CN114622325B - 一种双面恒温织物及其制备方法 - Google Patents

一种双面恒温织物及其制备方法 Download PDF

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CN114622325B
CN114622325B CN202111166553.0A CN202111166553A CN114622325B CN 114622325 B CN114622325 B CN 114622325B CN 202111166553 A CN202111166553 A CN 202111166553A CN 114622325 B CN114622325 B CN 114622325B
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fiber
fabric
double
fibers
temperature
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CN114622325A (zh
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杨艳
杨涛
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Yang Yan
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Beijing Jinlunwode Technology Co ltd
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Priority to CN202111166553.0A priority Critical patent/CN114622325B/zh
Priority to PCT/CN2022/084895 priority patent/WO2023050751A1/zh
Priority to EP22874152.6A priority patent/EP4215657A4/en
Priority to JP2022581622A priority patent/JP7465588B2/ja
Priority to US18/271,276 priority patent/US20240044071A1/en
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Abstract

本申请提供一种双面恒温织物及其制备方法，包括：制备反光隔热纤维(即第二纤维)，用激光蚀刻其表面制成螺纹纤维，使其具有良好的光反射与热反射性能，作为织物外层；制备改性麻纤维，使其具有良好单向导湿、导热性能，作为织物内层；采用里经接表纬的接结方法使内外层布料复合形成双面织物。本发明通过修饰纤维表面结构并对纤维进行改性，使制备出的布料在炎热时可通过辐射散热与单向导湿实现降温，在寒冷时可通过热反射实现保温，可运用于人体温度调控的服装制造，并具有大规模批量制备、成本低、生产效率高的优点。

Description

一种双面恒温织物及其制备方法
技术领域
本申请涉及纺织技术领域，特别涉及一种双面恒温织物及其制备方法。
背景技术
由于温室效应与城市热岛效应的作用，全球暖化加剧，极端天气的发生愈发频繁，夏季高温天气的持续时间与高温程度也愈发严重。伴随高温天气而来的是制冷与空调热泵设备的使用量与需求量逐年增长。然而，传统制冷设备的大量使用易产生巨大的能源消耗，而其中CFC、HCFC类的工质对臭氧层亦有破坏作用。因此，对新型环保制冷产品的研究成为保护环境与提高人们生活质量的重要课题。其中，恒温织物可通过发挥辐射制冷与热反射等功能实现对人体温度的调控，是一种节能环保、便捷有效的热管理手段。
恒温织物主要利用辐射制冷、热反射、变温材料等技术，维持人体皮肤接触温度处于令人感到舒适的区间，即在寒冷时起到保温作用，炎热时起到降温作用。太阳辐射的大部分能量集中在可见光与红外光区，通过对材料的选择和结构的设计，制造出在太阳辐射0.3μm-2.5μm波段具有高反射率，在人体热辐射7μm-14μm波段具有高发射率的织物，就可以使人体能通过“大气窗口”与低温外太空和高层大气层之间进行辐射换热从而获得制冷效果。而增强材料对太阳光的反射，减少对太阳光的透过与吸收，就可降低对太阳辐射的热积累，并减少紫外线对人体健康的伤害。
中国台湾发明专利TWI707906B中公开了一种石墨烯恒温织物，利用石墨烯具有特殊的热学特性及优异的导电性，以低沸点及高表面张力的溶剂组合制备奈米石墨烯片悬浮溶液，混合奈米石墨烯片悬浮溶液及疏水性树脂制备石墨烯树脂溶液，以涂布或印刷的方式使石墨烯树脂溶液覆盖且崁入织物组织，形成石墨烯恒温层。在环境温度较高时，石墨烯恒温层可加速人体皮肤热量的逸散，达到凉爽的效果，在环境温度较低时，石墨烯恒温层可均化人体皮肤不同部位的温度，且藉由吸收及释放人体皮肤辐射的远红外线，同时达到保暖与恒温的效果。但目前还不能完全确定人类长期接触石墨烯的后果，将石墨烯应用于与人体长期接触的织物中缺乏安全性上的保证，且石墨烯在制造过程中对环境产生的污染较大。
美国发明专利US11058161B2中公开了一种热反射织物，该织物中含有至少一层金属层，可通过形成辐射屏障以减少人体对外辐射的热损失。将金属层与具有良好气隙以暴露金属层低发射率表面的3D经编织物进行结合，3D经编织物因具有一定厚度厚度，可在金属层和其它表面之间提供绝缘。该织物可将身体热量反射回系统中以身体的热量损失，但仅具备保温效果，不能在高温天气降低身体温度以实现恒温。
中国发明专利CN104127279B中公开了一种多功能自发调节温度的膜，该膜从外到内包括功能材料载体层和接近皮肤的保温层。功能材料载体层为由不透水的柔性材料构成的密封腔体结构，装载有制冷或制热化学原料；保温层由具有防水保温性能的材料构成。若使用制热化学原料，则功能材料载体层中可起制热效果；若使用制冷化学原料，则保温层可避免引起局部冻伤，同时功能材料载体层和皮肤之间发生均匀稳定的热交换，起到长效制冷效果。但该膜缺乏透气、透湿功能，且控温效果具有时效性，无法应用于日常穿着的服装。
中国实用新型专利CN211747098U中公开了一种可恒温工作的空调服，包括纺织品制成的上衣、温度调节模块、温度检测传感器、控制模块以及锂电池组，利用半导体制冷片与散热风扇进行制冷，之间设有散热片，控制模块与锂电池组、温度调节模块、温度检测传感器相连，锂电池组作为电源，温度检测传感器用于检测温度并将温度信息反馈给控制模块，控制模块根据设定温度开启温度调节模块实现制冷或者制热。该服装具有良好的制冷制热功能，但制造工艺复杂，成本高昂，且不能实现零能耗的个人热管理。
中国发明专利CN113136724A中公开了一种辐射制冷织物。该织物里含有丝纤维，辐射制冷织物包括附着在纤维上且折射率高于1.6低于3.0的材料，通过附着在纤维上具有高折射率的材料与纤维叠加在一起提高了紫外反射率，相比于未处理的织物，在紫外光的反射率提升了42％，使得在整个太阳光波段反射率达到了95％，处理后的织物在阳光下的温度可以比室温低3.6度左右，同时覆盖在皮肤上可以比棉质织物降低12度左右。但该织物不具备保温效果，不能在低温时创造恒温环境。
综上所述，现有专利缺乏便捷、有效、节能的方法制备兼具保温与降温功能的恒温织物，使其能够应用于人体热管理的日常穿着服装。
发明内容
有鉴于此，本申请实施例提供了一种双面恒温织物及其制备方法，以解决现有技术中存在的技术缺陷。
本申请提供一种双面恒温织物，其包括第一纤维和第二纤维，所述第一纤维为麻纤维；所述第二纤维为其表面还有螺纹状凹槽的螺旋纤维；所述第一纤维和第二纤维复合于一起形成所述织物，该织物的一侧为第一纤维，另一侧为第二纤维，穿着时，第一纤维侧和第二纤维侧均可朝向内侧或朝向外侧。
进一步地，所述麻纤维（天然麻纤维）为改性麻纤维。
进一步地，所述第二纤维包括聚酯纤维和包裹于所述聚酯纤维外围的防晒反光涂层，所述螺旋状凹槽设置于所述防晒反光涂层外侧。
进一步地，所述防晒反光涂层的组分包括醇酸树脂与纳米防晒颗粒，二者的重量比为1 : (0~0.3)。
进一步地，所述醇酸树脂为有机硅改性醇酸树脂；优选地，所述有机硅改性醇酸树脂为聚烷基有机硅树脂、聚芳基有机硅树脂或聚烷基芳基有机硅树脂与醇酸树脂共缩聚而得。
进一步地，所述螺旋纤维的外表面呈牙型，该牙型为梯形、矩形或三角形；优选地，所述牙型的牙型角为0~30°，牙顶到牙底宽度为0.1~3.0μm，螺距为0.1~5.0μm。
进一步地，所述纳米防晒颗粒的粒径范围为0.5~10μm。
本发明另一个发明点为提供一种根据以上任意一段所述的双面恒温织物的制备方法，所述制备方法为：
第二纤维的制备：方法1：① 将醇酸树脂熔融或在溶剂中溶解，加入纳米防晒颗粒，搅拌20-60分钟；② 使①中所得的物质成为粘稠状的半固体形态；③ 彻底去除溶剂或降温以使其成为固体薄膜，得所述防晒反光涂层；④ 然后将防晒反光涂层包覆在所述聚酯纤维外围；
方法2：① 与方法1中的步骤①一致；② 使①中所得的物质成为粘稠状的半固体形态；③ 将步骤②中所得的粘稠状半固体涂覆于所述聚酯纤维外围。
双面恒温织物的制备：然后将如上所述的任意一种第一纤维与所述第二纤维编织成双层织物。
进一步地，对于上述方法1，在步骤③中所得的防晒反光涂层上设置以上任意一段所述的螺纹状凹槽；
进一步地，对于上述方法1或方法2中的步骤②，成为粘稠状半固体的方法包括：A. 加入增稠剂；B. 若为溶解，则除去部分溶剂；C. 若为熔融，则降低温度使其成为粘稠状。
进一步地，在上述方法1或方法2中的步骤①中加入粘结剂，该粘结剂包括丁苯橡胶、氯丁橡胶、丁腈橡胶中的至少一种。
借由上述技术方案，本发明提供的技术方案至少具有下列优点：本申请中的双面恒温织物可双面穿着，即外侧可朝外但也可以朝里，对应地，内侧可朝但也可以朝外，不同穿着方式具有不同的效果。
硅改性醇酸树脂具有优异的反光性、隔热性、户外耐候性和耐紫外性能。将均匀沉淀法制得的纳米防晒颗粒以一定比例加入硅改性醇酸树脂中，可进一步提高其防晒、光反射能力。引入螺纹结构可增大在不同入射角度下对太阳光的反射。麻纤维既保留了麻纤维原本疏松、透气、传热导热快、凉爽挺括、出汗不贴身、防虫防霉、静电少的特性，又具有部分疏水的特性，强化了其导湿、散湿功能，无需进行更多导湿、透气孔洞设计或降低织物密度亦可起到良好的导湿、透气作用，确保了所制成的布料在反面穿着时具有较好的保温作用。故本发明提供的双面恒温织物可通过正反面穿着，选择性地通过辐射散热与单向导湿实现在高温条件下的降温，或通过热反射实现在低温条件下的保温。双层布料结构增加了散热性与透气性，通过在织物内部引入如空气孔、介质颗粒、聚合物纳米纤维等随机纳米结构，提供了强烈的米氏散射，从而实现对太阳辐射波段的高效调控。将合成纤维与天然纤维分别进行改进后混纺，较大提高了面料的舒适性，同时基于合成纤维与天然纤维吸湿性的差异，可制造出具有单向吸湿特性的面料，提高面料的干爽感。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚，本实用新型提供如下附图进行说明：
图1是本申请实施例所示的螺旋凹槽的结构示意图。
具体实施方式
下面结合附图对本申请的具体实施方式进行描述。
在本发明中，除非另有说明，否则本文中使用的科学和技术名词具有本领域技术人员所通常理解的含义。并且，本文中所用的试剂、材料和操作步骤均为相应领域内广泛使用的试剂、材料和常规步骤。
实施例1
本实施例提供一种能够调温的双面恒温织物，其包括第一纤维和第二纤维，二者复合成双层纤维结构，复合方式可参见现有技术中双层复合的方式，优选采用里经接表纬的接结方法使内外层布料复合形成双面织物。
所述第一纤维为麻纤维，优选天然麻纤维。所述第二纤维为其表面还有螺纹状凹槽的螺旋纤维。
作为进一步优选的实施方式，所述麻纤维优选为改性麻纤维，通过采用天然麻纤维，则对人体更健康，其吸湿性更高。通过对其改性，能够吸湿性的同时，增加导热性，优选改性麻纤维为将麻纤维与聚丁二酸丁二醇酯（PBS）进行接枝共聚得到，通过这样改性以后的麻纤维具有良好的单向导湿功能，还具有较佳的导热性能，其作为织物内层，实用性强，效果好。
作为进一步优选的实施方式，改性方法优选为：将麻纤维用高锰酸钾溶液进行预处理；使用十氢萘为溶剂，将丁二酸和丁二醇与催化剂SnCl2混合后，首先在150-160°C的温度条件下反应1-2h至酯化完全后，再升温至190-200°C，加入经过预处理的麻纤维，发生接枝共聚。保温10-12h，得到改性麻纤维。
作为进一步优选的实施方式，所述第二纤维的纤度为2.0dtex~5.0dtex，如2.0dtex、2.5dtex、3.0dtex、3.5dtex、4.0dtex、4.5dtex、5.0dtex等，纤维直径范围15.0~30.0μm。采用该纤度范围的纤维能够满足本发明的应用。
作为进一步优选的实施方式，所述第二纤维包括聚酯纤维和包裹于所述聚酯纤维外围的防晒反光涂层，所述螺旋状凹槽设置于所述防晒反光涂层外侧。优选地，所述聚酯纤维为聚对苯二甲酸乙二酯。
作为进一步优选的实施方式，所述防晒反光涂层的组分包括醇酸树脂与纳米防晒颗粒，二者的重量比为1 : (0~0.3)。
所述醇酸树脂优选为有机硅改性醇酸树脂。
作为进一步优选的实施方式，所述有机硅改性醇酸树脂为聚烷基有机硅树脂、聚芳基有机硅树脂或聚烷基芳基有机硅树脂与醇酸树脂共缩聚而得。
作为进一步优选的实施方式，所述螺旋纤维的外表面呈牙型，该牙型为梯形、矩形或三角形，更优选为梯形和矩形，最优选为梯形。
作为进一步优选的实施方式，所述牙型的牙型角为0~30°，优选为17-23°，如17°、18°、19°、20°、21°、22°、23°；牙顶到牙底宽度为0.1~3.0μm，优选0.2-1μm，如0.2 μm、0.4 μm、0.6 μm、0.8 μm、1.0 μm，螺距为0.1~5.0μm，优选0.5-2μm，如0.5 μm、0.8 μm、1.0 μm、1.3μm、1.5 μm、1.8 μm、2.0 μm。
作为进一步优选的实施方式，所述纳米防晒颗粒的粒径范围为0.5~10μm，优选2~6μm，该范围内的颗粒能够平衡防晒性能和比表面积，太小则防晒力度或效果不足，太大则比表面积小，影响防晒性能。更重要的是，该大小的纳米颗粒引入本发明的有机硅改性醇酸树脂中，能够提供强烈的米氏散射，从而实现对太阳辐射波段的高效调控，有助于调节温度。
作为进一步优选的实施方式，所述纳米防晒颗粒包括TiO2、ZnO、SiO2、ZrO2、CeO2、MgO、Al2O3、Fe2O3、Fe3O4、MgSiO3、Al2SiO5、BaCO3、BaSO4、玉石粉、云母粉、石英砂、白云石、蜡石、冰片、硅酸钙、聚乙烯(PE)、TiO2、ZnO、SiO2、ZrO2、CeO2、MgO、Al2O3、Fe2O3、Fe3O4、MgSiO3、Al2SiO5、BaCO3、BaSO4、ZrN、AlN、SiN、BN、Si3N4、SiC、Zn(NO3)2、酚醛树脂、双马来酰亚胺树脂、石墨、碳纳米管、铝-碳纳米管、氟树脂、四氟乙烯、有机硅改性丙烯酸树脂或氟碳树脂、三氟氯乙烯、水杨酸酯、二苯甲酮、苯并三唑、三嗪、三甲氧基苯甲酸酯、对氨基苯甲酸、肉桂酸苯酯、樟脑衍生物、四氟乙烯和全氟-2, 2-二甲基-1, 3-二唖茂的共聚物、苯甲脒中苯并噁嗪酮中的一种或多种。
本实施例的方案具有一定的调节温度的功效，能够保持较为恒温的状态。
当天气炎热阳光强烈时，可将第二纤维朝外穿着。第二纤维外的特定的防晒涂层，其在太阳热辐射的波段具有高反射性，更重要的是，第二纤维所在的侧面上所设计的特定的螺旋槽，尤其是当牙型角为17-23°时，使得照射来的阳光在槽中进行高效的反射和折射，同时，还存在一些漫反射的现象，其共同作用，则对于降温具有较大作用。而且第二纤维中醇酸树脂，尤其是有机硅改性醇酸树脂，其具有较强的隔温效果，能够较大限度的组织外界高温进入体内。通过上述防晒涂层的特殊反射性、螺旋槽的特殊结构并配合醇酸树脂，三者协同作用，对于降温和调节温度具有较佳的效果。且内侧的天然改性麻纤维还具有较强的吸湿、吸热和单向导湿等作用，也有利于降温，且使得人体更舒服。综合而言，降温防暑效果佳。
当寒冷的天气时，优选第二纤维朝内穿着，因为太阳热辐射的波段和人体热辐射的波段不重合，所以第二纤维上的特定的防晒涂层在人体热辐射波段具有高吸收性，在反穿的时候就可以起到保温的效果。而第二纤维中的醇酸树脂，尤其是有机硅改性醇酸树脂，其具有较强的隔温效果，能够较大限度的保持体内温度不被流失。更重要的是，外侧的麻纤维具有较好的吸光性，对于体内问题的保持或提升，具有很好的加持作用。
本实施例将特定大小的防晒颗粒与机硅改性醇酸树脂以及特定结构的螺旋纤维结合或联用，大大增加了织物的温控作用，综合效果提升。
实施例2
在实施例1的基础上，本实施例为一种双面恒温织物的制备方法，所述制备方法为：
第二纤维的制备：方法1：① 将醇酸树脂熔融或在溶剂中溶解(溶解度为60~100%便可，即其可以不完全溶解)，然后在加热条件下，加入纳米防晒颗粒，搅拌20-60分钟；②使①中所得的物质成为粘稠状的半固体形态；③ 彻底去除溶剂或降温以使其成为固体薄膜，得所述防晒反光涂层；④ 然后将防晒反光涂层包覆在所述聚酯纤维外围；此处的醇酸树脂可选择干性或半干性的树脂。溶剂只要能够部分溶剂醇酸树脂便可，如酯、醇、酮类溶剂。
方法2：① 与方法1中的步骤①一致；② 使①中所得的物质成为粘稠状的半固体形态，③ 将步骤②中所得的粘稠状半固体涂覆于所述聚酯纤维外围。
双面恒温织物的制备：然后将第一纤维与所述第二纤维编织成双层织物，编织方法依据现有技术中的双层布料便可，优选采用里经接表纬的接结方法使内外层布料复合形成双面织物，这样子的织法。
作为进一步优选的实施方式，对于上述方法1，在步骤③中所得的防晒反光涂层上，即一个侧面上设置所述的螺纹状凹槽。优选通过激光雕刻或蚀刻其表面制成的螺纹纤维，具有良好的光反射与热反射性能，为织物外层。
作为进一步优选的实施方式，在上述方法1或方法2中的步骤①中加入粘结剂，该粘结剂包括丁苯橡胶、氯丁橡胶、丁腈橡胶中的至少一种。
作为进一步优选的实施方式，对于上述方法1或方法2中的步骤②，成为粘稠状半固体的方法包括： A. 加入增稠剂；B. 若为溶解，则除去部分溶剂，即可待树脂为胶状时，停止除溶剂操作；C. 若为熔融，则降低温度使其成为粘稠状。
实施例3
实验例：通过本发明实施例2所制备的双面恒温织物。
对比例1：不加实验例中的防晒反光涂层，其他与实验例一致。
对比例2：不加实验例中的纳米防晒颗粒，其他与实验例一致。
对比例3：不加实施例中的醇酸树脂，改为将聚酯纤维置于浸轧机中，浸入纳米防晒颗粒液中，经浸轧辊组的浸轧，将纳米防晒颗粒微纳压在聚酯纤维的结构面中，烘干后形成沾满纳米防晒颗粒的聚酯纤维，其他与实验例一致。
对比例4：将实验例中的螺旋凹槽修改为表面含有很多凸点的粗糙结构，其他与实验例一致。
对比例5：将实验例中的改性麻纤维修改为麻纤维，其他与实验例一致。
实验方法：
1.在10℃条件下，用一热水袋模拟人体，将实施例1和对比例1-5的恒温双面织物覆盖于热水袋上，测定热水袋温度随时间变化，以反映不同双面恒温织物的保温性能。
结果如下表所示：
Figure DEST_PATH_IMAGE001
2.将实施例1和对比例1-5的双面恒温织物进行太阳光反射率和发射率的测试，反映其制冷效果。
结果如下表所示：
Figure 997616DEST_PATH_IMAGE002
3.将实施例1和对比例1-5的双面恒温织物进行透气性检测，具体步骤为：使用透气度测试仪，采用定压差测流量法，将试样装夹在透气度测试仪上，调节压力使试样两侧形成一个恒定的压差，测定在一定时间内垂直通过试样给定面积的气流流量来得出不同双面恒温织物的透气率（L/h）。
Figure DEST_PATH_IMAGE003
由上可知，本申请综合而言，其温度调节功能较佳，且其透气性整体较好。
在本发明中，所述的恒温双面织物可批量生产，通过修饰纤维表面结构并对纤维进行改性，使该织物在炎热时可通过辐射散热与单向导湿实现降温，在寒冷时可通过热反射实现保温，可运用于人体温度调控的服装制造。
在本文中，“上”、“下”、“前”、“后”、“左”、“右”等仅用于表示相关部分之间的相对位置关系，而非限定这些相关部分的绝对位置。
在本文中，“第一”、“第二”等仅用于彼此的区分，而非表示重要程度及顺序、以及互为存在的前提等。
在本文中，“相等”、“相同”等并非严格的数学和/或几何学意义上的限制，还包含本领域技术人员可以理解的且制造或使用等允许的误差。
除非另有说明，本文中的数值范围不仅包括其两个端点内的整个范围，也包括含于其中的若干子范围。
上面结合附图对本申请优选的具体实施方式和实施例作了详细说明，但是本申请并不限于上述实施方式和实施例，在本领域技术人员所具备的知识范围内，还可以在不脱离本申请构思的前提下做出各种变化。

Claims (11)

1.一种双面恒温织物，其包括第一纤维和第二纤维，其特征在于：
所述第一纤维为麻纤维；
所述第二纤维为其表面含有螺纹状凹槽的螺旋纤维；
所述第一纤维和第二纤维复合于一起形成所述织物，该织物的一侧为第一纤维，另一侧为第二纤维，穿着时，第一纤维侧和第二纤维侧均可朝向内侧或朝向外侧；
所述第二纤维为通过激光雕刻或蚀刻其表面制成的含有螺纹状凹槽的螺旋纤维；
所述第二纤维包括聚酯纤维和包裹于所述聚酯纤维外围的防晒反光涂层，所述螺纹状凹槽设置于所述防晒反光涂层外侧；
所述防晒反光涂层的组分包括醇酸树脂与纳米防晒颗粒，二者的重量比为1 : (0~0.3)；
所述醇酸树脂为有机硅改性醇酸树脂；
双面恒温织物的制备：然后将第一纤维与所述第二纤维编织成双层织物。
2.根据权利要求1所述的双面恒温织物，其特征在于，所述第二纤维的纤度为2.0dtex~5.0dtex。
3.根据权利要求1所述的双面恒温织物，其特征在于，所述麻纤维为改性麻纤维。
4.根据权利要求1所述的双面恒温织物，其特征在于，所述有机硅改性醇酸树脂为聚烷基有机硅树脂、聚芳基有机硅树脂或聚烷基芳基有机硅树脂与醇酸树脂共缩聚而得。
5.根据权利要求4所述的双面恒温织物，其特征在于，所述螺旋纤维的外表面呈牙型，该牙型为梯形、矩形或三角形。
6.根据权利要求5所述的双面恒温织物，其特征在于，所述牙型的牙型角为0~30°，牙顶到牙底宽度为0.1~3.0μm，螺距为0.1~5.0μm。
7.根据权利要求5所述的双面恒温织物，其特征在于，所述纳米防晒颗粒的粒径范围为0.5~10μm。
8.一种根据权利要求1-7中任意一项所述的双面恒温织物的制备方法，其特征在于：所述制备方法为：
第二纤维的制备：方法1：① 将醇酸树脂熔融或在溶剂中溶解，加入纳米防晒颗粒，搅拌20-60分钟；② 使①中所得的物质成为粘稠状的半固体形态；③ 彻底去除溶剂或降温以使其成为固体薄膜，得所述防晒反光涂层；④ 然后将防晒反光涂层包覆在所述聚酯纤维外围；
方法2：① 与方法1中的步骤①一致；② 使①中所得的物质成为粘稠状的半固体形态，③ 将步骤②中所得的粘稠状半固体涂覆于所述聚酯纤维外围。
9.根据权利要求8所述的制备方法，其特征在于，对于上述方法1，在步骤③中所得的防晒反光涂层上设置权利要求1-8中任意一项所述的螺纹状凹槽。
10.根据权利要求8所述的制备方法，其特征在于，对于上述方法1或方法2中的步骤②，成为粘稠状半固体的方法包括： A. 加入增稠剂；B. 若为溶解，则除去部分溶剂；C. 若为熔融，则降低温度使其成为粘稠状。
11.根据权利要求8所述的制备方法，其特征在于，在上述方法1或方法2中的步骤①中加入粘结剂，该粘结剂包括丁苯橡胶、氯丁橡胶、丁腈橡胶中的至少一种。
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