Modified inorganic particle and preparation process thereof

Abstract

The invention relates to the field of inorganic particle preparation, and particularly discloses a modified inorganic particle and a preparation process thereof. The preparation raw materials comprise the following components in parts by weight: a component 1: 100 parts of at least one of spherical porous silica, bentonite and diatomite; a component 2: 0.2-5 parts of at least one of hydrolyzed hyaluronic acid, sodium hyaluronate and zinc hyaluronate; a component 3: 0.5 to 10 parts of at least one of triethoxyoctyl silane, polydimethylsiloxane, polymethylsiloxane, polydimethylsiloxane alcohol, phenyl silicone oil, lauroyl lysine and hydrogenated lecithin; the preparation process comprises the following steps: adding the component 2 and the coating aid into deionized water to prepare a solution, and preserving heat at 10-15 DEG C; placing the component 1 in a boiling coating machine, and suspending and boiling in hot air; spraying the solution on the component 1, heating to 100-110 DEG C, treating for 6-8 hours to obtain powder, adding the powder into a high-speed mixer, adding the component 3, mixing for 20-30 minutes, drying, and crushing to obtain the modified inorganic particles. According to the present invention, the solution prepared from the hydrolyzed hyaluronic acid and the derivative thereof and the coating auxiliary agent is sprayed on the suspended boiling particles so as to coat the porous particles, such that the effective coating of the porous particles can be achieved compared with the conventional mixing process so as to achieve the oil absorption retarding effect;

Description

Technical Field

[0001] The present application relates to the field of inorganic particle preparation, and more specifically, to a modified inorganic particle and a preparation process thereof. Background Art

[0002] Due to its porous structure, inorganic porous particles have excellent adsorption properties. When in contact with a liquid, due to capillary action, the liquid will be quickly absorbed by the porous surface, so they can quickly absorb oil and have wide applications in environmental protection, such as adsorbing leaked oil, treating process wastewater and waste liquid, and can also be used for adsorbing grease in food processing and adsorbing grease in daily chemical products, etc.

[0003] In some field applications, it is not desirable for the oil absorption rate of porous particles to be as fast as possible. For example, as an active adsorbent, it is desirable that it does not absorb oil as much as possible before use to facilitate transportation and storage and improve the adsorption effect during use. Another example is for daily chemical skin care and makeup. The skin, as an organ for regulation, itself needs to quickly restore the water-oil balance. The faster the porous particles absorb oil, the more the skin instinctively regulates to prompt it to secrete sebum faster until it absorbs enough sebum and quickly loses its function. Therefore, slowing down oil absorption and achieving controllable oil absorption is a way to solve the above problems.

[0004] Some products on the market currently usually mix porous particles with oil-control active substances in order to achieve such a purpose, but there are several problems. One is that the addition ratio of active substances is generally not high. For liquid active substances, the porous surface of inorganic particles will absorb them into the pores, thus hiding the active substances and preventing them from playing a role, reducing the oil absorption of the particles. For solid active substances, due to the complex treatment process and the difficulty of maintaining the activity of active substances during the treatment process, the cost is extremely high.

[0005] Therefore, there is a need to develop a porous particle that can slow down its oil absorption rate and achieve controllable oil absorption. Summary of the Invention

[0006] In order to endow inorganic porous particles with the properties of slowing down oil absorption and achieving controllable oil absorption, the present application provides a modified inorganic particle and a preparation process thereof.

[0007] In the first aspect, the present application provides a modified inorganic particle, and its preparation raw materials include the following components in parts by weight: Component 1: at least one of spherical porous silica, porous bentonite, and porous diatomite, 100 parts; Component 2: at least one of hydrolyzed hyaluronic acid, sodium hyaluronate, zinc hyaluronate, and water-soluble zinc salts, 0.2 - 5 parts; Component 3: at least one of triethoxyoctylsilane, polydimethylsiloxane, polymethylsiloxane, polydimethylsiloxanol, phenyl silicone oil, lauroyl lysine, hydrogenated lecithin, 0.5 - 10 parts; The preparation process includes: adding Component 2 and the coating aid into deionized water to prepare a solution and keeping it at 10 - 15°C; placing Component 1 in a fluidized bed coater and suspending and fluidizing it in hot air; spraying the solution onto Component 1, heating to 100 - 110°C and treating for 6 - 8 h to obtain a powder, adding the powder into a high-speed mixer, then adding Component 3 and mixing for 20 - 30 min, drying and pulverizing to obtain the modified inorganic particles.

[0008] Spherical porous silica, bentonite, and diatomite are all particles with porous structures and can be used as adsorption materials. When the inventor was seeking to solve the problem of slow oil control, it was chosen to process the surface of the particles through a film-forming agent to form a film coating on the surface of the porous particles, temporarily closing the surface pores of the porous particles. When applied, in a specific environment, such as when encountering sebum, the sebum can destroy the surface film structure, expose the closed pores, and then restore the oil absorption capacity of the porous particles. Hydrolyzed hyaluronic acid and its derivatives are a good choice, and they also have the ability to regulate sebum secretion. In this application, the above specific process is used to form a coating film of hydrolyzed hyaluronic acid and its derivatives on the surface of silica. It can be understood that the hydrolyzed hyaluronic acid and its derivatives in this application include a series of substances with the structural characteristics of hyaluronic acid such as hydrolyzed hyaluronic acid and hydrolyzed hyaluronate. Directly mixing and stirring hydrolyzed hyaluronic acid and its derivatives with porous particles are ultimately easily adsorbed, or hydrolyzed hyaluronic acid and its derivatives can only adhere to the surface of the porous particles in the form of particles and cannot form a coating film. The surface is still a porous structure and cannot solve the problem of this application. The inventor processes through particle suspension fluidization and spraying the prepared liquid of hydrolyzed hyaluronic acid and its derivatives, which can better form a coating film on the surface of the porous particles. Keeping the solution at 10 - 15°C for heat preservation and cooling can prevent the subsequent spraying temperature from rising immediately and leave the contact time between the spray and the powder; this process treats the powder at a temperature of 100 - 110°C for 6 - 8 h after the solution is sprayed. It can be understood that the coating film in this application contains part or a trace amount of water to form a hydrogel coating film, which greatly increases the processing heat resistance. Therefore, at 100 - 110°C, it can not only ensure effective film formation but also ensure the removal of excess water. The addition of organosilicon substances, lauroyl lysine, and hydrogenated lecithin in Component 3 is beneficial for the modified porous particles to achieve more application fields. The addition of the coating aid can help hydrolyzed hyaluronic acid and its derivatives form a coating film better and reduce the possibility of hydrolyzed hyaluronic acid and its derivatives being adsorbed and the particle pores being blocked, providing a guarantee for the subsequent restoration of the oil absorption function.

[0009] Preferably, the amount of deionized water is 15 - 20 times the mass of Component 2.

[0010] Preferably, the temperature of the hot air is 50 - 70°C.

[0011] Preferably, component 3 contains solids and liquids. The feeding method includes first feeding the solids and mixing for 10 - 15 minutes, and then feeding the liquids and mixing for 10 - 15 minutes.

[0012] The amount of deionized water can ensure that hydrolyzed hyaluronic acid and its derivatives form a uniform spraying liquid. The control of the hot air temperature enables better suspension and boiling of the particles. By first feeding the solids and then the liquids, it is beneficial for the solids to adhere to the surface of the modified porous particles, thus facilitating the application.

[0013] Preferably, the mass ratio of component 2 to the coating aid is 1 - 10:1, preferably 3 - 8:1, and more preferably 4 - 6:1.

[0014] Furthermore, preferably, the mass ratio of component 2 to the coating aid is 5:1.

[0015] Preferably, the coating aid is a mass ratio of pentaerythritol-modified carnosine to polyether-modified polysiloxane of 3 - 5:1.

[0016] Furthermore, preferably, the mass ratio of pentaerythritol-modified carnosine to polyether-modified polysiloxane is 4:1.

[0017] Furthermore, preferably, the polyether-modified polysiloxane molecular chain contains hydroxyl groups.

[0018] Preferably, the pentaerythritol-modified carnosine in this application is obtained by conventional esterification process. The specific process includes: adding xylene to a reflux device, then adding 88 - 92 parts by mass of carnosine and 12 - 15 parts by mass of pentaerythritol and mixing and stirring, then adding 1 part by mass of p-toluenesulfonic acid, passing nitrogen, heating to 190 - 210°C and reacting for 4 - 6 hours, and removing the solvent after the reaction to obtain pentaerythritol-modified carnosine.

[0019] Through the conventional esterification process, the carboxylic acid in carnosine and pentaerythritol undergo esterification to form a multi-side-chain claw-shaped pentaerythritol ester. It can be known that the pentaerythritol ester and the raw material carnosine do not exclude the use of the particles in daily chemical products, thus broadening the scope of use of the modified particles.

[0020] When the inventors coated with hydrolyzed hyaluronic acid and its derivatives, they found that some of the pores on the surface of the porous particles were not well closed, and the oil absorption performance of the coated product was significantly lost compared with the original unmodified porous particles after the film was damaged. This may be because some hydrolyzed hyaluronic acid and its derivatives were adsorbed and blocked the pores of the particles during the coating process, resulting in a decrease in oil absorption, which is not conducive to the application of the product. Therefore, the inventors sought a better coating to seal and a coating film that does not block the pores of the particles. In this application, by using pentaerythritol-modified carnosine and polyether-modified polysiloxane as coating aids, a more complete coating film can be further formed on the particle surface and the blockage of the voids on the particle surface can be reduced, so as to slow down the oil absorption effect while ensuring that the oil absorption capacity after subsequent recovery remains at a good level. This may be because, on the one hand, pentaerythritol-modified carnosine has a four-side chain claw-like structure and there are also hydrogen bonds between molecules. This structure provides certain support for the coating film formed by hydrolyzed hyaluronic acid and its derivatives on the particle surface. After modification, carnosine loses its carboxyl group and shows a certain positive charge, and there is also an amino group in the molecule. Therefore, it can bond with hydrolyzed hyaluronic acid and its derivatives based on hydrogen bonds or charge bonds. Hydrolyzed hyaluronic acid and its derivatives can achieve better spreading based on the support of pentaerythritol-modified carnosine, reducing the adsorption of hydrolyzed hyaluronic acid and its derivatives by the porous pores. On the other hand, the bonding of pentaerythritol-modified carnosine and hydrolyzed hyaluronic acid is conducive to the dispersion of hydrolyzed hyaluronic acid. The imidazole ring in pentaerythritol-modified carnosine has a certain steric hindrance effect, promoting the better dispersion of hydrolyzed hyaluronic acid and its derivatives, which is beneficial to the formation of a continuous coating film. And polyether-modified polysiloxane can reduce the surface tension and improve the spreading property, which is beneficial to the formation of the coating film. The siloxane bond of polyether-modified polysiloxane reduces the surface tension and the modified segment penetrates into the solution system. The hydroxyl groups in the segment can further enhance the bonding between the components in the coating film, thereby improving the coating strength of the coating film and reducing the adsorption of hydrolyzed hyaluronic acid and its derivatives by the pores on the particle surface and blocking them.

[0021] When the mass ratio of pentaerythritol-modified carnosine to polyether-modified polysiloxane is 4:1, a better effect of reducing pore blockage can be obtained. This may be because through the adjustment of the ratio, the abilities of pentaerythritol-modified carnosine and polyether-modified polysiloxane can be better coordinated, jointly improving the coating strength and the particle coverage ability. Too little pentaerythritol-modified carnosine may result in insufficient film-forming strength and the easy adsorption of hyaluronic acid and its derivatives by the pores. If pentaerythritol-modified carnosine is excessive and polyether-modified polysiloxane is less, the solution spreads slowly, the coating integrity is poor, and the bonding effect of the hydroxyl groups in polyether-modified polysiloxane on the components is reduced, which also easily leads to adsorption by the pores. Therefore, by adjusting the ratio of the coating aids, the coating can be better completed while reducing pore blockage, maintaining the oil absorption capacity after film removal, and obtaining inorganic porous particles that can achieve slow oil control.

[0022] On the other hand, the present application provides a method for preparing modified inorganic particles, comprising the following steps: Step 1: Add Component 2 and the coating assistant to deionized water at 50 - 70 °C, which is 15 - 20 times the mass of Component 2, stir until completely dispersed, place it in a water bath, and keep the temperature of the water bath at 10 - 15 °C until the solution reaches the same temperature completely; Step 2: Place Component 1 in a fluidized bed coater, introduce air, and keep the air temperature at 50 - 70 °C to make Component 1 suspended and fluidized under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto Component 1 through a nozzle; Step 4: Keep for 20 - 40 min, raise the inlet air temperature to 100 - 110 °C, and end after 6 - 8 h to obtain a powder; Step 5: Put the obtained powder into a high - speed mixer with a rotation speed of 1200 - 1500 rpm, add Component 3 and mix for 20 - 30 min to end the mixing; Step 6: Put the mixed powder into an oven, set the temperature at 100 - 110 °C, and dry for 15 - 20 h; Step 7: Crush the dried powder with a hammer mill to obtain the finished product.

[0023] Preferably, Component 3 includes a solid and a liquid, and the feeding method includes first feeding the solid and mixing for 10 - 15 min, and then feeding the liquid and mixing for 10 - 15 min.

[0024] It can be known that the modified particles obtained by the preparation process of the present application have the above - mentioned performance effects, and through reasonable setting of process parameters, it is beneficial to achieve better particle treatment. In addition, when Component 3 contains a solid, the feeding method of adding the solid first and then the liquid is beneficial to the attachment of the solid on the coating.

[0025] To sum up, the present application has at least the following beneficial effects: 1. The present application coats the suspended and fluidized particles by spraying a solution prepared by hydrolyzing hyaluronic acid and its derivatives and the coating assistant, realizing the coating of porous particles. Compared with the conventional mixing process, it can achieve effective coating of porous particles instead of adhering to the porous particles in a granular form, thus achieving the effect of slowing down oil control.

[0026] 2. By using pentaerythritol - modified carnosine and polyether - modified polysiloxane as the coating assistant, the present application can further better form a complete coating film on the particle surface and reduce the blockage of voids on the particle surface, achieving the effect of slowing down the oil absorption effect while ensuring that the subsequent oil absorption capacity remains at a relatively good level.

[0027] 3. Controlling the mass ratio of pentaerythritol-modified carnosine to polyether-modified polysiloxane at 4:1 in this application can achieve a better effect of reducing pore blockage. By adjusting the ratio, the capabilities of pentaerythritol-modified carnosine and polyether-modified polysiloxane can be better coordinated, enhancing the coating strength and particle coverage ability together, and obtaining inorganic porous particles capable of slow oil control. Description of the Drawings

[0028] Figure 1 SEM electron micrograph of the modified porous inorganic particles of Example 1 of this application; Figure 2 SEM electron micrograph of the modified porous inorganic particles of Example 2 of this application; Figure 3 SEM electron micrograph of the modified porous inorganic particles of Example 3 of this application; Figure 4 SEM electron micrograph of the modified porous inorganic particles of Example 4 of this application; Figure 5 SEM electron micrograph of unmodified spherical porous silica, the raw material used in the examples of this application; Figure 6 Comparison chart of the oil absorption of D5 silicone oil by the untreated silica and the treated silica in the examples of this application; Figure 7 Comparison chart of the oil absorption of D5 silicone oil by the reduced silica after destroying the coating in the examples of this application; Figure 8 Application comparison chart of the silica and the conventionally treated silica in this application. Detailed Description of the Invention

[0029] To further help understand the technical solution of the present invention, several specific examples are provided to describe the technical solution of the present invention more specifically. All the described examples are only partial examples of the present invention, not all; the examples can be combined with each other, and the same or similar concepts or processes may not be repeated in some examples. The following examples are further explanations of the present invention, and the present invention is not limited thereto.

[0030] The raw materials used in the examples and preparation examples of this application are all conventional commercially available brands or can be obtained according to conventional processes. The spherical porous silica is SILIA LX-7, the hydrolyzed hyaluronic acid is Bloomage Biotechnology hydrolyzed hyaluronic acid HA-TLM 3-5, the zinc hyaluronate is Bloomage Biotechnology HA-ZN, the polydimethylsiloxane is Dow Corning PMX-200, the hydrogenated lecithin is Nisshin Oillio S-10; the polyether-modified polysiloxane is a hydroxyl polyether polyester copolymer-modified polysiloxane Klamar8244; the carnosine is L-carnosine, purchased from Zhejiang Yicun Biotechnology. Examples

[0031] In the embodiment of the present application, the preparation method of pentaerythritol-modified carnosine: Add 200 mL of xylene into a reflux device, then add 90.5 g of carnosine and 13.6 g of pentaerythritol, mix and stir, then add 1 g of p-toluenesulfonic acid, introduce nitrogen, heat up to 200 °C and react for 5 h. After the reaction is completed, remove the solvent to obtain pentaerythritol-modified carnosine. Example

[0032] Steps for preparing modified inorganic particles: Component 1: Spherical porous silica Component 2: Hydrolyzed hyaluronic acid Component 3: Triethoxyoctylsilane, polydimethylsiloxane Step 1: Add 0.11 kg of hydrolyzed hyaluronic acid, 17.6 g of pentaerythritol-modified carnosine, and 4.4 g of polyether-modified polysiloxane into 2.2 kg of deionized water at 60 °C, stir for 15 min until completely dispersed, place it in a water bath, and keep the temperature of the water bath at 12 °C until the solution reaches the same temperature completely; Step 2: Place 10 kg of spherical porous silica in a fluidized bed coater, introduce air, and keep the air temperature at 60 °C to make the spherical porous silica suspended and fluidized under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto the spherical porous silica through a nozzle until the spraying is completed; Step 4: Keep working for 30 min, raise the inlet air temperature to 105 °C, and continue for 7 h to obtain a powder; Step 5: Put the obtained powder into a high-speed mixer with a rotation speed of 1350 rpm, and sequentially add 0.45 kg of polydimethylsiloxane and 0.22 kg of triethoxyoctylsilane into it; mix for 25 min to end the mixing; Step 6: Put the mixed powder into an oven, set the temperature at 105 °C, and dry for 18 h; Step 7: Crush the dried powder with a hammer mill to obtain the finished product. Example

[0033] Steps for preparing modified inorganic particles: Component 1: Spherical porous silica Component 2: Zinc hyaluronate Component 3: Triethoxyoctylsilane, hydrogenated lecithin Step 1: Add 0.11 kg of zinc hyaluronate, 17.6 g of pentaerythritol-modified carnosine, and 4.4 g of polyether-modified polysiloxane into 2.2 kg of deionized water at 60 °C, stir for 20 min until completely dispersed, place it in a water bath, and keep the temperature of the water bath at 11 °C until the solution reaches the same temperature completely; Step 2: Place 10 kg of spherical porous silica in a fluidized bed coater, introduce air, and keep the air temperature at 65°C to make the spherical porous silica suspended and fluidized under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto the spherical porous silica through a nozzle until the spraying is completed; Step 4: Keep working for 30 min, raise the inlet air temperature to 105°C, and continue for 7 h to obtain a powder; Step 5: Put the obtained powder into a high-speed mixer with a rotation speed of 1300 rpm, add 0.05 kg of hydrogenated lecithin and mix for 10 min, then add 0.5 kg of triethoxysilane and mix for 15 min to complete the mixing; Step 6: Put the mixed powder into an oven, set the temperature at 105°C, and dry for 18 h; Step 7: Grind the dried powder with a hammer mill to obtain the finished product. Example

[0034] The process steps of Example 3 are substantially the same as those of Example 1, except that the coating auxiliary agent in Example 3 is only pentaerythritol-modified carnosine.

[0035] Preparation steps of modified inorganic particles: Component 1: Spherical porous silica Component 2: Hydrolyzed hyaluronic acid Component 3: Triethoxysilane, polydimethylsiloxane Step 1: Add 0.11 kg of hydrolyzed hyaluronic acid and 22 g of pentaerythritol-modified carnosine to 2.2 kg of deionized water at 60°C, stir for l5 min until completely dispersed, place it in a water bath, and keep the water bath temperature at 12°C until the solution reaches the same temperature completely; Step 2: Place 10 kg of spherical porous silica in a fluidized bed coater, introduce air, and keep the air temperature at 60°C to make the spherical porous silica suspended and fluidized under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto the spherical porous silica through a nozzle until the spraying is completed; Step 4: Keep working for 30 min, raise the inlet air temperature to 105°C, and continue for 7 h to obtain a powder; Step 5: Put the obtained powder into a high-speed mixer with a rotation speed of 1350 rpm, and sequentially add 0.45 kg of polydimethylsiloxane and 0.22 kg of triethoxysilane thereto; mix for 25 min to complete the mixing; Step 6: Put the mixed powder into an oven, set the temperature at 105°C, and dry for 18 h; Step 7: Grind the dried powder with a hammer mill to obtain the finished product. Example

[0036] Example 4 has substantially the same process steps as Example 1, except that the film coating aid in Example 4 is only polyether-modified polysiloxane.

[0037] Steps for preparing modified inorganic particles: Component 1: Spherical porous silica Component 2: Hydrolyzed hyaluronic acid Component 3: Triethoxyoctylsilane, polydimethylsiloxane Step 1: Add 0.11 kg of hydrolyzed hyaluronic acid and 22 g of polyether-modified polysiloxane to 2.2 kg of deionized water at 60 °C, stir for 15 min until completely dispersed, place it in a water bath, and keep the temperature of the water bath at 12 °C until the solution reaches the same temperature completely; Step 2: Place 10 kg of spherical porous silica in a fluidized bed coater, introduce air, and keep the air temperature at 60 °C to make the spherical porous silica suspended and fluidized under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto the spherical porous silica through a nozzle until the spraying of the liquid ends; Step 4: Keep working for 30 min, raise the inlet air temperature to 105 °C, and continue for 7 h to obtain a powder; Step 5: Put the obtained powder into a high-speed mixer with a rotation speed of 1350 rpm, and sequentially add 0.45 kg of polydimethylsiloxane and 0.22 kg of triethoxyoctylsilane to it; mix for 25 min to end the mixing; Step 6: Put the mixed powder into an oven, set the temperature at 105 °C, and dry for 18 h; Step 7: Crush the dried powder with a hammer mill to obtain the finished product.

[0038] Through Attachment Figure 1-2 and Attachment Figure 5 It can be seen that after the process treatment of Examples 1 and 2 of this application, hydrolyzed hyaluronic acid and its derivatives are coated on the surface of spherical porous silica, forming a relatively smooth film layer, which effectively seals the pores on the silica surface.

[0039] Through Attachment Figure 1 and 3 -4, it can be seen that compared with using only the same amount of pentaerythritol-modified carnosine or polyether-modified polysiloxane as the film coating aid alone, Example 1 selects a film coating aid with a mass ratio of pentaerythritol-modified carnosine to polyether-modified polysiloxane of 4:1 to assist in coating, covering more surface pores, and achieving a better film coating effect. The combined use of pentaerythritol-modified carnosine and polyether-modified polysiloxane can jointly improve the film coating strength and particle coverage ability, thereby forming a relatively complete and smooth coating film.

[0040] Figure 6 This is a comparison chart of the oil absorption capacity of untreated porous silica in this application and the silica powder coated with hydrolyzed hyaluronic acid obtained in Step 4 of Examples 1, 3, and 4 for D5 silicone oil. Among them, the oil absorption capacity test method is as follows: Take 5 g of powder and place it on a glass tabletop. Add D5 silicone oil to it, and at the same time stir with a stainless steel stirring knife until the powder agglomerates into a ball and the process ends. Oil absorption capacity = weight of absorbed silicone oil / weight of powder * 100, that is: Oil absorption capacity = weight of absorbed silicone oil / weight of powder, and then multiply by 100. It can be understood that this test and calculation formula are conventional tests and expressions for oil absorption capacity.

[0041] From Figure 6 It can be seen that the original oil absorption capacity of the untreated silicone oil is 163.47, the oil absorption capacity of Example 1 is 46.20, the oil absorption capacity of Example 3 is 65.35, and the oil absorption capacity of Example 4 is 72.16. Compared with the untreated silica, the silica coated with hydrolyzed hyaluronic acid in Example 1, Example 3, and Example 4 all showed a significant decrease in oil absorption capacity, further proving the effect of the particle modification of this application on closing pores and slowing down oil absorption; while the oil absorption capacity of Example 3 and Example 4 is slightly higher than that of Example 1, indicating that the combined use of the coating aids pentaerythritol-modified carnosine and polyether-modified polysiloxane is beneficial to forming a better coating film and further slowing down oil absorption. Example

[0042] The process steps of Example 5 are roughly the same as those of Example 1, except that the mass ratio of the coating aids pentaerythritol-modified carnosine and polyether-modified polysiloxane in Example 5 is 1:1.

[0043] Preparation steps of modified inorganic particles: Component 1: Spherical porous silica Component 2: Hydrolyzed hyaluronic acid Component 3: Triethoxyoctylsilane, polydimethylsiloxane Step 1: Add 0.11 kg of hydrolyzed hyaluronic acid, 11 g of pentaerythritol-modified carnosine, and 11 g of polyether-modified polysiloxane to 2.2 kg of deionized water at 60 °C, stir for 15 min until completely dispersed, place it in a water bath, and keep the temperature of the water bath at 12 °C until the solution reaches the same temperature completely; Step 2: Place 10 kg of spherical porous silica in a fluidized bed coater, introduce air, and the air temperature is 60 °C to make the spherical porous silica suspend and boil under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto the spherical porous silica through a nozzle until the spraying of the liquid ends; Step 4: Keep working for 30 min, raise the inlet air temperature to 105 °C, and continue for 7 h to obtain the powder; Step Five: Put the obtained powder into a high-speed mixer at a rotation speed of 1350 rpm, and sequentially add 0.45 kg of polydimethylsiloxane and 0.22 kg of triethoxyoctylsilane thereto; mix for 25 min and end the mixing. Step Six: Put the well-mixed powder into an oven, set the temperature at 105 °C, and dry for 18 h. Step Seven: Crush the dried powder with a hammer mill to obtain the finished product. Example

[0044] The process steps of Example 6 are substantially the same as those of Example 1, except that the coating auxiliary agent in Example 6 is a mass ratio of 6:1 of pentaerythritol-modified carnosine and polyether-modified polysiloxane.

[0045] Preparation steps of modified inorganic particles: Component 1: Spherical porous silica Component 2: Hydrolyzed hyaluronic acid Component 3: Triethoxyoctylsilane, polydimethylsiloxane Step One: Add 0.11 kg of hydrolyzed hyaluronic acid, 18.86 g of pentaerythritol-modified carnosine, and 3.14 g of polyether-modified polysiloxane to 2.2 kg of deionized water at 60 °C, stir for 15 min until completely dispersed, place it in a water bath, and keep the water bath temperature at 12 °C until the solution reaches the same temperature completely. Step Two: Put 10 kg of spherical porous silica into a fluidized bed coater, introduce air, and keep the air temperature at 60 °C to make the spherical porous silica suspended and fluidized under the action of hot air. Step Three: Place the solution prepared in Step One in a pressure tank and spray it onto the spherical porous silica through a nozzle until the spraying of the liquid ends. Step Four: Keep working for 30 min, raise the inlet air temperature to 105 °C, and continue for 7 h to end and obtain the powder. Step Five: Put the obtained powder into a high-speed mixer at a rotation speed of 1350 rpm, and sequentially add 0.45 kg of polydimethylsiloxane and 0.22 kg of triethoxyoctylsilane thereto; mix for 25 min and end the mixing. Step Six: Put the well-mixed powder into an oven, set the temperature at 105 °C, and dry for 18 h. Step Seven: Crush the dried powder with a hammer mill to obtain the finished product.

[0046] The powder obtained in Step 4 of Example 1, Examples 3-4, and Examples 5-6 was subjected to a restored oil absorption experiment: the coating film was damaged by artificial sebum, and then the oil absorption test was carried out. The specific steps were as follows: 20 g of artificial sebum was added to a 50 ml glass beaker, 8 g of powder was added, and it was completely infiltrated for 2 min. Immediately, a suction filter was used for suction filtration. The filter cake obtained by suction filtration was placed in an oven and dried at 100 °C for 6 hours and then pulverized to obtain a reduced powder. The oil absorption amount was measured using D5 silicone oil, and the oil absorption test standard was the same as above.

[0047] Figure 7 For the comparison of the oil absorption amount of the reduced powder. The oil absorption amount of Example 1 was 159.38, the oil absorption amount of Example 3 was 115.24, the oil absorption amount of Example 4 was 109.32, the oil absorption amount of Example 5 was 135.13, and the oil absorption amount of Example 6 was 142.21. It can be seen that the oil absorption capacity of the powders in Example 1 and Examples 3-4 was restored to a certain extent, proving that the sebum damaged the coating film. Further, by comparing with Examples 5-6, it can be seen that when the coating aids of pentaerythritol-modified carnosine and polyether-modified polysiloxane were used in combination, the oil absorption performance of silica was restored better, indicating that the above coating aids helped to reduce the adsorption of hydrolyzed hyaluronic acid by the pores of the particles during coating. And when the mass ratio of pentaerythritol-modified carnosine to polyether-modified polysiloxane was 4:1, the oil absorption amount was restored to a higher level, indicating that pentaerythritol-modified carnosine and polyether-modified polysiloxane at this ratio were more conducive to reducing pore blockage and could maintain a higher restored oil absorption property while achieving coating.

[0048] It can be understood that the modified inorganic particles of the present application have the functions mentioned above, and based on the above functions, they can be applied to various scenarios with a slow adsorption requirement for porous particles. As one of them, the present application discusses its situation as a slow oil control for makeup powder.

[0049] Reference Figure 8 For the comparison of the makeup oil and water of silica treated differently. The silica treated conventionally was the silica in Example 1 that was not subjected to the coating treatment from Step 1 to Step 4, that is, 10 kg of spherical porous silica was put into a high-speed mixer at a rotation speed of 1350 rpm, and 0.45 kg of polydimethylsiloxane and 0.22 kg of triethoxysilane were added thereto in sequence; after mixing for 25 min, the mixing was ended; the mixed powder was put into an oven, and the set temperature was 105 °C and dried for 18 h; the dried powder was pulverized by a hammer mill to obtain a finished product. The silica treated with hyaluronic acid was the silica obtained by the treatment method of Example 1. The specific test steps were as follows: The powder silica was applied to the left and right parts of the forehead of the same tester, and the oil and water were detected by a Real Bubee intelligent face oil and water detector.

[0050] From Figure 8It can be seen that the oil-water ratios of the silica treated by the conventional method at 1 h, 4 h, and 6 h of makeup application are 1.08, 0.95, 1.59, and 2.13 respectively, and the oil-water ratios of the silica treated by the method of Example 1 of the present application are 0.91, 0.91, 0.95, and 1.94 respectively. It can be seen from the line chart that, compared with the silica treated by the conventional method, the silica treated by the method of the present application maintains a lower oil-water ratio within 4 hours of makeup holding, indicating that the silica treated by the method of the present application has a certain slow oil control effect, and the modified inorganic powder of the present application has a good application scenario in the cosmetic field.

[0051] This specific embodiment is only an interpretation of the present application, and it does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment that do not contribute creatively as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A modified inorganic particle, characterized in that, The raw materials for its preparation include the following components in parts by weight: Component 1: at least one of spherical porous silica, porous bentonite, and porous diatomaceous earth, 100 parts; Component 2: at least one of hydrolyzed hyaluronic acid, sodium hyaluronate, and zinc hyaluronate, 0.2 - 5 parts; Component 3: at least one of triethoxysilane octane, polydimethylsiloxane, polymethylsiloxane, polydimethylsiloxane alcohol, phenyl silicone oil, lauroyl lysine, and hydrogenated lecithin, 0.5 - 10 parts; The preparation process includes: adding Component 2 and a coating aid to deionized water to prepare a solution and keeping it at 10 - 15°C; placing Component 1 in a fluidized bed coater and suspending it in hot air for fluidization; spraying the solution onto Component 1, heating to 100 - 110°C and treating for 6 - 8 h to obtain a powder, adding the powder to a high - speed mixer, then adding Component 3 and mixing for 20 - 30 min, followed by drying and pulverizing to obtain modified inorganic particles.

2. The modified inorganic particles according to claim 1, wherein The amount of deionized water is 15 - 20 times the mass of Component 2.

3. The modified inorganic particles according to claim 1, characterized in that, The temperature of the hot air is 50 - 70°C.

4. The modified inorganic particles according to claim 1, wherein Component 3 contains solids and liquids, and the feeding method includes first adding the solids and mixing for 10 - 15 min, then adding the liquids and mixing for 10 - 15 min.

5. The modified inorganic particles according to claim 1, wherein, The mass ratio of Component 2 to the coating aid is 3 - 8:

1.

6. The modified inorganic particles according to claim 1, wherein The mass ratio of Component 2 to the coating aid is 5:

1.

7. The modified inorganic particles according to claim 1, wherein The coating aid is pentaerythritol - modified carnosine and polyether - modified polysiloxane with a mass ratio of 3 - 5:

1.

8. The modified inorganic particles according to claim 7, characterized in that, The mass ratio of pentaerythritol - modified carnosine to polyether - modified polysiloxane is 4:

1.

9. A method for preparing the modified inorganic particles according to any one of claims 1-8, characterized in that, It includes the following steps: Step 1: Add Component 2 and the coating aid to deionized water at 50 - 70°C, which is 15 - 20 times the mass of Component 2, stir until completely dispersed, place it in a water bath, and keep the water bath temperature at 10 - 15°C until the solution reaches the same temperature completely; Step 2: Place Component 1 in a fluidized bed coater, introduce air, and keep the air temperature at 50 - 70°C to make Component 1 suspend and fluidize under the action of hot air; Step 3: Place the solution prepared in Step 1 in a pressure tank and spray it onto Component 1 through a nozzle; Step 4: Keep it for 20 - 40 min, raise the inlet air temperature to 100 - 110°C, and continue for 6 - 8 h to end and obtain a powder; Step 5: Put the obtained powder into a high - speed mixer with a rotation speed of 1200 - 1500 rpm, add Component 3 and mix for 20 - 30 min to end the mixing; Step 6: Put the mixed powder into an oven, set the temperature at 100 - 110°C, and dry for 15 - 20 h; Step 7: Pulverize the dried powder through a hammer mill to obtain the finished product.

10. The method for preparing the modified inorganic particles according to claim 9, characterized in that, Component 3 contains solids and liquids, and the feeding method includes first adding the solids and mixing for 10 - 15 min, then adding the liquids and mixing for 10 - 15 min.

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