CN116219746A - A kind of bio-based anti-mosquito finishing agent and its preparation method and application - Google Patents
A kind of bio-based anti-mosquito finishing agent and its preparation method and application Download PDFInfo
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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Abstract
Description
技术领域technical field
本发明属于纺织助剂技术领域，具体涉及一种生物基防蚊整理剂及其制备方法和应用。The invention belongs to the technical field of textile auxiliaries, and in particular relates to a bio-based anti-mosquito finishing agent and its preparation method and application.
背景技术Background technique
每到夏天，人们都是“浑身解数”，采用各种方法与蚊虫“斗智斗勇”，蚊虫除直接叮刺、吸血、骚扰睡眠外，更多的是传播多种疾病。随着蚊虫的吸吮，几十种病原体和其他的传染病微生物也流进温血动物的体内，导致疟疾、黄热病、登革热、脑炎等疾病的爆发。在亚洲、非洲和美洲，每年因蚊虫叮咬而感染疟疾死亡的人数超过100万。因此，蚊虫防治工作具有十分重要的意义。Every summer, people "do all their best" and use various methods to "fight wit and courage" with mosquitoes. In addition to direct stinging, blood-sucking, and sleep disturbance, mosquitoes are more likely to spread a variety of diseases. As the mosquito sucks, dozens of pathogens and other infectious disease microorganisms also flow into the body of warm-blooded animals, leading to outbreaks of malaria, yellow fever, dengue fever, encephalitis and other diseases. In Asia, Africa and the Americas, malaria kills more than 1 million people each year from mosquito bites. Therefore, mosquito control work is of great significance.
随着生活水平的提高，人们越来越重视生活的质量，希望能获得有舒适感的衣着以及卫生健康的居住环境，所以人们对于各种各样的纺织品要求越来越高，特别是安全、安心、舒适、健康、卫生、清洁等“绿色”观念的形成，使纺织品后整理加工更加受到人们的重视。With the improvement of living standards, people pay more and more attention to the quality of life, hoping to obtain comfortable clothing and a healthy living environment, so people have higher and higher requirements for various textiles, especially safety, The formation of "green" concepts such as peace of mind, comfort, health, sanitation, and cleanliness has made textile finishing more popular.
防蚊整理剂是用于织物后整理工序中，从而使织物获得防蚊效果的加工工艺。棉、涤纶、锦纶、涤棉等织物经过该助剂及工艺处理后，对蚊、虫等卫生害虫具有优异的杀灭和驱避效果，整理后的织物可广泛用于蚊帐、帐篷、睡袋等户外用品。The anti-mosquito finishing agent is used in the fabric finishing process, so that the fabric can obtain the anti-mosquito effect. Cotton, polyester, nylon, polyester-cotton and other fabrics have excellent killing and repelling effects on sanitary pests such as mosquitoes and insects after being treated with this additive and process. The finished fabrics can be widely used in mosquito nets, tents, sleeping bags, etc. outdoor product.
目前纺织品上广泛使用的防蚊产品主要为拟除虫菊酯类产品，这类广谱杀虫剂对昆虫具有强烈的触杀作用，但它对鱼类毒性高，且长期使用会导致害虫产生抗药性。At present, the anti-mosquito products widely used in textiles are mainly pyrethroid products. This kind of broad-spectrum insecticide has a strong contact effect on insects, but it is highly toxic to fish, and long-term use will lead to insect resistance.
发明内容Contents of the invention
本发明目的是提供一种生物基防蚊整理剂及其制备方法和应用，以解决上述问题，将该生物基防蚊整理剂按照设定的整理工艺作用在织物上，可达到良好的防蚊性能，且不影响织物的颜色和状态；同时该生物基防蚊整理剂来源天然，整理后的织物可直接接触人体，无细胞毒性，对皮肤无刺激；无耐药性，适合广泛使用。The object of the present invention is to provide a bio-based anti-mosquito finishing agent and its preparation method and application, in order to solve the above problems, the bio-based anti-mosquito finishing agent acts on the fabric according to the set finishing process, and can achieve good anti-mosquito performance without affecting the color and state of the fabric; at the same time, the bio-based anti-mosquito finishing agent comes from natural sources, the finished fabric can directly contact the human body, has no cytotoxicity, and has no irritation to the skin; it has no drug resistance and is suitable for wide use.
为解决上述技术问题，本发明所采取的技术方案如下：In order to solve the problems of the technologies described above, the technical scheme adopted in the present invention is as follows:
一种生物基防蚊整理剂，按照重量份数，包括如下组分：驱蚊酯2％-6％、红花除虫菊素2％-6％、生物基乳化剂5％-15％、多元醇5％-15％、聚氨酯1％-5％、去离子水65％-75％；A bio-based anti-mosquito finishing agent, comprising the following components in parts by weight: mosquito repellent 2%-6%, safflower pyrethrin 2%-6%, bio-based emulsifier 5%-15%, polyol 5%-15%, polyurethane 1%-5%, deionized water 65%-75%;
所述的生物基乳化剂为腰果酚聚氧乙烯醚、磺化菜籽油中的至少一种；The bio-based emulsifier is at least one of cardanol polyoxyethylene ether and sulfonated rapeseed oil;
所述的多元醇为1，3-丁二醇、乙二醇、丙二醇中的至少一种；Described polyhydric alcohol is at least one in 1,3-butanediol, ethylene glycol, propylene glycol;
所述的聚氨酯为乙烯基聚氨酯乳液、多异氰酸酯乳液、封闭型聚氨酯乳液中的至少一种，优选为封闭型聚氨酯乳液。The polyurethane is at least one of vinyl polyurethane emulsion, polyisocyanate emulsion and blocked polyurethane emulsion, preferably blocked polyurethane emulsion.
一种生物基防蚊整理剂的制备方法，包括以下步骤：A preparation method of bio-based anti-mosquito finishing agent, comprising the following steps:
将驱蚊酯、红花除虫菊素、生物基乳化剂、多元醇加入混合容器中，搅拌至乳化均匀，然后加入去离子水和聚氨酯，搅拌至混合均匀，得到生物基防蚊整理剂。Add mosquito repellent, safflower pyrethrin, bio-based emulsifier, and polyol into a mixing container, stir until emulsification is uniform, then add deionized water and polyurethane, and stir until uniformly mixed to obtain a bio-based mosquito repellent finishing agent.
一种生物基防蚊整理剂的应用，将生物基防蚊整理剂应用到织物上，包括浸轧和烘干步骤，所述的浸轧步骤包括：An application of a bio-based anti-mosquito finishing agent, applying the bio-based anti-mosquito finishing agent to fabrics, including padding and drying steps, the padding step comprising:
(1)配制工作液：将生物基防蚊整理剂溶解于水中，配制成防蚊整理液，控制生物基防蚊整理剂的质量浓度15-50g/L；(1) Preparation of working liquid: dissolve the bio-based mosquito repellent finishing agent in water to prepare the anti-mosquito finishing liquid, and control the mass concentration of the bio-based mosquito repellent finishing agent to 15-50g/L;
(2)将织物通过步骤(1)配制的工作液浸轧，轧余率70％-80％。(2) padding the fabric with the working liquid prepared in step (1), and the excess rate is 70%-80%.
所述烘干步骤为：在80-110℃温度下将织物烘干。The drying step is: drying the fabric at a temperature of 80-110°C.
一种生物基防蚊整理剂的应用，将生物基防蚊整理剂应用到织物上，包括浸渍、脱水和烘干步骤，所述的浸渍步骤为：将织物常温浸渍15-20分钟，生物基防蚊整理剂用量为1.0-3.0％o.w.f，浴比为1∶15-1∶30。An application of a bio-based anti-mosquito finishing agent, applying the bio-based anti-mosquito finishing agent to fabrics, including the steps of dipping, dehydrating and drying, the dipping step is: soaking the fabric at room temperature for 15-20 minutes, bio-based The dosage of the anti-mosquito finishing agent is 1.0-3.0% o.w.f, and the liquor ratio is 1:15-1:30.
所述烘干步骤为：在80-110℃温度下将织物烘干。The drying step is: drying the fabric at a temperature of 80-110°C.
有益效果Beneficial effect
本发明所使用的主要原料均来自天然植物提取，符合环保和法规的要求，对环境和人员没有危害，且完全顺应国家“双碳”政策的要求，真正做到环保绿色生产。The main raw materials used in the present invention are all extracted from natural plants, meet the requirements of environmental protection and laws and regulations, have no harm to the environment and personnel, and fully comply with the requirements of the national "double carbon" policy, truly achieving environmental protection and green production.
本发明生物基防蚊整理剂创新性地将天然原料作用于织物整理中，效果优良，具有良好的防蚊性，经过本发明所述的生物基防蚊整理剂处理后，对蚊虫有良好的趋避性能，使人们免受蚊虫侵扰，有效防止有关传染病的发生，织物与皮肤表面长期接触，安全无刺激，明显改善人们生活品质。The bio-based anti-mosquito finishing agent of the present invention innovatively uses natural raw materials in fabric finishing, and has excellent effect and good anti-mosquito performance. The avoidance property keeps people from being infested by mosquitoes and effectively prevents the occurrence of related infectious diseases. The long-term contact between the fabric and the skin surface is safe and non-irritating, which significantly improves people's quality of life.
本发明采用的驱蚊酯可以驱避苍蝇、虱子、蚂蚁、蚊子、蟑螂、蠓虫、牛虻、扁蚤、沙蚤、沙蠓、白蛉、蝉等在内的多种蚊虫，而且因为其化学性质稳定，具有高的热稳定性和高的耐汗性，可以在不同的环境和气候条件下使用，并且其驱避作用的时间长。同时，完全无毒无害，对皮肤和粘膜无毒副作用、无过敏性及无皮肤渗透性。The mosquito repellent used in the present invention can repel a variety of mosquitoes including flies, lice, ants, mosquitoes, cockroaches, midges, gadflies, flat fleas, sand fleas, sand midges, sandflies, cicadas, etc., and because of its chemical Stable in nature, with high thermal stability and high sweat resistance, it can be used in different environments and climate conditions, and its repellent effect lasts for a long time. At the same time, it is completely non-toxic and harmless, has no toxic side effects on the skin and mucous membranes, no allergies and no skin penetration.
本发明纺织抗菌整理剂采用水性聚氨酯，通过其与纤维发生反应，可以把有效物质固定在织物表面，使纺织品具有较好的耐洗性和耐磨性，保持其持久的防蚊虫效果，具有广泛的使用性。The textile antibacterial finishing agent of the present invention adopts water-based polyurethane, and through its reaction with fibers, the effective substance can be fixed on the surface of the fabric, so that the textile has better washability and abrasion resistance, and maintains its long-lasting anti-mosquito effect. usability.
具体实施方式Detailed ways
在一个优选的实施方式中，本发明的生物基防蚊整理剂，按照重量份数，包括如下组分：In a preferred embodiment, the bio-based mosquito repellent finishing agent of the present invention comprises the following components in parts by weight:
驱蚊酯2％-6％Mosquito repellent 2%-6%
红花除虫菊素2％-6％Safflower pyrethrins 2%-6%
生物基乳化剂5％-15％Bio-based emulsifier 5%-15%
多元醇5％-15％Polyol 5%-15%
聚氨酯1％-5％Polyurethane 1%-5%
去离子水65％-75％。Deionized water 65%-75%.
所述的生物基乳化剂为腰果酚聚氧乙烯醚、磺化菜籽油中的至少一种，优选为腰果酚聚氧乙烯醚NSS 1308。The bio-based emulsifier is at least one of cardanol polyoxyethylene ether and sulfonated rapeseed oil, preferably cardanol polyoxyethylene ether NSS 1308.
所述的多元醇为1，3-丁二醇、乙二醇、丙二醇中的至少一种，优选为1，3-丁二醇或丙二醇。The polyhydric alcohol is at least one of 1,3-butanediol, ethylene glycol and propylene glycol, preferably 1,3-butanediol or propylene glycol.
所述的聚氨酯为乙烯基聚氨酯乳液、多异氰酸酯乳液、封闭型聚氨酯乳液中的至少一种，优选为封闭型聚氨酯乳液S-100。The polyurethane is at least one of vinyl polyurethane emulsion, polyisocyanate emulsion and blocked polyurethane emulsion, preferably blocked polyurethane emulsion S-100.
在一个优选的实施方式中，所述红花除虫菊素为质量百分含量50％的油溶性液体除虫菊酯。In a preferred embodiment, the safflower pyrethrins are oil-soluble liquid pyrethrins with a mass percentage of 50%.
在一个优选的实施方式中，所述的生物基乳化剂为腰果酚聚氧乙烯醚NSS1308。In a preferred embodiment, the bio-based emulsifier is cardanol ethoxylate NSS1308.
在一个优选的实施方式中，所述生物基防蚊整理剂的制备方法，包括以下步骤：In a preferred embodiment, the preparation method of the bio-based mosquito repellent finishing agent comprises the following steps:
将驱蚊酯、红花除虫菊素、生物基乳化剂、多元醇加入混合容器中，搅拌至乳化均匀，然后加入去离子水和聚氨酯，搅拌至混合均匀，得到生物基防蚊整理剂。Add mosquito repellent, safflower pyrethrin, bio-based emulsifier, and polyol into a mixing container, stir until emulsification is uniform, then add deionized water and polyurethane, and stir until uniformly mixed to obtain a bio-based mosquito repellent finishing agent.
在一种优选的实施方式中，所述的搅拌的速度为30-50r/min。In a preferred embodiment, the stirring speed is 30-50 r/min.
在一个优选的实施方式中，所述生物基防蚊整理剂的应用工艺，包括浸轧、脱水和烘干步骤，所述的浸轧步骤包括：In a preferred embodiment, the application process of the bio-based mosquito repellent finishing agent includes the steps of padding, dehydration and drying, and the padding step includes:
(1)配制工作液：将本发明生物基防蚊整理剂溶解于水中，配制成防蚊整理液，控制防螨虫整理剂的质量浓度15-50g/L；(1) Prepare working liquid: dissolve the bio-based anti-mosquito finishing agent of the present invention in water, prepare the anti-mosquito finishing liquid, and control the mass concentration of the anti-mite finishing agent to 15-50g/L;
(2)将织物通过步骤(1)配制的工作液浸轧，轧余率70-80％。(2) padding the fabric with the working liquid prepared in step (1), and the excess rate is 70-80%.
所述烘干温度为80-110℃。The drying temperature is 80-110°C.
在一个优选的实施方式中，所述生物基防蚊整理剂的应用工艺，包括浸渍、脱水和烘干步骤。所述的浸渍步骤为：将织物常温浸渍15-20分钟，本发明生物基防蚊整理剂用量为1.0-3.0％o.w.f，浴比为1∶15-1∶30。所述烘干温度为80-110℃。In a preferred embodiment, the application process of the bio-based mosquito repellent finishing agent includes the steps of soaking, dehydrating and drying. The soaking step is: soaking the fabric at normal temperature for 15-20 minutes, the dosage of the bio-based mosquito repellent finishing agent of the present invention is 1.0-3.0% o.w.f, and the bath ratio is 1:15-1:30. The drying temperature is 80-110°C.
下面结合具体实施例，进一步阐释本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明。Below in conjunction with specific embodiment, further explain the present invention. It should be understood that these examples are only used to illustrate the present invention and not to limit the present invention.
实施例1Example 1
将重量比为4.5％驱蚊酯、2.5％除虫菊酯、10％1，3-丁二醇、7％NSS 1308加入混合釜中，30-50rpm搅拌30-50min至乳化均匀，然后加入73％去离子水、3％S-100，搅拌30-50min至混合均匀，即得所述生物基防蚊整理剂。Add 4.5% mosquito repellent ester, 2.5% pyrethrin, 10% 1,3-butanediol, 7% NSS 1308 into the mixing kettle, stir at 30-50rpm for 30-50min until the emulsification is uniform, and then add 73% to Ionized water and 3% S-100 are stirred for 30-50 minutes until the mixture is uniform, and the bio-based mosquito repellent finishing agent is obtained.
实施例2Example 2
将重量比为2％驱蚊酯、5％除虫菊酯、10％1，3-丁二醇、10％NSS 1308加入混合釜中，30-50rpm搅拌30-50min至乳化均匀，然后加入70％去离子水、3％S-100，搅拌30-50min至混合均匀，即得所述生物基防蚊整理剂。Add 2% mosquito repellent ester, 5% pyrethrin, 10% 1,3-butanediol, 10% NSS 1308 into the mixing kettle, stir at 30-50rpm for 30-50min until the emulsification is uniform, and then add 70% to Ionized water and 3% S-100 are stirred for 30-50 minutes until the mixture is uniform, and the bio-based mosquito repellent finishing agent is obtained.
实施例3Example 3
将重量比为3.5％驱蚊酯、3.5％除虫菊酯、8％丙二醇、9％NSS 1308加入混合釜中，30-50rpm搅拌30-50min至乳化均匀，然后加入73％去离子水、3％S-100，搅拌30-50min至混合均匀，即得所述生物基防蚊整理剂。Add 3.5% mosquito repellent ester, 3.5% pyrethrin, 8% propylene glycol, and 9% NSS 1308 into the mixing kettle, stir at 30-50rpm for 30-50min until the emulsification is uniform, then add 73% deionized water, 3% S -100, stir for 30-50 minutes until the mixture is uniform, and the bio-based mosquito repellent finishing agent is obtained.
对比例1Comparative example 1
市售防蚊整理剂PBS8300。Commercially available anti-mosquito finishing agent PBS8300.
本发明的生物基防蚊整理剂的应用效果通过如下实验验证。The application effect of the bio-based anti-mosquito finishing agent of the present invention is verified by the following experiments.
1.实验内容1. Experimental content
1.1.纺织品：白色全棉针织布、绿色全棉针织布。1.1. Textiles: white cotton knitted fabric, green cotton knitted fabric.
1.2.防蚊整理剂：上述实施例1、实施例2、实施例3、对比例1。1.2. Mosquito repellent finishing agent: above-mentioned embodiment 1, embodiment 2, embodiment 3, comparative example 1.
1.3.应用工艺：1.3. Application process:
1.3.1.防蚊整理工艺-浸轧法1.3.1. Anti-mosquito finishing process - padding method
包括如下步骤：Including the following steps:
(1)配制工作液：将本发明生物基防蚊整理剂和对比例1分别溶解于水中，配制成防蚊整理液，控制质量浓度40g/L；(1) Prepare working solution: Dissolve the bio-based anti-mosquito finishing agent of the present invention and Comparative Example 1 in water respectively, and prepare the anti-mosquito finishing solution, controlling the mass concentration to 40g/L;
(2)将织物通过步骤(1)配制的工作液浸轧，轧余率70-80％。(2) padding the fabric with the working liquid prepared in step (1), and the excess rate is 70-80%.
(3)80-100℃烘干，110℃焙烘120s。(3) Dry at 80-100°C and bake at 110°C for 120s.
1.3.2.防蚊整理工艺-浸渍法1.3.2. Anti-mosquito finishing process - dipping method
包括如下步骤：Including the following steps:
(1)将织物常温浸渍15-20分钟，本发明生物基防蚊整理剂用量为1.0-3.0％o.w.f，浴比为1∶15-1∶30。(1) Immerse the fabric at room temperature for 15-20 minutes, the dosage of the bio-based mosquito repellent finishing agent of the present invention is 1.0-3.0% o.w.f, and the bath ratio is 1:15-1:30.
(2)取出浸渍后的织物，脱水，80-100℃烘干，110℃焙烘120s。(2) Take out the impregnated fabric, dehydrate, dry at 80-100°C, and bake at 110°C for 120s.
2.性能测试2. Performance testing
2.1.防蚊效果测试2.1. Anti-mosquito effect test
将经过上述1.3.1.和1.3.2.防蚊整理工艺处理后的白色布样，与空白样取相同大小20cm×20cm，分别放入有100只白色伊蚊的玻璃箱中，玻璃箱规格为50cm×50cm×50cm，记录2min内蚊子在试样和空白样的表面停落数，以趋避率来评价，趋避率＝(空白样表面停落数-试样表面停落数)/空白样表面停落数×100％。放置5h后，再记录计算趋避率，趋避率越高，表示防蚊效果越好。Take the white cloth sample after the above-mentioned 1.3.1. and 1.3.2. anti-mosquito finishing process, take the same size as the blank sample (20cm×20cm), put them into glass boxes with 100 white Aedes mosquitoes respectively, and the glass box specifications It is 50cm×50cm×50cm, record the number of mosquitoes landing on the surface of the sample and the blank sample within 2 minutes, and evaluate it by the avoidance rate, the avoidance rate=(number of landing on the surface of the blank sample-number of landing on the surface of the sample)/blank sample Number of surface stops × 100%. After placing it for 5 hours, record and calculate the avoidance rate. The higher the avoidance rate, the better the anti-mosquito effect.
将经过上述1.3.1.和1.3.2.防蚊整理工艺处理后的布样，按照GB/T17596-1998进行水洗10次后，再次进行上述防蚊测试，检测结果见表1。After the above 1.3.1. and 1.3.2. anti-mosquito finishing process, the cloth sample was washed 10 times according to GB/T17596-1998, and then the above-mentioned anti-mosquito test was carried out again. The test results are shown in Table 1.
表1产品防蚊效果测试结果Table 1 Product anti-mosquito effect test results
2.2.对处理后织物的影响2.2. Effect on treated fabric
将经过上述1.3.1.和1.3.2.防蚊整理工艺处理后的白色全棉针织布样，按照AATCC 110-2015方法，用Datacolor测色仪进行测试，与未处理布样进行白度对比，白度变化越小，即对织物颜色影响越小。The white cotton knitted fabric sample after the above 1.3.1. and 1.3.2. anti-mosquito finishing process is tested with a Datacolor colorimeter according to the AATCC 110-2015 method, and the whiteness is compared with the untreated fabric sample , the smaller the change in whiteness, that is, the smaller the effect on the color of the fabric.
将经过上述1.3.1.和1.3.2.防蚊整理工艺处理后的绿色全棉针织布，按照GB/T250-2008，用评定变色用灰卡，与未处理布样进行色变对比，等级越高，则表示色变越小，即对织物影响越小，检测结果见表2。According to GB/T250-2008, the green cotton knitted fabric after the above 1.3.1. and 1.3.2. anti-mosquito finishing process is compared with the untreated fabric sample for color change with the gray card for assessing discoloration. The higher the value, the smaller the color change, that is, the smaller the impact on the fabric. The test results are shown in Table 2.
表2抗菌整理后织物性能测试结果Table 2 Fabric performance test results after antibacterial finishing
防蚊效果：由表1可知，实施例1-3所得生物基防蚊整理剂的防蚊效果明显优于市售产品，具有优良的防蚊效果，对蚊子的初始趋避率在97％以上，且耐水洗，持久性好，能够长效驱蚊。Anti-mosquito effect: As can be seen from Table 1, the anti-mosquito effect of the bio-based anti-mosquito finishing agent obtained in Examples 1-3 is obviously better than that of commercially available products, has excellent anti-mosquito effect, and the initial rate of repelling mosquitoes is above 97%. And washable, durable, can repel mosquitoes for a long time.
对处理后织物的影响：由表2可知，用实施例1-3经防蚊整理工艺处理后的布样，白度变化和色变较小，说明其对织物外观影响小，适合广泛使用。Influence on the fabric after treatment: As can be seen from Table 2, the cloth samples treated with the anti-mosquito finishing process with Examples 1-3 have less whiteness change and color change, which shows that it has little influence on the appearance of the fabric and is suitable for wide use.
应该注意到并理解，在不脱离权利要求所要求的本发明的精神和范围的情况下，能够对上述详细描述的本发明做出各种修改和改进。因此，要求保护的技术方案范围不受所给出的任何特定示范教导的限制。It should be noted and understood that various modifications and improvements can be made to the invention described in detail above without departing from the spirit and scope of the invention as claimed. Accordingly, the scope of the claimed technical solutions is not limited by any particular exemplary teaching given.
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.
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