Makeup removal composition containing bio-based raw material-surfactant supramolecular aggregate

Abstract

The invention discloses a makeup removing composition containing a bio-based raw material-surfactant supramolecular aggregate. The makeup removing composition is prepared from the following components in percentage by mass: 1 to 50 percent of micro-nano natural polymer material hydrogel, 0.1 to 20 percent of surfactant, 10 to 60 percent of grease and 0.1 to 1 percent of preservative, wherein the micro-nano natural polymer material in the micro-nano natural polymer material hydrogel is combined with the surfactant to form a supramolecular aggregate. According to the makeup removing composition disclosed by the invention, the residue of the surfactant on the skin is reduced, and the risk of sensitive skin stimulation is remarkably reduced; in addition, the attached cosmetics can be directly stripped through physical friction provided by the flexible micro-nano natural polymer material in the micro-nano natural polymer material hydrogel, meanwhile, the surfactant combined with the micro-nano natural polymer material can rapidly emulsify grease, and the removal rate of the cosmetics reaches 99%.

Description

Technical Field

[0001] This invention belongs to the field of daily necessities technology, specifically relating to a makeup remover composition containing bio-based raw material - surfactant supramolecular aggregates. Background Technology

[0002] In the modern beauty and skincare industry, makeup removers play a crucial role. With the increasing popularity of makeup and the growing pursuit of a more refined look, various makeup products such as foundation, eyeshadow, lipstick, and mascara are widely used. However, the powders, oils, and film-forming agents in these makeup products are difficult for the skin to absorb and tend to accumulate on the face. If makeup is not removed promptly and thoroughly, it can easily lead to skin problems such as pigmentation, dull skin tone, acne, and pimples, seriously affecting the health and appearance of the skin. Therefore, choosing a suitable makeup remover has become a key step in maintaining healthy skin. Makeup removers not only bear the responsibility of removing facial makeup but also effectively remove sweat, sebum, and airborne dirt adhering to the skin, offering a more powerful cleansing effect than ordinary facial cleansers. Especially for waterproof makeup, ordinary facial cleansers are often ineffective, further highlighting the importance of makeup removers.

[0003] Common makeup removers can be broadly categorized into three systems: water-based, oil-based, and emulsified. Water-based removers primarily rely on surfactants for cleansing, but this method is often incomplete and requires further wiping with cotton pads, sometimes necessitating a second cleanse. This approach increases the risk of skin damage due to over-cleansing. Oil-based removers achieve their cleansing effect through the mutual solubility of oils and surfactants, but they tend to feel heavy, and long-term use without thorough cleansing can lead to acne. Emulsified removers consist of water, oils, and surfactants forming a lotion; the oils remove makeup, while the water provides hydration, but their cleansing power is relatively limited. Furthermore, the safety of makeup remover ingredients remains a major concern for consumers and a significant challenge for the industry. From preservatives to fragrances, from oils to surfactants, many ingredients can pose a threat to skin health. For example, surfactants in some makeup removers not only affect the survival and reproduction of aquatic organisms and disrupt the aquatic ecological balance, but also have certain impacts on human health. This is mainly because human skin has gaps in its structure, and the amphiphilic structure of surfactants has a certain degree of permeability. Inevitably, some surfactants will not be washed away by water, thus adsorbing and penetrating into the stratum corneum, causing surfactant residue on the skin. Over time, this can have negative effects on the stratum corneum and even the deeper layers of the skin. Studies have found that the more surfactants are exposed, the more they bind to proteins on the skin, and the faster the penetration process. It has been proven that this reduces the skin's water-binding capacity, leading to dry skin, inflammation, functional impairment from repeated contact, and acne. These not only put pressure on the environment but also run counter to the concept of sustainable development.

[0004] Therefore, how to provide a makeup remover that has multiple functions such as cleansing, gentle exfoliation, and makeup removal, is made from natural sources, is gentle on the skin, and is easy to prepare, while achieving a perfect cleansing effect at the same time as makeup removal, has become an urgent problem to be solved. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a makeup remover composition based on a bio-based material-surfactant supramolecular aggregate structure. This makeup remover composition overcomes the problem of surfactants remaining independently in traditional makeup removers, which are prone to residue. It combines surfactants with micro-nano natural polymer materials in a hydrogel through hydrogen bonding to form a supramolecular aggregate structure. This supramolecular aggregate structure can remove makeup and dirt through emulsification and encapsulation, while reducing surfactant residue.

[0006] The specific technical solution of the present invention is as follows:

[0007] A makeup remover composition, by weight percentage, comprises the following components: 1-50% micro-nano natural polymer hydrogel, 0.1-20% surfactant, 10-60% oil, and 0.1-1% preservative; wherein the micro-nano natural polymer in the micro-nano natural polymer hydrogel combines with the surfactant to form supramolecular aggregates.

[0008] According to an embodiment of the present invention, the surfactant is selected from at least one or more of polyglycerol surfactants, PEG-hydrogenated castor oil derivatives, sorbitan derivatives, PEG-glycerol ester surfactants, PEG-laurate surfactants, olive oil ester surfactants, and alkyl glycoside surfactants.

[0009] Preferably, the olive oil ester surfactant is selected from at least one of olive oil PEG-7 ester, olive oil PEG-8 ester, PEG-4 oleate, and olive oil sodium carboxylate PEG-7.

[0010] Preferably, the polyglycerol surfactant is formed by polymerizing glycerol and then esterifying it with fatty acids, for example selected from polyglycerol-10 laurate, polyglycerol-4 isostearate, polyglycerol-3 stearate, polyglycerol-2 dihydroxystearate, polyglycerol-10 stearate, polyglycerol-10 decaoleate, polyglycerol mixed fatty acid esters, polyglycerol caprylic / capric acid ester, and polyglycerol monostearate.

[0011] Preferably, the PEG-laurate surfactant is obtained by reacting lauric acid with ethylene oxide or by esterifying it with polyethylene glycol (PEG), for example, selected from PEG-12 laurate.

[0012] Preferably, the PEG-hydrogenated castor oil derivative is polymerized from hydrogenated castor oil and ethylene oxide, and is selected from, for example, PEG-30 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-7 hydrogenated castor oil, PEG-25 hydrogenated castor oil, and PEG-100 hydrogenated castor oil.

[0013] Preferably, the sorbitan derivative is formed by dehydrating sorbitol and esterifying it with fatty acids, for example selected from sorbitol polyether-30 tetraoleate, sorbitan monostearate (span-60), sorbitan monolaurate (span-20), sorbitan tristearate (span-65), sorbitan monooleate (span-80), and sorbitol polyether-30 glyceryl tetraoleate.

[0014] Preferably, the PEG-glyceryl ester surfactant is polymerized from glyceryl ester and ethylene oxide, and is selected from, for example, PEG-10 glyceryl stearate, PEG-4 glyceryl stearate, PEG-20 glyceryl triisostearate, PEG-6 glyceryl isostearate, PEG-6 glyceryl cocoate, and PEG-8 glyceryl laurate.

[0015] Preferably, the alkyl glycoside surfactant is formed by reacting natural fatty alcohols (such as coconut alcohol, lauryl alcohol) with glucose (such as glucose from starch), for example selected from cocoyl glucoside (APG 1214), lauryl glucoside (APG0810), decyl glucoside (APG 0610), cetearyl glucoside (APG 1618).

[0016] Furthermore, the surfactant is selected from at least one, two, or three of the following: sorbitol polyether-30 tetraoleate, PEG-20 glyceryl triisostearate, cocoyl glucoside, polyglycerol-4 isostearate, and polyglycerol-10 decaoleate.

[0017] For example, the surfactant includes PEG-20 glyceryl triisostearate, cocoyl glucoside, and polyglycerol-10 decaoleate in a mass ratio of 15:1:0.5; the surfactant includes PEG-12 laurate and polyglycerol-10 decaoleate in a mass ratio of 1-4:1-5; the surfactant includes polyglycerol-10 decaoleate, cocoyl glucoside, and sorbitol polyether-30 glyceryl tetraoleate in a mass ratio of 0.1-0.5:1-4:5-10; the surfactant includes polyglycerol-10 decaoleate, PEG-20 glyceryl triisostearate, and cocoyl glucoside in a mass ratio of 0.8-1:5-10:0.1-0.5; the surfactant includes sodium PEG-7 olive oil carboxylate and olive oil PEG-7 esters in a mass ratio of 1-3:1-3.

[0018] According to an embodiment of the invention, the surfactant in the makeup remover composition has a mass percentage of, for example, 1%, 5%, 10%, or 15%.

[0019] According to an embodiment of the present invention, the micro / nano natural polymer hydrogel is prepared by dissolution, homogenization, and regeneration using an ionic liquid method.

[0020] According to an embodiment of the present invention, the micro-nano natural polymer hydrogel is free of animal-derived components and comprises micro-nano natural polymer materials and water.

[0021] According to an embodiment of the present invention, the micro / nano natural polymer material includes a micrometer-scale structure and a nanometer-scale structure distributed on the micrometer-scale structure.

[0022] According to an embodiment of the present invention, the micro-nano natural polymer material is provided by at least one of biomass-based dispersion, surface-modified biomass-based dispersion, substituted biomass-based dispersion, and multi-component biomass-based dispersion.

[0023] According to an embodiment of the present invention, the biomass-based dispersion comprises the micro / nano natural polymer material and a dispersing agent, wherein the micro / nano natural polymer material is distributed in the dispersing agent, and the dispersing agent is a solvent system capable of continuously dispersing the micro / nano natural polymer material.

[0024] According to an embodiment of the present invention, the surface-modified micro / nano natural polymer material is a surface-modified version of the micro / nano natural polymer material; or it is a material prepared by the preparation method of the micro / nano natural polymer material, except that the raw biomass is replaced with surface-modified biomass.

[0025] According to an embodiment of the present invention, the surface-modified biomass-based dispersion comprises surface-modified micro / nano natural polymer materials and a dispersing agent, wherein the surface-modified micro / nano natural polymer materials are dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the surface-modified micro / nano natural polymer materials.

[0026] According to an embodiment of the present invention, the substituted biomass-based material is a substitute for the micro-nano natural polymer material; or it is a material prepared by the preparation method of the micro-nano natural polymer material, except that the raw biomass is replaced with the substituted biomass.

[0027] According to an embodiment of the present invention, the substituted biomass dispersion comprises a substituted micro / nano natural polymer material and a dispersing agent, wherein the substituted micro / nano natural polymer material is dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the substituted micro / nano natural polymer material.

[0028] According to an embodiment of the present invention, the continuous phase of the multi-component biomass-based dispersion is a dispersion solvent, and the dispersed phase of the dispersion contains a functional component and at least one of the following components 1) to 3):

[0029] 1) The micro / nano natural polymer materials mentioned above;

[0030] 2) The aforementioned replacement micro / nano natural polymer materials;

[0031] 3) The surface-modified micro / nano natural polymer materials mentioned above.

[0032] According to an embodiment of the present invention, the particle size of the micro-nano natural polymer material in the micro-nano natural polymer material hydrogel is 1-150 micrometers, for example, 100 micrometers, 80 micrometers, 40 micrometers, 20 micrometers, 10 micrometers, and 5 micrometers.

[0033] According to an embodiment of the present invention, the solid content of the micro / nano natural polymer hydrogel is 1-20%, for example, 1%, 1.3%, 2%, 4%, 6%, 8%, 10%, or 15%.

[0034] According to an embodiment of the present invention, the mass percentage of the micro / nano natural polymer hydrogel in the makeup remover composition is, for example, 5%, 10%, 20%, 30%, or 40%.

[0035] According to an embodiment of the present invention, in the makeup remover composition, the mass ratio of the micro / nano natural polymer hydrogel to the surfactant is 1-50:0.1-20, for example, 10:0.1-20, 20:0.1-20, or 30:0.1-20.

[0036] According to an embodiment of the present invention, the oil is selected from at least one of natural oils, mineral oils, and synthetic oils.

[0037] Preferably, the natural oil is selected from at least one of shea butter, jojoba oil, camellia seed oil, sunflower seed oil, meadowfoam seed oil, sesame oil, olive fruit oil, etc.

[0038] Preferably, the mineral oil is selected from at least one of white oil, petrolatum, etc.

[0039] Preferably, the synthetic oil is selected from at least one of caprylic / capric triglyceride, cetyl ethylhexanoate, squalane, isopropyl myristate, beeswax, synthetic wax, microcrystalline wax, etc.

[0040] According to embodiments of the present invention, the oil content in the makeup remover composition is, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70% by mass.

[0041] According to an embodiment of the present invention, the preservative is selected from one or more of phenoxyethanol, benzyl alcohol, ethylhexylglycerin, 1,2-pentanediol, 1,2-hexanediol, p-hydroxyacetophenone, raspberry ketone, caprylyl glycol, DMDM ​​acetopropionyl urea, dipropylene glycol, caprylyl hydroxamic acid, O-cymene-5-ol, methylpropanediol, chlorophenoxyether, sodium benzoate, methylisothiazoline.

[0042] According to embodiments of the present invention, the preservative in the makeup remover composition comprises, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% by mass.

[0043] According to embodiments of the present invention, a diluent may also be added to the makeup remover composition. The amount of diluent can be selected according to the actual situation of the makeup remover composition, and the present invention does not impose a specific limitation. Preferably, the diluent may be a solvent known in the art, such as one or more selected from water, ethanol, glycerin, 1,3-butanediol, 1,2-propylene glycol, etc.

[0044] The present invention also provides a method for preparing the above-mentioned makeup remover composition, the method comprising the following steps: mixing oil, surfactant, micro-nano natural polymer hydrogel, preservative and optional diluent according to the above-mentioned mass percentage to obtain the makeup remover composition.

[0045] According to an embodiment of the present invention, the mixing may be performed using methods known in the art, such as stirring.

[0046] According to an embodiment of the present invention, in the preparation method, it is preferable to first mix the micro / nano natural polymer hydrogel with a surfactant to form a supramolecular aggregate, then mix it evenly with oil under heating conditions, and subsequently add a preservative and an optional diluent.

[0047] Preferably, the heating conditions can be determined according to the selected oil, as long as the oil can be melted, for example, 60℃, 70℃, 80℃, or 150℃.

[0048] The present invention also provides the application of the above-described makeup removal composition in the cosmetics field, for example, in the field of makeup removal.

[0049] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0050] The makeup removal composition of the present invention not only reduces surfactant residue on the skin and significantly reduces the risk of irritation to sensitive skin, but also the physical friction provided by the flexible micro-nano natural polymer materials in the micro-nano natural polymer hydrogel can directly peel off the attached makeup. At the same time, the surfactants combined with the micro-nano natural polymer materials can quickly emulsify oils, achieving a makeup removal rate of 99%.

[0051] This invention utilizes micro / nano-sized natural polymer hydrogels and surfactants. Through the hydrogen bonds at the ends of the micro / nano-sized natural polymers in the hydrogel and the hydrogen bonds in the surfactant, supramolecular aggregates are formed, reducing surfactant residue on the skin and minimizing skin irritation. When using this makeup remover composition, the supramolecular aggregates formed by the micro / nano-sized natural polymer hydrogel and surfactant come into contact with makeup on the skin. The surfactant emulsifies the oils, and the gentle massage from the micro / nano-sized natural polymers also helps to cleanse dead skin cells, significantly improving facial cleansing. During rinsing, because the surfactants have formed aggregates with the micro / nano-sized natural polymers in the hydrogel, water removes the surfactants along with the hydrogel, reducing surfactant residue on the skin and effectively minimizing skin irritation. The micro / nano-sized natural polymer hydrogel used in this invention is naturally derived, the process is simple and environmentally friendly, and it is easily applicable to industrial applications. Attached Figure Description

[0052] Figure 1 Fourier transform infrared spectrum of the micro / nano natural polymer hydrogel prepared in Example 1 after mixing with four surfactants.

[0053] Figure 2 Fourier transform infrared spectrum of the micro / nano natural polymer hydrogel prepared in Example 2 after mixing with four surfactants.

[0054] Figure 3 Fourier transform infrared spectra of commercially available natural cellulose (particle size 70 μm, VITACEL CS 70G, JRS, Germany) mixed with different surfactants.

[0055] Figure 4 The Fourier transform infrared spectra are of MCC mixed with different surfactants.

[0056] Figure 5 These are before-and-after comparison images of makeup removal in Examples 1-5.

[0057] Figure 6 Comparative examples 1-4 show before and after photos of makeup removal. Detailed Implementation

[0058] [Micro / Nano Natural Polymer Hydrogel]

[0059] As mentioned above, the present invention provides a micro-nano natural polymer hydrogel, which is free of animal-derived components and comprises micro-nano natural polymer materials and water.

[0060] According to an embodiment of the present invention, the content of the micro / nano natural polymer material can be 0.050-95 wt.%; for example, it can be 0.5-10 wt.%. High concentration results in high viscosity, making it inconvenient to use, but convenient for transportation and cost savings; too low a concentration results in poor dispersion stability.

[0061] According to an embodiment of the present invention, the micro / nano natural polymer material is a recycled natural polymer (e.g., type II cellulose, or a mixture of type I and type II cellulose), wherein the recycled natural polymer comprises a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0062] According to embodiments of the present invention, the micro / nano natural polymer material described herein is, for example, natural cellulose gum (CMG). The micro / nano natural polymer material described herein is, for example, at least one of the natural polymers, surface-modified natural polymers, and substituted natural polymers as described in patent document CN116284844A.

[0063] According to an embodiment of the present invention, the micro-nano natural polymer material is provided by at least one of biomass-based dispersion, surface-modified biomass-based dispersion, substituted biomass-based dispersion, and multi-component biomass-based dispersion.

[0064] According to an embodiment of the present invention, the size (i.e., the volume average size) of the micron-scale structure is 10 μm to 300 μm, preferably 50 μm to 250 μm, and more preferably 100 μm to 200 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 12 Any value from 5μm, 130μm, 135μm, 140μm, 145μm, 150μm, 155μm, 160μm, 165μm, 170μm, 175μm, 180μm, 185μm, 190μm, 195μm, 200μm, 210μm, 220μm, 230μm, 240μm, 250μm, 260μm, 270μm, 280μm, 290μm, 300μm, or any point value from the intermediate values ​​formed by any two points.

[0065] According to an embodiment of the present invention, the length of the nanoscale structure is 500nm to 1500nm, preferably 700nm to 1200nm, and more preferably 800nm ​​to 1000nm, for example, any value or any intermediate value among 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, and 1500nm.

[0066] According to an embodiment of the present invention, the diameter of the nanoscale structure is 200nm to 600nm, preferably 300nm to 500nm, for example, any value among 200nm, 300nm, 400nm, 500nm, and 600nm, or any intermediate value formed by any two of these values.

[0067] According to an embodiment of the present invention, the aspect ratio of the nanoscale structure is 1:1 to 1:150, preferably 1:1 to 1:100, and more preferably 1:1 to 1:50.

[0068] According to an embodiment of the present invention, the micron-level structure includes at least one of micron-sheets, micron-fibers, and micron-level structures.

[0069] According to an embodiment of the present invention, the micron-scale structure is fibrous or membrane-like, and may also be referred to as broom-like.

[0070] According to an embodiment of the present invention, the nanoscale structure is distributed on the surface and / or edges of the micrometer-scale structure. Specifically, the nanoscale structure is densely distributed on the surface and / or edges of the micrometer-scale structure.

[0071] According to an embodiment of the present invention, the nanoscale structure is distributed on a micrometer-scale structure and thus forms a flocculent structure as a whole.

[0072] According to an embodiment of the present invention, the nanoscale structure is distributed on a micrometer-scale structure and thus forms an integral structure similar to a porous sponge.

[0073] According to an embodiment of the present invention, the nanoscale structure and the micrometer-scale structure together form a feather-like structure.

[0074] According to an embodiment of the present invention, the nanoscale structure is in the form of a villous, tentacle-like, whisker-like, or other irregular structure.

[0075] According to an embodiment of the present invention, the micro-nano natural polymer material is in the form of granules, fibers, sheets, feathers, branches, flocs, or porous sponge structures.

[0076] [Preparation methods of micro / nano-sized natural polymer hydrogels]

[0077] According to an embodiment of the present invention, the preparation method of the micro / nano natural polymer hydrogel is selected from at least one of the following methods one to four:

[0078] Method 1: Preparation of biomass-based dispersion: A natural polymer solution is poured into a coagulation bath to form a natural polymer gel; the natural polymer gel is micronized and nano-sized using a homogenizer, colloid mill, or ball mill to obtain the biomass-based dispersion, which is the micro-nano natural polymer hydrogel.

[0079] Method 2: Preparation of the surface-modified biomass-based dispersion: The surface-modified natural polymer solution is poured into a coagulation bath to form a surface-modified natural polymer gel; the surface-modified natural polymer gel is then subjected to micro / nano-scale processing using a homogenizer, colloid mill, or ball mill to obtain the surface-modified biomass-based dispersion, which is the micro / nano-scale natural polymer hydrogel; or, the micro / nano-scale natural polymer dispersion is mixed with a modifying reagent or subjected to surface chemical modification to obtain the surface-modified biomass-based dispersion, which is the micro / nano-scale natural polymer hydrogel.

[0080] Method 3: Preparation of the substituted biomass-based dispersion: The substituted natural polymer solution is poured into a coagulation bath to form a substituted natural polymer gel; the substituted natural polymer gel is micronized or nanonized using a homogenizer, colloid mill, or ball mill to obtain the substituted biomass-based dispersion, which is the micro / nano natural polymer hydrogel; or, the micronized natural polymer dispersion is mixed with a functionalized derivatizing reagent or subjected to surface chemical modification to obtain the substituted biomass-based dispersion, which is the micro / nano natural polymer hydrogel.

[0081] Method 4: Preparation of the multi-component biomass-based dispersion: A solution containing at least one natural polymer, a substituted natural polymer, a surface-modified natural polymer, and a functional component is poured into a coagulation bath to form a gel; the gel is then subjected to micro / nano processing using a homogenizer, colloid mill, or ball mill to obtain the multi-component biomass-based dispersion, which is the micro / nano natural polymer hydrogel; or: at least one biomass-based dispersion, a substituted biomass-based dispersion, a surface-modified biomass-based dispersion, and a functional component are mixed, and then subjected to micro / nano processing using a homogenizer, colloid mill, or ball mill to obtain the multi-component biomass-based dispersion, which is the micro / nano natural polymer hydrogel.

[0082] [Preparation method of biomass-based dispersion]

[0083] The present invention also provides a method for preparing the above-mentioned biomass-based dispersion, comprising the following steps: pouring a natural polymer solution into a coagulation bath to form a natural polymer gel; and performing micro-nano processing on the natural polymer gel by means of a homogenizer, colloid mill or ball mill to obtain the natural polymer micro-nano dispersion, which is a biomass-based dispersion.

[0084] The natural polymers have the selections shown above.

[0085] According to an embodiment of the invention, the coagulation bath may be the same as or different from the continuous phase, for example, it may be the same; preferably water and / or alcohol.

[0086] According to an embodiment of the present invention, the natural polymer solution can be a homogeneous solution in which the natural polymer is completely dissolved or a heterogeneous dispersion in which the natural polymer is partially dissolved.

[0087] [Surface-Modified Biomass-Based Dispersion]

[0088] The present invention also provides a surface-modified biomass-based dispersion, wherein the continuous phase of the dispersion has the meaning as described above, preferably water and / or alcohol, and the dispersed phase of the dispersion is a surface-modified natural polymer.

[0089] According to an embodiment of the present invention, the surface-modified natural polymer can be a surface-cationized natural polymer, a surface-anionized natural polymer, or a surface-hydrophobic treated natural polymer.

[0090] According to an embodiment of the present invention, the natural polymer has the selections shown above.

[0091] According to an embodiment of the present invention, the content of the dispersed phase can be 0.050-95 wt.%; exemplaryly, it can be 0.5-10 wt.%.

[0092] According to an embodiment of the present invention, the dispersion is a micro / nano dispersion; specifically, in the dispersion, the surface-modified natural polymer has a structure that is substantially the same as that of the regenerated natural polymer, for example including a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0093] [Preparation method of surface-modified biomass-based dispersion]

[0094] The present invention also provides a method for preparing the above-mentioned surface-modified biomass-based dispersion, comprising the following steps: pouring a surface-modified natural polymer solution into a coagulation bath to form a surface-modified natural polymer gel; and performing micro-nano processing on the surface-modified natural polymer gel by means of a homogenizer, colloid mill or ball mill to obtain the surface-modified biomass-based dispersion.

[0095] Alternatively, the surface-modified biomass-based dispersion can be obtained by mixing the natural polymer micro-nano dispersion with a modifying agent or by surface chemical modification.

[0096] Preferably, the surface-modified natural polymer and the coagulation bath have the meanings described above.

[0097] According to an embodiment of the present invention, the modifying agent may be one or more of quaternary ammonium salts, sulfonates, phosphates, etc.; for example, sodium vinyl sulfonate or 3-chloro-2-hydroxypropyltrimethylammonium chloride.

[0098] According to an embodiment of the present invention, the surface-modified natural polymer solution can be obtained by homogeneous chemical derivatization or functionalization of natural polymers with modifying reagents in the following solvents.

[0099] According to an embodiment of the present invention, the surface-modified natural polymer micro / nano-sized solution can be a homogeneous solution in which the surface-modified natural polymer is completely dissolved or a heterogeneous dispersion in which the surface-modified natural polymer is partially dissolved.

[0100] [Replacement Biomass-Based Dispersion]

[0101] The present invention also provides a substituted biomass-based dispersion, wherein the continuous phase of the dispersion has the meaning as described above, preferably water and / or alcohol, and the dispersed phase of the dispersion is a substituted natural polymer.

[0102] According to an embodiment of the present invention, the substituted natural polymer is a low-substituted natural polymer. Preferably, the degree of substitution of the low-substituted natural polymer is 0.0001 to 2.0, more preferably 0.001 to 1.8, for example 0.1, 0.5, 0.65, 0.86, 1.46, 1.6.

[0103] According to an embodiment of the present invention, the substituted natural polymer may be selected from one or more of the following substances: esterified natural polymer, acylated natural polymer, etherified natural polymer, amidated natural polymer, ammonified natural polymer, etc.

[0104] Preferably, the substituted natural polymer can be prepared by reacting a functionalized derivatizing agent with a natural polymer. For example, the functionalized derivatizing agent can be selected from esterification agents, acylation agents, etherification agents, ammoniation agents, and / or amidation agents.

[0105] According to an embodiment of the present invention, the substituted natural polymer may be selected from cellulose acetate (e.g., cellulose acetate with a degree of substitution of 0.65, 0.86, 1.46, or 1.6) or cellulose-g-PLA.

[0106] According to an embodiment of the present invention, the natural polymer has the selections shown above.

[0107] According to an embodiment of the present invention, the content of the dispersed phase can be 0.050-95 wt.%; exemplaryly, it can be 0.5-10 wt.%.

[0108] According to an embodiment of the present invention, the dispersion is a micro / nano dispersion; specifically, in the dispersion, the substituted natural polymer has a structure substantially the same as that of the regenerated natural polymer, for example including a micron-scale structure and a nano-scale structure distributed on the micron-scale structure.

[0109] [Preparation method of biomass-based dispersant]

[0110] The present invention also provides a method for preparing the above-mentioned substituted biomass-based dispersion, comprising the following steps: pouring the substituted natural polymer solution into a coagulation bath to form a substituted natural polymer gel; and performing micro-nano processing on the substituted natural polymer gel by means of a homogenizer, colloid mill or ball mill to obtain the substituted biomass-based dispersion.

[0111] Alternatively, the substituted biomass-based dispersion can be obtained by mixing the natural polymer micro-nano dispersion with functionalized derivatizing reagents or by surface chemical modification.

[0112] Preferably, the substituted natural polymer, coagulation bath, and functionalized derivatized reagent have the meanings described above.

[0113] According to an embodiment of the present invention, the substituted natural polymer solution can be obtained by homogeneous chemical derivatization or functionalization of a natural polymer with a functionalizing derivatizing agent in the following [solvent].

[0114] According to an embodiment of the present invention, the micro / nano-sized solution replacing the natural polymer can be a homogeneous solution in which the natural polymer is completely dissolved or a heterogeneous dispersion in which the natural polymer is partially dissolved.

[0115] [Multi-component biomass-based dispersion]

[0116] The present invention also provides a multi-component biomass-based dispersion, wherein the continuous phase of the dispersion has the selections shown above, preferably water and / or alcohol, and the dispersed phase of the dispersion contains at least one of a natural polymer, a substituted natural polymer, a surface-modified natural polymer, and a functional component.

[0117] According to an embodiment of the present invention, the natural polymer has the meaning as described above, or may be selected from at least one of methylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, cyanoethylcellulose, benzylcyanoethylcellulose, carboxymethylhydroxyethylcellulose, chitosan, sodium alginate, starch, and gelatin.

[0118] According to an embodiment of the present invention, the functional component is selected from one or more of the following substances: nanocellulose, carbon nanotubes, graphene, fullerene, carbon black, silver nanowires, quantum dots, carbon dots, nanoFe3O4, drugs, etc.

[0119] According to an embodiment of the present invention, the content of the dispersed phase can be 0.050-95 wt.%; exemplaryly, it can be 0.5-10 wt.%.

[0120] According to an embodiment of the present invention, the dispersion is a micro / nano dispersion; specifically, in the dispersion, the natural polymer or the substituted natural polymer has the structure described above.

[0121] [Preparation method of multi-component biomass-based dispersion]

[0122] The present invention also provides a method for preparing the above-mentioned multi-component biomass-based dispersion, selected from Scheme 1 or Scheme 2 below:

[0123] Option 1: A solution containing at least one of a natural polymer, a substituted natural polymer, a surface-modified natural polymer, and a functional component is poured into a coagulation bath to form a gel; the gel is then subjected to micro-nano processing using a homogenizer, colloid mill, or ball mill to obtain the multi-component biomass-based dispersion.

[0124] Option 2: Mix at least one of the following: biomass-based dispersion, substituted biomass-based dispersion, and surface-modified biomass-based dispersion, with a functional component, and then perform micro-nano processing by means of homogenizer, colloid mill, or ball mill to obtain the multi-component biomass-based dispersion.

[0125] Preferably, the natural polymer, the substituted natural polymer, the functional component, the coagulation bath, the biomass-based dispersion, and the substituted biomass-based dispersion are all selected as shown above.

[0126] Preferably, a cross-linking agent may be added before gel formation. Preferably, the cross-linking agent is selected from at least one of boric acid, calcium chloride, acetic acid, and ethylenediaminetetraacetic acid.

[0127] According to an embodiment of the present invention, the solution is a homogeneous solution or a heterogeneous dispersion.

[0128] [Biomass]

[0129] Cellulose or other biomass extracted from plant tissues. For example, cellulose extracted from plant tissues is selected from one or more of the following substances: microcrystalline cellulose, bacterial cellulose, cotton pulp, wood pulp, bamboo pulp, straw pulp, refined cotton, defatted cotton, cotton linters, sugarcane bagasse, wood, and straw, etc.; preferably, one or more of microcrystalline cellulose, refined cotton, defatted cotton, and wood pulp. Alternatively, starch, chitosan, chitin, lignin, hemicellulose, dextran, etc., extracted from plant tissues.

[0130] The starch is selected from at least one of amylopectin, amylose, high amylose, modified starch, and cross-linked starch; or, the starch is selected from soluble starch; or, the starch is selected from at least one of potato starch, corn starch, cassava starch, wheat starch, sweet potato starch, kudzu starch, pea starch, water chestnut starch, soybean starch, and lotus root starch.

[0131] There are no particular limitations on the selection of chitosan, chitin, lignin, hemicellulose, dextran, etc., as those skilled in the art can know and apply to the system described in this invention.

[0132] Preferably, the degree of deacetylation of the chitosan is 50-100%; more preferably, the degree of deacetylation of the chitosan is 70-95%.

[0133] Preferably, the lignin may be selected from one or more of syringyl lignin, guaiacyl lignin, and p-hydroxyphenyl lignin; or, the lignin may be selected from one or more of alkaline lignin, acidic lignin, dealkalized lignin, and organic solvent-soluble lignin.

[0134] The low-quality cellulose is plant tissue containing at least cellulose and lignin, such as herbaceous plants and / or agricultural and forestry waste.

[0135] For example, the herbaceous plant is selected from one or more of trees, shrubs, vines, leaves, and bamboo.

[0136] For example, the agricultural and forestry waste is selected from one or more of the following: tree bark, leaves, sawdust, crop straw, fruit shells or kernels, corn cobs, sugarcane bagasse, etc.

[0137] Preferably, the crop straw can be selected from one or more of wheat straw, rice straw, corn straw, soybean straw, cotton straw, ginger straw, and sesame straw.

[0138] [solvent]

[0139] In the aforementioned methods for preparing micro / nano-sized natural polymer dispersions, surface-modified biomass-based dispersions, substituted biomass-based dispersions, or multi-component micro / nano-sized natural polymer dispersions, the solvent in the homogeneous solution and / or heterogeneous dispersion is not particularly limited and can be selected from any excellent solvent known in the art capable of dissolving (including complete and partial dissolution) the solute (e.g., the natural polymer). Preferably, depending on the type of natural polymer, the selected solvent can be selected from one or more of the following systems: copper ammonia solution, copper ethylenediamine solution, organic solvent, ionic liquid, mixed solvent of ionic liquid and organic solvent, choline-type ionic liquid eutectic solvent system, organic solvent / salt system, amine oxide system (NMMO), urethane system, alkali / water system, alkali / urea system, alkali / thiourea system, liquid ammonia / NH4SCN, organic acid, aqueous solution of metal salt, alcoholic solution of metal hydrate, aqueous-alcoholic mixed solution of metal hydrate, etc.

[0140] The organic solvent may be selected from one or more of N,N-dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylimidazolium, imidazolium, pyridine, ethylenediamine, hexafluoroacetone, hexafluoroisopropanol, glycerol, methyl isobutyl ketone, tetrahydrofuran, dioxane, and γ-valerol (GVL).

[0141] The organic solvent / salt system may be selected from one or more of the following: N,N-dimethylacetamide / lithium chloride (DMAc / LiCl) system, N-methyl-2-pyrrolidone / NMP, and N,N-dimethyl sulfoxide / tetrabutylamine fluoride system (DMSO / TBAF).

[0142] The alkali / water system can be selected from one or both of NaOH / H2O and KOH / H2O.

[0143] The alkali / urea system can be selected from NaOH / Urea.

[0144] The alkaline / thiourea system is selected from NaOH / thiourea.

[0145] The organic acid may be selected from one or more of formic acid, acetic acid, propionic acid, butyric acid, succinic acid, lactic acid, glutamic acid, glycine, dichloroacetic acid, trichloroacetic acid, and benzylsulfonic acid.

[0146] The aqueous solution of the metal salt is preferably an aqueous solution of metal salts such as CaCl2, ZnCl2, LiClO4, Ca(SCN)2, and LiSCN.

[0147] The alcoholic solution of the metal hydrate can be selected from a methanol solution of CaBr2·H2O or a methanol solution of CaCl2·2H2O.

[0148] The aqueous-alcoholic mixed solution of the metal hydrate can be selected from the methanol aqueous solution of CaBr2·H2O or the methanol aqueous solution of CaCl2·2H2O.

[0149] The amine oxide system can be an NMMO / H2O / DMSO system, an NMMO / H2O / diethyltriamine system, or an NMMO / H2O system.

[0150] The ionic liquid is selected from organic molten salts formed by cations and anions with a melting point below 100°C, and is preferably an organic molten salt capable of dissolving the biomass natural polymer.

[0151] For example, the cation of the ionic liquid is selected from one or more of substituted or unsubstituted imidazole, pyridine, pyrrole, amine, phosphine, choline, diazabicyclic, and amino acid-type cations; for example, the substituent can be C. 1-6 Alkyl, C 1-6 One or more of alkenyl, phenyl, or substituted phenyl groups; preferably one or more of methyl, ethyl, butyl, and allyl groups;

[0152] Preferably, the cation is selected from one or more of the following cations: 1-ethyl-3-methylimidazolium cation ([EMIM]), 3-methylimidazolium cation ([MIM]), 1-propyl-3-methylimidazolium cation ([PMIM]), 1-allyl-3-methylimidazolium cation ([AMIM]), 1-butyl-3-methylimidazolium cation ([BMIM]), 1-butyl-2,3-dimethylimidazolium cation ([BMMIM]), 1,3-dimethylimidazolium cation ([MMIM]), 1-methoxyethyl-3-methylimidazolium cation ([MeOEMIM]), 1-methoxymethyl-3-methylimidazolium cation ([MeOMMIM]), 1-hydroxy-3-methylimidazolium cation ([HMIM]), 1-(2-hydroxyethyl)-3-methylimidazolium cation ([HOEMIM]), 1-methyl-3-benzylmethylimidazolium cation ([MBzIM]), 1 The following cations are listed: pentyl-3-methylimidazolium cation ([PeMIM]), 1-benzyl-3-methylimidazolium cation ([BzMIM]), 1-m-methoxybenzyl-3-methylimidazolium cation ([MeOBzMIM]), 1-m-methylbenzyl-3-methylimidazolium cation ([MeBzMIM]), N-methylpyridine cation ([MPyr]), N-ethylpyridine cation ([EPyr]), N-butylpyridine cation ([BPyr]), N-hexylpyridine cation ([HPyr]), 1-butyl-3-methylpyrrolidone ion ([BMPyrr]), tris(2-hydroxyethyl)methylamine ([THEMA]), tetrabutylamine ([TBA]), tetrabutylphosphine ([PBu4]), glycine cation ([Gly]), choline cation ([Ch]), and 1,5-diazazobicyclo[4.3.0]one-5-ene ([DBNH]).

[0153] More preferably, the cation is selected from one or more of the following cations: 1-ethyl-3-methylimidazolium cation ([EMIM]), 1-allyl-3-methylimidazolium cation ([AMIM]), 1-butyl-3-methylimidazolium cation ([BMIM]), and choline cation ([Ch]).

[0154] For example, the anion is selected from one or more of the following: halogen anions, organic acid radicals, organic acid ester anions, and amino acid anions.

[0155] Preferably, the anion shown is selected from one or more of the following anions: chloride ion ([Cl]), bromide ion ([Br]), fluoride ion ([F]), formate ion ([HCOO]), acetate ion ([CH3COO] or [Ac]), glycolate ion ([HOCH2COO]), propionate ion ([CH3CH2COO] or [OPr]), butyrate ion ([CH3CH2CH2COO] or [OBu]), octanoate ion ([Oct]), benzoate ion ([C6H5COO] or [PhCOO]), lactate ion ([CH3CH(OH)COO] or [Lac]), and thioglycolate ion ([HSCH2COO]). The anions include one or more of the following: hexafluorophosphate ([PF6]), trifluoroborate ([BF3]), methyl phosphate ([(MeO)HPO2] or [MP]), dimethyl phosphate ([(MeO)2PO2] or [DMP]), diethyl phosphate ([(EtO)2PO2] or [DEP]), methanesulfonate anion ([MeOSO3]), trifluoromethanesulfonate anion ([CF3SO3]), glycine anion ([Gly]), lysine anion ([Lys]), valine anion ([Val]), dicyandiamide anion ([N(CN)2] or [DCA]), and bis(trifluoromethanesulfonylimide) ([Tf2N]).

[0156] More preferably, the anion is selected from one or more of the following anions: chloride ion ([Cl]), formate ion ([HCOO]), acetate ion ([Ac]), methyl phosphate ion ([(MeO)HPO2] or [MP]), dimethyl phosphate ion ([(MeO)2PO2] or [DMP]) and dicyandiamide anion ([N(CN)2] or [DCA]).

[0157] According to the present invention, the ionic liquid may be selected from one or more of the following ionic liquids: 1-ethyl-3-methylimidazolium chloride ionic liquid ([EMIM][Cl]), 1-ethyl-3-methylimidazolium bromide ionic liquid ([EMIM][Br]), 1-ethyl-3-methylimidazolium formate ionic liquid ([EMIM][HCOO]), 1-ethyl-3-methylimidazolium acetate ionic liquid ([EMIM][Ac]), 1-ethyl-3-methylimidazolium octanoate ionic liquid ([EMIM][Oct]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][Cl]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium octanoate ionic liquid ([EMIM][Oct]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][CLOOD]), 1-ethyl-3-methylimidazolium ... [EMIM][DMP]), 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid ([EMIM][DEP]), 1-ethyl-3-methylimidazolium propionate ionic liquid ([EMIM][OPr]), 1-ethyl-3-methylimidazolium octate ionic liquid ([EMIM][OBu]), 1-ethyl-3-methylimidazolium glycinate ionic liquid ([EMIM][Gly]), 1-ethyl-3-methylimidazolium lysine ionic liquid ([EMIM][Lys]), 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]), 1-allyl-3-methylimidazolium bromide ionic liquid ([AMIM][Br]), 1-ene 1-Butyl-3-methylimidazolium carbamate ionic liquid ([AMIM][HCOO]), 1-allyl-3-methylimidazolium acetate ionic liquid ([AMIM][Ac]), 1-butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]), 1-butyl-3-methylimidazolium bromide ionic liquid ([BMIM][Br]), 1-butyl-3-methylimidazolium carbamate ionic liquid ([BMIM][HCOO]), 1-butyl-3-methylimidazolium acetate ionic liquid ([BMIM][Ac]), 1-butyl-3-methylimidazolium hydroxyacetate ionic liquid ([BMIM][HOCH2COO]), 1-butyl-3-methylimidazolium propionate ionic liquid The following ionic liquids are available: [BMIM][CH3CH2COO], [BMIM][Lac], [BMIM][CH3CH2CH2COO], [BMIM][C6H5COO], [BMIM][H2NCH2COO], [BMIM][N(CN)2], and [BMIM][Tf2N].1-Butyl-3-methylimidazolium hexafluorophosphate ionic liquid ([BMIM][PF6]), 1-Butyl-3-methylimidazolium tetrafluoroborate ionic liquid ([BMIM][BF4]), 1-Butyl-3-methylimidazolium methanesulfonate ionic liquid ([BMIM][MeOSO3]), 1-Butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid ([BMIM][CF3SO3]), 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate ionic liquid ([BMMIM][BF4]), 3-methylimidazolium formate ionic liquid ([MIM][HCOO]), 1,3-dimethylimidazolium chloride ionic liquid ([MMIM][Cl]), 1,3-dimethylimidazolium chloride ionic liquid ([MMIM][Cl]), 1,3-dimethylimidazolium chloride... 1,3-Dimethylimidazolium methyl phosphate ionic liquid ([MMIM][MP]), 1,3-dimethylimidazolium dimethyl phosphate ionic liquid ([MMIM][DMP]), 1,3-dimethylimidazolium methanesulfonate ionic liquid ([MMIM][MeOSO3]), 1-hydroxy-3-methylimidazolium chloride ionic liquid ([HMIM][Cl]), 1-hydroxy-3-methylimidazolium trifluoromethyl sulfonate ionic liquid ([HMIM][CF3SO3]), 1-(2-hydroxyethyl)-3-methylimidazolium chloride ionic liquid ([HOEMIM][Cl]), 1-methoxymethyl-3-methylimidazolium bromide ionic liquid ([MeOMMIM][Br]), 1-methoxyethyl N-methyl-3-methylimidazolium bromide ionic liquid ([MeOEMIM][Br]), N-ethylpyridine chloride ionic liquid ([EPyr][Cl]), N-ethylpyridine bromide ionic liquid ([EPyr][Br]), N-methylpyridine carboxylate ionic liquid ([MPyr][HCOO]), tris(2-hydroxyethyl)methylamine acetate ionic liquid ([THEMA][Ac]), tris(2-hydroxyethyl)methylamine methanesulfonate ionic liquid ([THEMA][MeOSO3]), tris(2-hydroxyethyl)methylamine trifluoromethanesulfonate ionic liquid [THEMA][CF3SO3], tetrabutylphosphine valine ionic liquid [PBu4][Val], tetrabutylphosphine lis Amino acid salt ionic liquids [PBu4][Lys], tetrabutylphosphine glycine salt ionic liquid [PBu4][Gly], 1-benzyl-3-methylimidazolium chloride ionic liquid ([BzMIM][Cl]), 1-benzyl-3-methylimidazolium dicyandiamide salt ionic liquid ([BzMIM][DCA]), 1-m-methylbenzyl-3-methylimidazolium chloride ionic liquid ([MeBzMIM][Cl]), 1-m-methoxybenzyl-3-methylimidazolium chloride ionic liquid ([MeOBzMIM][Cl]), choline chloride ionic liquid ([Ch][Cl]), choline bromide ionic liquid (Ch][Br]), and choline acetate ionic liquid ([Ch][CH3COO]).Ionic liquids include propionic choline ([Ch][CH3CH2COO]), butyrate choline ([Ch][CH3CH2CH2COO]), glycine hydrochloride ([Gly][Cl]), and 1,5-diazabicyclo[4.3.0]ketone-5-ene acetate ([DBNH][Ac]).

[0158] Preferably, the choline-type eutectic solvent system is selected from one or more of [Ch][Cl] / urea, [Ch][Br] / urea, [Ch][Cl] / thio-urea, [Ch][Cl] / glycerol, and [Ch][Cl] / lactic acid.

[0159] Preferably, the solvent system for dissolving cellulose is selected from the ionic liquid and / or the NaOH / Urea system; more preferably, the ionic liquid for dissolving cellulose is selected from one or more of [AMIM][Cl], [BMIM][Cl], [EMIM][Ac], and [BMIM][Ac].

[0160] Preferably, the solvent for dissolving starch is selected from one or more of the following solvent systems: aqueous solutions of DMSO, CaCl2, ZnCl2, LiClO4, Ca(SCN)2, LiSCN, NaOH, KOH, NaOH / urea, ethylenediamine, pyridine, NMMO, DMAc / LiCl, and ionic liquids such as [AMIM][Cl], [EMIM][Ac], [EMIM][DEP], [BMIM][Cl], [BMIM][Ac], [BMIM][PF6], [BMIM][DCA], [MMIM][(MeO)HPO2], [AMIM][HCOO], [MeOEMIM][Br], and [MeOMMIM][Br], and aqueous solutions of said ionic liquids. More preferably, the ionic liquid for dissolving starch is selected from one or more of [AMIM][Cl], [EMIM][Ac], [BMIM][Cl], [BMIM][Ac], [BMIM][PF6], [BMIM][DCA], [EMIM][DEP], and [MMIM][MP].

[0161] Preferably, the solvent for dissolving chitosan is selected from any one or more of the following solvents: formic acid, acetic acid, hexafluoroisopropanol, hexafluoroacetone, DMAc / LiCl, and [AMIM][Cl], [BMIM][Cl], [BMIM][Ac], [BMIM][HCOO], [BMIM][CH3COO], [BMIM][CH3CH2COO], [BMIM][CH3CH2CH2COO], [BMIM][HOCH2COO], [BMIM][C6H5COO], [BMIM][CH3CH(OH)COO], [BMIM][N(CN)2], [BMIM][BF4], [EMIM][Cl], [EMIM][Ac], [HMIM][Cl], [MM] The ionic liquids used to dissolve chitosan are: [IM][Cl], [Ch][Cl], [Ch][CH3COO], [Ch][CH3CH2COO], [Ch][CH3CH2CH2COO], [Gly][Cl] / [BMIM][Cl]. More preferably, the ionic liquid for dissolving chitosan is selected from one or more of the following: [AMIM][Cl], [BMIM][Cl], [BMIM][Ac], [EMIM][Ac], [BMIM][CH3CH2COO], [BMIM][CH3CH2CH2COO], [BMIM][BF4], [Gly][Cl], [HMIM][Cl], [MMIM][Cl], [Ch][Cl], and [Ch][CH3CH2CH2COO].

[0162] Preferably, the solvent system for dissolving chitosan is selected from one or more of the following solvent systems: formic acid, acetic acid, glutamic acid, lactic acid, succinic acid, dichloroacetic acid (DCA), trichloroacetic acid (TCA), N-methyl-2-pyrrolidone (NMP), hexafluoroisopropanol, hexafluoroacetone, NMP / LiCl, DMAc / LiCl, CaBr2·H2O or CaCl2·2H2O methanol saturated solution, LiCl, LiSCN, NaOH-urea aqueous solution, and [AMIM][Cl], [AMIM][Br], [AMIM][Ac], [BMIM][Ac], [BMIM][Cl], [MMIM][DMP], [...] Ionic liquids or mixed ionic liquid systems such as EMIM][Ac], [EMIM][DMP], [EMIM][Ac], [EMIM][OPr], [EMIM][OBu], [EMIM][Gly], [EMIM][Lys], [HOEMIM][Cl], [THEMA][Ac], [THEMA][MeOSO3], [THEMA][CF3SO3], [PBu4][Val], [PBu4][Lys], [PBu4][Gly], [Ch][Cl] / urea, [Ch][Br] / urea, [Ch][Cl] / thio-urea. More preferably, the ionic liquid for dissolving chitin is selected from one or more of the following: [AMIM][Ac], [BMIM][Ac], [EMIM][Ac], [BMIM][Cl], [AMIM][Cl], [AMIM][Br], [EMIM][OPr], [EMIM][OBu], [Ch][Cl] / urea, [Ch][Br] / urea, and [Ch][Cl] / thio-urea.

[0163] Preferably, the solvent for dissolving lignin is selected from one or more of DMSO / TBAF, imidazole / DMSO, and ionic liquids such as [EMIM][Ac], [BMIM][Cl], [BMIM][Br], [AMIM][Cl], [HMIM][CF3SO3], [MMIM][MeOSO3], [BMIM][MeOSO3], [BMMIM][BF4], [BMIM][CF3SO3], [BzMIM][DCA], [MeOBzMIM][Cl], and [MeBzMIM][Cl]. More preferably, the ionic liquid for dissolving lignin is selected from one or more of [BMIM][Cl], [EMIM][Ac], [BMIM][Br], [AMIM][Cl], [HMIM][CF3SO3], [MMIM][MeOSO3], [BMIM][MeOSO3], and [BMMIM][BF4].

[0164] According to the present invention, the ionic liquid can be a single ionic liquid or a mixed ionic liquid composed of multiple ionic liquids; for example, the single ionic liquid is an ionic liquid that can completely dissolve or partially dissolve biomass macromolecules such as cellulose, starch, chitosan, chitin, lignin, and hemicellulose; for example, the mixed ionic liquid can be an ionic liquid that can dissolve cellulose, starch, chitosan, chitin, lignin, and hemicellulose, or it can be a mixture of an ionic liquid that can dissolve cellulose, starch, chitosan, chitin, lignin, and hemicellulose and an ionic liquid that cannot dissolve cellulose, starch, chitosan, chitin, lignin, and hemicellulose.

[0165] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0166] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0167] Unless otherwise specified, the commercially available natural cellulose mentioned in the following examples refers to natural cellulose purchased from Germany JRS, model VITACEL CS 70G, with a particle size of 70μm.

[0168] Preparation Example 1

[0169] The micro / nano-sized natural polymer hydrogel was prepared using an ionic liquid method. The preparation process involved dissolution, homogenization, and regeneration to obtain a micro / nano-sized natural polymer hydrogel with an 8% solid content and a particle size of 40 μm. The specific preparation method is as follows:

[0170] 12g of wood pulp was premixed with the ionic liquid AMIMCl. The wood pulp was dried in an oven at 80℃ for at least 1 hour beforehand. The mass of AMIMCl was 2388g. The premixed material was heated to 80℃ and stirred under vacuum for 2 hours. After complete dissolution, the solution was slowly poured into warm water at 40±5℃ to form natural cellulose gum (CMG), i.e., micro-nano natural polymer material. The gel was washed 6-8 times with a solution such as water, ethanol, DMF, or NaOH aqueous solution to remove residual AMIMCl. The washed natural cellulose gum was redispersed in pure water at a water-to-natural cellulose gel mass ratio of 9:1. The gel was then pulverized and further pulverized to a particle size of 40μm using a colloid mill or high-pressure homogenizer. The concentration was increased until the solid content of CMG was 8%. After autoclaving, the CMG emulsion was obtained, which is the micro-nano natural polymer material hydrogel.

[0171] Preparation Example 2

[0172] The micro-nano natural polymer hydrogel was prepared by ionic liquid method through dissolution, homogenization and regeneration to obtain a micro-nano natural polymer hydrogel with 8% solid content and 80μm particle size. The specific preparation method is basically the same as that in Preparation Example 1, except that the particle size after pulverization is 80μm.

[0173] Test Example 1

[0174] The micro / nano-sized natural polymer hydrogels prepared in Preparation Examples 1 and 2 were mixed with four different surfactants: sorbitan polyether-30 tetraoleate, PEG-20 glycerol triisostearate, cocoyl glucoside, and polyglycerol-4 isostearate, with a mass ratio of 1:1 between the micro / nano-sized natural polymer hydrogel and the surfactant. Fourier transform infrared spectroscopy analysis was performed, and the results are as follows: Figure 1-2 .

[0175] The above four different surfactants were then mixed with aqueous solutions of different celluloses (e.g., commercially available natural cellulose 70μm, MCC, with a solid content of 8% in the aqueous solutions of different celluloses) and subjected to Fourier transform infrared spectroscopy analysis. The results are as follows: Figure 3-4 .

[0176] from Figure 1 It can be seen that the hydroxyl peak shifted from 3372 to 3357, 3357, 3334, and 3345, respectively. Figure 2 The shift of the hydroxyl peak from 3372 to 3353, 3355, 3338, and 3345 indicates an interaction between the surfactant and the micro / nano-sized natural polymer hydrogel, leading to the red shift of the hydroxyl peak. This suggests that the hydroxyl groups are participating in the formation of hydrogen bonds. Figure 3 and Figure 4 The hydroxyl peak (3372) hardly moved, indicating that cellulose from other sources does not interact with surfactants.

[0177] Example 1

[0178] By weight percentage, the makeup remover composition comprises the following components: 42% cetyl ethylhexanoate, 7% jojoba oil, 7% synthetic wax, 12.2% PEG-20 glyceryl triisostearate, 1% cocoyl glucoside, 0.5% polyglycerol-10 decaole ester, 30% micro / nano natural polymer hydrogel, and 0.3% phenoxyethanol.

[0179] The makeup remover composition is prepared as follows: Weigh the corresponding cetyl ethylhexanoate, jojoba oil, and synthetic wax and place them in a water bath at 100°C. Weigh the corresponding PEG-20 glyceryl triisostearate, cocoyl glucoside, polyglycerol-10 decaoleate, and micro / nano natural polymer hydrogel and stir until homogeneous to obtain a supramolecular polymer. After the oil melts, mix and stir with the oil. During the stirring process, add phenoxyethanol and stir until there are no particles. Pour the mixture into a sample bottle while hot and allow it to cool to obtain the makeup remover composition.

[0180] Referring to the preparation method of the makeup remover composition in Example 1, makeup remover compositions of Examples 2-5 were prepared, and their components are shown below.

[0181] Example 2

[0182] The makeup remover composition comprises the following components by weight percentage: 40% #15 white oil, 5% shea butter, 5.5% PEG-12 laurate, 4% polyglycerol-10 decaoleate, 45% micro / nano natural polymer hydrogel, and 0.5% phenoxyethanol.

[0183] Example 3

[0184] The makeup remover composition comprises, by weight percentage, the following components: 35% squalane, 10% sorbitol polyether-30 glyceryl tetraoleate, 0.5% polyglyceryl-10 decaoleate, 50% micro / nano natural polymer hydrogel, 4% cocoyl glucoside, and 0.5% phenoxyethanol.

[0185] Example 4

[0186] By weight percentage, the makeup remover composition comprises the following components: 30% caprylic / capric triglyceride, 5% shea butter, 15% jojoba oil, 2% PEG-8 beeswax, 0.8% polyglycerol-10 decaoleate, 7.4% PEG-20 glyceryl triisostearate, 0.5% cocoyl glucoside, 39% micro / nano natural polymer hydrogel, and 0.3% PE9010.

[0187] Example 5

[0188] The makeup remover composition comprises the following components by weight percentage: 45% cetyl ethylhexanoate, 12% jojoba oil, 3% sodium PEG-7 olive oil carboxylate, 3% olive oil PEG-7 esters, 36.5% micro-nano natural polymer hydrogel, and 0.5% phenoxyethanol.

[0189] Referring to the preparation method of the makeup remover composition in Example 1, makeup remover compositions of Comparative Examples 1-4 were prepared, the difference being that their components are as follows.

[0190] Comparative Example 1

[0191] The makeup remover composition comprises, by weight percentage, the following components: 42% cetyl ethylhexanoate, 7% jojoba oil, 7% synthetic wax, 12.2% PEG-20 glyceryl triisostearate, 1% cocoyl glucoside, 0.5% polyglycerol-10 decaole ester, 0.5% phenoxyethanol, and the remainder being water.

[0192] Comparative Example 2

[0193] The makeup remover composition comprises, by weight percentage, the following components: 42% cetyl ethylhexanoate, 7% jojoba oil, 7% synthetic wax, 12.2% PEG-20 glyceryl triisostearate, 1% cocoyl glucoside, 0.5% polyglycerol-10 decaoleate, 30% aqueous solution of commercially available natural cellulose (VITACEL CS 70G, JRS, Germany, with a solid content of 8%), and 0.3% phenoxyethanol.

[0194] Comparative Example 3

[0195] The makeup remover composition comprises, by weight percentage, the following components: 35% squalane, 10% sorbitan-30 glyceryl tetraoleate, 0.5% polyglyceryl-10 decaoleate, and an aqueous solution of MCC (the aqueous solution of MCC has a solid content of 8%).

[0196] 50%, cocoyl glucoside 4%, phenoxyethanol 0.5%.

[0197] Comparative Example 4

[0198] This comparative example uses a commercially available brand of cleansing balm as the comparison product.

[0199] Test Example 2

[0200] The makeup removal compositions of Examples 1-5 and Comparative Examples 1-4 were tested as follows:

[0201] (1) Stability test: The makeup remover compositions prepared in Examples 1-5 and Comparative Examples 1-4 were used as products for stability testing. The test method was to put the product (contents) into several 30ML PE bags, label them with the product name, formula number, test conditions and other information, and test the stability of the products at -18℃, 26℃ and 50℃ respectively. After 24h, 1 week, 2 weeks, 4 weeks, 8 weeks and 12 weeks, the products were taken out and allowed to return to room temperature to observe the changes in appearance and odor. The test results are shown in Tables 1 and 2.

[0202] Table 1 Results of Appearance Stability Test

[0203]

[0204] Note: The change level in Table 1 is determined as follows: A is no change; B is slight change; C is significant change; D is serious change.

[0205] Table 2 Results of Odor Stability Test

[0206]

[0207] Note: The change level in Table 2 is determined as follows: A is no change; B is slight change; C is significant change; and D is severe change.

[0208] As shown in Tables 1 and 2, under the same conditions, Comparative Example 1, without the addition of micro / nano natural polymer hydrogel, showed slight changes at 50°C after 8 weeks. This was mainly due to the rancidity of the oils caused by prolonged exposure to high temperatures. Comparative Examples 2 and 3, with the addition of commercially available natural cellulose and MCC, showed varying degrees of stratification, oil precipitation, and spoilage. This may be because MCC and commercially available natural cellulose did not bind with the surfactant, and their density differed from the oil phase. Under the long-term influence of gravity, the powder gradually sank to the bottom of the container. The exposed oils then showed signs of rancidity, producing an unpleasant odor. The makeup remover composition, primarily composed of micro / nano natural polymer hydrogel and surfactant, showed no changes in appearance or odor after 12 weeks, indicating that the makeup remover composition prepared according to the formulation of this invention has good stability.

[0209] (2) pH value test: The makeup removal compositions prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to pH value test according to GB / T 13531.1-2008. The test results are shown in Table 3.

[0210] Table 3 pH test results

[0211]

[0212] As shown in Table 3, the pH values ​​of the makeup remover compositions prepared using micro / nano natural polymer hydrogels and surfactants meet the requirements of GB / T 35914-2018, all falling within the range of 4-11. Furthermore, these pH values ​​are close to the slightly acidic pH of human skin, effectively preventing skin irritation during use.

[0213] (3) Makeup Removal Efficacy Test: The makeup removal compositions prepared in Examples 1-5 and Comparative Examples 1-4 were tested for their makeup removal efficacy. Twenty subjects aged 21-49 years (10 males and 10 females) were randomly selected for the test. The test method was as follows: BB cream, eyeliner, and mascara that last for 4 hours were applied to the inside of both arms of the 20 subjects. Then, 2 grams of the test sample were placed on the makeup area and wiped off 3 times. The samples were then washed with water. The subjects rated the results based on their own feelings. The rating criteria are shown in Table 4. The average score was calculated and recorded. The specific test results are shown in Table 5.

[0214] Table 4 Evaluation Criteria for Makeup Removal Effectiveness

[0215]

[0216] Table 5. Makeup Removal Effectiveness Rating Results

[0217]

[0218] As shown in Table 5, the makeup remover composition prepared with micro-nano natural polymer hydrogel and surfactant is similar to commercially available makeup removers in terms of appearance, texture, rinseability, and post-use feel, and its makeup removal ability even surpasses that of commercially available makeup removers. The vast majority of subjects reported a noticeable grainy feel during use in proportions 2 and 3, discomfort on the face during rubbing, and facial redness after use. In contrast, the micro-nano natural polymer hydrogel exhibits a more significant advantage in terms of flexible friction.

[0219] (4) Makeup Removal Test: The makeup removal compositions prepared in Examples 1-5 and Comparative Examples 1-4 were tested for their makeup removal effects. Foundation, lipstick, eyeliner, eyeshadow, blush, and other makeup were evenly applied to simulated skin and photographed. Then, 5g of each of the makeup removal compositions prepared in Examples 1-5 and Comparative Examples 1-4 were taken and rubbed evenly in circular motions for 1 minute. Afterward, they were rinsed under the same water flow for 1 minute. Finally, excess water was gently absorbed with a tissue, and photographed. The test results are shown in [reference needed]. Figure 5 and 6 .

[0220] from Figure 5 As can be seen, the makeup remover composition formed by using micro-nano natural polymer hydrogel and surfactants has a significant effect on removing makeup, leaving almost no residue. From... Figure 6 As can be seen, the products without added micro-nano natural polymer hydrogel, the products with added commercially available natural cellulose and MCC, and commonly used makeup removers all have a good removal effect on foundation and lipstick, but they are not completely effective at removing some eyeliner and eyeshadow, leaving obvious residue.

[0221] The above tests show that this invention uses micro-nano natural polymer hydrogel and surfactant to form supramolecular aggregates through hydrogen bonds. When using the makeup remover composition of this invention, the supramolecular aggregates formed by the micro-nano natural polymer hydrogel and surfactant come into contact with makeup on the skin. The surfactant emulsifies the oil, and combined with the gentle massage of the micro-nano natural polymer hydrogel, it also cleanses the keratinocytes of aged skin, significantly improving the facial cleansing effect. During rinsing, because the surfactant and micro-nano natural polymer hydrogel have formed aggregates, water removes the surfactant along with the micro-nano natural polymer hydrogel, reducing surfactant residue on the skin and effectively reducing skin irritation. The micro-nano natural polymer hydrogel used in this invention is naturally derived, the operation process is simple and environmentally friendly, and it is easy to achieve industrial application.

[0222] The exemplary embodiments of the present invention have been described above. However, the scope of protection of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A makeup remover composition, characterized in that, Based on mass percentage, it comprises the following components: 1-50% micro-nano natural polymer hydrogel, 0.1-20% surfactant, 10-60% oil, and 0.1-1% preservative; wherein the micro-nano natural polymer in the micro-nano natural polymer hydrogel combines with the surfactant to form supramolecular aggregates.

2. The makeup remover composition according to claim 1, characterized in that, The surfactant is selected from at least one or more of the following: polyglycerol surfactants, PEG-hydrogenated castor oil derivatives, sorbitan derivatives, PEG-glycerol ester surfactants, PEG-laurate ester surfactants, olive oil ester surfactants, and alkyl glycoside surfactants. The olive oil ester surfactant is selected from at least one of olive oil PEG-7 esters, olive oil PEG-8 esters, PEG-4 oleate, and olive oil sodium carboxylate PEG-7. Polyglycerol surfactants are produced by polymerizing glycerol and then esterifying it with fatty acids. Examples of such surfactants include polyglycerol-10 laurate, polyglycerol-4 isostearate, polyglycerol-3 stearate, polyglycerol-2 dihydroxystearate, polyglycerol-10 stearate, polyglycerol-10 decaoleate, polyglycerol mixed fatty acid esters, polyglycerol caprylic / capric acid ester, and polyglycerol monostearate. The PEG-laurate surfactants are obtained by reacting lauric acid with ethylene oxide or by esterifying it with polyethylene glycol (PEG), for example, selected from PEG-12 laurate. The PEG-hydrogenated castor oil derivative is polymerized from hydrogenated castor oil and ethylene oxide, and is selected from, for example, PEG-30 hydrogenated castor oil, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-7 hydrogenated castor oil, PEG-25 hydrogenated castor oil, and PEG-100 hydrogenated castor oil. The sorbitan derivative is formed by dehydrating sorbitol and esterifying it with fatty acids, for example selected from sorbitol polyether-30 tetraoleate, sorbitan monostearate, sorbitan monolaurate, sorbitan tristearate, sorbitan monooleate (Span-80), and sorbitol polyether-30 glycerol tetraoleate. PEG-glyceryl ester surfactants are polymerized from glyceryl esters and ethylene oxide, and are selected from PEG-10 glyceryl stearate, PEG-4 glyceryl stearate, PEG-20 glyceryl triisostearate, PEG-6 glyceryl isostearate, PEG-6 glyceryl cocoate, and PEG-8 glyceryl laurate. Alkyl glycoside surfactants are produced by reacting natural fatty alcohols with glucose, such as cocoyl glucoside, lauryl glucoside, decyl glucoside, and cetearyl glucoside.

3. The makeup remover composition according to claim 1, characterized in that, The micro-nano natural polymer hydrogel was prepared using an ionic liquid method through dissolution, homogenization, and regeneration. The micro-nano natural polymer hydrogel contains no animal-derived components and comprises micro-nano natural polymer materials and water. The micro-nano natural polymer material includes a micron-scale structure and a nano-scale structure distributed on the micron-scale structure; In the makeup remover composition, the mass ratio of the micro-nano natural polymer hydrogel to the surfactant is 1-50:0.1-20.

4. The makeup remover composition according to claim 3, characterized in that, The micro-nano natural polymer material is provided by at least one of the following: biomass-based dispersion, surface-modified biomass-based dispersion, substituted biomass-based dispersion, and multi-component biomass-based dispersion. The biomass-based dispersion includes the micro-nano natural polymer material and a dispersing agent, wherein the micro-nano natural polymer material is distributed in the dispersing agent, and the dispersing agent is a solvent system that enables the micro-nano natural polymer material to be continuously dispersed. The surface-modified micro / nano natural polymer material is a surface-modified version of the micro / nano natural polymer material; or it is a material prepared by the preparation method of the micro / nano natural polymer material, except that the raw biomass is replaced with surface-modified biomass. The surface-modified biomass-based dispersion comprises surface-modified micro / nano natural polymer materials and a dispersing agent, wherein the surface-modified micro / nano natural polymer materials are dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the surface-modified micro / nano natural polymer materials. The substituted biomass-based material is a substitute for the micro-nano natural polymer material; or it is a material prepared by the preparation method of the micro-nano natural polymer material, except that the raw biomass is replaced with the substituted biomass. The substituted biomass dispersion comprises substituted micro / nano natural polymer materials and a dispersing agent, wherein the substituted micro / nano natural polymer materials are dispersed in the dispersing agent; the dispersing agent is a solvent system capable of continuously dispersing the substituted micro / nano natural polymer materials. The continuous phase of the multi-component biomass-based dispersion is a dispersion solvent, and the dispersed phase of the dispersion contains a functional component and at least one of the following components 1) to 3): 1) The micro / nano natural polymer materials mentioned above; 2) The aforementioned replacement micro / nano natural polymer materials; 3) The surface-modified micro / nano natural polymer materials mentioned above.

5. The makeup remover composition according to claim 3, characterized in that, The particle size of the micro-nano natural polymer material in the hydrogel is 1-150 micrometers. The solid content of the micro / nano natural polymer hydrogel is 1-20%.

6. The makeup remover composition according to claim 1, characterized in that, The oil is selected from at least one of natural oils, mineral oils, and synthetic oils; The natural oil is selected from at least one of shea butter, jojoba oil, camellia seed oil, sunflower seed oil, meadowfoam seed oil, sesame oil, and olive fruit oil. The mineral oil is selected from at least one of white oil and petrolatum; The synthetic oil is selected from at least one of the following: caprylic / capric triglyceride, cetyl ethylhexanoate, squalane, isopropyl myristate, beeswax, synthetic wax, and microcrystalline wax.

7. The makeup remover composition according to claim 1, characterized in that, The preservative is selected from one or more of phenoxyethanol, benzyl alcohol, ethylhexylglycerin, 1,2-pentanediol, 1,2-hexanediol, p-hydroxyacetophenone, raspberry ketone, caprylyl glycol, DMDM ​​acetopropionyl urea, dipropylene glycol, caprylyl hydroxamic acid, O-cymene-5-ol, methylpropanediol, chlorophenoxyether, sodium benzoate, and methylisothiazoline.

8. A method for preparing the makeup remover composition according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: mixing oil, surfactant, micro / nano natural polymer hydrogel, preservative and optional diluent according to the above-mentioned mass percentages to obtain the makeup remover composition.

9. The preparation method according to claim 8, characterized in that, In the preparation method, the micro-nano natural polymer hydrogel is first mixed with a surfactant to form a supramolecular aggregate, then mixed evenly with oil under heating conditions, and then a preservative and optional diluent are added.

10. The use of the makeup remover composition according to any one of claims 1-7 in the cosmetics field.

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