Phosphorylated chickpea 11s protein for improving lipstick wax cracking and preparation method thereof

Abstract

The application relates to the technical field of natural cosmetic functional material processing, and discloses phosphated broad bean 11S protein for improving lipstick wax cracking and a preparation method thereof. The special anti-cracking agent for lipstick is prepared through the following steps of salt solution extraction of broad bean 11S protein, sodium tripolyphosphate phosphating modification, acid high-temperature induced protein self-assembly into nanofibril, and castor oil compounding. The application destroys the rigid spherical structure of the broad bean 11S protein through phosphating, and forms a cross-linked flexible nanofiber network through acid-heat induction. The nanofibril has excellent compatibility with paraffin, carnauba wax and candelilla wax, is uniformly dispersed in the interstitial gap of the wax matrix, buffers and reduces the crystallization internal stress, and prevents crack propagation. The raw material is all-natural and free of chemical synthetic additives, solves the problems of easy oiling and sensitization of traditional chemical plasticizers, and poor compatibility and weak anti-cracking effect of the original broad bean protein, and significantly reduces the paste cracking rate under the conditions of low-temperature storage and rapid cooling mass production of the lipstick.

Description

Technical Field

[0001] This invention relates to the field of processing technology of functional raw materials for natural cosmetics, specifically to a phosphorylated broad bean 11S protein for improving lipstick wax cracking and its preparation method. Background Technology

[0002] Paraffin wax is a commonly used base material for lipstick molding. It plays a crucial role in lipstick formulations by providing excellent setting and film-forming properties, imparting suitable hardness, gloss, and performance characteristics to the lipstick. Besides paraffin wax, other lipstick waxes such as carnauba wax and candelilla wax are prone to crystallization and shrinkage during cooling, generating significant internal stress. This can lead to cracks and breakage, severely affecting the product's appearance and stability. This phenomenon not only prolongs cooling time during processing but also hinders storage and transportation at low temperatures. Existing improvement methods primarily rely on synthetic plasticizers and flexible polymers, which can alleviate cracking to some extent, but suffer from poor compatibility, oil seepage, and reduced lipstick strength, and fail to meet the requirements of green, safe, and naturally sourced products. Plant 11S globulins (such as Glycinin in soybeans) are storage proteins with excellent processing properties. Their molecular structure contains abundant disulfide bonds and thiol groups, enabling them to form a high-hardness, highly elastic gel network during food processing. However, the dense, spherical structure of natural 11S globulin limits its functionality. Chemical treatment can unfold its molecules, exposing more hydrophobic groups and reaction sites, thus significantly improving its solubility, emulsifying properties, and foaming ability. Broad bean 11S protein is a widely available, safe, and biocompatible plant protein with the potential to be used as a natural functional modification material. However, the natural structure of broad bean 11S protein is rigid and compact, resulting in poor interfacial binding with hydrophobic polyethylene wax. Studies have reported that phosphorylated modified proteins have better spreadability and emulsifying properties. However, its application in wax-based cosmetics has not been reported. This invention prepares phosphorylated broad bean 11S protein fibrils based on broad beans and discovers that its application in lipstick anti-fragrance can alleviate breakage during the processing of brittle wax-based lipsticks, reducing the cracking rate of batches of finished lipsticks. This is a direction with significant research and application value.

[0003] Current technologies only emulsify and foam the native broad bean protein, directly incorporating unmodified broad bean 11S powder into lipstick wax. Natural broad bean 11S protein has a dense, rigid, spherical spatial structure with hydrophobic groups encapsulated within the protein molecules, resulting in extremely poor compatibility with nonpolar lipstick wax. Powder agglomeration easily causes granules and a matte finish in the lipstick. Simply mixing castor oil or native broad bean protein can only slightly improve cracking, with negligible anti-cracking effects under low-temperature, rapid cooling conditions. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a phosphorylated broad bean 11S protein and its preparation method for improving lipstick wax cracking. It can be compounded with castor oil to form a natural anti-cracking agent, which is uniformly dispersed inside the lipstick wax matrix, buffering the internal stress of wax crystal shrinkage and inhibiting crack propagation. This achieves the advantages of green and efficient improvement of lipstick wax cooling cracking, thus solving the problem of lipstick wax cooling cracking.

[0005] To achieve the goal of creating a natural anti-cracking agent by combining castor oil with the above-mentioned compound, which is uniformly dispersed within the lipstick wax matrix to buffer the internal stress of wax crystal shrinkage and inhibit crack propagation, thus achieving a green and efficient improvement in the cooling and cracking of lipstick wax, this invention provides the following technical solution: A method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking, comprising the following steps: Step 1: Crude extraction process of broad bean 11S protein: After the broad beans are crushed and air-dried, the protein is extracted by salting with sodium chloride aqueous solution. After centrifugation to remove residue, isoelectric point precipitation, and secondary centrifugation to collect the protein precipitate, the protein is then dialyzed and freeze-dried to obtain refined broad bean 11S protein powder. Step 2: Protein phosphorylation modification process: Refined broad bean 11S protein powder is dispersed in sodium tripolyphosphate solution, and phosphorylation grafting reaction is carried out under controlled temperature alkaline environment. The reaction solution is dialyzed to remove impurities and freeze-dried to obtain phosphorylated broad bean 11S solid powder. Step 3: Acid-heat induced self-assembly of nanofibrils: Phosphorylated broad bean 11S powder is mixed with water to prepare a protein aqueous solution. After being adjusted to an acidic environment, it is stirred at a constant temperature. The protein is induced to stretch and self-assemble into nanofibrils by the synergistic effect of acid and heat. The reaction system is dialyzed and freeze-dried to obtain phosphorylated broad bean 11S protein fibril powder. Step 4: Anti-breakage agent compounding process: Phosphorylated broad bean 11S protein fiber powder and castor oil are mixed and dissolved at a mass ratio of 1:(5-20) to obtain a natural anti-breakage agent for lipstick.

[0006] Preferably, in step 1, the sodium chloride aqueous solution has a molar concentration of 0.5 mol / L, the pH of the salting system is controlled at 8.0-8.5, the dissolution temperature is 40-45℃, the stirring speed is 350-400 rpm, and the salting soaking time is 1.5-2 h. After salting, the mixture is centrifuged at 4-8℃ and 10000×g centrifugal force for 25-30 min, and the supernatant is separated and retained.

[0007] Preferably, after filtering the supernatant, the pH of the system is adjusted to 4.5-5.0 to achieve protein isoelectric point precipitation. The precipitation environment temperature is 20-25℃, the stirring speed is 350-400rpm, and the stirring precipitation time is 1-1.5h. After precipitation, the mixture is centrifuged at 4-8℃ and 10000×g for 15-20min, and the bottom protein precipitate is collected.

[0008] Preferably, the protein precipitation is performed by dialyzing with pure water using a dialysis membrane with a molecular weight cutoff of 500 Da for 48-72 hours, followed by freeze-drying for 48-72 hours after dialysis to obtain refined broad bean 11S protein powder.

[0009] Preferably, in step 2, the molar concentration of sodium tripolyphosphate aqueous solution is 0.1 mol / L, the pH of the system is adjusted to 8.5-9.0 after dissolution, the phosphorylation reaction temperature is 40-45℃, the stirring speed is 200-300 rpm, and the constant temperature reaction time is 2-3 hours.

[0010] Preferably, in step 2, after the protein phosphorylation modification process is completed, the solution is dialyzed with a 500 Da molecular weight cutoff dialysis membrane for 48-72 hours to remove free phosphate impurities, and the dialysate is freeze-dried for 48-72 hours to obtain phosphorylated broad bean 11S solid powder.

[0011] Preferably, in step 3, after the phosphorylated broad bean 11S powder is dissolved in water, the pH of the system is controlled at 1.8-2.0, the high-temperature stirring temperature is 80-85℃, the stirring speed is 130-150rpm, and the constant-temperature self-assembly reaction time is 24-30h.

[0012] Preferably, after the self-assembly reaction is completed, the protein solution is dialyzed with a 500 Da molecular weight cutoff dialysis membrane for 48-72 hours to remove small molecule degradation impurities, and then freeze-dried for 48-72 hours to obtain phosphorylated broad bean 11S protein fibrils powder.

[0013] Preferably, in step 4, the ratio of fibrillary fiber powder to castor oil is 1:10 by mass, and the mixture is stirred at room temperature until the powder is completely dissolved to obtain a homogeneous liquid lipstick anti-breakage agent.

[0014] A phosphorylated broad bean 11S protein for improving lipstick wax cracking is prepared by the above-mentioned method. The phosphorylated broad bean 11S protein is phosphorylated and grafted with oxygen-containing phosphorus groups, and the molecule has a loose and relaxed configuration. It self-assembles under acid and heat to form a long, uniform, cross-linked flexible nanofiber network structure. When used for lipstick wax modification, it is uniformly dispersed in paraffin wax, carnauba wax, and candelilla wax matrix to buffer the internal stress of wax crystal shrinkage and inhibit the cooling cracking of the paste.

[0015] Compared with the prior art, the present invention provides a phosphorylated broad bean 11S protein for improving lipstick wax cracking and its preparation method, which has the following beneficial effects: 1. This method for preparing phosphorylated broad bean 11S protein fibrils to improve lipstick wax cracking uses natural and safe raw materials, avoiding the defects of sensitization and oil seepage caused by chemical additives. All raw materials used in this invention are edible-grade broad beans and castor oil, without petroleum-based chemical plasticizers or artificial synthetic polymers. The resulting anti-cracking agent is natural and non-toxic, exhibits excellent compatibility with lipstick wax, and prevents oil seepage and softening of the lipstick during long-term storage. This method is suitable for the development of natural raw materials in cosmetics and solves the problems of sensitization caused by existing synthetic additives and oil seepage in waxes.

[0016] 2. This invention relates to a method for preparing phosphorylated broad bean 11S protein fibrils that improves lipstick wax cracking. The method involves innovative molecular structure modification to enhance the interfacial bonding between the protein and wax. Through sodium tripolyphosphate phosphorylation modification, phosphorylated oxygen-containing groups are introduced into the broad bean 11S protein molecule, disrupting the dense, rigid spherical structure of the native protein and fully exposing the hydrophobic groups within the protein. This overcomes the defects of native broad bean protein, such as encapsulation by hydrophobic groups, incompatibility with non-polar waxes, and powder agglomeration. Subsequent acid-thermal self-assembly forms a nano-interwoven fiber network, resulting in a functional material that reduces the cooling and cracking of polyethylene wax used in lipsticks, further enhancing interfacial wetting ability and thus improving the stability and safety of the lipstick. Attached Figure Description

[0017] Figure 1 This is a SEM scan of broad bean 11S protein fibrils, as presented in this invention. Figure 2 This is an XPS image of phosphorylated groups in the 11S protein fibrils of broad beans according to the present invention. Detailed Implementation

[0018] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1 (Phosphorylated broad bean 11S protein fibrillary anti-breakage agent A) raw material Dried broad beans (commercially available whole edible broad beans, crude protein content 27.5%), food-grade sodium chloride, food-grade sodium tripolyphosphate, purified water, and pharmaceutical-grade castor oil (purity ≥99%).

[0020] A method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking includes the following steps: Step 1: Crude extraction of broad bean 11S protein: Broad beans are cleaned, pulverized, and sieved through a 40-mesh sieve. The powder is air-dried at room temperature until the moisture content is ≤8%. A 0.5 mol / L NaCl aqueous solution is added at a material-to-liquid ratio of 1:10 to adjust the pH to 8.5. The mixture is mechanically stirred at 42℃ and 400 rpm for 2 hours. The mixture is then centrifuged at 4℃ and 10000×g for 30 minutes. The bottom residue is discarded, and all supernatant is collected. The supernatant is filtered through filter paper to remove fine suspended solids. The pH is adjusted to 4.5 with dilute hydrochloric acid, and the mixture is stirred at 25℃ and 400 rpm for 1 hour to achieve isoelectric precipitation of the protein. The suspension is centrifuged at 4℃ and 10000×g for 20 minutes, and the protein precipitate is collected. The precipitate is placed in a dialysis bag with a molecular weight cutoff of 500 Da and dialyzed continuously with deionized water for 48 hours, with the dialysate replaced every 8 hours. The dialysis product is then freeze-dried under vacuum for 48 hours to obtain refined broad bean 11S protein powder.

[0021] Step 2: The refined 11S protein powder was prepared as a 5 wt% protein solution in a 0.1 mol / L sodium tripolyphosphate solution. The pH of the system was adjusted to 8.5, and the reaction was carried out at 45℃ with stirring at 300 rpm for 2 h. After the reaction, the mixture was dialyzed with pure water in a 500 Da dialysis bag for 48 h to remove free phosphate. The mixture was then freeze-dried for 48 h to obtain phosphorylated broad bean 11S solid powder.

[0022] Step 3: The phosphorylated protein powder was mixed with water to prepare a 3 wt% aqueous solution, the pH was adjusted to 2.0 with dilute acid, and the mixture was continuously stirred at 85℃ and 130 rpm for 24 h in a sealed container to induce acid-heat self-assembly; after discharge, the mixture was dialyzed at 500 Da for 48 h to remove small molecule degradation products, and then freeze-dried for 48 h to obtain phosphorylated broad bean 11S protein fibrils powder.

[0023] Step 4: Anti-fracture agent compounding process: Raw fiber powder: castor oil = mass ratio 1:10, stir at low speed at room temperature (25℃) for 30 min until the powder is completely swollen and dispersed, and there are no visible solid particles, to obtain liquid anti-fracture agent A.

[0024] Example 2 (Unphosphorylated refined broad bean 11S protein combined with castor oil and anti-breakage agent B) raw material Commercially refined broad bean 11S protein powder (labeled protein content 90%, not phosphorylated, not modified with acid-thermal fiber) and the same batch of pharmaceutical castor oil (≥99%).

[0025] Preparation process The anti-crack agent B was prepared by directly mixing the dry powder and castor oil in a mass ratio of 1:10 at room temperature for 30 minutes. The entire process involved no phosphorylation reagent treatment or high-temperature acid self-assembly process, only simple physical mixing.

[0026] Example 3 (Commonly available compound broad bean protein powder with anti-fracture agent C) raw material Commercially available mixed broad bean plant protein powder (protein content 90%, production process is only physical pressing and defatting, without purification, phosphorylation, or acid heat treatment) and castor oil from the same batch.

[0027] Preparation process The same ratio of 1:10 is used to mix castor oil at room temperature to prepare anti-fracture agent C, without protein purification, chemical modification, or nanofiberization steps.

[0028] Example 4 (Direct compounding of coarse broad bean flour with anti-crack agent D) raw material The same broad beans as in Example 1 were used, but only the beans were crushed and air-dried to obtain coarse powder. All components retained starch and crude fiber, and the measured total protein was 20%. The same castor oil was used in conjunction with the beans.

[0029] Preparation process Without any salting, centrifugation, purification, or modification, broad bean coarse powder was directly mixed with 1 part castor oil at room temperature to prepare anti-fracture agent D.

[0030] Example 5 (Blank control group - pure castor oil anti-crack agent E) Raw material: only medicinal castor oil with a purity of ≥99%, without any added protein materials, used directly as anti-fracture agent E.

[0031] Standardized sample preparation and crack resistance testing (test conditions were completely consistent across groups). 1. Wax base raw materials: industrial lipstick-grade carnauba wax, fully refined paraffin wax, and candelilla wax. The three types of wax were prepared separately as samples.

[0032] 2. Sample addition ratio: Each type of wax is heated to 95℃ and completely melted. The corresponding anti-crack agent (A / B / C / D / E) is added at 20% of the wax mass. The mixture is stirred at a constant temperature for 40 min until the system is homogeneous. The system is degassed under vacuum of -0.08 MPa for 15 min to remove tiny air bubbles. The mixture is then poured into a lipstick mold that has been preheated to 50℃ while still hot. 100 samples are prepared for each type of wax in each group.

[0033] 3. Cooling Test Standards for Hot and Cold Platforms The samples were placed on the silver stage of the Abona CH562-ABN optical heating and cooling stage. The initial environment was 25℃, and the temperature was uniformly reduced to -10℃ at a rate of 5℃ / min. The temperature was then maintained for 6 h. Cracks were observed and determined by a 10x stereomicroscope: cracks with a length >2 mm and a width >20 μm were recorded as cracked samples. The number of cracks was counted. The results are shown in Table 1.

[0034] Table 1. Number of fractures (n, total number of each group 100) of typical fracture waxes after cooling by different anti-cracking agents.

[0035] As can be seen from the table above, both Examples 1 and 2 have obvious anti-breakage effects. Anti-breakage agent A prepared in Example 1 has the best effect on the three types of lipstick waxes: carnauba wax, paraffin wax, and candelilla wax. However, phosphorylated broad bean 11S protein fiber has a better effect than unphosphorylated broad bean 11S protein fiber, and the effect of castor oil (anti-breakage agent E in Example 5) is excluded.

[0036] Comparison Conclusion 1. The combination of castor oil (E) and broad bean powder (E, D) alone showed extremely poor anti-cracking effect, proving that castor oil itself has a weak anti-cracking effect, and the high amount of impurities and dense protein structure of the broad bean powder cannot improve the internal stress of the wax. 2. High-purity native broad bean protein (B, C) only slightly reduces the cracking rate, lacks phosphorylated ring-opening and acid-heat nanofiberization structure, and cannot form a flexible network; 3. The crack resistance of the fibrils modified by phosphorylation and acid-heat self-assembly was significantly better than that of all control groups (Examples 2-5), confirming that phosphoric acid chemical modification and acid-heat fibrils self-assembly are necessary technologies to achieve high-efficiency crack resistance.

[0037] Test results are as follows Figure 1 and Figure 2 As shown 1. Morphology of broad bean 11S protein fibrils.

[0038] Figure 1 Figure (a) shows that broad bean 11S protein fibrils (11SFB-24) exhibit a heterogeneous network structure composed of short, irregular filaments and residual amorphous aggregates, indicating an incomplete transition from the proto-spherical state. In contrast, Figure 1 In Figure (b), the phosphorylated broad bean 11S protein fibrils (P11SFB-24) formed significantly thinner and more uniformly distributed fibrils, creating an interconnected and uniform network structure.

[0039] 2. Phosphorylation groups of broad bean 11S protein fibrils.

[0040] Figure 2 Figure (a) shows the full XPS spectrum of broad bean 11SFB-24 and P11SFB-24. The spectrum shows characteristic signals at 531.5 eV, 399.8 eV, 286.4 eV, and 133.3 eV, corresponding to O1s, N1s, C1s, and P2p, respectively. Figure 2As shown in Figure (b), the P2p peak fitting results reveal a significant P2p characteristic peak at 133.3 eV for the P11SFB-24 sample compared to the 11S peak, indicating that phosphorus-containing groups were successfully introduced into the sample after hydrothermal phosphorylation, confirming that the phosphorylation reaction has occurred. Simultaneously, the O1s peak intensity of P11SFB-24 is significantly enhanced, and the binding energy shifts towards higher energy regions, possibly related to the introduction of phosphorus-containing oxygen functional groups and their impact on the surface chemical environment. Based on existing literature, it is speculated that when sodium tripolyphosphate is used as the phosphorylation reagent, the phosphorylation reaction may mainly occur on hydroxyl-containing amino acid residues such as serine, threonine, and tyrosine.

[0041] Working principle: First, broad bean 11S globulin is purified by salt dissolution-isoelectric precipitation; then, sodium tripolyphosphate is used for alkaline phosphorylation, which introduces phosphoroxane groups into the protein molecules, destroying the original dense spherical structure and exposing hydrophobic groups to improve wax compatibility; then, under strong acid and high temperature conditions, the protein peptide chains are induced to stretch and self-assemble to generate nano-flexible interwoven fibers; after the fibers and castor oil are compounded, they are uniformly dispersed inside the molten lipstick wax. When the wax cools, crystallizes, and shrinks, generating internal stress, the three-dimensional flexible fiber network interspersed in the gaps between the wax crystals absorbs and disperses the internal stress through its own elastic deformation, blocking the crack extension path, and ultimately achieving cooling of the lipstick and preventing cracking during low-temperature storage and transportation.

[0042] In summary, the preparation method of phosphorylated broad bean 11S protein fibrillation fiber (P11SFB-24) for improving lipstick wax cracking uses natural and safe raw materials, avoiding the defects of sensitization and oil leakage caused by chemical additives. All raw materials used in this invention are edible-grade broad beans and castor oil, without petroleum-based chemical plasticizers or artificial synthetic polymers. The resulting anti-cracking agent is natural and non-toxic, exhibits excellent compatibility with lipstick wax, and does not cause oil separation or softening of the lipstick during long-term storage. This method is suitable for the development of natural raw materials in cosmetics, solving the problems of sensitization caused by existing synthetic additives and oil leakage from the wax. The innovative molecular structure modification enhances the interfacial bonding between the protein and wax. This invention introduces phosphate-containing groups into the 11S protein molecules of broad beans through sodium tripolyphosphate phosphorylation modification, thereby disrupting the dense, spherical, rigid structure of the native protein and fully exposing the hydrophobic groups inside the protein. This overcomes the defects of native broad bean protein, such as being encapsulated by hydrophobic groups, having poor compatibility with non-polar waxes, and agglomerating into particles. Subsequently, acid-thermal self-assembly forms a nano-interwoven fiber network, resulting in a functional material that reduces the cooling and cracking of polyethylene wax used in lipsticks, further enhancing the interfacial wetting ability, and thus improving the stability and safety of the paste.

[0043] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0044] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking, characterized in that: Includes the following steps: Step 1: Crude extraction process of broad bean 11S protein: After the broad beans are crushed and air-dried, the protein is extracted by salting with sodium chloride aqueous solution. After centrifugation to remove residue, isoelectric point precipitation, and secondary centrifugation to collect the protein precipitate, the protein is then dialyzed and freeze-dried to obtain refined broad bean 11S protein powder. Step 2: Protein phosphorylation modification process: Refined broad bean 11S protein powder is dispersed in sodium tripolyphosphate solution, and phosphorylation grafting reaction is carried out under controlled temperature alkaline environment. The reaction solution is dialyzed to remove impurities and freeze-dried to obtain phosphorylated broad bean 11S solid powder. Step 3: Acid-heat induced self-assembly of nanofibrils: Phosphorylated broad bean 11S powder is mixed with water to prepare a protein aqueous solution. After being adjusted to an acidic environment, it is stirred at a constant temperature. The protein is induced to stretch and self-assemble into nanofibrils by the synergistic effect of acid and heat. The reaction system is dialyzed and freeze-dried to obtain phosphorylated broad bean 11S protein fibril powder. Step 4: Anti-breakage agent compounding process: Phosphorylated broad bean 11S protein fiber powder and castor oil are mixed and dissolved at a mass ratio of 1:(5-20) to obtain a natural anti-breakage agent for lipstick.

2. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 1, characterized in that: In step 1, the sodium chloride aqueous solution has a molar concentration of 0.5 mol / L, the pH of the salting system is controlled at 8.0-8.5, the dissolution temperature is 40-45℃, the stirring speed is 350-400 rpm, and the salting soaking time is 1.5-2 h. After salting, the mixture is centrifuged at 4-8℃ and 10000×g centrifugal force for 25-30 min, and the supernatant is separated and retained.

3. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 2, characterized in that: After filtration of the supernatant, the pH of the system is adjusted to 4.5-5.0 to achieve protein isoelectric point precipitation. The precipitation environment temperature is 20-25℃, the stirring speed is 350-400rpm, and the stirring precipitation time is 1-1.5h. After precipitation, the mixture is centrifuged at 4-8℃ and 10000×g for 15-20 minutes, and the bottom protein precipitate is collected.

4. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 3, characterized in that: The protein precipitation was performed by dialyzing with pure water using a dialysis membrane with a molecular weight cutoff of 500 Da for 48-72 hours, followed by freeze-drying for 48-72 hours after dialysis to obtain refined broad bean 11S protein powder.

5. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 1, characterized in that: In step 2, the sodium tripolyphosphate aqueous solution has a molar concentration of 0.1 mol / L. After dissolution, the pH of the system is adjusted to 8.5-9.0, the phosphorylation reaction temperature is 40-45℃, the stirring speed is 200-300 rpm, and the constant temperature reaction time is 2-3 hours.

6. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 1, characterized in that: After the protein phosphorylation modification process in step 2 is completed, the solution is dialyzed with a 500 Da molecular weight cutoff dialysis membrane for 48-72 hours to remove free phosphate impurities. The dialysate is then freeze-dried for 48-72 hours to obtain phosphorylated broad bean 11S solid powder.

7. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 1, characterized in that: In step 3, after the phosphorylated broad bean 11S powder is dissolved in water, the pH of the system is controlled at 1.8-2.0, the high temperature stirring temperature is 80-85℃, the stirring speed is 130-150rpm, and the constant temperature self-assembly reaction time is 24-30h.

8. The method for preparing phosphorylated broad bean 11S protein for improving lipstick wax cracking according to claim 7, characterized in that: After the self-assembly reaction, the protein solution was dialyzed with a 500 Da molecular weight cutoff dialysis membrane for 48-72 hours to remove small molecule degradation impurities, and then freeze-dried for 48-72 hours to obtain phosphorylated broad bean 11S protein fibrils powder.

9. The method for preparing phosphorylated broad bean 11S protein to improve lipstick wax cracking according to claim 1, characterized in that: In step 4, the preferred mass ratio of fibrillary fiber powder to castor oil is 1:

10. The mixture is stirred at room temperature until the powder is completely dissolved to obtain a homogeneous liquid lipstick anti-breakage agent.

10. A phosphorylated broad bean 11S protein for improving lipstick wax cracking, characterized in that, The preparation method described in any one of claims 1-9 is used to obtain the phosphorylated broad bean 11S protein. The phosphorylated protein is grafted with oxygen-containing phosphorus groups, and the molecules are loosely extended. The protein undergoes acid-heat self-assembly to form a long, uniform, cross-linked flexible nanofiber network structure. When used for lipstick wax modification, it is uniformly dispersed in paraffin wax, carnauba wax, and candelilla wax matrix to buffer the internal stress of wax crystal shrinkage and inhibit the cooling and cracking of the paste.

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