Use of pollen hollow particles in the preparation of wash and care products

Abstract

The application provides a use of pollen hollow particles in the preparation of washing and protecting products, and belongs to the technical field of daily chemical products. The pollen hollow particles are prepared by using plant pollen as raw material, defatting and removing protoplasm by acid treatment. The pollen hollow particles have strong cleaning ability, and the effect of removing cosmetics is significantly better than that of commercially available hydrated silica. The pollen hollow particles have strong affinity for oil and grease, and the adsorption performance is obviously improved, so that the demand of washing and protecting products can be met. The pollen hollow particles have smaller skin irritation and better safety. The raw material pollen is a natural renewable resource, and can be degraded in the natural environment after use, so that environmental pollution is not caused. The pollen hollow particles can be used for preparing various human washing and protecting products. In addition to human washing and protecting products, the excellent cleaning ability of the pollen hollow particles makes them also be used for preparing washing and protecting products for pets or articles, so that the pollen hollow particles have good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of daily chemical products technology, specifically relating to the use of hollow pollen particles in the preparation of personal care products. Background Technology

[0002] Exfoliating materials, through moderate physical friction, can effectively remove accumulated dead skin cells, excess oil, and dirt from pores, while promoting blood circulation and accelerating epidermal cell renewal. However, the plastic microbeads used in traditional skincare products have long been a global environmental problem due to their difficulty in degradation and their ease of entry into natural water bodies through wastewater treatment systems. Plastic microbeads have a density similar to water, and once in natural water bodies, they can be widely distributed on the surface, in the middle and bottom layers, causing pollution throughout the entire body of water. Their smooth surface and hydrophobic properties make them prone to combining with suspended particles in the water to form aggregates, clogging the stomata of aquatic plant roots and damaging the primary productivity of aquatic ecosystems. Furthermore, the microplastic particles formed from the slow physical degradation of plastic microbeads in the natural environment are even more difficult to filter by water purification systems, and can remain in water bodies for decades or even centuries, posing a long-term and persistent pollution hazard. More seriously, plastic microbeads and the microplastic particles produced by their degradation can be actively ingested by various aquatic organisms and accumulate in their bodies. Through the food chain, they are passed down and enriched step by step, ultimately posing a threat to human health at the top of the food chain. This may cause health problems such as digestive tract inflammation and decreased immune function, and long-term accumulation may also damage organs such as the liver and kidneys.

[0003] Given the aforementioned hazards, over 30 countries worldwide have enacted legislation banning the use of plastic microbeads in personal care products. Existing alternative materials all have significant shortcomings: natural mineral materials (such as talc and calcium carbonate) are too hard, easily causing scratches and irritation to the skin, and have poor abrasive effects; plant fiber materials (such as cellulose granules and nutshell powder) are highly absorbent, easily agglomerating and settling in personal care products, affecting product stability; synthetic polymer materials (such as polylactic acid granules and polycaprolactone granules) have high production costs and still consume fossil resources during production, failing to meet sustainable development requirements. Currently, commercially available personal care products containing exfoliating particles commonly use hydrated silica, which, although primarily composed of silica-rich minerals, has extremely limited oil absorption capacity and possesses certain respiratory irritant properties. Therefore, developing a plastic microbead alternative material that combines good performance, environmental friendliness, and economy has become a critical issue urgently needing to be addressed in the personal care industry.

[0004] Plant pollen, as an important carrier of male reproductive cells in seed plants, can be transformed into functional materials after specific processing. For example, hollow spore pollen microcapsules obtained by defatting and acid treatment to remove protoplasm from pollen have been extensively studied in materials science, with main applications including drug delivery carriers, taste masking, and the cosmetics industry. Their primary function is as a carrier of active ingredients. For instance, patent application CN118831010A discloses hollow camellia pollen microcapsules prepared by purifying camellia pollen, defatting with acetone, acid hydrolyzing, and drying. These hollow camellia pollen microcapsules serve as novel carriers of active ingredients for use in cosmetics and health food applications.

[0005] Currently, there are no reports of hollow pollen particles being used as adsorbent or abrasive materials for skin, hair, or teeth cleaning. Summary of the Invention

[0006] The purpose of this invention is to provide the use of hollow pollen grains in the preparation of personal care products.

[0007] This invention provides the use of hollow pollen particles in the preparation of personal care products. The hollow pollen particles are obtained by degreasing and acid treatment of natural pollen. The hollow pollen particles are used as a cleaning ingredient in personal care products.

[0008] In this invention, the cleaning and care product is a daily chemical industrial product used for cleaning human bodies, pets, or items. It uses hollow pollen particles as functional particles, and exerts its cleaning effect through physical friction, adsorption, or synergistic action with surfactants to remove sweat, dirt, oil, blackheads, dead skin cells, pesticide residues, and cosmetic residues, etc.

[0009] Furthermore, the method for preparing the hollow pollen grains includes the following steps: (1) Take natural pollen, first wash it with ethanol aqueous solution until the filtrate is clear and transparent, then wash it with acetone until the filtrate is clear and transparent, and collect the washed pollen powder; (2) Add the cleaned pollen powder to acetone, reflux and extract, filter, recover the pollen powder and dry to obtain defatted pollen; (3) Add defatted pollen to acid, reflux and wash until the pH of the filtrate is neutral, then dry to obtain hollow pollen grains.

[0010] Furthermore, In step (1), the volume ratio of anhydrous ethanol to water in the ethanol-water solution is (1-5):1; And / or, in step (1), the solid-liquid ratio of the natural pollen and the ethanol aqueous solution is 1 g: (1-100) mL; And / or, in step (1), the cleaning with ethanol aqueous solution is ultrasonic cleaning; And / or, in step (1), the solid-liquid ratio of the natural pollen to acetone is 1 g: (1-100) mL; And / or, in step (2), the solid-liquid ratio of the pollen powder and acetone is 1 g: (1-100) mL; And / or, in step (2), the temperature of the condensation reflux is 50-60°C; And / or, in step (2), the condensation reflux time is 10-20h; And / or, in step (2), the stirring is performed during the condensation reflux, and the stirring speed is 100~300 rpm; And / or, in step (2), the drying temperature is 50-60°C; And / or, in step (2), the drying time is 10-20 hours; And / or, in step (3), the acid is an aqueous solution of phosphoric acid with a mass fraction of 70-95%; And / or, in step (3), the solid-liquid ratio of the defatted pollen to the acid is 1 g: (1-100) mL; And / or, in step (3), the temperature of the condensation reflux is 70~90℃; And / or, in step (3), the condensation reflux time is 1-10h; And / or, in step (3), the stirring is performed during the condensation reflux, and the stirring speed is 100~300 rpm; And / or, in step (3), the cleaning includes the following steps: filtration, cleaning with water at a temperature of 70~90℃, then cleaning with acetone, then cleaning with hydrochloric acid aqueous solution, and finally cleaning with deionized water; And / or, in step (3), the pH value is 6.5-7.5; And / or, in step (3), the drying temperature is 50-60°C; And / or, in step (3), the drying time is 10-20 hours.

[0011] Furthermore, the hollow pollen grains are selected from one or more combinations of lotus hollow pollen grains, pine hollow pollen grains, and sunflower hollow pollen grains; each type of hollow pollen grain is prepared using the aforementioned method.

[0012] Furthermore, the aforementioned washing and care products are washing and care products for cleaning human bodies, pets, and items; Preferably, The aforementioned personal care products are for cleaning the face, body, hair, mouth, and other special areas of the human body. The pet grooming products mentioned are for cleaning the pet's face, body, fur, mouth, and other special areas. The cleaning products mentioned are cleaning and care products for household appliances, beauty tools, and fruits and vegetables.

[0013] For the human body, facial cleansing products include, but are not limited to, facial cleansers, makeup removers, cleansing masks, blackhead strips, exfoliating products, cleansing effervescent tablets, post-medical aesthetic treatment cleansing supplies, beauty salon exfoliating gels, disposable exfoliating cotton pads, and exfoliating facial cleansing sticks; body cleansing products include, but are not limited to, shower gels, body scrubs, bath salts, exfoliating bath soaps, SPA exfoliating oils, pre-treatment exfoliating scrubs before hair removal, and scented bath scrub balls; hair cleansing products include, but are not limited to, shampoos, hair creams, and scalp scrubs; oral cleansing products include, but are not limited to, toothpaste, mouthwash, tooth powder, and denture / braces cleansing effervescent tablets; and cleansing products for special areas include, but are not limited to, feminine washes, baby care products, foot bath packs, exfoliating foot masks, and hand and foot exfoliating scrubs.

[0014] For pets, grooming products include, but are not limited to, pet body scrub, paw pad cleaning scrub, and gentle ear canal cleaning paste.

[0015] For items, cleaning and care products include, but are not limited to, fruit and vegetable dishwashing scrub, leather and furniture gentle cleaner, and beauty tool cleaner.

[0016] Furthermore, the washing and care product is a washing and care product containing physical exfoliants, and the hollow pollen particles serve as physical exfoliants.

[0017] In this invention, physical exfoliants refer to functional fillers in washing and care products that are dispersed in the form of solid particles in a matrix (paste, gel, emulsion, etc.) and achieve physical cleaning or exfoliation through mechanical friction.

[0018] Furthermore, the washing and care product is a washing and care product that absorbs and removes grease.

[0019] Furthermore, the aforementioned cleansing and care product is a makeup-removing cleansing and care product.

[0020] The present invention also provides a personal care product comprising hollow pollen particles; the hollow pollen particles are obtained by degreasing and acid treatment of natural pollen; the hollow pollen particles are used as a cleaning ingredient in the personal care product.

[0021] Furthermore, the hollow pollen grains are selected from one or more combinations of lotus hollow pollen grains, pine hollow pollen grains, and sunflower hollow pollen grains; each type of hollow pollen grain is prepared using the aforementioned method.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention develops hollow pollen particles prepared from plant pollen through degreasing and acid treatment to remove allergenic protein protoplasm. Research in this invention has found that these hollow pollen particles have strong cleansing power, effectively removing dead skin cells upon contact with the skin, and are significantly more effective at removing cosmetics such as foundation, lipstick, and eyeliner than commercially available products (hydrated silica). Simultaneously, these hollow pollen particles have a strong affinity for oils, exhibiting significantly improved oil adsorption compared to commercially available products, meeting the needs of cleansing and care products. Furthermore, compared to existing exfoliating materials, these hollow pollen particles are less irritating and safer. In addition, the pollen used in this invention is a natural and renewable resource; when used as an exfoliating material, it is biodegradable in the natural environment and does not cause environmental pollution like plastic microbeads, meeting current consumer demand for environmentally friendly skincare products. Hollow pollen grains can absorb oil and exfoliate, while also providing nourishment and antioxidant benefits to the skin. They can be used to prepare various personal care products (such as facial cleansers, cleansing masks, body scrubs, and toothpaste). In addition to personal care products, the excellent cleaning ability of hollow pollen grains also makes them suitable for preparing pet care products, thus showing promising application prospects.

[0023] In summary, the natural pollen-based personal care material prepared by this invention achieves a breakthrough in both performance and sustainability, effectively overcoming the limitations of traditional plastic microbeads and existing alternative materials. It exhibits excellent cleaning power and oil absorption properties, and is highly environmentally friendly, being biodegradable and environmentally friendly. Furthermore, natural pollen raw materials are low-cost, a sustainable renewable resource, and possess both good environmental and economic advantages, aligning with current global environmental policies and industry development trends, and is expected to promote the green and sustainable development of the personal care industry.

[0024] Obviously, based on the above description of the present invention, and according to common technical knowledge and conventional methods in the field, various other modifications, substitutions or alterations can be made without departing from the basic technical concept of the present invention.

[0025] The following detailed embodiments further illustrate the above-described content of the present invention. However, this should not be construed as limiting the scope of the present invention to the following examples. All technologies implemented based on the above-described content of the present invention fall within the scope of the present invention. Attached Figure Description

[0026] Figure 1 This is a schematic diagram illustrating the preparation of washing solutions from three types of hollow pollen particles in Examples 1-3.

[0027] Figure 2The images show macroscopic morphology diagrams and microscopic images of the three types of hollow pollen grains prepared in Examples 1-3. In the images, the first row shows macroscopic morphology diagrams, the second row shows SEM images, and the third row shows morphology diagrams taken with an optical microscope.

[0028] Figure 3 The figure shows the particle size distribution of the three hollow pollen grains prepared in Examples 1-3.

[0029] Figure 4 The images show the SEM morphology and EDS surface distribution of C, N, and O elements of the natural pollen raw materials from Examples 1-3 and the hollow pollen grains of pine, lotus, and sunflower prepared according to the methods described in Examples 1-3.

[0030] Figure 5 Laser confocal microscopy images of the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus and sunflower prepared according to the methods described in Examples 1-3.

[0031] Figure 6 Thermogravimetric analysis (TG) and differential thermogravimetric analysis (DTG) curves are shown for the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus and sunflower prepared according to the methods described in Examples 1-3.

[0032] Figure 7 The graph shows the protein removal rate of the three types of hollow pollen grains prepared in Examples 1-3; in the graph, ns indicates no significant difference. express p <0.05, express p <0.01.

[0033] Figure 8 The graph shows the test results of the cleaning power of different cleansing liquids on foundation.

[0034] Figure 9 The graph shows the test results of the cleaning power of different detergents on lipstick.

[0035] Figure 10 The graph shows the test results of the cleaning power of different cleansing solutions on liquid eyeliner.

[0036] Figure 11 The graph shows the cleaning efficiency of different cleansers on foundation, lipstick, and eyeliner; in the graph, ns indicates no significant difference. express p <0.05, express p <0.01, express p <0.001, express p <0.0001.

[0037] Figure 12 The graph shows the maximum oil absorption of the three hollow pollen particles prepared in Examples 1-3 and commercially available hydrated silica for silicone oil, olive oil and oleic acid, respectively; in the graph, ns indicates no significant difference. express p <0.05, express p <0.01, express p <0.001, express p <0.0001.

[0038] Figure 13 The graph shows the maximum oil absorption of three types of natural pollen, three types of defatted pollen prepared in Examples 1-3, and hollow pollen particles for silicone oil, olive oil, and oleic acid, respectively; in the graph, express p <0.0001.

[0039] Figure 14 The diagram shows the interfacial wetting properties of the three types of hollow pollen particles prepared in Examples 1-3.

[0040] Figure 15 H&E staining results of mouse skin sections subjected to allergic stimulation from the three types of hollow pollen grains prepared in Examples 1-3.

[0041] Figure 16 H&E staining results of major organ tissues of mice subjected to allergic stimulation from the three types of hollow pollen grains prepared in Examples 1-3. Detailed Implementation

[0042] Unless otherwise specified, the chemical reagents used in the specific embodiments are all conventional commercially available reagents, and the technical means used are all conventional means well known to those skilled in the art.

[0043] The specific sources of natural pollen used in the implementation are as follows: (1) Natural pine pollen ( Pinus massoniana Lamb. mainly comes from Masson pine. Every year from March to May, when the male flowers have just turned yellow and have not yet released pollen, the male flower spikes are picked by hand, dried, rubbed, and sieved to separate pure pollen and remove pine branches and impurities.

[0044] (2) Natural lotus pollen ( Nelumbo nucifera Gaertn. is mainly derived from pollen clumps collected by bees using their pollinators after pollination.

[0045] (3) Natural sunflower powder ( Helianthus annuus L.) mainly comes from pollen clumps collected by bees using their pollinators after pollination.

[0046] All of the above-mentioned natural pollens are unprocessed and can be obtained by purchasing commercially available products.

[0047] Example 1: Preparation of hollow pine pollen granules (1) Preparation of defatted pollen Weigh 20 g of natural pine pollen and add 100 mL of a 2:1 (v:v) mixture of ethanol and water. Sonicate the mixture for 15 min, then vacuum filter to collect the pollen powder. Repeat the ultrasonic cleaning process with the same ethanol and water mixture until the filtrate is clear and transparent. Add 20 mL of acetone and continue cleaning the pollen powder. Vacuum filter to collect the pollen powder, then repeat the acetone cleaning process until the filtrate is clear and transparent. Collect the pollen powder.

[0048] Add 20 mL of acetone to the washed pollen powder, stir at 200 rpm at 50°C, and reflux for 12 h. Vacuum filter to recover the pollen powder, and dry it in an oven at 50°C for 12 h to obtain defatted pine pollen.

[0049] (2) Preparation of hollow pollen grains (acid treatment) Weigh 3.5 g of dried, defatted pine pollen and add 40 mL of 85% (w / w) phosphoric acid aqueous solution. Stir at 200 rpm at 80℃ and reflux for 6 h. Add 120 mL of 80℃ hot water to the suspension, dilute, and then filter under vacuum. Wash the pollen three times with 80℃ hot water. Then wash the pollen grains twice with 20 mL of acetone. Next, wash the pollen grains once with 30 mL of 2 mol / L hydrochloric acid aqueous solution. Finally, wash the pollen grains with deionized water until the pH of the filtrate is neutral (pH=6.5-7.5). Dry the obtained pollen grains in an oven at 50℃ for 12 h. Finally, dry to obtain hollow pine pollen grains.

[0050] Example 2: Preparation of hollow lotus pollen granules (1) Preparation of defatted pollen Weigh 20 g of natural lotus pollen and add 100 mL of a 2:1 (v:v) mixture of ethanol and water. Sonicate the mixture for 15 min, then vacuum filter to collect the pollen powder. Repeat the ultrasonic cleaning process with the same ethanol and water mixture until the filtrate is clear and transparent. Add 20 mL of acetone and continue cleaning the pollen powder. Vacuum filter to collect the pollen powder, then repeat the acetone cleaning process until the filtrate is clear and transparent. Collect the pollen powder.

[0051] Add 20 mL of acetone to the washed pollen powder, stir at 200 rpm at 50℃, and reflux for 12 h. Vacuum filter to recover the pollen powder, and dry it in an oven at 50℃ for 12 h to obtain defatted lotus pollen.

[0052] (2) Preparation of hollow pollen grains (acid treatment) Weigh 3.5 g of dried, defatted lotus pollen and add 40 mL of 85% (w / w) phosphoric acid aqueous solution. Stir at 200 rpm at 80℃ and reflux for 6 h. Add 120 mL of 80℃ hot water to the suspension, dilute, and then filter under vacuum. Wash the pollen three times with 80℃ hot water. Then wash the pollen grains twice with 20 mL of acetone. Next, wash the pollen grains once with 30 mL of 2 mol / L hydrochloric acid aqueous solution. Finally, wash the pollen grains with deionized water until the pH of the filtrate is neutral (pH=6.5-7.5). Dry the obtained pollen grains in an oven at 50℃ for 12 h. Finally, dry to obtain hollow lotus pollen grains.

[0053] Example 3: Preparation of hollow sunflower pollen granules (1) Preparation of defatted pollen Weigh 20 g of natural sunflower pollen and add 100 mL of a 2:1 (v:v) mixture of ethanol and water. Sonicate the mixture for 15 min, then vacuum filter to collect the pollen powder. Repeat the ultrasonic cleaning process with the same ethanol and water mixture until the filtrate is clear and transparent. Add 20 mL of acetone and continue cleaning the pollen powder. Vacuum filter to collect the pollen powder, then repeat the acetone cleaning process until the filtrate is clear and transparent. Collect the pollen powder.

[0054] Add 20 mL of acetone to the washed pollen powder, stir at 200 rpm at 50°C, and reflux for 12 h. Vacuum filter to recover the pollen powder, and dry it in an oven at 50°C for 12 h to obtain defatted sunflower pollen.

[0055] (2) Preparation of hollow pollen grains (acid treatment) Weigh 3.5 g of dried, defatted sunflower pollen and add 40 mL of 85% (w / w) phosphoric acid aqueous solution. Stir at 200 rpm at 80℃ and reflux for 6 h. Add 120 mL of 80℃ hot water to the suspension, dilute, and then filter under vacuum. Wash the pollen three times with 80℃ hot water. Then wash the pollen grains twice with 20 mL of acetone. Next, wash the pollen grains once with 30 mL of 2 mol / L hydrochloric acid aqueous solution. Finally, wash the pollen grains with deionized water until the pH of the filtrate is neutral (pH=6.5-7.5). Dry the obtained pollen grains in an oven at 50℃ for 12 h. Finally, dry to obtain hollow sunflower pollen grains.

[0056] Example 4: Preparation of washing solution for hollow pollen grains The preparation method of hollow pollen grain washing solution is as follows: Weigh 50 mg of soap block, add 10 mL of deionized water, vortex the bubbles, measure 5 mL of soap foam into a small beaker, add 5 mg of abrasive particles (one or more of the three hollow pollen particles prepared in Examples 1-3) and stir to mix well to obtain hollow pollen particle washing solution (i.e. washing solution with hollow pollen particles as abrasive material).

[0057] The schematic diagrams and appearance diagrams of the washing solutions prepared using the three types of hollow pollen grains prepared in Examples 1-3 according to the above method are shown below. Figure 1 As shown.

[0058] The following specific experimental examples demonstrate the beneficial effects of the present invention.

[0059] Example 1: Morphology and particle size characterization results of hollow pollen grains of the present invention I. Experimental Methods Hollow pollen grains of pine, lotus, and sunflower were prepared according to the methods described in Examples 1-3, respectively. The macroscopic morphology of these three types of hollow pollen grains was photographed, and their microscopic morphology was characterized using optical microscopy and scanning electron microscopy (SEM). The particle size of these three types of hollow pollen grains was measured using a laser particle size analyzer.

[0060] SEM-EDS elemental surface scan analysis was performed on the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus and sunflower prepared according to the methods described in Examples 1-3 to evaluate the compositional changes of the pollen before and after acid treatment.

[0061] Laser confocal microscopy imaging was performed on the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus and sunflower prepared according to the methods described in Examples 1-3.

[0062] Thermogravimetric analysis (TG) and differential thermogravimetric analysis (DTG) were performed on the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus, and sunflower prepared according to the methods described in Examples 1-3. Thermogravimetric analysis was carried out using a simultaneous thermal analyzer under a nitrogen atmosphere, with a heating rate of 20°C / min and a test range from room temperature to 800°C.

[0063] II. Experimental Results Figure 2 Macroscopic morphology images and microscopic images of the three types of hollow pollen grains prepared in Examples 1-3 are shown. Figure 2 It can be seen that all three types of hollow pollen grains are brown. SEM images and optical microscope images show that the hollow pollen grains retain the complete structure of the pollen and have a uniformly distributed porous structure on the surface.

[0064] Figure 3 The image shows the particle size distribution of the three types of hollow pollen grains prepared in Examples 1-3. Figure 3 It can be seen that the particle size of hollow pine pollen grains is approximately 48.2 μm; the particle size of hollow lotus pollen grains is approximately 67.7 μm; and the particle size of hollow sunflower pollen grains is approximately 41.2 μm.

[0065] Figure 4 The images show the SEM morphology and EDS surface distribution of C, N, and O elements of the natural pollen raw materials from Examples 1-3, and the hollow pollen grains of pine, lotus, and sunflower prepared according to the methods described in Examples 1-3. Figure 4 It can be seen that, compared with natural pollen, the relative content of nitrogen (N) is significantly reduced after acid treatment, while the contents of carbon (C) and oxygen (O) remain basically unchanged. Since the nitrogen-containing components in pollen mainly come from proteins and other biomolecules, the reduction in nitrogen signal indicates that the extraction process significantly reduced the nitrogen-containing components on and near the surface of the pollen.

[0066] Figure 5 Laser confocal microscopy images of the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus, and sunflower prepared according to the methods described in Examples 1-3, respectively. Figure 5 It is known that natural pollen can produce inherent autofluorescence due to its internal biological components. Observation using a laser confocal scanning microscope shows that natural pollen exhibits uniform autofluorescence overall, while the fluorescence signal of hollow pollen grains is highly concentrated on the outer wall of the sporophytin, with no fluorescence signal in the central region of the inner cavity. This indicates that acid treatment can remove internal components, forming a hollow structure.

[0067] Figure 6Thermogravimetric analysis (TG) and differential thermogravimetric analysis (DTG) curves are shown for the natural pollen raw materials of Examples 1-3 and the hollow pollen grains of pine, lotus, and sunflower prepared according to the methods described in Examples 1-3, respectively. Figure 6 Thermogravimetric analysis revealed three typical thermal degradation stages in both natural pollen and hollow pollen grains. Slight weight loss at 150 °C was attributed to the evaporation of adsorbed water and the volatilization of volatile substances within the natural pollen. Natural pollen underwent primary thermal decomposition between 200-350 °C, mainly due to the degradation of intracellular components such as proteins, pectin, lipids, and polysaccharides. The maximum thermal decomposition temperatures of hollow pollen grains increased to 466.21 °C, 458.13 °C, and 468.01 °C, respectively. This further indicates that acid treatment effectively removes thermally unstable intracellular substances, leaving behind a highly cross-linked sporophytin exowall framework, which is beneficial for the adsorption and removal of lipids.

[0068] Experimental Example 2: Determination of Pollen Protein Removal Rate I. Experimental Methods Accurately weigh 0.1 g each of three types of natural pollen (pine pollen, lotus pollen, and sunflower pollen) and hollow pollen grains prepared according to Examples 1-3, and freeze-store them at -20℃ for 24 h. Add 2 mL of constant-temperature deionized water to the frozen pollen and extract by ultrasonication at 65℃ for 60 min. Then centrifuge at 12000 r / min for 15 min, and collect the supernatant as the pollen protein extract. Use a BCA protein concentration assay kit to determine the protein content in natural pollen and acid-treated hollow pollen grains, and calculate the pollen protein removal rate.

[0069] Pollen protein removal rate = (Natural pollen protein content - Hollow pollen grain protein content) / Natural pollen protein content × 100% II. Experimental Results Figure 7 The graph shows the protein removal rates of the three types of hollow pollen grains prepared in Examples 1-3. Figure 7 It can be seen that the protein removal rate of the three types of hollow pollen grains prepared by this invention is all above 90%. This indicates that the preparation method of this invention can effectively remove endogenous proteins in pollen and reduce the risk of sensitization.

[0070] Test Example 3: Cleaning Power Test of Hollow Pollen Granule Wash I. Experimental Methods 1. Sample preparation Pine pollen grain washing solution, lotus pollen grain washing solution, and sunflower pollen grain washing solution were prepared according to the method described in Example 4. The hollow pollen grains were replaced with the same amount of commercially available hydrated silica, and a hydrated silica washing solution was prepared according to the method described in Example 4. In addition, soap foam prepared according to the method described in Example 4 (50 mg of soap block was weighed, added to 10 mL of deionized water, and vortexed to create bubbles) served as a control group.

[0071] 2. Cleaning power test Take fresh pigskin, wash away surface oil stains, and cut into 3 cm × 3 cm pieces. Apply foundation, lipstick, and eyeliner evenly to the surface of each pigskin piece (the amount, pressure, and area of ​​application are the same for each group). Use the prepared cleaning solutions (pine hollow pollen grain solution, lotus hollow pollen grain solution, sunflower hollow pollen grain solution, hydrated silica solution, and soap foam) and wipe with the same amount and pressure, then rinse with water. Repeat the wiping 30 times, recording the cleaning effect under a microscope. Calculate the cleaning efficiency of each group of cleaning solutions for foundation, lipstick, and eyeliner.

[0072] ImageJ software was used to perform quantitative statistical analysis on the area of ​​residual foundation, lipstick, and eyeliner on each group of pigskin and to calculate the cleaning efficiency.

[0073] Cleaning efficiency = (Area of ​​makeup before cleaning - Area of ​​residual makeup after cleaning) / Area of ​​makeup before cleaning × 100% II. Experimental Results Figure 8 The graph shows the test results of the cleaning power of different cleansing liquids on foundation. Figure 9 The graph shows the test results of the cleaning power of different detergents on lipstick. Figure 10 The graph shows the test results of the cleaning power of different cleansing solutions on liquid eyeliner. Figure 11 The graph shows the cleaning efficiency of different cleansers on foundation, lipstick, and eyeliner. Figure 8-11 It can be seen that, compared with soap foam (blank group) and hydrated silica wash, all three hollow pollen particle washes have significant cleaning power against foundation, lipstick, and eyeliner. The cleaning efficiency of the three hollow pollen particle washes is comparable and significantly better than that of hydrated silica, the main ingredient in commercially available scrubs.

[0074] Experimental Example 4: Determination of the oil adsorption capacity of hollow pollen grains I. Experimental Methods 1. Maximum oil absorption The oil adsorption capacity of the hollow pollen particles prepared in Examples 1-3 and commercially available hydrated silica was tested. The oil adsorption capacity of the defatted pollen prepared in Examples 1-3 and the natural pollen used in Examples 1-3 was also tested. The specific test methods are as follows: The mass of the empty centrifuge tube (M0) was determined. 50 mg of the test sample (M1) was weighed and placed in the centrifuge tube. 2 mL of silicone oil, olive oil, and oleic acid were added separately, and the mixture was thoroughly mixed. After adsorption for 5 min, the tube was centrifuged at 10000 r / min for 10 min to remove excess oil. The "centrifugation-removal of upper layer oil" operation was repeated until no free oil precipitated. The total weight of the centrifuge tube and the sample after oil removal (M2) was then measured. The maximum oil absorption capacity A for each sample was determined. max (Unit: g / g) The calculation formula is as follows: A max =(M2-M0-M1) / M1 2. Wetting properties Weigh 10 mg of the hollow pollen grains prepared in Examples 1-3 and place them at the silicone oil-water two-phase interface: (1) Place equal amounts of each hollow pollen grain separately in equal amounts of water or silicone oil (water and silicone oil of equal volume). (2) First, place an equal amount of hollow pollen grains in a glass bottle, add an equal amount of water, then add an equal amount of silicone oil (water and silicone oil are of equal volume), and then let the mixture stand for 10 minutes. (3) Mix silicone oil and water in equal volumes, then add equal amounts of each hollow pollen grain, and let the mixture stand for 10 minutes.

[0075] The interfacial affinity behavior of hollow pollen particles in aqueous solution, pure silicone oil, and oil-water mixtures was observed to evaluate the interfacial wetting characteristics of hollow pollen.

[0076] II. Experimental Results 1. Maximum oil absorption Figure 12 The graph shows the maximum oil absorption of silicone oil, olive oil, and oleic acid by the three types of hollow pollen particles prepared in Examples 1-3 and commercially available hydrated silica, respectively. Figure 12 It can be seen that the adsorption values ​​of commercially available hydrated silica granules for washing and conditioning products, pine hollow pollen granules, lotus hollow pollen granules, and sunflower hollow pollen granules for silicone oil are 3.55, 8.26, 5.79, and 6.95 g / g, respectively; for olive oil, they are 3.60, 8.65, 6.51, and 6.89 g / g, respectively; and for oleic acid, they are 3.34, 7.70, 6.58, and 7.15 g / g, respectively.

[0077] Figure 13 The graph shows the maximum oil absorption of three types of natural pollen, three types of defatted pollen prepared in Examples 1-3, and hollow pollen particles for silicone oil, olive oil, and oleic acid, respectively. Figure 13 It can be known that: The maximum oil absorption capacity of natural pine pollen for silicone oil, olive oil, and oleic acid is 2.48, 2.62, and 2.36 g / g, respectively; the maximum oil absorption capacity of defatted pine pollen for silicone oil, olive oil, and oleic acid is 2.30, 2.21, and 2.19 g / g, respectively; and the maximum oil absorption capacity of hollow pine pollen particles for silicone oil, olive oil, and oleic acid is 8.26, 8.65, and 7.70 g / g, respectively.

[0078] The maximum oil absorption capacity of natural lotus pollen for silicone oil, olive oil, and oleic acid is 0.67, 0.62, and 0.60 g / g, respectively; the maximum oil absorption capacity of defatted lotus pollen for silicone oil, olive oil, and oleic acid is 1.54, 1.70, and 1.64 g / g, respectively; and the maximum oil absorption capacity of hollow lotus pollen granules for silicone oil, olive oil, and oleic acid is 5.79, 6.51, and 6.58 g / g, respectively.

[0079] The maximum oil absorption capacity of natural sunflower pollen for silicone oil, olive oil, and oleic acid is 1.30, 1.42, and 1.32 g / g, respectively; the maximum oil absorption capacity of defatted sunflower pollen for silicone oil, olive oil, and oleic acid is 1.27, 1.55, and 1.62 g / g, respectively; and the maximum oil absorption capacity of hollow sunflower pollen grains for silicone oil, olive oil, and oleic acid is 6.95, 6.89, and 7.15 g / g, respectively.

[0080] The above results demonstrate that the hollow pollen grains prepared by this invention have a significantly improved oil adsorption capacity. Among them, the hollow pine pollen grains exhibit the best oil adsorption capacity.

[0081] 2. Wetting properties Figure 14 The figures show the interfacial wetting properties of the three types of hollow pollen grains prepared in Examples 1-3. Figure 14 It can be seen that the hollow pollen particles prepared by this invention have good lipophilicity and can effectively adsorb oils.

[0082] Test Example 5: Skin Allergy Test of Hollow Pollen Grains I. Experimental Methods The three hollow pollen particles prepared in Examples 1-3 were mixed with petroleum jelly at a mass ratio of 1:19 to obtain different hollow pollen particle petroleum jelly ointments (pine pollen petroleum jelly ointment, lotus pollen petroleum jelly ointment, and sunflower pollen petroleum jelly ointment).

[0083] Thirty KM mice (20-22 g), half male and half female, were randomly divided into five groups (Vaseline ointment group, 2,4-dinitrochlorobenzene group, pine pollen Vaseline ointment group, lotus pollen Vaseline ointment group, and sunflower pollen Vaseline ointment group). After 3 days of acclimatization culture, a 3 cm shave was made on the back of each mouse. A 3cm hairless area makes it easier to apply medication.

[0084] 760 mg of petroleum jelly ointment was applied to the test area of ​​the skin of mice in the control group (petroleum jelly ointment group), and 0.1 mL of 1% 2,4-dinitrochlorobenzene solution (a mixture of acetone and olive oil in a 4:1 ratio) was applied to the test area of ​​the skin of mice in the 2,4-dinitrochlorobenzene group. The remaining three groups were treated with 800 mg of petroleum jelly ointment containing 40 mg of each of the three hollow pollen grains. After administration, the test area of ​​the skin was wrapped and fixed with non-irritating gauze, and the drug was removed after 6 h. The same method was repeated on days 7 and 14 after the initial administration. A challenge treatment was performed 14 days after the initial administration on day 14, using the same method and dosage. Skin erythema, edema, and other abnormal reactions were observed and scored at 6 h, 24 h, 48 h, and 72 h after application (evaluation methods are shown in Tables 1-3). Mice were euthanized after 72 hours of scoring. Organs were collected, weighed, and skin and major organ tissues were stained with H&E for sectioning and pathological examination.

[0085] Table 1. Skin Reaction Scoring Table for Allergic Reactions Table 2. Stimulation Evaluation Form Table 3. Sensitization Evaluation Table II. Experimental Results Figure 15 Images of H&E staining of mouse skin sections after allergic reactions to the three types of hollow pollen grains prepared in Examples 1-3. Figure 15 The results showed that the positive control group (2,4-dinitrochlorobenzene) exhibited significant epidermal acanthosis, hyperkeratosis, and localized epidermal necrosis, accompanied by dermal inflammatory cell infiltration. The three hollow pollen grain groups showed intact epidermal structures with clear layers, and no epidermal thickening, necrosis, or inflammatory reaction was observed, showing no significant difference from the blank control group. This indicates that hollow pollen grains are non-irritating and non-sensitizing to the skin, and are suitable for use in human skin cleansing products.

[0086] Figure 16 Images of H&E staining of major organ tissues from mice subjected to allergic stimulation from the three types of hollow pollen grains prepared in Examples 1-3. Figure 16 It can be seen that after stimulation with the three types of hollow pollen grains, there were no obvious pathological changes in the major organs of mice, indicating that the hollow pollen grains have good biocompatibility.

[0087] Table 4 shows the skin reaction scores of the three hollow pollen grains in the allergy test; Table 5 shows the irritation evaluation results of the three hollow pollen grains; and Table 6 shows the sensitization rate evaluation results of the three hollow pollen grains.

[0088] Table 4. Results of skin reaction scores in allergic tests for three types of hollow pollen grains. Note: One mouse in the 2,4-dinitrochlorobenzene group died during the experiment.

[0089] Table 5. Evaluation results of the irritation of three types of hollow pollen grains. Note: One mouse in the 2,4-dinitrochlorobenzene group died during the experiment.

[0090] Table 6. Evaluation results of sensitization rate of three types of hollow pollen grains Note: One mouse in the 2,4-dinitrochlorobenzene group died during the experiment.

[0091] Tables 4-6 show that lotus hollow pollen grains and sunflower hollow pollen grains have no obvious skin irritation and do not cause skin allergic reactions. Pine hollow pollen grains have a mild irritant effect on male mice, and further investigation of skin allergic reactions is needed before use.

[0092] In summary, this invention develops hollow pollen granules prepared from plant pollen through degreasing and acid treatment to remove allergenic protein protoplasm. These hollow pollen granules possess strong cleaning power, significantly outperforming commercially available hydrated silica in removing cosmetics; they exhibit strong affinity for oils, resulting in significantly improved adsorption capacity, meeting the needs of personal care products; furthermore, they are less irritating to the skin and offer better safety. The raw pollen is a natural and renewable resource, degradable in the natural environment after use, and does not cause environmental pollution. The hollow pollen granules of this invention can be used to prepare various personal care products. In addition to personal care products, the excellent cleaning ability of the hollow pollen granules also makes them suitable for preparing pet or personal care products, thus demonstrating promising application prospects.

Claims

1. The use of hollow pollen particles in the preparation of personal care products, characterized in that: The hollow pollen particles are obtained by degreasing and acid treatment of natural pollen; the hollow pollen particles are used as a cleaning ingredient in personal care products.

2. The use according to claim 1, characterized in that: The method for preparing the hollow pollen grains includes the following steps: (1) Take natural pollen, first wash it with ethanol aqueous solution until the filtrate is clear and transparent, then wash it with acetone until the filtrate is clear and transparent, and collect the washed pollen powder; (2) Add the cleaned pollen powder to acetone, reflux and extract, filter, recover the pollen powder and dry to obtain defatted pollen; (3) Add defatted pollen to acid, reflux and wash until the pH of the filtrate is neutral, then dry to obtain hollow pollen grains.

3. The use according to claim 2, characterized in that: In step (1), the volume ratio of anhydrous ethanol to water in the ethanol-water solution is (1-5):1; And / or, in step (1), the solid-liquid ratio of the natural pollen and the ethanol aqueous solution is 1 g: (1-100) mL; And / or, in step (1), the cleaning with ethanol aqueous solution is ultrasonic cleaning; And / or, in step (1), the solid-liquid ratio of the natural pollen to acetone is 1 g: (1-100) mL; And / or, in step (2), the solid-liquid ratio of the pollen powder and acetone is 1 g: (1-100) mL; And / or, in step (2), the temperature of the condensation reflux is 50-60°C; And / or, in step (2), the condensation reflux time is 10-20h; And / or, in step (2), the stirring is performed during the condensation reflux, and the stirring speed is 100~300 rpm; And / or, in step (2), the drying temperature is 50-60°C; And / or, in step (2), the drying time is 10-20 hours; And / or, in step (3), the acid is an aqueous solution of phosphoric acid with a mass fraction of 70-95%; And / or, in step (3), the solid-liquid ratio of the defatted pollen to the acid is 1 g: (1-100) mL; And / or, in step (3), the temperature of the condensation reflux is 70~90℃; And / or, in step (3), the condensation reflux time is 1-10h; And / or, in step (3), the stirring is performed during the condensation reflux, and the stirring speed is 100~300 rpm; And / or, in step (3), the cleaning includes the following steps: filtration, cleaning with water at a temperature of 70~90℃, then cleaning with acetone, then cleaning with hydrochloric acid aqueous solution, and finally cleaning with deionized water; And / or, in step (3), the pH value is 6.5-7.5; And / or, in step (3), the drying temperature is 50-60°C; And / or, in step (3), the drying time is 10-20 hours.

4. The use according to claim 1, characterized in that: The hollow pollen grains are selected from one or more of lotus pollen grains, pine pollen grains, and sunflower pollen grains; each type of hollow pollen grain is prepared by the method described in claim 2 or 3.

5. The use according to any one of claims 1-4, characterized in that: The aforementioned personal care products are for cleaning human bodies, pets, and items. Preferably, The aforementioned personal care products are for cleaning the face, body, hair, mouth, and other special areas of the human body. The pet grooming products mentioned are for cleaning the pet's face, body, fur, mouth, and other special areas. The cleaning products mentioned are cleaning and care products for household appliances, beauty tools, and fruits and vegetables.

6. The use according to claim 5, characterized in that: The washing and care product is a washing and care product containing physical exfoliants, and the hollow pollen particles serve as physical exfoliants.

7. The use according to claim 6, characterized in that: The aforementioned washing and care products are those that absorb and remove grease.

8. The use according to claim 6, characterized in that: The aforementioned cleansing and care products are makeup removers.

9. A washing and care product, characterized in that: It contains hollow pollen particles; the hollow pollen particles are obtained by degreasing and acid treatment of natural pollen; the hollow pollen particles are used as a cleaning ingredient in personal care products.

10. The washing and care product according to claim 9, characterized in that: The hollow pollen grains are selected from one or more of lotus pollen grains, pine pollen grains, and sunflower pollen grains; each type of hollow pollen grain is prepared by the method described in claim 2 or 3.

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