技术领域Technical Field
本申请涉及可降解胶带领域，尤其涉及一种可降解胶带及其制备方法和应用。The present application relates to the field of degradable adhesive tapes, and in particular to a degradable adhesive tape and a preparation method and application thereof.
背景技术Background technique
随着快递行业的高速发展，包装类产品用量的急剧增加给社会和环境带来了巨大的负担。以最简单的胶带为例，快递行业每年所使用的胶带用量巨大，已经达到胶带总体长度可以绕地球上千圈的程度，所以，目前在胶带领域方面，环境压力是巨大的。现阶段行业使用胶带大多数为传统BOPP胶带，原料来自石油资源，其不可再生且伴随着用量增多日益枯竭，使用后短时间内不可降解。所用材质完成包装使命后，直接变为包装废弃物，不仅加剧了白色污染，封装后纸箱与塑料胶带的分离也提高了回收利用的成本。With the rapid development of the express delivery industry, the sharp increase in the use of packaging products has brought a huge burden to society and the environment. Taking the simplest tape as an example, the amount of tape used by the express delivery industry each year is huge, and the total length of the tape has reached the level that it can circle the earth thousands of times. Therefore, the current environmental pressure in the field of tape is huge. At present, most of the tapes used in the industry are traditional BOPP tapes. The raw materials come from petroleum resources, which are non-renewable and increasingly depleted with the increase in usage. They are not degradable in a short time after use. After the material used completes its packaging mission, it directly becomes packaging waste, which not only aggravates white pollution, but also the separation of the carton and the plastic tape after packaging also increases the cost of recycling.
因此，为了实现快递行业和胶带行业的可持续发展，可降解胶带这一产品应运而生。但因为可降解胶带在近些年还属于新兴产品，尚处在初期阶段，进而还存在着一些不可避免的技术问题，这其中就包括了可降解胶带其自身的力学机械性能、防水性能、耐老化性能较差的问题。Therefore, in order to achieve sustainable development of the express delivery industry and the tape industry, the product of degradable tape came into being. However, because degradable tape is still a new product in recent years and is still in its early stages, there are still some inevitable technical problems, including the poor mechanical properties, waterproof properties, and aging resistance of degradable tape itself.
所以，为了解决上述技术问题，本申请提供了一种可降解胶带及其制备方法。本申请所制得的可降解胶带能够在保证其具有优异的粘结性的同时，大幅提高其防水、力学以及耐老化性等性能，有效解决了现有市场上的可降解胶带的性能症结，具有十分优异的市场前景，且进一步拓宽了可降解胶带的应用领域和使用环境，制备方法简单易行，为后续大规模化生产提供了方案基础。Therefore, in order to solve the above technical problems, the present application provides a degradable tape and a preparation method thereof. The degradable tape prepared in the present application can significantly improve its waterproof, mechanical and aging resistance properties while ensuring its excellent adhesion, effectively solving the performance problems of degradable tapes on the existing market, having a very excellent market prospect, and further broadening the application field and use environment of degradable tapes. The preparation method is simple and easy, providing a solution basis for subsequent large-scale production.
发明内容Summary of the invention
为了解决上述问题，本申请第一方面提供了一种可降解胶带，可降解胶带包括可降解基体层，可降解基体层表面的可降解粘结层，以及可降解粘结层的另一侧具有保护作用的离型层。In order to solve the above problems, the first aspect of the present application provides a degradable tape, which includes a degradable base layer, a degradable adhesive layer on the surface of the degradable base layer, and a release layer with a protective function on the other side of the degradable adhesive layer.
作为一种优选的方案，所述可降解基体层的厚度为20~100μm。As a preferred solution, the thickness of the degradable substrate layer is 20-100 μm.
作为一种优选的方案，所述可降解基体层的厚度为30~60μm。As a preferred solution, the thickness of the degradable substrate layer is 30-60 μm.
作为一种优选的方案，所述可降解粘结层的厚度为5~50μm。As a preferred solution, the thickness of the degradable adhesive layer is 5-50 μm.
作为一种优选的方案，所述可降解粘结层的厚度为5~30μm。As a preferred solution, the thickness of the degradable adhesive layer is 5-30 μm.
作为一种优选的方案，所述可降解基体层和可降解粘结层的厚度比为（3.5~5.5）：（0.5~2）。As a preferred solution, the thickness ratio of the degradable base layer to the degradable adhesive layer is (3.5-5.5): (0.5-2).
作为一种优选的方案，所述可降解基体层和可降解粘结层的厚度比为（4~4.5）：（1.2~1.5）。As a preferred solution, the thickness ratio of the degradable base layer to the degradable adhesive layer is (4-4.5):(1.2-1.5).
作为一种优选的方案，所述离型层的厚度为15~30μm。As a preferred solution, the thickness of the release layer is 15-30 μm.
作为一种优选的方案，所述可降解基体层，以质量份计，原料包括：基体树脂100~150份，填充剂40~60份，润滑剂5~10份，填料20~40份，助剂1~10份。As a preferred solution, the raw materials of the degradable base layer include, by weight: 100-150 parts of base resin, 40-60 parts of filler, 5-10 parts of lubricant, 20-40 parts of filler, and 1-10 parts of auxiliary agent.
作为一种优选的方案，所述基体树脂为PVC树脂和PLA树脂的组合物。As a preferred solution, the base resin is a composition of PVC resin and PLA resin.
作为一种优选的方案，所述PVC树脂和PLA树脂的质量比为（8~12）：（3~5）。As a preferred solution, the mass ratio of the PVC resin to the PLA resin is (8-12): (3-5).
作为一种优选的方案，所述PVC树脂和PLA树脂的质量比为（9~10）：（4~4.5）。As a preferred solution, the mass ratio of the PVC resin to the PLA resin is (9-10): (4-4.5).
作为一种优选的方案，所述PVC树脂的聚合度为1100~1200。As a preferred solution, the degree of polymerization of the PVC resin is 1100-1200.
作为一种优选的方案，所述PLA树脂的粘度为4000~8000mPa·s。As a preferred solution, the viscosity of the PLA resin is 4000-8000 mPa·s.
作为一种优选的方案，所述PLA树脂的粘度为4500~6500mPa·s。As a preferred solution, the viscosity of the PLA resin is 4500-6500 mPa·s.
作为一种优选的方案，所述填充剂为支链淀粉和直链淀粉的组合物。As a preferred solution, the filler is a combination of amylopectin and amylose.
作为一种优选的方案，所述支链淀粉和直链淀粉的质量比为（0.6~1.2）：（2~4）。As a preferred solution, the mass ratio of amylopectin to amylose is (0.6-1.2):(2-4).
作为一种优选的方案，所述支链淀粉和直链淀粉的质量比为（0.8~1）：（3~4）。As a preferred solution, the mass ratio of amylopectin to amylose is (0.8-1):(3-4).
本申请中通过特定聚合度以及粘度下的PVC、PLA树脂与混合支/直链淀粉进行组合，有效提高了可降解胶带整体的力学机械性能，并且还进一步有效保证了其防水性能。采用上述的PVC和PLA树脂其多壁多支链结构能够通过加入的支链淀粉结构的桥梁作用与加入的长螺旋直链淀粉结构形成稳定的连接网络，该结构网络的存在不仅能够增强树脂之间的分散相容性能，减少多相界面间的阻力，从而大幅增强体系的内聚力，进而在外力作用下能够极大地提高其支撑和连接作用，从而充分提高其力学机械性能。另一方面，上述的连接网络结构因为支链淀粉的连接作用容易形成多网络膜层结构，该结构的存在能够大幅提高分子间的紧密性，并且极大地增加了水分子在体系内的流通阻力和流通路径，进而避免了因为淀粉的加入而导致的多亲水基团引发的吸湿亲水现象，提高防水性能。In this application, PVC, PLA resin and mixed branched/straight-chain starch are combined under specific polymerization degree and viscosity to effectively improve the mechanical properties of the whole degradable tape, and further effectively ensure its waterproof performance. The multi-walled multi-branched structure of the above-mentioned PVC and PLA resin can form a stable connection network with the added long spiral straight-chain starch structure through the bridge effect of the added branched starch structure. The existence of this structural network can not only enhance the dispersion compatibility between the resins, reduce the resistance between the multiphase interface, thereby greatly enhancing the cohesion of the system, and then under the action of external force, it can greatly improve its support and connection effect, thereby fully improving its mechanical properties. On the other hand, the above-mentioned connection network structure is easy to form a multi-network membrane structure because of the connection effect of branched starch. The existence of this structure can greatly improve the tightness between molecules, and greatly increase the circulation resistance and circulation path of water molecules in the system, thereby avoiding the hygroscopic hydrophilic phenomenon caused by the multi-hydrophilic groups caused by the addition of starch, and improving waterproof performance.
作为一种优选的方案，所述润滑剂为植物油或石蜡油。As a preferred solution, the lubricant is vegetable oil or paraffin oil.
作为一种优选的方案，所述填料为改性氧化锌。As a preferred solution, the filler is modified zinc oxide.
作为一种优选的方案，所述改性氧化锌的平均粒径为250~300nm。As a preferred solution, the average particle size of the modified zinc oxide is 250-300 nm.
作为一种优选的方案，所述改性氧化锌的制备方法包括以下步骤：S1：将氧化锌加入至水和无水乙醇混合溶剂当中，之后将硅烷偶联剂加入混合搅拌均匀，升温至50~55℃，并滴加含有正硅酸乙酯的无水乙醇溶液，滴加反应时间为2~3h；S2：滴加反应完成之后，继续保温反应0.5~1.5h，之后将粒子产物过滤洗涤，将粒子产物加入至水和DMF的混合溶剂当中，二次加入硅烷偶联剂和有机酸酐，升温至60~65℃，超声震荡反应1~3h，完成后过滤、洗涤、烘干即得。As a preferred scheme, the preparation method of the modified zinc oxide includes the following steps: S1: adding zinc oxide to a mixed solvent of water and anhydrous ethanol, then adding a silane coupling agent and stirring the mixture evenly, heating the mixture to 50-55°C, and dripping an anhydrous ethanol solution containing ethyl orthosilicate, wherein the dripping reaction time is 2-3 hours; S2: after the dripping reaction is completed, continuing the heat preservation reaction for 0.5-1.5 hours, then filtering and washing the particle product, adding the particle product to a mixed solvent of water and DMF, adding a silane coupling agent and an organic anhydride for a second time, heating the mixture to 60-65°C, and ultrasonically shaking the mixture for 1-3 hours, and filtering, washing, and drying the mixture after completion.
作为一种优选的方案，所述氧化锌和正硅酸乙酯的质量比为（1.5~2.5）：（1~2）。As a preferred solution, the mass ratio of zinc oxide to tetraethyl orthosilicate is (1.5-2.5):(1-2).
作为一种优选的方案，所述氧化锌的平均粒径为25~50nm。As a preferred solution, the average particle size of the zinc oxide is 25-50 nm.
作为一种优选的方案，所述助剂为稳定剂、阻燃剂、耐紫外剂、分散剂、防水剂、成膜剂中的至少一种。As a preferred solution, the auxiliary agent is at least one of a stabilizer, a flame retardant, a UV resistant agent, a dispersant, a waterproofing agent, and a film-forming agent.
作为一种优选的方案，所述可降解粘结层，以质量份计，原料包括：甲基丙烯酸甲酯20~30份，丙烯酸乙酯50~60份，丙烯酸异辛酯5~10份，功能单体1~10份，引发剂0.5~1份，成盐剂2~3份，乳化剂0.5~1份，溶剂300~350份。As a preferred solution, the raw materials of the degradable adhesive layer include, by weight: 20 to 30 parts of methyl methacrylate, 50 to 60 parts of ethyl acrylate, 5 to 10 parts of isooctyl acrylate, 1 to 10 parts of functional monomers, 0.5 to 1 part of initiator, 2 to 3 parts of salt-forming agent, 0.5 to 1 part of emulsifier, and 300 to 350 parts of solvent.
作为一种优选的方案，所述甲基丙烯酸甲酯，丙烯酸乙酯和丙烯酸异辛酯的质量比为（2~2.5）：（5.5~6）：（0.6~0.8）。As a preferred solution, the mass ratio of methyl methacrylate, ethyl acrylate and isooctyl acrylate is (2-2.5): (5.5-6): (0.6-0.8).
作为一种优选的方案，所述功能单体为双环戊烯基丙烯酸酯和改性甲基丙烯酸丁酯。As a preferred solution, the functional monomers are dicyclopentenyl acrylate and modified butyl methacrylate.
作为一种优选的方案，所述双环戊烯基丙烯酸酯和改性甲基丙烯酸丁酯的质量比为（1~3）：（5~6）。As a preferred solution, the mass ratio of the dicyclopentenyl acrylate to the modified butyl methacrylate is (1-3):(5-6).
作为一种优选的方案，所述改性甲基丙烯酸丁酯的制备方法包括以下步骤：S1：将ε-己内酯，丁二酸酐以及乙酸乙酯加入至反应釜内混合均匀，反应釜惰性气体保护，升温至60~80℃保温2~3h；S2：保温完成后，将甲基丙烯酸丁酯的乙酸乙酯溶液以及反应催化剂同时滴加至反应釜中，滴加时反应釜以100~200r/min持续搅拌，滴加温度为80~100℃；S3：控制甲基丙烯酸丁酯的乙酸乙酯溶液以及反应催化剂滴加同时完成，滴加完成后升温至110~130℃保温反应3~4h，反应完成后将产物移送至另一容器中加入混合表面活性剂，搅拌均匀后即得。As a preferred scheme, the preparation method of modified butyl methacrylate comprises the following steps: S1: adding ε-caprolactone, succinic anhydride and ethyl acetate into a reactor and mixing them evenly, protecting the reactor with inert gas, heating it to 60-80°C and keeping it warm for 2-3 hours; S2: after the insulation is completed, simultaneously adding ethyl acetate solution of butyl methacrylate and a reaction catalyst dropwise into the reactor, the reactor is continuously stirred at 100-200 r/min during the addition, and the dropping temperature is 80-100°C; S3: controlling the simultaneous addition of ethyl acetate solution of butyl methacrylate and the reaction catalyst, heating it to 110-130°C and keeping it warm for 3-4 hours after the addition is completed, and transferring the product to another container, adding a mixed surfactant, and stirring it evenly to obtain the product.
作为一种优选的方案，所述ε-己内酯和甲基丙烯酸丁酯的质量比为（3~3.5）：（2~4）。As a preferred solution, the mass ratio of ε-caprolactone to butyl methacrylate is (3-3.5):(2-4).
作为一种优选的方案，所述反应催化剂为有机锡催化剂中的任一种。As a preferred solution, the reaction catalyst is any one of the organotin catalysts.
作为一种优选的方案，所述混合表面活性剂为烷基糖苷和脂肪醇聚氧乙烯醚的混合物。As a preferred solution, the mixed surfactant is a mixture of alkyl glycoside and fatty alcohol polyoxyethylene ether.
作为一种优选的方案，所述混合表面活性剂的加入量为S3中产物总质量的5~8%。As a preferred solution, the amount of the mixed surfactant added is 5-8% of the total mass of the product in S3.
作为一种优选的方案，所述烷基糖苷和脂肪醇聚氧乙烯醚的质量比为（2~3）：（1~1.5）。As a preferred solution, the mass ratio of the alkyl glycoside to the fatty alcohol polyoxyethylene ether is (2-3): (1-1.5).
作为一种优选的方案，所述脂肪醇聚氧乙烯醚为鲸蜡硬脂醇聚氧乙烯醚。As a preferred solution, the fatty alcohol polyoxyethylene ether is cetearyl alcohol polyoxyethylene ether.
作为一种优选的方案，所述鲸蜡硬脂醇聚氧乙烯醚的羟值为110~150mgKOH/g。As a preferred solution, the hydroxyl value of the cetearyl alcohol polyoxyethylene ether is 110-150 mgKOH/g.
本申请中通过上述加入的改性甲基丙烯酸丁酯单体制备可降解粘结层，能够有效提高粘结层的可降解效率的同时，还能够提高其耐老化性能。本申请中加入的改性甲基丙烯酸丁酯单体其优异分子结构参与到可降解基体层的化学交联反应当中，能够在粘合剂体系中形成优异的长分子链缠结效果，并且能够大幅扩展直链的长度，进而使得整体的粘结层体系形成了立体多维度的复杂缠结结构，这些结构的存在能够大幅限制体系内电子和活性基团的迁移速率和活性，进而降低了对于活性分子的吸引效果，在长期的使用过程中能够有效降低失活反应的发生概率进而大幅提高老化性；但同时因为改性后的甲基丙烯酸丁酯单体与粘合剂体系的相容性下降，且容易出现反应体系的快速团聚现象，从而在反应过程中出现局部的爆聚现象甚至最终无法反应成型，而本申请人发现采用本申请所述的混合表面活性剂组合，能够有效提高反应成功并且最终提高粘合层质量，这可能是因为在反应过程中，上述的混合表面活性助剂能够在改性单体表面体系中形成多层包裹结构，该结构的存在能够有效降低其在反应体系中的快速团聚现象，且因为其包裹相的存在，在反应体系中也非常容易形成反应液滴相，该相的存在能够规律反应的整体反应进程，且通过对于不同原料的亲和性，加快改性单体反应交联的程度和速率，进而有效增强最终粘合层的各项性能。In the present application, the degradable adhesive layer is prepared by adding the modified butyl methacrylate monomer mentioned above, which can effectively improve the degradability of the adhesive layer and improve its aging resistance. The modified butyl methacrylate monomer added in the present application has an excellent molecular structure that participates in the chemical cross-linking reaction of the degradable base layer, and can form an excellent long molecular chain entanglement effect in the adhesive system, and can greatly extend the length of the straight chain, thereby allowing the overall adhesive layer system to form a three-dimensional multi-dimensional complex entanglement structure. The existence of these structures can greatly limit the migration rate and activity of electrons and active groups in the system, thereby reducing the attraction effect on active molecules, and can effectively reduce the probability of inactivation reactions during long-term use, thereby greatly improving aging resistance; but at the same time, because the compatibility of the modified butyl methacrylate monomer with the adhesive system is reduced, and the reaction system is prone to rapid agglomeration, During the reaction process, local explosion and aggregation may occur, and the reaction may not be able to form. However, the applicant has found that the use of the mixed surfactant combination described in the present application can effectively improve the success of the reaction and ultimately improve the quality of the bonding layer. This may be because during the reaction process, the above-mentioned mixed surfactant additive can form a multi-layer encapsulation structure in the modified monomer surface system. The presence of this structure can effectively reduce its rapid agglomeration phenomenon in the reaction system, and because of the presence of its encapsulation phase, it is also very easy to form a reaction droplet phase in the reaction system. The presence of this phase can regulate the overall reaction process of the reaction, and through the affinity for different raw materials, accelerate the degree and rate of cross-linking of the modified monomer reaction, thereby effectively enhancing the various properties of the final bonding layer.
作为一种优选的方案，所述引发剂为过硫酸铵、过硫酸钾中的任一种。As a preferred solution, the initiator is any one of ammonium persulfate and potassium persulfate.
作为一种优选的方案，所述成盐剂为三乙醇胺。As a preferred solution, the salt-forming agent is triethanolamine.
作为一种优选的方案，所述溶剂为丙酮和去离子水的混合溶剂。As a preferred solution, the solvent is a mixed solvent of acetone and deionized water.
作为一种优选的方案，所述丙酮和去离子水的质量比为（1~2）：（4~6）。As a preferred solution, the mass ratio of acetone to deionized water is (1-2):(4-6).
本申请第二方面提供了一种上述可降解胶带的制备方法，制备方法包括以下步骤：S1：将可降解基体层原料加入高速混合机中进行搅拌混合均匀，之后将混合物料加入密炼机中密炼塑化，再经过挤出机塑化，180~220℃压延成型，冷却分割得到所需厚度可降解基体层；S2：将甲基丙烯酸甲酯，丙烯酸乙酯，丙烯酸异辛酯以及溶剂混合加入反应釜中,搅拌混合完全，之后将功能单体，乳化剂，成盐剂以及引发剂依次加入反应釜中混合搅拌，升温至60~80℃，搅拌保温反应3~5h，最后中和破乳得到可降解粘结剂；S3：将可降解粘结剂喷涂于离型层表面，经过烘干固化以及熟化后形成可降解粘结层，将可降解粘结层与可降解基体层复合，得到可降解胶带。The second aspect of the present application provides a preparation method for the above-mentioned degradable tape, which comprises the following steps: S1: adding the raw materials of the degradable base layer into a high-speed mixer and stirring and mixing them evenly, then adding the mixed materials into an internal mixer for internal mixing and plasticization, then plasticizing through an extruder, calendering and forming at 180-220°C, cooling and dividing to obtain a degradable base layer of required thickness; S2: adding methyl methacrylate, ethyl acrylate, isooctyl acrylate and a solvent into a mixture into a reactor, stirring and mixing them thoroughly, then sequentially adding a functional monomer, an emulsifier, a salt-forming agent and an initiator into the reactor for mixing and stirring, heating to 60-80°C, stirring and keeping warm for reaction for 3-5 hours, and finally neutralizing and demulsifying to obtain a degradable adhesive; S3: spraying the degradable adhesive onto the surface of the release layer, forming a degradable adhesive layer after drying, curing and aging, and compounding the degradable adhesive layer with the degradable base layer to obtain a degradable tape.
本申请第三方面提供了一种上述可降解胶带的应用，包括该可降解胶带在快递物流领域、食品包装领域、办公文具领域、电子制造领域、一次性产品领域中的应用。The third aspect of the present application provides an application of the above-mentioned degradable tape, including the application of the degradable tape in the fields of express logistics, food packaging, office stationery, electronic manufacturing, and disposable products.
本申请具有的有益效果：The beneficial effects of this application are:
1、本申请中提供的一种可降解胶带，其能够在保证其具有优异的粘结性的同时，大幅提高其防水、力学以及耐老化性等性能，有效解决了现有市场上的可降解胶带的性能症结，具有十分优异的市场前景，且进一步拓宽了可降解胶带的应用领域和使用环境，制备方法简单易行，为后续大规模化生产提供了方案基础。1. The degradable tape provided in the present application can significantly improve its waterproof, mechanical and aging resistance properties while ensuring its excellent adhesion, effectively solving the performance problems of the degradable tapes on the existing market, and has a very excellent market prospect. It also further broadens the application field and use environment of the degradable tapes. The preparation method is simple and easy, providing a solution basis for subsequent large-scale production.
2、本申请中提供的一种可降解胶带，其通过特定聚合度以及粘度下的PVC、PLA树脂与混合支/直链淀粉进行组合，有效提高了可降解胶带整体的力学机械性能，并且还进一步有效保证了其防水性能；PVC和PLA树脂其多壁多支链结构能够通过加入的支链淀粉结构的桥梁作用与加入的长螺旋直链淀粉结构形成稳定的连接网络，该结构网络的存在不仅能够增强树脂之间的分散相容性能，减少多相界面间的阻力，从而大幅增强体系的内聚力，进而在外力作用下能够极大地提高其支撑和连接作用，从而充分提高其力学机械性能。2. A degradable tape provided in the present application effectively improves the overall mechanical properties of the degradable tape by combining PVC, PLA resins and mixed branched/amylose starch at specific polymerization degrees and viscosities, and further effectively ensures its waterproof performance; the multi-walled and multi-branched structures of PVC and PLA resins can form a stable connection network with the added long-helical amylose structure through the bridging effect of the added branched starch structure. The existence of this structural network can not only enhance the dispersion compatibility between resins and reduce the resistance between multiphase interfaces, thereby greatly enhancing the cohesion of the system, and then greatly improve its support and connection function under the action of external force, thereby fully improving its mechanical properties.
3、本申请中提供的一种可降解胶带，其通过加入的改性甲基丙烯酸丁酯单体制备可降解粘结层，能够有效提高粘结层的可降解效率的同时，还能够提高其耐老化性能；加入的改性甲基丙烯酸丁酯单体其优异分子结构参与到可降解基体层的化学交联反应当中，能够在粘合剂体系中形成优异的长分子链缠结效果，并且能够大幅扩展直链的长度，进而使得整体的粘结层体系形成了立体多维度的复杂缠结结构，这些结构的存在能够大幅限制体系内电子和活性基团的迁移速率和活性，进而降低了对于活性分子的吸引效果，在长期的使用过程中能够有效降低失活反应的发生概率进而大幅提高老化性。3. A degradable adhesive tape provided in the present application has a degradable adhesive layer prepared by adding modified butyl methacrylate monomer, which can effectively improve the degradability of the adhesive layer while also improving its aging resistance; the added modified butyl methacrylate monomer has an excellent molecular structure that participates in the chemical cross-linking reaction of the degradable base layer, and can form an excellent long molecular chain entanglement effect in the adhesive system, and can greatly extend the length of the straight chain, thereby allowing the overall adhesive layer system to form a three-dimensional multi-dimensional complex entanglement structure. The presence of these structures can greatly limit the migration rate and activity of electrons and active groups in the system, thereby reducing the attraction effect on active molecules, and can effectively reduce the probability of deactivation reactions during long-term use, thereby greatly improving aging resistance.
4、本申请中提供的一种可降解胶带，其通过特定复配混合表面活性剂组合，能够有效提高反应成功并且最终提高粘合层质量；反应过程中，上述的混合表面活性助剂能够在改性单体表面体系中形成多层包裹结构，该结构的存在能够有效降低其在反应体系中的快速团聚现象，且因为其包裹相的存在，在反应体系中也非常容易形成反应液滴相，该相的存在能够规律反应的整体反应进程，且通过对于不同原料的亲和性，加快改性单体反应交联的程度和速率，进而有效增强最终粘合层的各项性能。4. A degradable adhesive tape provided in the present application can effectively improve the reaction success and ultimately improve the quality of the bonding layer through a specific compounded mixed surfactant combination; during the reaction process, the above-mentioned mixed surfactant additive can form a multi-layer encapsulation structure in the modified monomer surface system, and the presence of this structure can effectively reduce its rapid agglomeration phenomenon in the reaction system, and because of the presence of its encapsulation phase, it is also very easy to form a reaction droplet phase in the reaction system. The presence of this phase can regulate the overall reaction process of the reaction, and through the affinity for different raw materials, it accelerates the degree and rate of cross-linking of the modified monomer reaction, thereby effectively enhancing the various properties of the final bonding layer.
具体实施方式Detailed ways
下文将以具体实施方案的方式对本申请上述发明内容中的技术方案做更进一步的说明和展示。且下述实施例仅为实际的实例用于说明和解释说明书中技术方案的内容，不应限制本申请所要保护的权利要求范围。凡是基于本申请发明内容所述的技术方案的技术产物均应该涵盖在本申请所要保护的范围之中。The following will further explain and demonstrate the technical solutions in the above invention content of this application in the form of specific implementation schemes. The following embodiments are only practical examples used to illustrate and explain the contents of the technical solutions in the specification and should not limit the scope of the claims to be protected by this application. All technical products based on the technical solutions described in the invention content of this application should be included in the scope to be protected by this application.
在以下实施例中，除有特殊说明之外，原料均为可以获得的市售产品，或者可以以本领域技术人员的所熟知的方法进行制备。In the following examples, unless otherwise specified, the raw materials are all commercially available products, or can be prepared by methods well known to those skilled in the art.
实施例1:实施例1第一方面提供了一种可降解胶带包括可降解基体层，可降解基体层表面的可降解粘结层，以及可降解粘结层的另一侧具有保护作用的离型层。Example 1: Example 1 provides a first aspect of a degradable tape comprising a degradable base layer, a degradable adhesive layer on the surface of the degradable base layer, and a release layer having a protective function on the other side of the degradable adhesive layer.
可降解基体层的厚度为40μm；可降解粘结层的厚度为15μm；离型层的厚度为25μm。The thickness of the degradable base layer is 40 μm; the thickness of the degradable adhesive layer is 15 μm; and the thickness of the release layer is 25 μm.
可降解基体层，以质量份计，原料包括：基体树脂140份，填充剂45份，润滑剂6份，填料25份，助剂2份。The raw materials of the degradable base layer include, by weight: 140 parts of base resin, 45 parts of filler, 6 parts of lubricant, 25 parts of filler and 2 parts of auxiliary agent.
基体树脂为PVC树脂和PLA树脂的组合物，两者的质量比为10:4。The matrix resin is a composition of PVC resin and PLA resin, and the mass ratio of the two is 10:4.
PVC树脂的聚合度为1200，购买自日本普立万公司的170型PVC树脂料产品；PLA树脂的粘度为5500mPa·s，购买自上海一轮塑化有限公司出售的相应粘度树脂产品。The polymerization degree of the PVC resin is 1200, and it is a 170 type PVC resin product purchased from PolyOne Corporation of Japan; the viscosity of the PLA resin is 5500 mPa·s, and it is a resin product of corresponding viscosity purchased from Shanghai Yilun Plastic Chemical Co., Ltd.
填充剂为支链淀粉和直链淀粉的组合物，两者的质量比为0.8:3.5。The filler is a composition of amylopectin and straight-chain starch, and the mass ratio of the two is 0.8:3.5.
支链淀粉和直链淀粉分别购买自武汉华翔科洁生物科技有限公司出售的支链和直链淀粉产品，支链/直链含量≥70wt%。Amylopectin and amylose were purchased from amylopectin and amylose products sold by Wuhan Huaxiang Kejie Biotechnology Co., Ltd., respectively, with amylopectin/amylose content ≥70wt%.
润滑剂为氢化大豆油，购买自武汉斯麦克生物科技有限公司出售的辅料级氢化大豆油产品。The lubricant was hydrogenated soybean oil, which was purchased from Wuhan Smek Biotechnology Co., Ltd. as an auxiliary material grade hydrogenated soybean oil product.
填料为改性氧化锌，改性氧化锌的平均粒径为280nm；改性氧化锌的制备方法包括以下步骤，以质量份计：S1：将2份氧化锌（平均粒径30nm）加入至50份水和无水乙醇（水和无水乙醇的质量比为4:1）混合溶剂当中，之后将1.5份3-氨基丙基三乙氧基硅烷加入混合搅拌均匀，升温至55℃，并滴加含有2份正硅酸乙酯的40份无水乙醇溶液，滴加反应时间为2.5h；S2：滴加反应完成之后，继续保温反应1h，之后将粒子产物过滤洗涤，将2份粒子产物加入至50份水和DMF（水和DMF的质量比为4:1）的混合溶剂当中，二次加入1.5份3-氨基丙基三乙氧基硅烷和2份丁二酸酐，升温至65℃，超声震荡反应2.5h，完成后过滤、洗涤、烘干即得。The filler is modified zinc oxide, and the average particle size of the modified zinc oxide is 280nm; the preparation method of modified zinc oxide includes the following steps, calculated by mass: S1: adding 2 parts of zinc oxide (average particle size 30nm) to a mixed solvent of 50 parts of water and anhydrous ethanol (the mass ratio of water to anhydrous ethanol is 4:1), then adding 1.5 parts of 3-aminopropyltriethoxysilane to the mixture and stirring evenly, heating to 55°C, and dripping 40 parts of anhydrous ethanol solution containing 2 parts of ethyl orthosilicate, and the dripping reaction time is 2.5h; S2: after the dripping reaction is completed, continue to keep warm for 1h, then filter and wash the particle product, add 2 parts of the particle product to a mixed solvent of 50 parts of water and DMF (the mass ratio of water to DMF is 4:1), add 1.5 parts of 3-aminopropyltriethoxysilane and 2 parts of succinic anhydride for the second time, heating to 65°C, ultrasonically shaking for 2.5h, filtering, washing and drying after completion.
助剂为稳定剂，购买自南京米兰新材料公司出售的783型号稳定剂产品。The auxiliary agent is a stabilizer, which is a 783 type stabilizer product purchased from Nanjing Milan New Materials Company.
可降解粘结层，以质量份计，原料包括：甲基丙烯酸甲酯25份，丙烯酸乙酯55份，丙烯酸异辛酯8份，功能单体7份，引发剂0.5份，成盐剂2.5份，乳化剂1份，溶剂320份。The raw materials of the degradable adhesive layer include, by weight: 25 parts of methyl methacrylate, 55 parts of ethyl acrylate, 8 parts of isooctyl acrylate, 7 parts of functional monomer, 0.5 parts of initiator, 2.5 parts of salt-forming agent, 1 part of emulsifier and 320 parts of solvent.
功能单体为双环戊烯基丙烯酸酯和改性甲基丙烯酸丁酯，两者的质量比为1.5：5.5。The functional monomers are dicyclopentenyl acrylate and modified butyl methacrylate, and the mass ratio of the two is 1.5:5.5.
改性甲基丙烯酸丁酯的制备方法包括以下步骤，以质量份计：S1：将3.5份ε-己内酯，2份丁二酸酐以及40份乙酸乙酯加入至反应釜内混合均匀，反应釜惰性气体保护，升温至65℃保温2h；S2：保温完成后，将含有3份甲基丙烯酸丁酯的30份乙酸乙酯溶液以及0.3份反应催化剂（二月桂酸二丁基锡）同时滴加至反应釜中，滴加时反应釜以150r/min持续搅拌，滴加温度为90℃；S3：控制甲基丙烯酸丁酯的乙酸乙酯溶液以及反应催化剂滴加同时完成，滴加完成后升温至120℃保温反应4h，反应完成后将产物移送至另一容器中加入混合表面活性剂，搅拌均匀后即得。The preparation method of modified butyl methacrylate comprises the following steps, calculated by mass: S1: 3.5 parts of ε-caprolactone, 2 parts of succinic anhydride and 40 parts of ethyl acetate are added into a reactor and mixed evenly, the reactor is protected by inert gas, and the temperature is raised to 65°C and kept warm for 2 hours; S2: after the insulation is completed, 30 parts of ethyl acetate solution containing 3 parts of butyl methacrylate and 0.3 parts of reaction catalyst (dibutyltin dilaurate) are simultaneously added dropwise into the reactor, the reactor is continuously stirred at 150r/min during the addition, and the dropping temperature is 90°C; S3: the ethyl acetate solution of butyl methacrylate and the reaction catalyst are controlled to be added dropwise at the same time, after the addition is completed, the temperature is raised to 120°C and kept warm for reaction for 4 hours, after the reaction is completed, the product is transferred to another container, a mixed surfactant is added, and the product is obtained after being stirred evenly.
混合表面活性剂为烷基糖苷和脂肪醇聚氧乙烯醚的混合物，混合表面活性剂的加入量为S3中产物总质量的8%。The mixed surfactant is a mixture of alkyl glycoside and fatty alcohol polyoxyethylene ether, and the added amount of the mixed surfactant is 8% of the total mass of the product in S3.
烷基糖苷和脂肪醇聚氧乙烯醚的质量比为2.5：1.5；脂肪醇聚氧乙烯醚为鲸蜡硬脂醇聚氧乙烯醚，购买自海安国云化工有限公司出售的O-3产品，羟值为145mgKOH/g。The mass ratio of alkyl glycoside to fatty alcohol polyoxyethylene ether is 2.5:1.5; the fatty alcohol polyoxyethylene ether is cetearyl alcohol polyoxyethylene ether, which is an O-3 product purchased from Hai'an Guoyun Chemical Co., Ltd., and has a hydroxyl value of 145 mgKOH/g.
引发剂为过硫酸铵；成盐剂为三乙醇胺；乳化剂为DNS-86；可降解粘结层的溶剂为丙酮和去离子水的混合溶剂，丙酮和去离子水的质量比为1：4。The initiator is ammonium persulfate; the salt-forming agent is triethanolamine; the emulsifier is DNS-86; the solvent of the degradable adhesive layer is a mixed solvent of acetone and deionized water, and the mass ratio of acetone to deionized water is 1:4.
本实施例第二方面提供了一种上述可降解胶带的制备方法，制备方法包括以下步骤：S1：将可降解基体层原料加入高速混合机中进行搅拌混合均匀，之后将混合物料加入密炼机中密炼塑化，密炼温度为200℃，密炼时间3min，再经过挤出机塑化，190℃压延成型，冷却分割得到所需厚度可降解基体层；S2：将甲基丙烯酸甲酯，丙烯酸乙酯，丙烯酸异辛酯以及溶剂混合加入反应釜中,搅拌混合完全，之后将功能单体，乳化剂，成盐剂以及引发剂依次加入反应釜中混合搅拌，升温至70℃，搅拌保温反应4h，最后中和破乳得到可降解粘结剂；S3：将可降解粘结剂喷涂于离型层表面，经过烘干固化以及熟化后形成可降解粘结层，将可降解粘结层与可降解基体层复合，得到可降解胶带。The second aspect of the present embodiment provides a preparation method of the above-mentioned degradable tape, which comprises the following steps: S1: adding the raw materials of the degradable base layer into a high-speed mixer and stirring and mixing them evenly, then adding the mixed materials into a mixer for mixing and plasticizing, the mixing temperature is 200°C, the mixing time is 3 minutes, and then plasticizing through an extruder, calendering and forming at 190°C, cooling and dividing to obtain a degradable base layer of required thickness; S2: adding methyl methacrylate, ethyl acrylate, isooctyl acrylate and solvent into a reaction kettle, stirring and mixing them thoroughly, then adding functional monomers, emulsifiers, salt-forming agents and initiators into the reaction kettle in turn, mixing and stirring, heating to 70°C, stirring and keeping warm for 4 hours, and finally neutralizing and demulsifying to obtain a degradable adhesive; S3: spraying the degradable adhesive on the surface of the release layer, forming a degradable adhesive layer after drying, curing and aging, and compounding the degradable adhesive layer with the degradable base layer to obtain a degradable tape.
烘干固化温度为120℃，熟化温度为60℃，熟化时间为80h。The drying and curing temperature is 120°C, the aging temperature is 60°C, and the aging time is 80h.
离型层购买自利亨新材料科技公司出售的透明级PET离型膜产品。The release layer was purchased from the transparent PET release film product sold by Liheng New Material Technology Co., Ltd.
实施例2:实施例2第一方面提供了一种可降解胶带包括可降解基体层，可降解基体层表面的可降解粘结层，以及可降解粘结层的另一侧具有保护作用的离型层。Example 2: Example 2 provides a first aspect of a degradable tape comprising a degradable base layer, a degradable adhesive layer on the surface of the degradable base layer, and a release layer having a protective function on the other side of the degradable adhesive layer.
可降解基体层的厚度为40μm；可降解粘结层的厚度为15μm；离型层的厚度为25μm。The thickness of the degradable base layer is 40 μm; the thickness of the degradable adhesive layer is 15 μm; and the thickness of the release layer is 25 μm.
可降解基体层，以质量份计，原料包括：基体树脂135份，填充剂40份，润滑剂6份，填料20份，助剂2份。The raw materials of the degradable base layer include, by weight: 135 parts of base resin, 40 parts of filler, 6 parts of lubricant, 20 parts of filler and 2 parts of auxiliary agent.
基体树脂为PVC树脂和PLA树脂的组合物，两者的质量比为9:4.5。The matrix resin is a composition of PVC resin and PLA resin, and the mass ratio of the two is 9:4.5.
PVC树脂的聚合度为1200，购买自日本普立万公司的170型PVC树脂料产品；PLA树脂的粘度为5500mPa·s，购买自上海一轮塑化有限公司出售的相应粘度树脂产品。The polymerization degree of the PVC resin is 1200, and it is a 170 type PVC resin product purchased from PolyOne Corporation of Japan; the viscosity of the PLA resin is 5500 mPa·s, and it is a resin product of corresponding viscosity purchased from Shanghai Yilun Plastic Chemical Co., Ltd.
填充剂为支链淀粉和直链淀粉的组合物，两者的质量比为1:2.8。The filler is a composition of amylopectin and straight-chain starch, and the mass ratio of the two is 1:2.8.
支链淀粉和直链淀粉分别购买自武汉华翔科洁生物科技有限公司出售的支链和直链淀粉产品，支链/直链含量≥70wt%。Amylopectin and amylose were purchased from amylopectin and amylose products sold by Wuhan Huaxiang Kejie Biotechnology Co., Ltd., respectively, with amylopectin/amylose content ≥ 70 wt%.
润滑剂为氢化大豆油，购买自武汉斯麦克生物科技有限公司出售的辅料级氢化大豆油产品。The lubricant was hydrogenated soybean oil, which was purchased from Wuhan Smek Biotechnology Co., Ltd. as an auxiliary material grade hydrogenated soybean oil product.
填料为改性氧化锌，改性氧化锌的平均粒径为280nm；改性氧化锌的制备方法包括以下步骤，以质量份计：S1：将2份氧化锌（平均粒径30nm）加入至50份水和无水乙醇（水和无水乙醇的质量比为4:1）混合溶剂当中，之后将1.5份3-氨基丙基三乙氧基硅烷加入混合搅拌均匀，升温至55℃，并滴加含有2份正硅酸乙酯的40份无水乙醇溶液，滴加反应时间为2.5h；S2：滴加反应完成之后，继续保温反应1h，之后将粒子产物过滤洗涤，将2份粒子产物加入至50份水和DMF（水和DMF的质量比为4:1）的混合溶剂当中，二次加入1.5份3-氨基丙基三乙氧基硅烷和2份丁二酸酐，升温至65℃，超声震荡反应2.5h，完成后过滤、洗涤、烘干即得。The filler is modified zinc oxide, and the average particle size of the modified zinc oxide is 280nm; the preparation method of modified zinc oxide includes the following steps, calculated by mass: S1: adding 2 parts of zinc oxide (average particle size 30nm) to a mixed solvent of 50 parts of water and anhydrous ethanol (the mass ratio of water to anhydrous ethanol is 4:1), then adding 1.5 parts of 3-aminopropyltriethoxysilane to the mixture and stirring evenly, heating to 55°C, and dripping 40 parts of anhydrous ethanol solution containing 2 parts of ethyl orthosilicate, and the dripping reaction time is 2.5h; S2: after the dripping reaction is completed, continue to keep warm for 1h, then filter and wash the particle product, add 2 parts of the particle product to a mixed solvent of 50 parts of water and DMF (the mass ratio of water to DMF is 4:1), add 1.5 parts of 3-aminopropyltriethoxysilane and 2 parts of succinic anhydride for the second time, heating to 65°C, ultrasonically shaking for 2.5h, filtering, washing and drying after completion.
助剂为稳定剂，购买自南京米兰新材料公司出售的783型号稳定剂产品。The auxiliary agent is a stabilizer, which is a 783 type stabilizer product purchased from Nanjing Milan New Materials Company.
可降解粘结层，以质量份计，原料包括：甲基丙烯酸甲酯20份，丙烯酸乙酯60份，丙烯酸异辛酯6份，功能单体6份，引发剂0.5份，成盐剂2份，乳化剂1份，溶剂300份。The raw materials of the degradable adhesive layer include, by weight: 20 parts of methyl methacrylate, 60 parts of ethyl acrylate, 6 parts of isooctyl acrylate, 6 parts of functional monomer, 0.5 parts of initiator, 2 parts of salt former, 1 part of emulsifier and 300 parts of solvent.
功能单体为双环戊烯基丙烯酸酯和改性甲基丙烯酸丁酯，两者的质量比为1：5。The functional monomers are dicyclopentenyl acrylate and modified butyl methacrylate, and the mass ratio of the two is 1:5.
改性甲基丙烯酸丁酯的制备方法包括以下步骤，以质量份计：S1：将3.5份ε-己内酯，2份丁二酸酐以及40份乙酸乙酯加入至反应釜内混合均匀，反应釜惰性气体保护，升温至65℃保温2h；S2：保温完成后，将含有3份甲基丙烯酸丁酯的30份乙酸乙酯溶液以及0.3份反应催化剂（二月桂酸二丁基锡）同时滴加至反应釜中，滴加时反应釜以150r/min持续搅拌，滴加温度为90℃；S3：控制甲基丙烯酸丁酯的乙酸乙酯溶液以及反应催化剂滴加同时完成，滴加完成后升温至120℃保温反应4h，反应完成后将产物移送至另一容器中加入混合表面活性剂，搅拌均匀后即得。The preparation method of modified butyl methacrylate comprises the following steps, calculated by mass: S1: 3.5 parts of ε-caprolactone, 2 parts of succinic anhydride and 40 parts of ethyl acetate are added into a reactor and mixed evenly, the reactor is protected by inert gas, and the temperature is raised to 65°C and kept warm for 2 hours; S2: after the insulation is completed, 30 parts of ethyl acetate solution containing 3 parts of butyl methacrylate and 0.3 parts of reaction catalyst (dibutyltin dilaurate) are simultaneously added dropwise into the reactor, the reactor is continuously stirred at 150r/min during the addition, and the dropping temperature is 90°C; S3: the ethyl acetate solution of butyl methacrylate and the reaction catalyst are controlled to be added dropwise at the same time, after the addition is completed, the temperature is raised to 120°C and kept warm for reaction for 4 hours, after the reaction is completed, the product is transferred to another container, a mixed surfactant is added, and the product is obtained after being stirred evenly.
混合表面活性剂为烷基糖苷和脂肪醇聚氧乙烯醚的混合物，混合表面活性剂的加入量为S3中产物总质量的8%。The mixed surfactant is a mixture of alkyl glycoside and fatty alcohol polyoxyethylene ether, and the added amount of the mixed surfactant is 8% of the total mass of the product in S3.
烷基糖苷和脂肪醇聚氧乙烯醚的质量比为2.5：1.5；脂肪醇聚氧乙烯醚为鲸蜡硬脂醇聚氧乙烯醚，购买自海安国云化工有限公司出售的O-3产品，羟值为145mgKOH/g。The mass ratio of alkyl glycoside to fatty alcohol polyoxyethylene ether is 2.5:1.5; the fatty alcohol polyoxyethylene ether is cetearyl alcohol polyoxyethylene ether, which is an O-3 product purchased from Hai'an Guoyun Chemical Co., Ltd., and has a hydroxyl value of 145 mgKOH/g.
引发剂为过硫酸铵；成盐剂为三乙醇胺；乳化剂为DNS-86；可降解粘结层的溶剂为丙酮和去离子水的混合溶剂，丙酮和去离子水的质量比为1：4。The initiator is ammonium persulfate; the salt-forming agent is triethanolamine; the emulsifier is DNS-86; the solvent of the degradable adhesive layer is a mixed solvent of acetone and deionized water, and the mass ratio of acetone to deionized water is 1:4.
本实施例第二方面提供了一种上述可降解胶带的制备方法，制备方法包括以下步骤：S1：将可降解基体层原料加入高速混合机中进行搅拌混合均匀，之后将混合物料加入密炼机中密炼塑化，密炼温度为200℃，密炼时间3min，再经过挤出机塑化，190℃压延成型，冷却分割得到所需厚度可降解基体层；S2：将甲基丙烯酸甲酯，丙烯酸乙酯，丙烯酸异辛酯以及溶剂混合加入反应釜中,搅拌混合完全，之后将功能单体，乳化剂，成盐剂以及引发剂依次加入反应釜中混合搅拌，升温至70℃，搅拌保温反应4h，最后中和破乳得到可降解粘结剂；S3：将可降解粘结剂喷涂于离型层表面，经过烘干固化以及熟化后形成可降解粘结层，将可降解粘结层与可降解基体层复合，得到可降解胶带。The second aspect of the present embodiment provides a preparation method of the above-mentioned degradable tape, which comprises the following steps: S1: adding the raw materials of the degradable base layer into a high-speed mixer and stirring and mixing them evenly, then adding the mixed materials into a mixer for mixing and plasticizing, the mixing temperature is 200°C, the mixing time is 3 minutes, then plasticizing through an extruder, calendering at 190°C, cooling and dividing to obtain a degradable base layer of required thickness; S2: adding methyl methacrylate, ethyl acrylate, isooctyl acrylate and solvent into a reactor, stirring and mixing them thoroughly, then adding functional monomers, emulsifiers, salt-forming agents and initiators into the reactor in turn, mixing and stirring, heating to 70°C, stirring and keeping warm for 4 hours, and finally neutralizing and demulsifying to obtain a degradable adhesive; S3: spraying the degradable adhesive on the surface of the release layer, forming a degradable adhesive layer after drying, curing and aging, and compounding the degradable adhesive layer with the degradable base layer to obtain a degradable tape.
烘干固化温度为120℃，熟化温度为60℃，熟化时间为80h。The drying and curing temperature is 120°C, the aging temperature is 60°C, and the aging time is 80h.
离型层购买自利亨新材料科技公司出售的透明级PET离型膜产品。The release layer was purchased from the transparent PET release film product sold by Liheng New Material Technology Co., Ltd.
对比例1Comparative Example 1
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：PVC树脂和PLA树脂的质量比为10：1。The specific implementation of this comparative example is basically the same as that of Example 1, except that the mass ratio of PVC resin to PLA resin is 10:1.
对比例2Comparative Example 2
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：PLA树脂的粘度为3000mPa·s，购买自湖北鑫宏宇生物医药技术有限公司出售的相应粘度产品。The specific implementation of this comparative example is basically the same as that of Example 1, except that the viscosity of the PLA resin is 3000 mPa·s, and the corresponding viscosity product is purchased from Hubei Xinhongyu Biomedical Technology Co., Ltd.
对比例3Comparative Example 3
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：PVC树脂的聚合度为1350，购买自SG-3型号的PVC树脂。The specific implementation of this comparative example is basically the same as that of Example 1, except that the polymerization degree of the PVC resin is 1350, and the PVC resin purchased is of model SG-3.
对比例4Comparative Example 4
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：填充剂为支链淀粉和直链淀粉的组合物，两者的质量比为2:1。The specific implementation of this comparative example is basically the same as that of Example 1, except that the filler is a composition of amylopectin and amylose, and the mass ratio of the two is 2:1.
对比例5Comparative Example 5
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：填料为氧化锌和氧化钛的混合粒子，两者的质量比为1:1。The specific implementation of this comparative example is basically the same as that of Example 1, except that the filler is a mixed particle of zinc oxide and titanium oxide, and the mass ratio of the two is 1:1.
对比例6Comparative Example 6
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：改性氧化锌的制备方法中，氧化锌的平均粒径为80nm，所得改性氧化锌的平均粒径为400nm。The specific implementation of this comparative example is basically the same as that of Example 1, except that in the preparation method of the modified zinc oxide, the average particle size of the zinc oxide is 80 nm, and the average particle size of the obtained modified zinc oxide is 400 nm.
对比例7Comparative Example 7
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：功能单体为双环戊烯基丙烯酸酯和改性甲基丙烯酸丁酯，两者的质量比为1：1。The specific implementation of this comparative example is basically the same as that of Example 1, except that the functional monomers are dicyclopentenyl acrylate and modified butyl methacrylate, and the mass ratio of the two is 1:1.
对比例8Comparative Example 8
本对比例的具体实施方式与实施例1基本相同，不同之处仅在于：烷基糖苷和脂肪醇聚氧乙烯醚的质量比为5：1；脂肪醇聚氧乙烯醚为鲸蜡硬脂醇聚氧乙烯醚，购买自海安国云化工有限公司出售的O-30产品，羟值为36~40mgKOH/g。The specific implementation method of this comparative example is basically the same as that of Example 1, except that the mass ratio of alkyl glycoside to fatty alcohol polyoxyethylene ether is 5:1; the fatty alcohol polyoxyethylene ether is cetearyl alcohol polyoxyethylene ether, which is purchased from Hai'an Guoyun Chemical Co., Ltd. O-30 product sold, and has a hydroxyl value of 36~40mgKOH/g.
性能评价Performance Evaluation
剥离强度：根据标准GB/T2792-2014对实施例和对比例制得胶带进行剥离强度测试，将标准胶带(25mm*200mm)，贴在用酒精擦拭干净的不锈钢板上，用2kg的压辊来回压，室温放置8h后，通过剥离力试验机进行测试，测得的数值取10次平行测试的平均值记入表1。Peel strength: According to the standard GB/T2792-2014, the peel strength test was carried out on the adhesive tapes prepared in the examples and comparative examples. The standard adhesive tape (25 mm*200 mm) was attached to a stainless steel plate wiped clean with alcohol, pressed back and forth with a 2 kg pressure roller, and placed at room temperature for 8 hours. The peel strength tester was used for the test, and the measured values were taken as the average value of 10 parallel tests and recorded in Table 1.
耐老化性：对实施例和对比例制得胶带进行耐老化测试，将胶带放置在75℃，湿度100%的恒温恒湿箱中，保存7天，对其剥离强度进行测试，计算其剥离强度保留率，剥离强度保留率%=测试后剥离强度/测试前剥离强度×100%，测得的数值取10次平行测试的平均值记入表1。Aging resistance: The adhesive tapes prepared in the embodiments and comparative examples were subjected to an aging resistance test. The adhesive tapes were placed in a constant temperature and humidity chamber at 75°C and 100% humidity for 7 days. The peel strength was tested and the peel strength retention rate was calculated. Peel strength retention rate (%) = peel strength after test / peel strength before test × 100%. The measured values were averaged over 10 parallel tests and recorded in Table 1.
可降解性：参考ISO 20200-2015标准对实施例和对比例的降解率进行测试，记录胶带的可降解率，测得的数值取10次平行测试的平均值记入表1。Degradability: The degradation rates of the embodiments and comparative examples were tested with reference to the ISO 20200-2015 standard, and the degradation rates of the tapes were recorded. The measured values were taken as the average values of 10 parallel tests and recorded in Table 1.
拉伸强度：参考ASTM D-638标准对实施例和对比例的拉伸强度进行测试，试样的长度是125mm，宽度是12.5mm，测得的数值取10次平行测试的平均值记入表1。Tensile strength: The tensile strength of the embodiments and comparative examples was tested with reference to ASTM D-638. The length of the specimen was 125 mm and the width was 12.5 mm. The measured values were the average values of 10 parallel tests and recorded in Table 1.
从本申请实施例和对比例以及表1的数据结果可以得知，采用本申请必要技术方案的实施例1和2能够在耐老化性、粘结性、防水性、力学性能等方面明显地强于对比例1~8，这主要是因为，实施例1和2采用正确的集体层材料和粘合层材料组合，确保了体系自身强度的提高以及分子紧密度的提高，加强胶带体系内聚力，减少活性分子移动和反应碰撞，进而客服现有技术的可降解胶带在力学性能、防水性以及耐老化性上的前提，具有十分优异的市场前景。而对比例1~8则因为并未采用正确的限定技术方案，导致其性能并不全面，容易在某一性能方面和实施例1和2具有明显差距，这更加证明了本申请的技术方案对于最终技术效果的必要性。From the examples and comparative examples of the present application and the data results in Table 1, it can be seen that Examples 1 and 2 using the necessary technical solution of the present application can be significantly stronger than Comparative Examples 1 to 8 in terms of aging resistance, adhesion, waterproofness, mechanical properties, etc. This is mainly because Examples 1 and 2 use the correct combination of collective layer materials and adhesive layer materials to ensure the improvement of the system's own strength and the improvement of molecular compactness, strengthen the cohesion of the tape system, reduce the movement of active molecules and reaction collisions, and thus overcome the mechanical properties, waterproofness and aging resistance of the degradable tape of the prior art, and have a very excellent market prospect. However, because Comparative Examples 1 to 8 do not use the correct limited technical solution, their performance is not comprehensive, and they are prone to have a significant gap with Examples 1 and 2 in a certain performance aspect, which further proves the necessity of the technical solution of the present application for the final technical effect.
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| CN202410611204.2ACN118271987B (en) | 2024-05-16 | 2024-05-16 | Degradable adhesive tape and preparation method and application thereof |
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| CN202410611204.2ACN118271987B (en) | 2024-05-16 | 2024-05-16 | Degradable adhesive tape and preparation method and application thereof |
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| CN119264834A (en)* | 2024-11-07 | 2025-01-07 | 苏州恒瑞电子材料有限公司 | A soft polyvinyl chloride electrical tape and a processing method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109321153A (en)* | 2018-09-19 | 2019-02-12 | 广东星宇耐力新材料股份有限公司 | The ultralow viscous protective film water-borne pressure sensitive adhesive of one kind, ultralow viscous protective film and preparation method thereof |
| CN111187586A (en)* | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Ultra-high viscosity acrylate emulsion pressure-sensitive adhesive and preparation method thereof |
| CN111410923A (en)* | 2020-05-15 | 2020-07-14 | 广东洪运洋科技有限公司 | Degradable sealing adhesive tape |
| CN116355327A (en)* | 2023-04-10 | 2023-06-30 | 舒氏集团有限公司 | Preparation method of degradable PVC film and adhesive tape |
| WO2023173457A1 (en)* | 2022-03-18 | 2023-09-21 | 上海工程技术大学 | Flame retardant and degradable adhesive tape, and preparation method therefor |
| CN117659896A (en)* | 2023-12-11 | 2024-03-08 | 临沂天勤塑业有限公司 | Environment-friendly composite adhesive tape and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109321153A (en)* | 2018-09-19 | 2019-02-12 | 广东星宇耐力新材料股份有限公司 | The ultralow viscous protective film water-borne pressure sensitive adhesive of one kind, ultralow viscous protective film and preparation method thereof |
| CN111187586A (en)* | 2020-01-21 | 2020-05-22 | 江苏景宏新材料科技有限公司 | Ultra-high viscosity acrylate emulsion pressure-sensitive adhesive and preparation method thereof |
| CN111410923A (en)* | 2020-05-15 | 2020-07-14 | 广东洪运洋科技有限公司 | Degradable sealing adhesive tape |
| WO2023173457A1 (en)* | 2022-03-18 | 2023-09-21 | 上海工程技术大学 | Flame retardant and degradable adhesive tape, and preparation method therefor |
| CN116355327A (en)* | 2023-04-10 | 2023-06-30 | 舒氏集团有限公司 | Preparation method of degradable PVC film and adhesive tape |
| CN117659896A (en)* | 2023-12-11 | 2024-03-08 | 临沂天勤塑业有限公司 | Environment-friendly composite adhesive tape and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN119264834A (en)* | 2024-11-07 | 2025-01-07 | 苏州恒瑞电子材料有限公司 | A soft polyvinyl chloride electrical tape and a processing method thereof |
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