate and titanium isopropoxide triisostearate, the surface of titanium dioxide has hydrophilicity and lipophilicity at the same time, and the titanium dioxide is endowed with excellent interface wettability. The modified titanium dioxide can show good dispersibility and stability in a wax-based makeup ointment system, a silicone oil system, a synthetic ester grease system and an oil-in-water (O / W) system, and is not limited by the polarity of an oil phase, the compatibility and adaptation range of a formula are remarkably improved, and the titanium dioxide treated by the method effectively resists the problem of darkness.

Description

Technical Field

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

[0002] Titanium dioxide (Titanium dioxide), a commonly used inorganic pigment, offers excellent hiding power, dispersibility, and light reflectivity, making it widely used in cosmetics systems such as makeup, foundation, sunscreen, cushion makeup, and primers. However, titanium dioxide's highly hydrophilic surface makes it prone to agglomeration and difficult to disperse in hydrophobic oil phases or silicone oil systems. Therefore, it is often necessary to perform oleophilic or hydrophobic surface modification to improve its stability and skin feel in various cosmetic systems.

[0003] At present, the two most common modification methods in the industry include:

[0004] 1. Titanium dioxide treated with triethoxyoctylsilane (OTES)

[0005] 2. Amino acid surface treated titanium dioxide (such as sodium stearoyl glutamate)

[0006] However, the application of the above two modified titanium dioxides in makeup or base makeup products has obvious limitations. Specifically, titanium dioxide treated with triethoxycaprylylsilane has high hydrophobicity and silicone oil affinity, and only shows good dispersibility in systems with volatile silicone oil (such as Cyclopentasiloxane, D5) as the main oil phase. However, when the proportion of synthetic ester oils (such as isooctyl isononanoate, caprylic / capric triglyceride, etc.) in the product is high, this type of titanium dioxide cannot maintain uniform dispersion in the system, and the "floating color band" phenomenon is very likely to occur, that is, titanium dioxide migrates in the system, floats powder or has uneven color at the boundary. This dispersion instability phenomenon is particularly evident in makeup ointment products. For example, in high-viscosity systems with high powder loadings such as lipsticks, contour sticks, and concealers, titanium dioxide treated with triethoxycaprylylsilane is almost impossible to use.

[0007] On the other hand, amino acid-treated titanium dioxide powders contain hydrophilic and polar groups on their surfaces, such as carboxyl and amino groups, which are suitable for forming good interfacial affinity with polar synthetic oils. Therefore, they have good dispersibility and skin feel in oil-in-water systems or base makeup products with synthetic esters as the main oil phase. However, when such powders are used in low-polarity silicone oil systems (such as dimethicone and cyclomethicone systems), due to the large difference in polarity between the two, amino acid-treated titanium dioxide powders are not easily wetted in the silicone oil, resulting in difficulty in dispersion, particle agglomeration, severe powder floating, and the inability to form a stable system. This leads to a decrease in formula performance and a significant deterioration in makeup effect, especially in liquid foundations, where dulling is easily observed.

[0008] Therefore, the current titanium dioxide processing method has the problem of limited system adaptability:

[0009] On the one hand, hydrophobic silane-treated powders are only suitable for volatile silicone oil systems and cannot be adapted to multi-oil formulas;

[0010] On the other hand, although polar amino acid treated powder is suitable for synthetic ester oil phase, it is not compatible with silicone oil.

[0011] In the existing technology, there is still a lack of a composite modification method for the surface of titanium dioxide that is simultaneously applicable to multiple oil phase systems (especially compatible with silicone oil and ester mixed systems) and has good dispersibility, resistance to color banding, excellent skin feel, and effective anti-dulling. Summary of the Invention

[0012] To solve the above technical problems, the present invention provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide; and the mass ratio of sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide is (2-4): (0.2-1): (1-3): (93-97).

[0013] As an embodiment of the present invention, the mass ratio of sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide is 3:0.8:2.1:93.7.

[0014] As an embodiment of the present invention, the silica comprises spherical silica.

[0015] As an embodiment of the present invention, the raw material of the modified titanium dioxide further includes silicone elastic powder or spherical polymethylsiloxane powder.

[0016] As an embodiment of the present invention, the titanium dioxide is hollow polymer microsphere composite titanium dioxide.

[0017] As an embodiment of the present invention, the raw materials for preparing the modified titanium dioxide further include PEG-100 stearate.

[0018] As an embodiment of the present invention, the silica comprises hexamethylene diisocyanate-modified silica.

[0019] The second aspect of the present invention provides a method for preparing the modified titanium dioxide for cosmetics, comprising the following steps:

[0020] (1) TiO2 was added to isopropyl alcohol, and titanium triisostearate was added, and the mixture was stirred at 2000 rpm and allowed to stand at room temperature for 30 min.

[0021] (2) Sodium stearoyl glutamate and PEG-100 stearate were dissolved in water and then mixed, 0.1 g of NaOH was added to assist dissolution and the pH was adjusted to 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution, stirred for 45 minutes, and the temperature was controlled not to exceed 40° C.;

[0022] (3) After filtering and drying, the powder is dry-mixed with hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, and spherical PMMA, and stirred evenly.

[0023] As an embodiment of the present invention, the average particle size D50 of the modified titanium dioxide is 3 to 8 μm.

[0024] The modified titanium dioxide for cosmetics of the present invention is used in the cosmetics field.

[0025] By adopting the above technical solution, the present invention has the following beneficial effects:

[0026] Through the synergistic modification of sodium acyl glutamate and isopropyl titanium triisostearate, the titanium dioxide surface is rendered both hydrophilic and lipophilic, imparting excellent interfacial wetting properties. The modified titanium dioxide exhibits excellent dispersibility and stability in wax-based cosmetic creams, silicone oils, synthetic esters, and oil-in-water (O / W) systems, unrestricted by the polarity of the oil phase, significantly improving formulation compatibility and adaptability.

[0027] Even in makeup or base makeup systems with high powder loadings (≥30%), the modified titanium dioxide of this invention maintains excellent system stability, without flocculation, agglomeration, sedimentation, or interfacial delamination. Its surface treatment effectively reduces interpowder static electricity and van der Waals forces, preventing powder self-aggregation or migration, thereby avoiding "color banding" or powder separation caused by high powder loadings.

[0028] By using isopropyl titanium triisostearate, the wetting coordination between the powder and colored pigments such as iron oxide and pearlescent powder is enhanced, so that titanium dioxide can be evenly distributed with the color powder in the multi-phase system, significantly improving the color migration phenomenon, and effectively suppressing the common "floating color bands", "floating powder", "uneven color development" and "dullness" problems in makeup / foundation products, resulting in a natural and delicate makeup effect. DETAILED DESCRIPTION

[0029] The present invention will be further explained below with reference to specific embodiments.

[0030] Disclosed is a modified titanium dioxide for use in cosmetics. The modified titanium dioxide is prepared from raw materials comprising sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, PEG-100 stearate, and hollow polymer microsphere composite titanium dioxide, wherein the mass ratio is (2-4): (0.2-1): (1-3): (0.5-2): (0.5-1): (93-97).

[0031] As an embodiment of the present invention, the mass ratio of sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate modified silica, spherical polymethylsiloxane powder, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide is 3:0.8:2.1:0.8:0.6:93.7.

[0032] The raw materials for preparing the hollow polymer microsphere composite titanium dioxide are hollow spherical TiO2 and spherical PMMA, and the mass ratio is 92.9:0.8.

[0033] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0034] (1) Add hollow spherical TiO2 to isopropyl alcohol, add isopropyl titanium triisostearate, stir at 2000 rpm, and let it stand at room temperature for 30 minutes;

[0035] (2) Sodium stearoyl glutamate and PEG-100 stearate were dissolved in water and then mixed, 0.1 g of NaOH was added to assist dissolution and the pH was adjusted to 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution, stirred for 45 minutes, and the temperature was controlled not to exceed 40° C.;

[0036] (3) After filtering and drying the product of step (2), dry-mix the powder with hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, and spherical PMMA, and stir until uniform.

[0037] The present invention provides a highly superior multiple surface modification system with high dispersibility, high compatibility, and multi-phase adaptability, exhibiting excellent stability and skin feel in makeup, foundation, and even skin care. Sodium stearoyl glutamate provides good water dispersibility and skin affinity, and can be used as a biogenic hydrophilic coating layer; isopropyl titanium triisostearate, due to its long hydrophobic chain, provides good wettability to oils, silicone oils, mineral oils, etc., forming an organic titanium network structure on the surface of titanium dioxide, significantly enhancing the wettability and hydrophobicity to the oil phase, and is particularly suitable for oil phase systems such as synthetic esters / silicone oils; silica is amorphous particles with fine particle size, and the hydroxyl groups on the surface can provide mechanical dispersion stability and anti-caking properties, and can also form a weak charge layer to prevent pigment reaggregation or sedimentation, thereby improving touch and fluidity.

[0038] However, the liquid foundation used suffers from a lack of smooth, ductility. This is because while silica coating helps prevent agglomeration and enhances tactile feel, excessive silica (especially coarse particles) can easily lead to a slightly dry, powdery feel. Therefore, spherical polymethylsiloxane is added to the formula to balance this out. Meanwhile, titanium dioxide particles treated with isopropyl titanium triisostearate offer strong hiding power and high reflectivity, but the makeup effect is less natural, with a white cast and strong light reflection. Therefore, hollow spheres are used when selecting titanium dioxide to improve this. Furthermore, sodium stearoyl glutamate, an anionic surfactant with surfactant properties, can cause viscosity instability in the liquid foundation, leading to thinning or caking of the liquid foundation after a period of time. Therefore, other surfactants are added to the formula for better results.

[0039] The present invention also provides a liquid foundation, the raw materials for preparing the liquid foundation include:

[0040] A1: 0.35 parts of trihydroxystearin, 3 parts of isohexadecane, 2 parts of a mixture of phytosterol / isostearyl alcohol / cetyl alcohol / stearyl alcohol / behenyl alcohol dimer linoleate and tridecyl trimellitate (mass ratio 4:6), 4.5 parts of a C9-12 alkane and a mixture of coconut oil caprylate / caprate (mass ratio 9:1), 8 parts of an undecane and tridecane mixture (mass ratio 3:1), 3 parts of isodecyl neopentanoate, 3 parts of hydrogenated polyisobutene, 1 part of diisostearyl malate, 4 parts of polyglyceryl-6 polyricinoleate, 1 part of PEG-30 dipolyhydroxystearate, 2 parts of polyglyceryl-3 diisostearate, and 1 part of synthetic wax.

[0041] A2: 12 parts of modified titanium dioxide;

[0042] A3: 1.0 part of disteardimethylammonium hectorite;

[0043] Phase B: 5 parts of butylene glycol, 1 part of glycerin, 1.5 parts of sodium chloride, 2 parts of ethanol, 0.6 parts of a mixture of phenoxyethanol and ethylhexylglycerin (mass ratio 1:4), and water to 100 parts.

[0044] The present invention provides a preparation method of the liquid foundation as follows:

[0045] (1) Clean and disinfect necessary containers and equipment;

[0046] (2) Weigh A1 completely and heat in a water bath to 70°C until the solid raw material is completely dissolved;

[0047] (3) Add phase A2 to phase A1 and homogenize at medium speed until the toner is completely dispersed;

[0048] (4) Activate the A3 phase and add it directly to the A1A2 phase to homogenize and disperse it completely;

[0049] (5) Dissolve all the raw materials of phase B until transparent and heat to 70°C;

[0050] (6) Slowly pour phase B into phase A and homogenize at medium speed. After all the ingredients are poured in, homogenize at high speed for 1 minute.

[0051] The following describes the details in conjunction with specific embodiments.

[0052] Example 1

[0053] This embodiment provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide; and the mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide is 3:0.8:2.1:0.8:0.6:93.7.

[0054] The raw materials for preparing the hollow polymer microsphere composite titanium dioxide are hollow spherical TiO2 and spherical PMMA, and the mass ratio is 92.9:0.8.

[0055] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0056] (1) Add hollow spherical TiO2 to isopropyl alcohol (1 g / 10 ml), add isopropyl titanium triisostearate, stir at 2000 rpm, and let it stand at room temperature for 30 min;

[0057] (2) Sodium stearoyl glutamate (1 g / 100 ml) and PEG-100 stearate (1 g / 50 ml) were dissolved in water and then mixed. 0.1 M NaOH was added to assist dissolution and the pH was adjusted to 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes. The temperature was controlled not to exceed 40° C.

[0058] (3) After filtering and drying the product of step (2), dry-mix the powder with hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, and spherical PMMA, and stir until uniform.

[0059] In this embodiment, the preparation method of the hexamethylene diisocyanate-modified silica is:

[0060] (1) Weigh 10 g of dried fumed silica, add it to 200 mL of anhydrous isopropyl alcohol, and stir it for 30 minutes under high-speed dispersion conditions; then heat it to 60°C under nitrogen protection and maintain stirring.

[0061] (2) Hexamethylene diisocyanate (HDI) was added to the system at a ratio of 5 wt% (based on the mass of SiO2); at the same time, 0.1% DBTDL was added, the temperature was maintained at about 70°C, and the reaction time was 4 hours. The entire reaction process was kept in an inert atmosphere to avoid moisture interference.

[0062] (3) After the reaction is completed, cool to room temperature and filter out the solid. Wash with anhydrous ethanol or toluene several times to remove unreacted HDI and by-products. Place the washed modified powder in a vacuum dryer at 50°C for 12 hours.

[0063] In this embodiment, the hollow spherical titanium dioxide is prepared by the preparation method of Example 1 in reference patent CN104085918B.

[0064] In this embodiment, the spherical polymethylsiloxane powder is Argan Co., Sil-Pearl 4F08.

[0065] In this embodiment, the spherical PMMA is MP-1451 produced by Kowa Chemicals USA.

[0066] This embodiment also provides a liquid foundation, the raw materials for its preparation include:

[0067] 0.35 parts of trihydroxystearin

[0068] 3 parts of isohexadecane

[0069] 2 parts of a mixture of phytosterols, isostearyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol dimer linoleate, and tridecyl trimellitate (mass ratio 4:6)

[0070] C9-12 alkane, 4.5 parts coconut oil alcohol-caprylate / caprate mixture (mass ratio 9:1)

[0071] 8 parts of undecane and tridecane mixture (mass ratio 3:1)

[0072] 3 parts of Isodecyl Neopentanoate

[0073] 3 parts hydrogenated polyisobutylene

[0074] 1 part diisostearyl malate

[0075] 4 parts of polyglyceryl-6 polyricinoleate

[0076] 1 part PEG-30 dipolyhydroxystearate

[0077] 2 parts of polyglyceryl-3 diisostearate

[0078] 1 part synthetic wax

[0079] 12 parts modified titanium dioxide

[0080] 1.0 parts of disteardimethylammonium hectorite

[0081] 5 parts of butanediol

[0082] 1 part glycerin

[0083] 1.5 parts sodium chloride

[0084] 2 parts ethanol

[0085] 0.6 parts of a mixture of phenoxyethanol and ethylhexylglycerin (mass ratio 1:4)

[0086] Add water to 100 parts.

[0087] The preparation method of the liquid foundation provided in this embodiment is as follows:

[0088] (1) Clean and disinfect necessary containers and equipment;

[0089] (2) Weigh A1 completely and heat in a water bath to 70°C until the solid raw material is completely dissolved;

[0090] (3) Add phase A2 to phase A1 and homogenize at medium speed until the toner is completely dispersed;

[0091] (4) Activate the A3 phase and add it directly to the A1A2 phase to homogenize and disperse it completely;

[0092] (5) Dissolve all the raw materials of phase B until transparent and heat to 70°C;

[0093] (6) Slowly pour phase B into phase A and homogenize at medium speed. After all the ingredients are poured in, homogenize at high speed for 1 minute.

[0094] Example 2

[0095] This embodiment provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder and hollow polymer microsphere composite titanium dioxide; and the mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder and hollow polymer microsphere composite titanium dioxide is 3.6:0.8:2.1:0.8:93.7.

[0096] The raw materials for preparing the hollow polymer microsphere composite titanium dioxide are hollow spherical TiO2 and spherical PMMA, and the mass ratio is 92.9:0.8.

[0097] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0098] (1) Add hollow spherical TiO2 to isopropyl alcohol (1 g / 10 ml), add isopropyl titanium triisostearate, stir at 2000 rpm, and let it stand at room temperature for 30 min;

[0099] (2) Sodium stearoyl glutamate (1 g / 100 ml) was dissolved in water and then mixed, 0.1 M NaOH was added to assist dissolution and adjusted to pH 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes, with the temperature controlled not to exceed 40° C.;

[0100] (3) After filtering and drying the product of step (2), dry-mix the powder with hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, and spherical PMMA, and stir until uniform.

[0101] In this embodiment, the preparation method of the hexamethylene diisocyanate-modified silica is:

[0102] (4) Weigh 10 g of dried fumed silica, add it to anhydrous isopropyl alcohol (200 mL), and stir it for 30 minutes under high-speed dispersion conditions; then heat it to 60° C. under nitrogen protection and maintain stirring.

[0103] (5) Hexamethylene diisocyanate (HDI) was added to the system at a ratio of 5 wt% (based on the mass of SiO2); at the same time, 0.1% DBTDL was added. The temperature was maintained at about 70°C and the reaction time was 4 hours. The entire reaction process was kept in an inert atmosphere to avoid moisture interference.

[0104] (6) After the reaction is completed, cool to room temperature and filter out the solid. Wash with anhydrous ethanol or toluene several times to remove unreacted HDI and by-products. Place the washed modified powder in a vacuum dryer at 50°C for 12 hours.

[0105] In this embodiment, the hollow spherical titanium dioxide is prepared by the preparation method of Example 1 in reference patent CN104085918B.

[0106] In this embodiment, the spherical polymethylsiloxane powder is Argan Co., Sil-Pearl 4F08.

[0107] In this embodiment, the spherical PMMA is MP-1451 produced by Kowa Chemicals USA.

[0108] This embodiment also provides a liquid foundation, the raw materials for its preparation are the same as those in Example 1.

[0109] The preparation method of the liquid foundation provided in this embodiment is the same as that in Example 1.

[0110] Example 3

[0111] This embodiment provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, silica, spherical polymethylsiloxane powder, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide; and the mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, silica, spherical polymethylsiloxane powder, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide is 3:0.8:2.1:0.8:0.6:93.7.

[0112] The raw materials for preparing the hollow polymer microsphere composite titanium dioxide are hollow spherical TiO2 and spherical PMMA, and the mass ratio is 92.9:0.8.

[0113] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0114] (1) Add hollow spherical TiO2 to isopropyl alcohol (1 g / 10 ml), add isopropyl titanium triisostearate, stir at 2000 rpm, and let it stand at room temperature for 30 min;

[0115] (2) Sodium stearoyl glutamate (1 g / 100 ml) and PEG-100 stearate (1 g / 50 ml) were dissolved in water and then mixed. 0.1 M NaOH was added to assist dissolution and the pH was adjusted to 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes. The temperature was controlled not to exceed 40° C.

[0116] (3) After filtering and drying the product of step (2), dry-mix the powder with hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, and spherical PMMA, and stir until uniform.

[0117] In this embodiment, the hollow spherical titanium dioxide is prepared by the preparation method of Example 1 in reference patent CN104085918B.

[0118] In this embodiment, the spherical polymethylsiloxane powder is Argan Co., Sil-Pearl 4F08.

[0119] In this embodiment, the spherical PMMA is MP-1451 produced by Kowa Chemicals USA.

[0120] This embodiment also provides a liquid foundation, the raw materials for its preparation are the same as those in Example 1.

[0121] The preparation method of the liquid foundation provided in this embodiment is the same as that in Example 1.

[0122] Example 4

[0123] This embodiment provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, PEG-100 stearate and titanium dioxide; and the mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, PEG-100 stearate and titanium dioxide is 3:0.8:2.1:0.8:0.6:93.7.

[0124] The titanium dioxide is hollow spherical TiO2.

[0125] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0126] (1) Add hollow spherical TiO2 to isopropyl alcohol (1 g / 10 ml), add isopropyl titanium triisostearate, stir at 2000 rpm, and let it stand at room temperature for 30 min;

[0127] (2) Sodium stearoyl glutamate (1 g / 100 ml) and PEG-100 stearate (1 g / 50 ml) were dissolved in water and then mixed. 0.1 M NaOH was added to assist dissolution and the pH was adjusted to 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes. The temperature was controlled not to exceed 40° C.

[0128] (3) After filtering and drying the product of step (2), dry-mix the powder with hexamethylene diisocyanate-modified silica and spherical polymethylsiloxane powder and stir until uniform.

[0129] In this embodiment, the preparation method of the hexamethylene diisocyanate-modified silica is:

[0130] (7) Weigh 10 g of dried fumed silica, add it to anhydrous isopropyl alcohol (200 mL), and stir it for 30 minutes under high-speed dispersion conditions; then heat it to 60°C under nitrogen protection and maintain stirring.

[0131] (8) Hexamethylene diisocyanate (HDI) was added to the system at a ratio of 5 wt% (based on the mass of SiO2); at the same time, 0.1% DBTDL was added. The temperature was maintained at about 70°C and the reaction time was 4 hours. The entire reaction process was kept in an inert atmosphere to avoid moisture interference.

[0132] (9) After the reaction is completed, cool to room temperature and filter out the solid. Wash with anhydrous ethanol or toluene several times to remove unreacted HDI and by-products. Place the washed modified powder in a vacuum dryer at 50°C for 12 hours.

[0133] In this embodiment, the hollow spherical titanium dioxide is prepared by the preparation method of Example 1 in reference patent CN104085918B.

[0134] In this embodiment, the spherical polymethylsiloxane powder is Argan Co., Sil-Pearl 4F08.

[0135] This embodiment also provides a liquid foundation, the raw materials for its preparation are the same as those in Example 1.

[0136] The preparation method of the liquid foundation provided in this embodiment is the same as that in Example 1.

[0137] Example 5

[0138] This embodiment provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide; and the mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, hexamethylene diisocyanate-modified silica, PEG-100 stearate and hollow polymer microsphere composite titanium dioxide is 3:0.8:2.1:1.4:93.7.

[0139] The raw materials for preparing the hollow polymer microsphere composite titanium dioxide are hollow spherical TiO2 and spherical PMMA, and the mass ratio is 92.9:0.8.

[0140] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0141] (1) Add hollow spherical TiO2 to isopropyl alcohol (1 g / 10 ml), add isopropyl titanium triisostearate, stir at 2000 rpm, and let it stand at room temperature for 30 min;

[0142] (2) Sodium stearoyl glutamate (1 g / 100 ml) and PEG-100 stearate (1 g / 50 ml) were dissolved in water and then mixed. 0.1 M NaOH was added to assist dissolution and the pH was adjusted to 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes. The temperature was controlled not to exceed 40° C.

[0143] (3) After filtering and drying the product of step (2), dry-mix the powder with hexamethylene diisocyanate-modified silica and spherical PMMA and stir until uniform.

[0144] In this embodiment, the preparation method of the hexamethylene diisocyanate-modified silica is:

[0145] (10) Weigh 10 g of dried fumed silica, add it to anhydrous isopropyl alcohol (200 mL), and stir it for 30 minutes under high-speed dispersion conditions; then heat it to 60°C under nitrogen protection and maintain stirring.

[0146] (11) Hexamethylene diisocyanate (HDI) was added to the system at a ratio of 5 wt% (based on the mass of SiO2); at the same time, 0.1% DBTDL was added. The temperature was maintained at about 70°C and the reaction time was 4 hours. The entire reaction process was kept in an inert atmosphere to avoid moisture interference.

[0147] (12) After the reaction is completed, cool to room temperature and filter out the solid. Wash with anhydrous ethanol or toluene several times to remove unreacted HDI and by-products. Place the washed modified powder in a vacuum dryer at 50°C for 12 hours.

[0148] In this embodiment, the hollow spherical titanium dioxide is prepared by the preparation method of Example 1 in reference patent CN104085918B.

[0149] In this embodiment, the spherical PMMA is MP-1451 produced by Kowa Chemicals USA.

[0150] This embodiment also provides a liquid foundation, the raw materials for its preparation are the same as those in Example 1.

[0151] The preparation method of the liquid foundation provided in this embodiment is the same as that in Example 1.

[0152] Example 6

[0153] The difference between this embodiment and embodiment 1 is that this embodiment provides a modified titanium dioxide for cosmetics, which is a D-phase functional powder material according to embodiment 3 of patent CN116889514A.

[0154] Example 7

[0155] This embodiment provides a modified titanium dioxide for cosmetics, wherein the raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide; and the mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide is 3:0.8:2.1:93.7.

[0156] The titanium dioxide is gas-phase TiO2, purchased from Hubei Huifu Nanomaterials Co., Ltd., NT-50.

[0157] A method for preparing the modified titanium dioxide for cosmetics comprises the following steps:

[0158] (1) TiO2 was added to isopropyl alcohol (1 g / 10 ml), and titanium triisostearate was added, and the mixture was stirred at 2000 rpm and allowed to react at room temperature for 30 min.

[0159] (2) Sodium stearoyl glutamate (1 g / 100 ml) was dissolved in water and then mixed, 0.1 M NaOH was added to assist dissolution and adjusted to pH 7. After the solution was mixed, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes, with the temperature controlled not to exceed 40° C.;

[0160] (3) After filtering and drying the product of step (2), dry-mix the powder with silica and stir until evenly mixed.

[0161] This embodiment also provides a liquid foundation, the raw materials for its preparation are the same as those in Example 1.

[0162] The preparation method of the liquid foundation provided in this embodiment is the same as that in Example 1.

[0163] Performance Testing

[0164] Test 1: 10% of each of the modified titanium dioxide prepared in Examples 1 to 7 was added to the same silicone oil + synthetic ester mixed oil phase system (Cyclopentasiloxane:C12-15Alkyl Benzoate = 1:1). After shear stirring for 10 minutes, the wetting, sedimentation, and uniformity of the powder in the oil phase were observed.

[0165] Table 1 Test results of test 1

[0166]

[0167]

[0168] Test 2: The modified titanium dioxide prepared in Examples 1 to 7 was added to a concealer system containing iron oxide (ointment-type formula, total powder content 35%). A film was drawn on a black and white contrasting base plate using a scraper coating method to observe whether "floating color bands" such as color band deviation and localized whitening occurred.

[0169] Table 2 Test results of test 2

[0170] Example Color ribbon uniformity Color band phenomenon Example 1 Extremely uniform none Example 2 Slightly better Very slight Example 3 Slightly better There is a small amount of edge offset Example 4 Half evenly obvious Example 5 Almost uniform Slightly scattered edges Example 6 A large part is uneven Obvious whitening Example 7 A large part is uneven Obvious sense of boundary

[0171] Test 3: Coverage and soft focus effect test

[0172] Each powder was used in the same liquid foundation system (same titanium dioxide content) to make a color emulsion. The film was then drawn onto a standard black and white hiding power test chart. The black background reflectance value (L value) was measured using a colorimeter, and micrographs were taken to observe the diffuse reflection uniformity.

[0173] Table 3 Test results of test 3

[0174]

[0175]

[0176] Test 4: Accelerated stability test

[0177] The liquid foundations of Examples 1 to 7 were respectively stored in an oven at 45° C. for 30 days, and the stability changes of the systems, including oil-water separation, powder sedimentation, color change, etc., were observed.

[0178] Table 4 Test results of test 4

[0179] Example Whether to layer Whether it is subsided Color changes Example 1 no no Stablize Example 2 no Very little sedimentation Stablize Example 3 no Very little sedimentation Slightly lighter Example 4 yes obvious Slightly white Example 5 no Very little sedimentation Stablize Example 6 yes obvious Grayish white precipitation Example 7 yes obvious Layered yellowing

[0180] Test 5: Skin feel evaluation

[0181] A sensory evaluation panel of 30 female subjects (aged 20-40, with a balanced distribution of skin types) conducted a user experience test on the concealer systems prepared in different examples. The test sample numbers were blinded, and each subject applied the sample to their face at a standard dosage. The subjects were then rated based on the following four dimensions:

[0182] Table 5 Rating dimensions

[0183]

[0184] Here are the results:

[0185] Table 6 Test results of test 5

[0186]

[0187] Test 6: Dullness Test

[0188] Comparative Example 1: Titanium dioxide coated with triethoxycaprylylsilane (inci: CI 77492 / triethoxycaprylylsilane) was added to the liquid foundation in the same proportion instead of the titanium dioxide in Example 1 to obtain Comparative Example 1; Example 1 and Comparative Example 1 were applied to the left and right faces of volunteers, respectively (test environment: indoors, room temperature 28-30 degrees Celsius). After the makeup was completed, photos were taken with a mobile phone. The facial foundation condition was observed every half hour and compared with the initial photos. The observation time point when darkening visibly appeared was recorded.

[0189] Table 7: Observation time of darkening

[0190]

[0191] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A modified titanium dioxide for cosmetics, characterized in that: The raw materials for preparing the modified titanium dioxide include: sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide; and the mass ratio of sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide is (2-4): (0.2-1): (1-3): (93-97).

2. The modified titanium dioxide for cosmetics according to claim 1, characterized in that: The mass ratio of the sodium stearoyl glutamate, isopropyl titanium triisostearate, silica and titanium dioxide is 3:0.8:2.1:93.

7.

3. The modified titanium dioxide for cosmetics according to claim 1, characterized in that: The silica includes spherical silica.

4. The modified titanium dioxide for cosmetics according to claim 3, characterized in that: The raw materials of the modified titanium dioxide further include silicone elastic powder or spherical polymethylsiloxane powder.

5. The modified titanium dioxide for cosmetics according to claim 1, characterized in that: The titanium dioxide is hollow polymer microsphere composite titanium dioxide.

6. The modified titanium dioxide for cosmetics according to claim 1, characterized in that: The raw materials for preparing the modified titanium dioxide also include PEG-100 stearate.

7. The modified titanium dioxide for cosmetics according to claim 1, characterized in that: The silica includes hexamethylene diisocyanate-modified silica.

8. A method for preparing the modified titanium dioxide for cosmetics according to claim 7, characterized in that: Here are the steps: (1) TiO2 was added to isopropyl alcohol, and titanium triisostearate was added, and the mixture was stirred at 2000 rpm and allowed to stand at room temperature for 30 min. (2) Sodium stearoyl glutamate and PEG-100 stearate were dissolved in water and then mixed, 0.1 g of NaOH was added to assist dissolution and adjusted to a pH of 7. After the mixed solution, the slurry obtained in step (1) was slowly added dropwise to the solution and stirred for 45 minutes, with the temperature controlled not to exceed 40° C.; (3) After filtering and drying, the powder is dry-mixed with hexamethylene diisocyanate-modified silica, spherical polymethylsiloxane powder, and spherical PMMA, and stirred evenly.

9. The preparation method according to claim 8, characterized in that The average particle size D50 of the modified titanium dioxide is 3 to 8 μm.

10. The modified titanium dioxide for cosmetics according to any one of claims 1 to 7, characterized in that: Used in the field of cosmetics.

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