Method for preparing a composite film containing a tea residue extract, and products and uses thereof

Abstract

The present application relates to a kind of preparation method of composite film containing tea dregs extract and its product and application.The method of the present application extracts tea dregs to prepare composite film, has excellent performance, realizes tea dregs resourceization.Tea dregs, the waste left after tea processing, is usually directly discarded or landfilled, causing resource waste and environmental pollution, especially the cellulose and polyphenol contained therein are not utilized as solid waste burden.Tea dregs are effectively extracted and used to prepare a composite film for cigarettes, which not only consumes waste tea dregs, turns waste into treasure and reduces the pressure of solid waste treatment, but also low-cost produces functional films such as antioxidant and antibacterial, prolongs the shelf life of cigarettes and improves product quality.This technical path reduces carbon emissions from tea dregs incineration or landfill, is in line with the concept of green and low carbon, and provides a practical solution.

Description

Technical Field

[0001] This invention belongs to the field of cigarette technology, specifically relating to a method for preparing a composite membrane containing tea residue extract, its product, and its application. Background Technology

[0002] The tobacco industry has two core demands for supporting membrane materials: first, they must be green, low-carbon, and fully biodegradable to respond to domestic and international plastic restriction policies and the "dual-carbon" strategy; second, they must functionalize cigarettes to enhance their sensory and harm-reduction properties, achieving additional effects such as aroma enhancement, irritation reduction, and adsorption of harmful components in cigarette smoke, while ensuring processing suitability and barrier preservation. However, existing cigarette membrane materials are mostly non-degradable synthetic polymers (such as polypropylene and polyethylene), which are difficult to degrade naturally after disposal, causing long-term solid waste pollution. Furthermore, existing membrane materials have limited functionality, making it difficult to simultaneously achieve multiple composite functions such as anti-oxidation, antibacterial properties, and sweetness release. Of particular concern is the large amount of tea residue waste generated after tea processing, which is usually directly discarded or landfilled, wasting its rich polyphenols, polysaccharides, and other active ingredients, increasing environmental pollution, and lacking effective resource utilization technologies.

[0003] First, most existing tobacco films lack smoke regulation functions, cannot improve the inhalation of impurities and oral irritation, and do not have the ability to adsorb harmful substances such as phenol, crotonaldehyde, and tar free radicals in smoke. They are difficult to match the tobacco industry's development direction of reducing tar and harm and improving smoking comfort.

[0004] Secondly, the mechanical properties are weak and the molding and processing properties are poor. Pure cellulose and starch films have low tensile strength and high brittleness, and are prone to breakage during the slitting and high-speed wrapping process. This requires a significant reduction in production line speed, which seriously restricts the production capacity of cigarette factories.

[0005] Furthermore, although there are currently pure bio-based biodegradable membranes that can solve the degradation and environmental protection issues, most of them cannot achieve the added value of enhancing the aroma of tea, relieving irritation, and selectively adsorbing harmful substances in smoke, resulting in low material added value.

[0006] Finally, my country is the world's largest tea producer, with a large amount of tea residue resources lying idle. Existing tea residue utilization pathways have low added value, and the mainstream treatment methods are direct burial in farmland and simple composting. The coarse fiber of tea residue degrades slowly, and the effect on soil improvement is limited. Large amounts of tea residue are easily piled up indiscriminately, which can easily breed mold and leachate pollute water and soil, resulting in a serious waste of biomass resources. Although a small amount of tea residue is added to reconstituted tobacco, tobacco flavoring, and filter rod adsorption particles, a tea residue bio-based composite membrane suitable for use in the entire cigarette manufacturing process has not yet been developed.

[0007] Therefore, given the abundant reserves of natural functional raw materials from tea residue and its good compatibility with tobacco smoke, the market urgently needs to provide a composite membrane for tobacco containing active ingredients from tea residue. This would solve the dual problems of the environmental defects of traditional materials and the insufficient performance of bio-based membranes, while simultaneously enabling the high-value recycling of tea processing waste, aligning with the tobacco industry's development trend of green harm reduction and solid waste resource utilization. Summary of the Invention

[0008] In view of the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing a composite membrane containing tea residue extract, as well as its product and application.

[0009] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing a composite membrane containing tea residue extract, the method comprising: (1) After mixing tea residue with a low eutectic solvent, extract it using the DES method. Then, centrifuge the extract and collect the supernatant and extracted tea residue separately. Mix the supernatant with water, let it stand and separate the layers. Collect the lower water layer, concentrate and dry it to obtain crude tea polyphenols. (2) Mix the extracted tea residue with alkaline solution, extract with ultrasound, centrifuge the extract, collect the supernatant and concentrate it, mix the concentrate with anhydrous ethanol, let it stand and separate into layers, take the lower precipitate, dry it to obtain tea residue extract. (3) Mix tea residue extract with water, then add gelatin, plasticizer and crude tea polyphenols from step (1) in sequence, mix to obtain film-forming liquid, put the film-forming liquid into a mold and dry to obtain the composite film containing tea residue extract.

[0010] The method of this invention enables the stepwise extraction and separate utilization of tea polyphenols, proteins, and polysaccharides from tea residue, transforming waste into high-value-added products with significant economic and environmental benefits. The resulting composite membrane integrates antioxidant, antibacterial, and slow-release sweetness properties, and also has antitussive and expectorant effects, making it safe for use after smoking and meeting modern consumers' pursuit of healthy and natural products.

[0011] Preferably, the method for preparing the eutectic solvent in step (1) includes: mixing eugenol with octanoic acid, then adding NaOH solution, and mixing evenly to obtain the eutectic solvent.

[0012] Preferably, the molar ratio of eugenol to octanoic acid is 1:(1-3), for example, it can be 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.7, 1:2.9 or 1:3, etc.

[0013] Preferably, the volume concentration of the NaOH solution is 4-5%, for example, it can be 4.1%, 4.3%, 4.5%, 4.7% or 4.9%, etc.

[0014] Preferably, the NaOH solution is 3-5 times the total volume of eugenol and octanoic acid, for example, 3 times, 3.5 times, 4 times or 4.5 times, etc.

[0015] The eutectic solvent prepared by the specific method of this invention replaces the traditional organic solvent used in extraction, achieving precise control and recycling of solvent polarity, significantly reducing solvent consumption and environmental pollution, which is in line with the development direction of green chemistry. Eugenol and octanoic acid are both natural compounds with high biosafety and low residue risk.

[0016] Preferably, the ratio of tea residue to eutectic solvent in step (1) is 1:(35-50) g / mL, for example, it can be 1:35 g / mL, 1:38 g / mL, 1:40 g / mL, 1:42 g / mL, 1:44 g / mL, 1:46 g / mL, 1:47 g / mL, 1:48 g / mL, 1:49 g / mL or 1:50 g / mL, etc.

[0017] Preferably, the extraction temperature in step (1) is 55-65℃ (e.g., 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, 61℃, 62℃, 63℃, 64℃ or 65℃, etc.), and the time is 30-60min (e.g., 30min, 34min, 38min, 42min, 46min, 50min, 53min, 56min, 58min or 60min, etc.).

[0018] Preferably, the extraction is performed under ultrasound assistance.

[0019] Preferably, the power of the ultrasound is 300-500 W, for example, it can be 300W, 320W, 350W, 380W, 400W, 430W, 450W, 470W, 490W or 500W.

[0020] Preferably, the centrifugation speed in step (1) is 7000-10000 rpm (e.g., 7000 rpm, 7400 rpm, 7800 rpm, 8200 rpm, 8600 rpm, 9000 rpm, 9300 rpm, 9600 rpm, 9800 rpm or 10000 rpm, etc.), and the time is 10-20 min (e.g., 10 min, 11 min, 13 min, 15 min, 16 min, 17 min, 18 min, 19 min, 19.5 min or 20 min, etc.).

[0021] Preferably, the ratio of tea residue to alkaline solution after extraction in step (2) is 1:(30-40)g / mL, for example, it can be 1:30g / mL, 1:32g / mL, 1:33g / mL, 1:35g / mL, 1:36g / mL, 1:37g / mL, 1:38g / mL, 1:39g / mL, 1:39.5g / mL or 1:40g / mL, etc.

[0022] Preferably, the alkaline solution comprises a NaOH solution.

[0023] Preferably, the concentration of the NaOH solution is 0.8-1.5 mol / L, for example, it can be 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.35 mol / L, 1.4 mol / L, 1.45 mol / L or 1.5 mol / L, etc.

[0024] Preferably, the ultrasonic extraction in step (2) is performed at a temperature of 50-60℃ (e.g., 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 57℃, 58℃, 59℃ or 60℃, etc.), for a time of 20-40min (e.g., 20min, 23min, 26min, 29min, 32min, 34min, 36min, 37min, 39min or 40min, etc.), and with an ultrasonic power of 300-500W (e.g., 300W, 330W, 360W, 390W, 410W, 440W, 460W, 480W, 490W or 500W, etc.).

[0025] Preferably, the centrifugation speed in step (2) is 3000-5000 rpm (e.g., 3000 rpm, 3200 rpm, 3500 rpm, 3700 rpm, 4000 rpm, 4200 rpm, 4400 rpm, 4600 rpm, 4800 rpm or 5000 rpm, etc.), and the time is 5-15 min (e.g., 5 min, 7 min, 8 min, 10 min, 11 min, 12 min, 13 min, 14 min, 14.5 min or 15 min, etc.).

[0026] Preferably, the concentration in step (2) to 40-60% of the original volume can be, for example, 40%, 43%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, or 60%.

[0027] Preferably, the volume ratio of the concentrate to anhydrous ethanol is 1:(1.2-2), for example, it can be 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.85, 1:1.9 or 1:2, etc.

[0028] Preferably, the precipitate in step (2) is washed with an aqueous ethanol solution before drying.

[0029] Preferably, the concentration of the ethanol aqueous solution is 60-75%, for example, it can be 60%, 62%, 64%, 66%, 68%, 70%, 71%, 73%, 74% or 75%, etc.

[0030] Preferably, the number of washing cycles is 1-4 times, for example, 1 time, 2 times, 3 times or 4 times.

[0031] Preferably, after washing, the precipitate is mixed with water and reconstituted, and then the reconstituted solution is dialyzed.

[0032] Preferably, the dialysis treatment is performed in a dialysis bag, and the molecular weight cutoff of the dialysis bag is 3000-3500 Da, for example, 3000 Da, 3100 Da, 3200 Da, 3300 Da, 3400 Da or 3500 Da.

[0033] Preferably, the permeate is collected after dialysis and dried to obtain tea residue extract.

[0034] Preferably, the ratio of tea residue extract to water in step (3) is 1:(90-100)g / mL, for example, it can be 1:90g / mL, 1:92g / mL, 1:94g / mL, 1:95g / mL, 1:96g / mL, 1:97g / mL, 1:98g / mL, 1:99g / mL, 1:99.5g / mL or 1:100g / mL, etc.

[0035] Preferably, the mass ratio of the tea residue extract, gelatin, plasticizer and crude tea polyphenols is (0.5-1.5):(2-4):(1-2):(0.05-0.5).

[0036] "0.5-1.5" can be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3 or 1.4, etc. “2-4” can be 2.1, 2.3, 2.5, 2.7, 2.9, 3.0, 3.1, 3.3, 3.5, 3.7 or 3.9, etc.; “1-2” can be 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, etc.; "0.05-0.5" can be 0.06, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.48, etc.

[0037] Preferably, the plasticizer comprises glycerin.

[0038] Preferably, the mixing in step (4) further includes the addition of a sweetener; Preferably, the amount of sweetener added is 0.5-3% of the mass of the film-forming solution, for example, it can be 0.5%, 0.8%, 1.1%, 1.4%, 1.7%, 2.0%, 2.3%, 2.6%, 2.8% or 3%, etc.

[0039] Preferably, the sweetener comprises any one or a combination of at least two of sodium saccharin, neomethylhesperidin dihydrochalcone, or erythritol.

[0040] Secondly, the present invention provides a composite membrane containing tea residue extract, wherein the composite membrane containing tea residue extract is prepared by the method described in the first aspect.

[0041] Thirdly, the present invention provides the application of a composite membrane containing tea residue extract as described in the second aspect in the preparation of cigarettes.

[0042] The application of the composite film containing tea residue extract of the present invention in cigarettes includes, but is not limited to, the following: ① Directly coating the film-forming liquid onto one side of the tipping paper base paper, drying and rolling it to form a functional coated tipping paper, which is convenient for use in conventional tipping processes; ② Directly wrapping the independently formed composite film around the outside of the tipping paper of the cigarette filter as an additional functional layer, which can further inhibit surface microorganisms and slow-release sweetness; ③ First wrapping the composite film around the outer surface of the filter rod, and then wrapping the tipping paper around it, so that the functional film is located between the filter rod and the tipping paper, avoiding direct contact with the lips while still exerting antioxidant, adsorbing harmful components of smoke and slow-releasing sweetness effects. All three methods can realize the resource utilization of tea residue extract and endow the cigarette film material with biodegradability and composite functions.

[0043] All the specific point values ​​within the above range can be selected, and will not be elaborated on here.

[0044] Compared with the prior art, the present invention has the following beneficial effects: (1) The method of this invention extracts tea residue to prepare a composite membrane with excellent performance, realizing the resource utilization of tea residue. Waste tea residue left after tea processing is often directly discarded or landfilled, causing resource waste and environmental pollution, especially since the rich cellulose and polyphenols are not utilized and become a burden of solid waste. Effectively extracting tea residue and using it to prepare a composite membrane for cigarettes can not only consume waste tea residue and turn waste into treasure, reducing the pressure of solid waste treatment, but also prepare antioxidant, antibacterial, and other functional films at low cost, extending the shelf life of cigarettes and improving product quality. This technical approach reduces carbon emissions from tea residue incineration or landfill, aligns with the green and low-carbon concept, and provides a practical solution.

[0045] (2) The composite film containing tea residue extract prepared by this invention contains cellulose and polysaccharide components, which can form an interwoven network structure with gelatin, effectively improving the defects of pure bio-based films, such as high brittleness and easy cracking. The composite film is highly flexible and can adapt to industrial production processes such as high-speed wrapping, slitting, and heat sealing of cigarettes. It is not prone to problems such as film damage, edge curling, and breakage during processing. At the same time, the film is suitable for high and low temperature storage environments, is not prone to embrittlement and deformation, and can stably maintain the integrity of cigarette outer packaging.

[0046] (3) The composite membrane containing tea residue extract prepared by the present invention relies on the unique porous microstructure of tea residue. The composite membrane forms a uniform microporous channel inside, which can block the intrusion of external water vapor and dust, prevent the tobacco from getting damp and moldy; and can also realize micro-gas exchange, release excess impurities generated during the storage of tobacco, balance the internal air pressure of the packaging, avoid the problem of the cigarettes having a musty smell, and ensure the long-term quality of cigarette storage.

[0047] (4) The composite membrane of the present invention contains tea residue extract, which is rich in natural active ingredients such as tea polyphenols and tea aromatic substances. The membrane can adsorb and seal tea aroma and other aroma-enhancing materials, and has excellent aroma storage and slow release capabilities. During the room temperature storage stage, the aroma is locked and not easily lost. During the smoking process, it is slowly released under temperature stimulation. It can not only neutralize the spiciness of the smoke and weaken the impurities, but also optimize the smoking taste and achieve the effect of enhancing aroma and harmonizing.

[0048] (5) The composite membrane containing tea residue extract of the present invention is rich in tea polyphenols and flavonoids, which are natural antioxidants that can inhibit the oxidation and decomposition of tobacco oil and aromatic substances, and delay the aging and deterioration of tobacco. At the same time, it can remove some free radicals in the smoke, reduce the irritation of cigarettes, and extend the shelf life of cigarettes.

[0049] (6) In this invention, a compound sweetener consisting of sodium saccharin, neomethyl hesperidin dihydrochalcone and erythritol is added to a composite membrane containing tea residue extract. This can form a good synergistic effect with the tea residue extract. The compound sweetener can soften the tea aroma and mask the bitterness of tobacco. At the same time, it complements the active components of tea polyphenols, optimizes the sweetness of the smoke, coordinates the aroma and flavor, and further improves the overall smoking comfort of cigarettes. Detailed Implementation

[0050] To further illustrate the technical means and effects of the present invention, the following describes the technical solution of the present invention in conjunction with preferred embodiments of the present invention. However, the present invention is not limited to the scope of the embodiments.

[0051] The following detailed description of the features and advantages of the present invention is sufficient to enable those skilled in the art to understand the technical content of the present invention and implement it accordingly. Furthermore, based on this specification and the claims, those skilled in the art can easily understand the related objectives and advantages of the present invention.

[0052] The terminology and expressions used herein are for descriptive purposes only, and the invention should not be limited to these terms and expressions. The use of these terms and expressions does not imply the exclusion of any illustrative and descriptive equivalents (or parts thereof), and it should be recognized that various modifications that may exist should also be included within the scope of the claims. Other modifications, variations, and substitutions may also exist. Accordingly, the claims should be considered to cover all such equivalents.

[0053] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0054] The raw materials used in the embodiments or comparative examples of this invention can be used as long as they are purchased from authorized distributors.

[0055] Preparation Example 1 This preparation example provides a eutectic solvent, which is prepared by mixing eugenol and octanoic acid at a molar ratio of 1:2 and stirring at 75°C until a uniform and transparent liquid is formed, which is a hydrophobic switchable DES. Then, a 4% NaOH solution (the volume ratio of the hydrophobic switchable DES to the NaOH solution is 1:4) is added and mixed evenly to obtain the eutectic solvent.

[0056] Preparation Example 2 This preparation example provides a eutectic solvent, which is prepared by mixing eugenol and octanoic acid in a molar ratio of 1:3 and stirring at 70°C until a uniform and transparent liquid is formed, which is a hydrophobic switchable DES. Then, a 4% NaOH solution (the volume ratio of the hydrophobic switchable DES to the NaOH solution is 1:5) is added and mixed evenly to obtain the eutectic solvent.

[0057] Preparation Example 3 This preparation example provides a eutectic solvent, which is prepared by mixing eugenol and n-octanoic acid in a molar ratio of 1:1 and stirring at 80°C until a uniform and transparent liquid is formed, which is a hydrophobic switchable DES. Then, a 5% NaOH solution (the volume ratio of the hydrophobic switchable DES to the NaOH solution is 1:3) is added and mixed evenly to obtain the eutectic solvent.

[0058] Preparation Example 4 This preparation example provides a eutectic solvent, which is prepared by adding a 4% NaOH solution (the volume ratio of eugenol to NaOH solution is 1:4) to eugenol and mixing them evenly to obtain the eutectic solvent.

[0059] Preparation Example 5 This preparation example provides a eutectic solvent, which is prepared by adding a 4% (v / v) NaOH solution to octanoic acid (the volume ratio of eugenol to NaOH solution is 1:4), and mixing them evenly to obtain the eutectic solvent.

[0060] Preparation Example 6 This preparation example provides a eutectic solvent, which is prepared by mixing eugenol and octanoic acid in a molar ratio of 1:2 and stirring at 75°C until a uniform and transparent liquid is formed, which is a hydrophobic switchable DES, and is the eutectic solvent.

[0061] Example 1 This embodiment provides a composite membrane containing tea residue extract, and the preparation method of the composite membrane containing tea residue extract is as follows: (1) The tea residue produced in the production of tea beverages is dried at 50°C for 4 hours, pulverized and passed through an 80-mesh sieve to obtain tea residue powder; (2) Add the eutectic solvent (DES) of Preparation Example 1 to the tea residue powder at a solid-liquid ratio of 1:40, and extract with ultrasonic assistance at 60°C and 400 W for 40 min. Centrifuge the extract at 8000 r / min for 15 min, collect the extracted tea residue for later use, collect the supernatant and add an appropriate amount of water to the supernatant to promote the hydrophilicity switching of DES and phase separation. Collect the lower phase layer containing water-containing tea polyphenols, concentrate under reduced pressure and freeze dry to obtain crude tea polyphenols. (3) After extraction, the residual solvent of the tea residue was evaporated at low temperature, and then a 1 mol / L NaOH solution (solid-liquid ratio of 1:35 with the tea residue) was added. The extract was ultrasonically extracted at 55℃ and 400 W for 30 min. Then the extract was centrifuged at 4000 r / min for 10 min. The supernatant was concentrated under reduced pressure to 50% of the original volume. Then anhydrous ethanol (1.5 times the volume of the concentrated liquid) was added. After mixing, the mixture was allowed to stand for 24 h. Then the precipitate was collected by centrifugation at 3000 r / min for 15 min. The precipitate was washed twice with 70% ethanol. The precipitate was then reconstituted with water and placed in a dialysis bag with a molecular weight cutoff of 3500 Da. The permeate was collected and freeze-dried to obtain the tea residue extract. (4) Prepare a 1% (w / v) solution of tea residue extract with deionized water and stir at 60℃ and 500 r / min for 30 min to ensure it is fully dispersed and uniform. Then add gelatin and continue stirring for 60 min until a homogeneous solution is formed. Then add glycerin as a plasticizer and continue stirring until it is mixed evenly. Then add crude tea polyphenols and continue stirring for 10 min. The mass ratio of tea residue extract, gelatin, plasticizer and crude tea polyphenols is 1:3:1.5:0.3 to obtain a film-forming solution. (5) Add sweetener (sodium saccharin, neomethyl hesperidin dihydrochalcone and erythritol in a mass ratio of 1:1:1) to the film-forming solution, and continue stirring for 30 minutes. The sweetener is 1.5% of the mass of the film-forming solution. After the film-forming solution is put into a mold and dried, the composite film containing tea residue extract is obtained.

[0062] Example 2 This embodiment provides a composite membrane containing tea residue extract, and the preparation method of the composite membrane containing tea residue extract is as follows: (1) The tea residue produced in the production of tea beverages is dried at 45°C for 5 hours, pulverized and passed through a 70-mesh sieve to obtain tea residue powder; (2) Add the eutectic solvent (DES) of Preparation Example 2 to the tea residue powder at a solid-liquid ratio of 1:35, and extract with ultrasonic assistance at 65°C and 300 W for 30 min. Centrifuge the extract at 7000 r / min for 20 min, collect the extracted tea residue for later use, collect the supernatant and add an appropriate amount of water to the supernatant to promote the hydrophilicity switching of DES and phase separation. Collect the lower phase layer containing water-containing tea polyphenols, concentrate under reduced pressure and freeze dry to obtain crude tea polyphenols. (3) After extraction, the residual solvent of the tea residue was evaporated at low temperature, and then a 1.5 mol / L NaOH solution (solid-liquid ratio of 1:30 with the tea residue) was added. The extract was ultrasonically extracted at 50℃ and 300 W for 40 min. The extract was then centrifuged at 5000 r / min for 8 min. The supernatant was collected and concentrated under reduced pressure to 40% of the original volume. Then anhydrous ethanol (1.2 times the volume of the concentrated liquid) was added. After mixing, the mixture was allowed to stand for 24 h. The precipitate was collected by centrifugation at 4000 r / min for 20 min. The precipitate was washed three times with 65% ethanol. The precipitate was then reconstituted with water and placed in a dialysis bag with a molecular weight cutoff of 3000 Da. The permeate was collected and freeze-dried to obtain the tea residue extract. (4) Prepare a 1.1% (w / v) solution of tea residue extract with deionized water and stir at 50℃ and 600 r / min for 30 min to ensure it is fully dispersed and uniform. Then add gelatin and continue stirring for 50 min until a homogeneous solution is formed. Then add glycerin as a plasticizer and continue stirring until it is mixed evenly. Then add crude tea polyphenols and continue stirring for 20 min. The mass ratio of tea residue extract, gelatin, plasticizer and crude tea polyphenols is 0.5:4:1:0.5 to obtain a film-forming solution. (5) Add sweetener (sodium saccharin, neomethyl hesperidin dihydrochalcone and erythritol in a mass ratio of 2:1:2) to the film-forming solution, and continue stirring for 40 minutes. The sweetener is 2% of the mass of the film-forming solution. After the film-forming solution is put into a mold and dried, the composite film containing tea residue extract is obtained.

[0063] Example 3 This embodiment provides a composite membrane containing tea residue extract, and the preparation method of the composite membrane containing tea residue extract is as follows: (1) The tea residue produced in the production of tea beverages is dried at 40°C for 6 hours, pulverized and passed through an 80-mesh sieve to obtain tea residue powder; (2) Add the eutectic solvent (DES) of Preparation Example 3 to the tea residue powder at a solid-liquid ratio of 1:45, and extract with ultrasonic assistance at 55°C and 500 W for 60 min. Centrifuge the extract at 9000 r / min for 10 min, collect the extracted tea residue for later use, collect the supernatant and add an appropriate amount of water to the supernatant to promote the hydrophilicity switching of DES and phase separation. Collect the lower phase layer containing water-containing tea polyphenols, concentrate under reduced pressure and freeze dry to obtain crude tea polyphenols. (3) After extraction, the residual solvent of the tea residue was evaporated at low temperature, and then a NaOH solution with a concentration of 0.8 mol / L (solid-liquid ratio of 1:40 with tea residue) was added. The extract was ultrasonically extracted at 60℃ and 500 W for 20 min. Then the extract was centrifuged at 3000 r / min for 15 min. The supernatant was collected and concentrated under reduced pressure to 60% of the original volume. Then anhydrous ethanol (1.8 times the volume of the concentrated liquid) was added. After mixing, the mixture was allowed to stand for 24 h. Then the precipitate was collected by centrifugation at 5000 r / min for 25 min. The precipitate was washed three times with 75% ethanol. The precipitate was then reconstituted with water and placed in a dialysis bag with a molecular weight cutoff of 3200 Da. The permeate was collected and freeze-dried to obtain the tea residue extract. (4) Prepare a 1.05% (w / v) solution of tea residue extract with deionized water, and stir at 60℃ and 400 r / min for 35 min to ensure it is fully dispersed and uniform; then add gelatin and continue stirring for 40 min until a homogeneous solution is formed; then add glycerin as a plasticizer and continue stirring until it is mixed evenly; then add crude tea polyphenols and continue stirring for 25 min. The mass ratio of tea residue extract, gelatin, plasticizer and crude tea polyphenols is 1.5:2:2:0.1 to obtain a film-forming solution; (5) Add sweetener (sodium saccharin, neomethyl hesperidin dihydrochalcone and erythritol in a mass ratio of 2:1:1) to the film-forming solution, and continue stirring for 35 minutes. The sweetener is 1% of the mass of the film-forming solution. After the film-forming solution is put into a mold and dried, the composite film containing tea residue extract is obtained.

[0064] Examples 4-6 The embodiments provide three composite membranes containing tea residue extract. The only difference between them and Embodiment 1 is that the eutectic solvent used in step (2) of Embodiment 1 is replaced with the eutectic solvent of Embodiments 4-6, while keeping the amount of eutectic solvent unchanged. The remaining steps and process parameters are the same as in Embodiment 1.

[0065] Example 7 This embodiment provides a composite membrane containing tea residue extract. The only difference between this embodiment and Example 1 is that in step (3) of the preparation method, after collecting the precipitate, the precipitate is freeze-dried to obtain tea residue extract. The remaining steps and process parameters are the same as in Example 1.

[0066] Example 8 This embodiment provides a composite membrane containing tea residue extract. The only difference between this membrane and Example 1 is that the molecular weight cutoff of the dialysis bag in step (3) of the preparation method is 4000 Da. The remaining steps and process parameters are the same as in Example 1.

[0067] Example 9 This embodiment provides a composite membrane containing tea residue extract. The only difference between this membrane and Example 1 is that the molecular weight cutoff of the dialysis bag in step (3) of the preparation method is 2000 Da. The remaining steps and process parameters are the same as in Example 1.

[0068] Example 10 This embodiment provides a composite membrane containing tea residue extract. The only difference between this embodiment and Example 1 is that step (5) in the preparation method does not include the addition of sweeteners, and the film-forming liquid is directly placed into the mold for drying. The remaining steps and process parameters are the same as in Example 1.

[0069] Example 11 This embodiment provides a composite membrane containing tea residue extract. The only difference between this membrane and Example 1 is that in step (5) of the preparation method, the sweetener is a mixture of sodium saccharin and neomethyl hesperidin dihydrochalcone in a mass ratio of 1:1, and the amount of sweetener remains unchanged. The remaining steps and process parameters are the same as in Example 1.

[0070] Example 12 This embodiment provides a composite membrane containing tea residue extract. The only difference between this membrane and Example 1 is that in step (5) of the preparation method, the sweetener is a combination of sodium saccharin and erythritol in a mass ratio of 1:1, and the amount of sweetener remains unchanged. The remaining steps and process parameters are the same as in Example 1.

[0071] Example 13 This embodiment provides a composite membrane containing tea residue extract. The only difference between this membrane and Example 1 is that in step (5) of the preparation method, the sweetener is a combination of neomethylhesperidin dihydrochalcone and erythritol in a mass ratio of 1:1, and the amount of sweetener remains unchanged. The remaining steps and process parameters are the same as in Example 1.

[0072] Comparative Example 1 This comparative example provides a composite membrane containing tea residue extract, the preparation method of which is as follows: (1) The tea residue produced in the production of tea beverages is dried at 50°C for 4 hours, pulverized and passed through an 80-mesh sieve to obtain tea residue powder; (2) Add the eutectic solvent (DES) of Preparation Example 1 to the tea residue powder at a solid-liquid ratio of 1:40, and extract with ultrasonic assistance at 60°C and 400 W for 40 min. Centrifuge the extract at 8000 r / min for 15 min, collect the extracted tea residue for later use, collect the supernatant and add an appropriate amount of water to the supernatant to promote the hydrophilicity switching of DES and phase separation. Collect the lower phase layer containing water-containing tea polyphenols, concentrate under reduced pressure and freeze dry to obtain crude tea polyphenols. (3) Prepare a 1% (w / v) solution of crude tea polyphenols with deionized water, and stir at 60℃ and 500 r / min for 30 min to ensure that it is fully dispersed and uniform; then add gelatin and continue stirring for 60 min until a homogeneous solution is formed; then add glycerol as a plasticizer and continue stirring until the mixture is uniform. The mass ratio of gelatin, plasticizer and crude tea polyphenols is 3:1.5:0.3 to obtain the film-forming solution. (4) Add sweetener (sodium saccharin, neomethyl hesperidin dihydrochalcone and erythritol in a mass ratio of 1:1:1) to the film-forming solution, and continue stirring for 30 minutes. The sweetener is 1.5% of the mass of the film-forming solution. After drying the film-forming solution in a mold, the composite film containing tea residue extract is obtained.

[0073] Comparative Example 2 This comparative example provides a composite membrane containing tea residue extract, the preparation method of which is as follows: (1) The tea residue produced in the production of tea beverages is dried at 50°C for 4 hours, pulverized and passed through an 80-mesh sieve to obtain tea residue powder; (2) Add a 1 mol / L NaOH solution (solid-liquid ratio of 1:35 with tea residue) to the tea residue powder, and extract by ultrasonication at 55℃ and 400 W for 30 min. Then centrifuge the extract at 4000 r / min for 10 min, take the supernatant and concentrate it under reduced pressure to 50% of the original volume. Then add anhydrous ethanol (1.5 times the volume of the concentrated liquid), mix well and let stand for 24 h. Then centrifuge at 3000 r / min for 15 min to collect the precipitate. Wash the precipitate twice with 70% ethanol, then reconstitute the precipitate with water and put it into a dialysis bag with a molecular weight cutoff of 3500 Da. Collect the permeate and freeze-dry the permeate to obtain the tea residue extract. (3) Prepare a 1% (w / v) solution of tea residue extract with deionized water, and stir at 60℃ and 500 r / min for 30 min to ensure that it is fully dispersed and uniform; then add gelatin and continue stirring for 60 min until a homogeneous solution is formed; then add glycerin as a plasticizer and continue stirring until the mixture is uniform. The mass ratio of tea residue extract, gelatin and plasticizer is 1:3:1.5 to obtain film-forming solution. (4) Add sweetener (sodium saccharin, neomethyl hesperidin dihydrochalcone and erythritol in a mass ratio of 1:1:1) to the film-forming solution, and continue stirring for 30 minutes. The sweetener is 1.5% of the mass of the film-forming solution. After drying the film-forming solution in a mold, the composite film containing tea residue extract is obtained.

[0074] Test Example 1: Flexibility and Breathability Test The flexibility and air permeability of the composite membranes containing tea residue extract obtained in Examples 1-3 and Comparative Examples 1-2 were tested.

[0075] The flexibility was tested according to GB / T1731-1993; the air permeability was tested five times using a GTR-704R cigarette paper air permeability tester and the average value was taken. The results are shown in Table 1.

[0076] Table 1 As shown in Table 1, the composite membrane containing tea residue extract obtained by the method of the present invention not only has better flexibility, but also has excellent air permeability.

[0077] Test Example 2: Sensory Effect Evaluation Test cigarettes were prepared by wrapping the filter rod (outside the tipping paper) of finished cigarettes containing no flavoring or sweetening ingredients with the composite film containing tea residue extract obtained in Examples 1-13 and Comparative Examples 1-2. A control cigarette was prepared by wrapping the filter rod of a finished cigarette containing no flavoring or sweetening ingredients with a mouthpiece made of acrylate resin (loaded with 0.8g of a sweetener composed of sodium saccharin, neomethyl hesperidin dihydrochalcone, and erythritol in a mass ratio of 1:1:1). Sensory quality tests were conducted on both the test and control cigarettes according to national standards.

[0078] Seven top-level tasters were organized to conduct sensory evaluations of the various indicators of the cigarettes obtained above, according to GB5606.4-2005 "Cigarettes Part 4: Sensory Technical Requirements". At the same time, the test cigarettes were placed in an environment of 40℃ and 75% relative humidity for one month before sensory testing was conducted again. The specific definitions of the sensory quality evaluation indicators are shown in Table 1, the scoring criteria are shown in Table 2, and the scoring results are shown in Table 3 (the average value of each group is taken and one decimal place is retained).

[0079] Table 2 Table 3 Table 4 As shown in Table 4, compared with the control cigarettes, the cigarettes containing the composite film obtained in Examples 1-3 of this invention have a rich and complex aroma, and the cigarettes have better harmony and taste. Moreover, the sensory properties of the cigarettes do not change much after being stored for 6 months, indicating that the composite film has excellent aroma-carrying performance. Furthermore, the sweeteners do not migrate under high temperature and high pressure. Compared with traditional processes, the aroma-enhancing effect of the composite film of this invention makes the cigarette taste more stable.

[0080] Test Example 3: Antioxidant Test The free radical scavenging effects of the composite membranes containing tea residue extract in Examples 1-13 and Comparative Examples 1-2 (tested using film-forming solutions) were evaluated: The free radical content was determined according to DB45 / T 1494-2017, "Determination of Gas Phase Free Radical Content in Mainstream Cigarette Smoke - Electron Spin Resonance Spectroscopy". The results are shown in Table 5 (each sample was measured in parallel 5 times, and the data are presented as average values).

[0081] Table 5 The results show that the composite membranes containing tea residue extract involved in Examples 1-3 of the present invention have excellent antioxidant properties due to the presence of tea polyphenols.

[0082] As can be seen from Examples 4-6, the choice of eutectic solvent has a significant impact on the extraction of tea polyphenols; As can be seen from Examples 7-9, the purity of the proteoglycan component in the tea residue extract is higher through dialysis, which in turn makes the final composite membrane have a better antioxidant effect. As can be seen from Comparative Examples 1-2, only by performing two different extractions can the extraction effect of tea polyphenols and proteoglycans in tea residue be better, thereby improving the antioxidant properties of the final composite membrane.

[0083] The applicant declares that the technical solution of this invention is illustrated by the above embodiments, but this invention is not limited to the above embodiments, that is, it does not mean that this invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the products of this invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

[0084] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0085] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

Claims

1. A method for preparing a composite membrane containing tea residue extract, characterized in that, The preparation method includes: (1) After mixing tea residue with a low eutectic solvent, extract it using the DES method. Then, centrifuge the extract and collect the supernatant and extracted tea residue separately. Mix the supernatant with water, let it stand and separate the layers. Collect the lower water layer, concentrate and dry it to obtain crude tea polyphenols. (2) Mix the extracted tea residue with alkaline solution, extract with ultrasound, centrifuge the extract, collect the supernatant and concentrate it, mix the concentrate with anhydrous ethanol, let it stand and separate into layers, take the lower precipitate, dry it to obtain tea residue extract. (3) Mix tea residue extract with water, then add gelatin, plasticizer and crude tea polyphenols from step (1) in sequence, mix to obtain film-forming liquid, put the film-forming liquid into a mold and dry to obtain the composite film containing tea residue extract.

2. The method for preparing the composite membrane containing tea residue extract as described in claim 1, characterized in that, The method for preparing the eutectic solvent in step (1) includes: mixing eugenol with octanoic acid, then adding NaOH solution, and mixing evenly to obtain the eutectic solvent; Preferably, the molar ratio of eugenol to octanoic acid is 1:(1-3). Preferably, the volume concentration of the NaOH solution is 4-5%; Preferably, the NaOH solution is 3-5 times the total volume of eugenol and octanoic acid; Preferably, the ratio of tea residue to eutectic solvent in step (1) is 1:(35-50)g / mL.

3. The method for preparing the composite membrane containing tea residue extract as described in claim 1 or 2, characterized in that, The extraction temperature in step (1) is 55-65℃, and the extraction time is 30-60 min; Preferably, the extraction is performed under ultrasound assistance; Preferably, the power of the ultrasound is 300-500 W; Preferably, the centrifugation speed in step (1) is 7000-10000 rpm and the time is 10-20 min.

4. The method for preparing the composite membrane containing tea residue extract as described in any one of claims 1-3, characterized in that, In step (2), the ratio of tea residue to alkaline solution after extraction is 1:(30-40)g / mL; Preferably, the alkaline solution comprises a NaOH solution; Preferably, the concentration of the NaOH solution is 0.8-1.5 mol / L.

5. The method for preparing the composite membrane containing tea residue extract as described in any one of claims 1-4, characterized in that, In step (2), the ultrasonic extraction is performed at a temperature of 50-60℃ for 20-40 minutes and with an ultrasonic power of 300-500W. Preferably, the centrifugation speed in step (2) is 3000-5000 rpm and the time is 5-15 min; Preferably, step (2) involves concentrating the volume to 40-60% of its original volume; Preferably, the volume ratio of the concentrate to anhydrous ethanol is 1:(1.2-2).

6. The method for preparing the composite membrane containing tea residue extract as described in any one of claims 1-5, characterized in that, The precipitate described in step (2) is washed with an aqueous ethanol solution before drying; Preferably, the concentration of the ethanol-water solution is 60-75%; Preferably, the number of washing cycles is 1-4. Preferably, after washing, the precipitate is mixed with water and reconstituted, and then the reconstituted solution is dialyzed. Preferably, the dialysis treatment is performed in a dialysis bag, and the molecular weight cutoff of the dialysis bag is 3000-3500 Da; Preferably, the permeate is collected after dialysis and dried to obtain tea residue extract.

7. The method for preparing the composite membrane containing tea residue extract as described in any one of claims 1-6, characterized in that, In step (3), the ratio of tea residue extract to water is 1:(90-100)g / mL; Preferably, the mass ratio of the tea residue extract, gelatin, plasticizer, and crude tea polyphenols is (0.5-1.5):(2-4):(1-2):(0.05-0.5). Preferably, the plasticizer comprises glycerin.

8. The method for preparing the composite membrane containing tea residue extract as described in any one of claims 1-7, characterized in that, Step (4) also includes adding a sweetener during the mixing process; Preferably, the amount of sweetener added is 0.5-3% of the mass of the film-forming solution; Preferably, the sweetener comprises any one or a combination of at least two of sodium saccharin, neomethylhesperidin dihydrochalcone, or erythritol.

9. A composite membrane containing tea residue extract, characterized in that, The composite membrane containing tea residue extract is prepared by the method described in any one of claims 1-8.

10. The application of a composite membrane containing tea residue extract as described in claim 9 in the preparation of cigarettes.

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