Cosmetic nanometer biological calcium carbonate, its preparation method and application

Abstract

This invention relates to the field of nanofiller technology, specifically to a cosmetic-grade nano-bio-calcium carbonate, its preparation method, and its application. The preparation method includes: using calcium carbonate-rich biomaterials as raw materials, processing them through carbonation, acid hydrolysis, or microbial-induced carbonate precipitation processes to obtain nano-calcium carbonate; dispersing the obtained nano-calcium carbonate in a solvent, adding a biocompatible modifier for surface modification treatment, so that the biocompatible modifier coats the surface of the nano-calcium carbonate; after modification, centrifugation, washing, and drying are performed to obtain surface-functionalized cosmetic-grade nano-bio-calcium carbonate. This invention combines biomass resource utilization with nanotechnology, reducing the pressure of mineral mining. The preparation process uses mild conditions, and the surface modification is combined with a biocompatible modifier, ultimately obtaining nano-bio-calcium carbonate with uniform particle size, excellent dispersibility, and high biocompatibility, solving the problem of poor performance of traditional nano-calcium carbonate raw materials.

Description

Technical Field

[0001] This invention relates to the field of nanofiller technology, specifically to a cosmetic nano-bio-calcium carbonate, its preparation method, and its application. Background Technology

[0002] Nano-calcium carbonate, as an important inorganic nanomaterial, has the advantages of being non-toxic, odorless, highly white, and inexpensive. Due to its unique small size effect, surface effect, and quantum size effect, it shows potential application value in the cosmetics field.

[0003] Current conventional methods for preparing nano-calcium carbonate suffer from problems such as complex processes, poor absorbability, and unstable product quality. Nano-calcium carbonate is typically derived from non-renewable minerals such as limestone, and the mining process can easily cause ecological damage, failing to meet the requirements of green and sustainable development. Furthermore, conventional nano-calcium carbonate has low biocompatibility, which may cause skin irritation, limiting its application in sensitive skin or long-lasting cosmetics. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a method for preparing nano-bio-calcium carbonate for cosmetics, which exhibits good dispersibility, compatibility, and stability, and can effectively improve the texture and performance of cosmetics. The specific method is as follows:

[0005] A method for preparing nano-bio-calcium carbonate for cosmetic use includes the following steps:

[0006] 1) Using calcium carbonate-rich biomaterials as raw materials, clean them to remove surface impurities, and process them through carbonation, acid hydrolysis or microbial-induced carbonate precipitation processes to obtain nano-calcium carbonate.

[0007] The biological material is an eggshell or a seashell, including oyster shells, scallop shells or mussel shells, and the microorganism used in the microbial induced carbonate precipitation process is Bacillus pasteurellii.

[0008] 2) Disperse the nano-calcium carbonate obtained in step 1 in a solvent, add a biocompatible modifier for surface modification treatment, so that the biocompatible modifier is coated on the surface of the nano-calcium carbonate. After modification, centrifuge, wash and dry to obtain surface-functionalized cosmetic nano-bio-calcium carbonate.

[0009] The solvent is an acetic acid solution, deionized water, or ethanol solution, and the biocompatibility modifier is one or more combinations of phospholipids, sodium polyacrylate, chitosan, polyacrylamide, and hyaluronic acid.

[0010] Preferably, the preparation of nano-calcium carbonate using a microbial-induced carbonate precipitation process includes the following steps:

[0011] 1) Eggshells were selected as biological material, crushed into 1cm square fragments, soaked in acetic acid solution with a concentration of 6mol / L, filtered and separated to obtain eggshell membrane and calcium acetate solution.

[0012] 2) Add 5% sodium polyacrylate by mass to the obtained calcium acetate solution, stir until completely dissolved, and add sodium carbonate solution with a concentration of 1 mol / L dropwise at a rate of 2 mL / min. After the reaction is completed, amorphous calcium carbonate colloid is obtained.

[0013] 3) Add the eggshell membrane to the Bacillus pasteurellium culture medium and incubate at 30°C for 6 hours to load Bacillus pasteurellium onto the eggshell membrane, thus obtaining the bacteria-membrane complex;

[0014] 4) Add the bacteria-film complex to amorphous calcium carbonate colloid, and simultaneously add a urea solution with a concentration of 1 mol / L to obtain the bacteria-film-calcium carbonate complex;

[0015] 5) The obtained bacteria-membrane-calcium carbonate complex was subjected to gradient alcohol washing to remove the eggshell membrane and release the precipitate. The collected precipitate was placed in a muffle furnace and calcined at 300°C for 2 hours. After calcination, it was sieved to finally obtain nano-calcium carbonate.

[0016] Preferably, the gradient alcohol washing step includes: sequentially immersing the bacteria-film-calcium carbonate complex in ethanol solutions with volume fractions of 30%, 50%, and 75%, with each immersion time controlled at 1 hour.

[0017] Preferably, the molar ratio of urea to calcium ions in amorphous calcium carbonate colloid in the system is 1.2:1.

[0018] Preferably, the preparation of nano-calcium carbonate using an acid hydrolysis process includes the following steps:

[0019] 1) Eggshells were selected as biological material, and after being crushed, they were passed through a 100-mesh sieve to obtain eggshell powder with uniform particle size.

[0020] 2) Add the eggshell powder to a 1 mol / L hydrochloric acid solution to fully dissolve the calcium carbonate in the eggshell powder. Filter to remove insoluble impurities and collect the filtrate to obtain a solution containing calcium ions.

[0021] 3) Add a 1 mol / L ammonium carbonate solution to the calcium ion-containing solution at a dropping rate of 2 mL / min. Stop adding the solution when the pH value stabilizes at neutral and no longer changes. Wash the precipitate with deionized water, centrifuge, collect the precipitate and dry it to obtain nano-calcium carbonate.

[0022] Preferably, the preparation of nano-calcium carbonate using an acid hydrolysis process includes the following steps:

[0023] 1) Oyster shells were selected as biological material. After washing, they were placed in a muffle furnace and calcined at 900℃ for 3 hours. The calcined product was ground into powder and passed through a 100-mesh sieve to obtain oyster shell powder with uniform particle size distribution.

[0024] 2) Add oyster shell powder to a 1.5 mol / L nitric acid solution, filter to remove insoluble impurities, and collect the filtrate to obtain a solution containing calcium ions;

[0025] 3) Slowly add a 1.5 mol / L ammonium carbonate solution to a calcium ion-containing solution to carry out a precipitation reaction. Stop adding the solution when the pH value stabilizes to neutral and no longer changes. Wash the precipitate with deionized water, centrifuge, collect the precipitate and dry it to finally obtain nano-calcium carbonate.

[0026] Preferably, the preparation of nano-calcium carbonate using a carbonation process includes the following steps:

[0027] 1) Select scallop shells or mussel shells as biological materials, wash them, and calcine them in a muffle furnace at 900℃ for 2 hours. Grind the calcined product into powder, pass it through a 50-mesh sieve, and obtain shell powder with uniform particle size distribution.

[0028] 2) Add the seashell powder to deionized water and stir until a uniform and stable suspension is formed;

[0029] 3) Carbon dioxide gas was continuously introduced into the suspension using a gas distributor, and a crystal form control agent of 3% by dry weight of the solution was added. The carbonation reaction was carried out at 25°C and a stirring speed of 250 r / min. After the reaction was completed, the precipitate was washed with deionized water, centrifuged, collected and dried to finally obtain nano-calcium carbonate.

[0030] Preferably, the crystal form control agent is one or more combinations of polyaspartic acid, carboxymethyl chitosan, and quaternized chitosan.

[0031] On the other hand, the present invention also provides a cosmetic nano-bio-calcium carbonate, which is prepared by any of the above-mentioned methods for preparing cosmetic nano-bio-calcium carbonate.

[0032] This invention also provides an application of nano-bio-calcium carbonate in cosmetics, which is added to cosmetics at a concentration of 1% to 5% of the total mass of the cosmetics.

[0033] After adopting the above technical solution, the beneficial effects of the present invention are:

[0034] This invention combines biomass resource utilization with nanotechnology to reduce the pressure of mineral extraction. The preparation process employs mild conditions, reducing energy consumption and waste emissions. Surface modification with biocompatible modifiers ultimately yields nano-bio-calcium carbonate with uniform particle size, excellent dispersibility, and high biocompatibility, solving the problem of poor performance of traditional nano-calcium carbonate raw materials. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and not intended to limit it. Those skilled in the art will recognize that the invention can be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the invention by illustrating examples of it.

[0036] Example 1

[0037] The following are the specific process steps and technical details for preparing nano-bio-calcium carbonate for cosmetics using a microbial-induced carbonate precipitation process.

[0038] 1) Pretreatment and acid hydrolysis

[0039] Eggshells were selected as the biological material. They were cleaned to remove surface impurities and then dried in an oven at 105℃ until constant weight. The dried eggshells were broken into 1cm square fragments and separated by a standard sieve. The material that passed through the sieve (eggshell fragments with a particle size ≥ 1cm) was collected as the raw material for acid hydrolysis, while the material that passed through the sieve was collected separately for later use.

[0040] Weigh 50g of eggshell fragments and place them in 500mL of 6mol / L acetic acid solution. Incubate the mixture in a constant temperature water bath at 40℃ with shaking for 24h at a shaking frequency of 150rpm. After the reaction is complete, separate the solid and liquid. Wash the filter residue with deionized water until neutral to obtain a pure eggshell membrane. The filtrate is a calcium acetate solution rich in calcium ions.

[0041] 2) Preparation of amorphous calcium carbonate

[0042] Add 5% (by mass) sodium polyacrylate to the calcium acetate solution obtained in step 1 as a dispersing stabilizer, and mechanically stir until completely dissolved. Add a 1 mol / L sodium carbonate solution dropwise at a rate of 2 mL / min using a constant pressure dropping funnel, continuously monitoring the pH value of the solution during the addition. When the pH value rises to 9.5, stop adding the sodium carbonate solution and let it stand for 10 min to obtain amorphous calcium carbonate colloid.

[0043] 3) Preparation of microbial-film complex

[0044] The eggshell membrane obtained in step 1 was rinsed three times with deionized water, dried, and then added to the culture medium in the late logarithmic growth stage (OD). 600 The bacteria were placed in 100 mL of *Bacillus pasteurellii* culture medium (0.8 g / mL) and then incubated at 30°C for 6 hours to allow *Bacillus pasteurellii* to attach to the eggshell membrane. After incubation, the bacteria-membrane complex was obtained by filtration.

[0045] 4) Microbial-induced mineralization regulation

[0046] The prepared bacterial-film complex was introduced into an amorphous calcium carbonate colloidal system, and a 1 mol / L urea solution was added simultaneously. The molar ratio of urea to calcium ions in the amorphous calcium carbonate colloidal system was 1.2:1.

[0047] During the metabolism of Bacillus pasteurella, urease secreted catalyzes the hydrolysis of urea, forming a high-concentration region of carbonate ions on the eggshell membrane surface. The fibrous network on the eggshell membrane surface provides a three-dimensional template for mineralization. Driven by continuous urease activity, amorphous calcium carbonate gradually transforms into crystalline calcium carbonate. The membrane structure acts as a template, guiding crystal growth along a specific direction and preventing disordered aggregation. Simultaneously, the ammonium ions generated by urea hydrolysis increase the local pH, promoting the stable existence of carbonate ions and accelerating nucleation.

[0048] 5) Gradient alcohol washing

[0049] The obtained bacterial-membrane-calcium carbonate complex was subjected to gradient alcohol washing. The complex was sequentially immersed in ethanol solutions with volume fractions of 30%, 50%, and 75%, with each immersion time controlled at 1 hour, to remove the eggshell membrane and release the precipitate. The collected precipitate was placed in a muffle furnace and calcined at 300°C for 2 hours. After calcination, it was sieved to obtain nano-calcium carbonate.

[0050] 6) Surface finishing

[0051] A 500 mL ethanol solution containing 5 g phospholipid and 2 g sodium polyacrylate was added, and the surface modification reaction was carried out at 40 °C and a stirring speed of 300 r / min for 3 h. After the reaction was completed, the mixture was centrifuged and washed again, and then dried in a vacuum drying oven at 60 °C to constant weight to obtain surface-modified nano-bio-calcium carbonate.

[0052] To prepare the sunscreen skincare product, the raw material composition of the control group, by weight, was as follows: 4 parts octyl p-methoxycinnamate, 2.5 parts benzophenone-3, 4 parts jojoba oil, 36 parts plant squalane, 3 parts glyceryl diisostearate, 1.5 parts modified montmorillonite, 38.5 parts deionized water, 2 parts 1,3-butanediol, 2 parts propylene glycol, 2 parts cetyl alcohol, 3 parts acetylated lanol, 0.4 parts triethanolamine, 0.2 parts rose fragrance, and 0.5 parts p-hydroxyacetophenone. The experimental group included nano-bio-calcium carbonate, added at 1% of the total mass of the control group.

[0053] The two groups of sunscreen products were compared according to 2mg / cm 2 The coating was evenly applied to the inner forearm and spread in the same direction until no obvious white residue remained. After 6 hours, the average moisture content of the control group was 31.8%, while that of the experimental group was 39.3%, indicating that the surface bio-nano calcium carbonate had a certain improvement in the moisturizing effect on the skin.

[0054] Example 2

[0055] The following are the specific process steps and technical details for preparing cosmetic nano-bio-calcium carbonate using acid hydrolysis.

[0056] 1) Eggshells were selected as biological material, and after being crushed, they were passed through a 100-mesh sieve to obtain eggshell powder with uniform particle size.

[0057] 2) Add 50g of eggshell powder to a 1mol / L hydrochloric acid solution to fully dissolve the calcium carbonate in the eggshell powder. Filter to remove insoluble impurities and collect the filtrate to obtain a solution containing calcium ions.

[0058] 3) Add a 1 mol / L ammonium carbonate solution to the calcium ion-containing solution at a dropping rate of 2 mL / min. Stop adding the solution when the pH value stabilizes to neutral and no longer changes. Wash the precipitate with deionized water, centrifuge, collect the precipitate and dry it to obtain nano-calcium carbonate.

[0059] 4) Add 500mL of ethanol solution containing 5g phospholipid and 2g sodium polyacrylate, and carry out the surface modification reaction for 3h at 40℃ and stirring speed of 300r / min. After the reaction is completed, centrifuge and wash again, and then dry to constant weight in a vacuum drying oven at 60℃ to obtain surface-modified nano-biocalcium carbonate.

[0060] A high-SPF sunscreen repair lotion was prepared. By weight, the control group contained the following ingredients: 5 parts ethylhexyl triazine, 3 parts octyl salicylate, 5 parts grape seed oil, 6 parts polydimethylsiloxane, 5 parts glycerin, 0.3 parts sodium hyaluronate, 0.5 parts bisabolol, 0.8 parts phenoxyethanol, and 65.4 parts deionized water. The experimental group included nano-bio-calcium carbonate, added at 3% of the total mass of the control group.

[0061] The two sets of high-SPF sunscreen repair lotion skincare products were divided into 2mg / cm 2 The coating was evenly applied to the inner forearm and spread in the same direction until no obvious white residue remained. After 6 hours, the average moisture content of the control group was 32.5%, while that of the experimental group was 42.1%, indicating that the surface-applied bio-nano calcium carbonate improved the skin's moisturizing effect. Glycerin, sodium hyaluronate, and bio-nano calcium carbonate had a synergistic effect, achieving long-lasting moisture retention.

[0062] Example 3

[0063] The following are the specific process steps and technical details for preparing cosmetic nano-bio-calcium carbonate using acid hydrolysis.

[0064] 1) Oyster shells were selected as biological material. After washing, they were placed in a muffle furnace and calcined at 900℃ for 3 hours. The calcined product was ground into powder and passed through a 100-mesh sieve to obtain oyster shell powder with uniform particle size distribution.

[0065] 2) Add oyster shell powder to a 1.5 mol / L nitric acid solution, filter to remove insoluble impurities, and collect the filtrate to obtain a solution containing calcium ions;

[0066] 3) Slowly add a 1.5 mol / L ammonium carbonate solution to a calcium ion-containing solution to carry out a precipitation reaction. Stop adding the solution when the pH value stabilizes to neutral and no longer changes. Wash the precipitate with deionized water, centrifuge, collect the precipitate and dry it to finally obtain nano-calcium carbonate.

[0067] 4) The washed nano-calcium carbonate precipitate was added to 500 mL of deionized water containing 4 g of hyaluronic acid. The surface modification reaction was carried out at 45 °C and a stirring speed of 350 r / min for 3.5 h. After the reaction was completed, the nano-calcium carbonate was separated by centrifugation, washed, and then dried in a vacuum drying oven at 65 °C to obtain surface-modified nano-biological calcium carbonate.

[0068] To prepare a highly effective nourishing sunscreen face cream, the raw materials for the control group, by weight, were: 4.5 parts bis-ethylhexylphenol methoxyphenyl triazine, 8 parts shea butter, 1 part ceramide NP, 6 parts plant squalane, 0.3 parts xanthan gum, 2 parts niacinamide, 0.5 parts vitamin E, and 69.2 parts deionized water. The experimental group included nano-bio-calcium carbonate, added at 3.5% of the total mass of the control group.

[0069] The two groups of highly effective nourishing sunscreen face creams were compared at 2mg / cm². 2The coating was evenly applied to the inner forearm and spread in the same direction until no obvious white residue remained. After 6 hours, the average moisture content of the control group was 28.3%, while that of the experimental group was 40.2%. Shea butter, ceramides, and bio-nano calcium carbonate have a synergistic effect, forming a moisture-locking barrier and prolonging the moisturizing time.

[0070] Example 4

[0071] The following are the specific process steps and technical details for preparing nano-bio-calcium carbonate for cosmetics using a carbonization process.

[0072] 1) Select scallop shells or mussel shells as biological materials, wash them, and calcine them in a muffle furnace at 900℃ for 2 hours. Grind the calcined product into powder, pass it through a 50-mesh sieve, and obtain shell powder with uniform particle size distribution.

[0073] 2) Add the seashell powder to deionized water and stir until a uniform and stable suspension is formed;

[0074] 3) Carbon dioxide gas was continuously introduced into the suspension using a gas distributor. A crystal form control agent, accounting for 3% of the dry weight of the solution, was added. The crystal form control agent was one or more combinations of polyaspartic acid, carboxymethyl chitosan, and quaternized chitosan. The carbonization reaction was carried out at 25°C and a stirring speed of 250 r / min. After the reaction was carried out for 1.5 h, the precipitate was washed with deionized water, centrifuged, collected and dried to finally obtain nano-calcium carbonate.

[0075] 4) The washed nano-calcium carbonate precipitate was added to a mixed solution containing 3g chitosan, 2g polyacrylamide, and 2g hyaluronic acid (the mixed solution was prepared from 500mL acetic acid solution and deionized water, with an acetic acid concentration of 1%). The surface modification reaction was carried out at 60℃ and a stirring speed of 350r / min for 3 hours. After the reaction, the precipitate was centrifuged, washed, and then dried in an oven at 105℃ to obtain surface-modified nano-bio-calcium carbonate.

[0076] To prepare the foundation cream, the raw materials for the control group, by weight, were: 5 parts butylene glycol, 0.2 parts xanthan gum, 0.1 parts sodium hyaluronate, 12 parts cyclopentamethoxysiloxane, 5 parts caprylic acid, 5 parts caprylic triglyceride, 1.5 parts cetearyl oleate, 2.5 parts polydimethylsiloxane, 0.5 parts vitamin E acetate, 2 parts titanium dioxide, 0.8 parts iron oxide red, 1 part iron oxide yellow, 0.1 part iron oxide black, 3 parts pearlescent mica, 15 parts ethanol, 4 parts glycerin, 1 part triethanolamine, 0.2 parts allantoin, 0.1 parts menthol, and 32 parts deionized water. Nano-bio-calcium carbonate was added to the experimental group at 5% of the total mass of the control group. A light layer of glycerin was applied to the surface of a card to simulate oily skin. After makeup application and standing for 1 hour, the control group showed makeup melting, while the experimental group showed no change.

[0077] The embodiments described above are not exhaustive and do not limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the above description. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to effectively utilize the invention and its modifications. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the invention should be included within the scope of protection of the invention.

Claims

1. A method for preparing a cosmetic nanobiocalcium carbonate, characterized by, Includes the following steps: 1) Using calcium carbonate-rich biomaterials as raw materials, clean them to remove surface impurities, and process them through a microbial-induced carbonate precipitation process to obtain nano-calcium carbonate; wherein, the biomaterial is an eggshell, and the microorganism used in the microbial-induced carbonate precipitation process is Bacillus pasteurellii. The microbial-induced carbonate precipitation process includes the following preparation steps: S1. Eggshells were selected as biological material, crushed into 1cm square fragments, soaked in acetic acid solution with a concentration of 6mol / L, filtered and separated to obtain eggshell membrane and calcium acetate solution. S2. Add 5% sodium polyacrylate by mass to the obtained calcium acetate solution and stir until completely dissolved. Add a 1 mol / L sodium carbonate solution dropwise at a rate of 2 mL / min until the reaction is complete, and obtain amorphous calcium carbonate colloid. S3. Add the eggshell membrane to the Bacillus pasteurellium culture medium and incubate at 30°C for 6 hours to load Bacillus pasteurellium onto the eggshell membrane, thus obtaining the bacteria-membrane complex. S4. Add the bacteria-film complex to the amorphous calcium carbonate colloid, and simultaneously add a urea solution with a concentration of 1 mol / L to obtain the bacteria-film-calcium carbonate complex. S5. The obtained bacterial-membrane-calcium carbonate composite was subjected to gradient alcohol washing. The bacterial-membrane-calcium carbonate composite was successively immersed in ethanol solutions with volume fractions of 30%, 50%, and 75%, with each immersion time controlled at 1 hour, in order to remove the eggshell membrane and release the precipitate therein. The collected precipitate was placed in a muffle furnace and calcined at 300°C for 2 hours. After calcination, it was sieved to finally obtain nano-calcium carbonate. 2) Disperse the nano-calcium carbonate obtained in step S5 in a solvent, add a biocompatible modifier for surface modification treatment, so that the biocompatible modifier is coated on the surface of the nano-calcium carbonate. After modification, centrifuge, wash and dry to obtain surface-functionalized cosmetic nano-bio-calcium carbonate. The solvent is an acetic acid solution, deionized water, or ethanol solution, and the biocompatibility modifier is one or more combinations of phospholipids, sodium polyacrylate, chitosan, polyacrylamide, and hyaluronic acid.

2. The method for preparing cosmetic-grade nano-bio-calcium carbonate according to claim 1, characterized in that: In the bacterial-film-calcium carbonate complex system, the molar ratio of urea to calcium ions in the amorphous calcium carbonate colloid is 1.2:

1.

3. A type of nano-bio-calcium carbonate for cosmetic use, characterized in that, It is prepared by the method for preparing cosmetic nano-bio-calcium carbonate according to any one of claims 1-2.

4. An application of the nano-bio-calcium carbonate for cosmetics as described in claim 3, characterized in that: Nano-bio-calcium carbonate is added to cosmetics at a rate of 1% to 5% of the total mass of the cosmetic.