CN113152115B - 一种医用矫形绷带及其制备方法 - Google Patents

一种医用矫形绷带及其制备方法 Download PDF

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CN113152115B
CN113152115B CN202110436231.7A CN202110436231A CN113152115B CN 113152115 B CN113152115 B CN 113152115B CN 202110436231 A CN202110436231 A CN 202110436231A CN 113152115 B CN113152115 B CN 113152115B
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钱秋梅
王敏
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Jiekang Medical Component Co ltd Yiwu City
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Abstract

本发明公开了一种医用矫形绷带及其制备方法,涉及医用卫生新材料技术领域。该医用矫形绷带,包括:绷带基材,上述基材为涤纶网眼织带或专用PU无纺布;涂覆材料,包括改性聚氨酯预聚体。制备方法具体为:将涂覆材料加热至50℃后,在氮气环境中采用双滚筒涂覆法,将改性聚氨酯预聚体均匀涂覆在基材上,经送布、辊压后,再经成卷、剪切、氮封、封口工序,制得成品。本发明制得的医用矫形绷带,力学性能优异,无毒副作用,透气性好、质量轻、易于塑性;且对人体无不良刺激,可以有效杀灭皮肤表面的细菌,防止皮肤红肿瘙痒,防止伤口感染,为患者提供干燥舒适的康复环境,使用方便,可广泛用于临床治疗中。

Description

一种医用矫形绷带及其制备方法
技术领域
本发明属于医用卫生新材料技术领域,具体涉及一种医用矫形绷带及其制备方法。
背景技术
外固定矫形或整形是临床骨科与矫形外科的常用方法,外固定材料是常用的消耗性医用卫生材料。已有100多年历史的石膏绷带是目前临床最常用的外固定材料之一。其主要优点是:原料易得,价格低廉,对皮肤无毒副作用,强度较高,操作时水温低。然而,石膏绷带存在着许多缺陷,如:操作复杂、硬化干燥时间长、拆除困难、重量大、耐磨性差、可吸收部分X光以及使拍片模糊等。近二十年来,国际上一直致力于新材料的寻求,以逐步替代传统的石膏绷带。聚合物材料作为石膏的升级换代产品得到了很大的发展,国内外研究人员开发了多种多样的聚合物外固定材料。其中包括:聚氨酯绷带,高分子水固化材料涂布织物叠制而成的层状夹板,由基体、添加剂和催化剂组成的矫形外科夹板或铸造材料等。
医用绷带材料发展十分迅速,从八十年代中期开始,湿固化型聚氨酯医用绷带已在美国商品化生产,这种绷带成功解决了石膏绷带的透光性、透气性差的问题,但同时也存在着伤肌肤、伤毛发和不可再生使用的缺点,因此,近年来,各医药企业与研究者不断地对其进行研究与开发,志在研究出不伤皮肤、固化时间短和抗冲击性强的矫形绷带材料。
发明内容
本发明的目的在于提供一种医用矫形绷带及其制备方法,该医用矫形绷带力学性能优异,无毒副作用,固化时间短,透气性好、透光性高、易于塑性;且对人体无不良刺激,可防止皮肤红肿瘙痒,防止伤口感染,为患者提供干燥舒适的康复环境。
本发明为实现上述目的所采取的技术方案为:
一种淀粉衍生物,其为N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉。淀粉及其衍生物作为一种廉价无毒的可再生资源,具有低毒、易降解、与环境适应性好和成本低廉等优点,将其用于合成高分子改性不仅能赋予目标分子新的性质,而且符合环境保护及资源的可持续利用与发展战略。采用N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉制得淀粉衍生物,更有利于其对聚氨酯进行改性,制得改性聚氨酯预聚体作为涂覆材料涂布在基布表面得到绷带,可显著增强绷带的力学性能,断裂强度明显提升;且有效提升绷带的透气性能,增长防护时间,改善产品质量,延长贮存期,提高使用寿命。
优选地,淀粉衍生物在制备医用绷带中的用途。
上述的淀粉衍生物的制备方法,包括,N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸与淀粉发生酯化反应制得淀粉衍生物。
更进一步地,淀粉衍生物的制备方法,具体为:
向淀粉中加入乙醇(固液比为0.3~0.5g:1mL),搅拌后加入DMSO(淀粉与DMSO的固液比为10~12g:1L),加热至100℃搅拌30min,超声;接着加入N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸,加入适量DCC,120~125℃下反应4~6h,经柱层析分离纯化后得到淀粉衍生物。
优选地,淀粉与N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸的质量比为1:3~5。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括,上述淀粉衍生物。
优选地,上述预聚体的原料组份包括,按重量计,50~66份多异氰酸酯、40~60份聚醚多元醇、35~50份淀粉衍生物、4~8份纳米碳酸钙、1~5份硅油、1~4份丙酮、1~2份DMDEE、0.2~2份甲苯磺酸。丁氧羰基-D-二氨基二酸羟基的加入,与其它组分复配,可有效提升绷带的固化时间,固定效果好,减轻护理工作量;延长绷带防护时间,更有利于患者康复。
优选地,预聚体的原料组份还包括25~32重量份松脂醇二葡萄糖苷。松脂醇二葡萄糖苷的加入有效提升绷带的力学性能和耐水性,改善绷带质量,进一步延长绷带的贮存期。可能原因在于松脂醇二葡萄糖苷对生成改性聚氨酯预聚体反应的反应速度具有一定的调节作用,使物料有充分时间混合,使弹性体结构致密,力学性能提高;同时可起到扩链交联作用。除此之外,松脂醇二葡萄糖苷与丁氧羰基-D-二氨基二酸羟基协同作用,进一步增强了绷带X光的透光度。
上述改性聚氨酯预聚体的制备方法,包括:
将淀粉衍生物、松脂醇二葡萄糖苷与聚醚多元醇在恒温70~80℃下混合搅拌1~2h,升温至105~120℃,高真空度下脱水1~2h,直至含水量低于0.05%,然后冷却至45~55℃,解除真空,加入到盛有DMDEE、硅油、甲苯磺酸、丙酮、纳米碳酸钙和多异氰酸酯的烧瓶中,反应30~40min后,缓慢加热到70~85℃,保温反应1.5~2.5h,取样用溴酚兰溶液做指示剂,用1M的盐酸溶液滴定来分析NCO-的含量,当NCO基团含量为14~18%时,脱泡即得改性聚氨酯预聚体。
一种医用矫形绷带,包括:
绷带基材,上述基材为涤纶网眼织带或专用PU无纺布;
涂覆材料,包括权利上述改性聚氨酯预聚体。本发明制得的医用矫形绷带,力学性能优异,无毒副作用,透气性好、透光性高、易于塑性;且对人体无不良刺激,可以有效杀灭皮肤表面的细菌,防止皮肤红肿瘙痒,防止伤口感染,为患者提供干燥舒适的康复环境,使用方便,可广泛用于临床治疗中。本发明所述制备方法绿色环保、全程无污染、原料利用率将近100%,制备过程简单,对设备要求低,节约生产成本,适用于工业化大规模生产。
上述医用矫形绷带的制备方法,包括:
将涂覆材料加热至50℃后,在氮气环境中采用双滚筒涂覆法,将改性聚氨酯预聚体均匀涂覆在基材上,经送布、辊压后,再经成卷、剪切、氮封、封口工序,制得成品。
优选地,涂覆材料在基材表面的涂覆量为560~700g/m2
优选地,绷带基材的单位重量为40~90g/m2,伸长率为30~60%,厚度0.3~0.6mm,网眼孔径为0.2~0.8mm。
相比于现有技术,本发明具有如下有益效果:
采用N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉得到淀粉衍生物,接着制得改性聚氨酯预聚体,作为涂覆材料涂布在基布表面得到绷带,可显著增强绷带的力学性能,断裂强度明显提升;且有效提升绷带的透气性能,增长防护时间,改善产品质量,延长贮存期,提高使用寿命。涂覆材料中加入丁氧羰基-D-二氨基二酸羟基,与其它组分复配,可有效提升绷带的固化时间,延长绷带防护时间,更有利于患者康复。而松脂醇二葡萄糖苷的存在有效提升绷带耐水性,改善绷带质量,进一步延长绷带的贮存期,提高其力学性能;且与丁氧羰基-D-二氨基二酸羟基协同作用,进一步增强了绷带X光的透光度。本发明制得的医用矫形绷带,力学性能优异,无毒副作用,透气性好、质量轻、易于塑性;且对人体无不良刺激,可以有效杀灭皮肤表面的细菌,防止皮肤红肿瘙痒,防止伤口感染,为患者提供干燥舒适的康复环境,使用方便,可广泛用于临床治疗中。
因此,本发明提供了一种医用矫形绷带及其制备方法,该医用矫形绷带力学性能优异,无毒副作用,固化时间短,透气性好、透光性高、易于塑性;且对人体无不良刺激,可防止皮肤红肿瘙痒,防止伤口感染,为患者提供干燥舒适的康复环境。
附图说明
图1为本发明试验例1中淀粉的SEM测试结果;
图2为本发明试验例1中淀粉衍生物的SEM测试结果。
具体实施方式
以下结合具体实施方式和附图对本发明的技术方案作进一步详细描述:
本发明实施例所用淀粉为高直链玉米淀粉购自美国National StarchCorporation。
实施例1:
淀粉衍生物的制备:
向淀粉中加入乙醇(固液比为0.46g:1mL),搅拌后加入DMSO(淀粉与DMSO的固液比为10g:1L),加热至100℃搅拌30min,超声;接着加入N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸(淀粉与N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸的质量比为1:4.2)中,加入适量DCC,125℃下反应5h,经柱层析分离纯化后得到淀粉衍生物。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括:按重量份计,60份多异氰酸酯、50份聚醚多元醇、40份淀粉衍生物、6份纳米碳酸钙、4份硅油、4份丙酮、2份DMDEE、1份甲苯磺酸。
改性聚氨酯预聚体的制备:
将淀粉衍生物、松脂醇二葡萄糖苷与聚醚多元醇在恒温80℃下混合,搅拌1.5h,然后加入到装有搅拌器、温度计、真空系统的三口反应烧瓶中,升温至115℃,高真空度下脱水1h,直至含水量低于0.05%,然后冷却至50℃,解除真空,加入到盛有DMDEE、硅油、丙酮、纳米碳酸钙、甲苯磺酸和多异氰酸酯的烧瓶中,反应30min后,缓慢加热到80℃,保温反应2h,取样用溴酚兰溶液做指示剂,用1M的盐酸溶液滴定来分析NCO-的含量,当NCO基团含量为16%时,脱泡即得改性聚氨酯预聚体;
高分子绷带的制备:
将改性聚氨酯预聚体加热至50℃后,在氮气环境中采用双滚筒涂覆法,将改性聚氨酯预聚体均匀涂覆在基布上,经送布、辊压后,再经成卷、剪切、氮封、封口工序,制得成品。其中,改性聚氨酯预聚体在基材表面的涂覆量为680g/m2
实验所用绷带基材是经水针法利用高压喷嘴将超细合成纤维结交织成网眼状PU无纺布,其单位重量为65g/m2,伸长率为53%,厚度0.45mm,网眼孔径为0.68mm。
实施例2:
淀粉衍生物的制备与实施例1相同。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括:按重量份计,55份多异氰酸酯、45份聚醚多元醇、45份淀粉衍生物、5份纳米碳酸钙、5份硅油、3份丙酮、1份DMDEE、1.4份甲苯磺酸。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
实施例3:
淀粉衍生物的制备与实施例1相同。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括:按重量份计,63份多异氰酸酯、54份聚醚多元醇、38份淀粉衍生物、7份纳米碳酸钙、3份硅油、2份丙酮、1.3份DMDEE、2份甲苯磺酸。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
实施例4:
淀粉衍生物的制备与实施例1相同。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括:按重量份计,60份多异氰酸酯、50份聚醚多元醇、40份淀粉衍生物、16份丁氧羰基-D-二氨基二酸羟基、6份纳米碳酸钙、4份硅油、4份丙酮、2份DMDEE、1份甲苯磺酸。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
实施例5:
淀粉衍生物的制备与实施例1相同。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括:按重量份计,60份多异氰酸酯、50份聚醚多元醇、40份淀粉衍生物、30份松脂醇二葡萄糖苷、6份纳米碳酸钙、4份硅油、4份丙酮、2份DMDEE、1份甲苯磺酸。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
实施例6:
淀粉衍生物的制备与实施例1相同。
一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括:按重量份计,60份多异氰酸酯、50份聚醚多元醇、40份淀粉衍生物、30份松脂醇二葡萄糖苷、16份丁氧羰基-D-二氨基二酸羟基、6份纳米碳酸钙、4份硅油、4份丙酮、2份DMDEE、1份甲苯磺酸。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
对比例1:
一种医用矫形绷带涂覆用改性聚氨酯预聚体与实施例1的不同之处在于:采用淀粉代替淀粉衍生物。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
对比例2:
一种医用矫形绷带涂覆用改性聚氨酯预聚体与实施例1的不同之处在于:采用聚醚二元醇代替淀粉衍生物。
改性聚氨酯预聚体及绷带的制备与实施例1相同。
试验例1:
1、扫描电镜测试(SEM)
用导电双面胶将样品粉末固定在金属样品平台上,在真空中喷金后,置于SEM中,拍摄有代表性的样品颗粒的形貌照片。测试条件:测试电压为10kV,工作距离为9.5mm。。
对淀粉和实施例1制得的淀粉衍生物进行上述测试,结果如图1和图2所示。从图中可以看出,淀粉呈现颗粒状,且表面较为光滑;而制得的淀粉衍生物,外观形貌发生了较大的变化,光滑的颗粒表面变得粗糙,产生较多凸起,因为颗粒表面部分加入基团,表明淀粉衍生物成功制备。
试验例2:
聚氨酯预聚体凝胶时间测定:用50mL的玻璃试管,装入约25mL聚氨酯预聚体,于70℃干燥气氛下放置。待玻璃棒不能插入预聚体时所经时间为凝胶时间。凝胶时间可以测定绷带的室温贮存期,凝胶时间为10d,相当于室温下绷带可保存9个月;凝胶时间为15d,则贮存期约为12个月。
绷带固化时间测定:取一段绷带,浸于40℃水中10s,取出后缠于大试管上。用手指在其上压痕,从浸水直至压不出凹痕的时间为固化时间。
对对比例1~2、实施例1~6制得的预聚体及绷带进行上述测试,结果如表1所示:
表1凝胶及固化时间测试结果
测试样 凝胶时间(d) 绷带固化时间(s)
对比例1 20.3 203
对比例2 17.6 256
实施例1 26.7 196
实施例2 25.1 198
实施例3 25.9 195
实施例4 26.3 136
实施例5 29.8 195
实施例6 29.2 132
从表1中可以看出,实施例1制得的预聚体的凝胶时间明显长于对比例1~2,表明采用N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉后制得改性聚氨酯预聚体,涂覆在基材表面得到绷带,可显著延长绷带的贮存期,提高贮存稳定性,延长其使用寿命;实施例5的效果好于实施例1,表明松脂醇二葡萄糖苷的存在具有协同增强的作用。而实施例1制得绷带的固化时间与对比例1相当,实施例4制得绷带的固化时间明显长于实施例1,实施例6的效果好于实施例5,表明丁氧羰基-D-二氨基二酸羟基的存在可有效减少绷带使用时的固化时间。
耐水性测试
对样品绷带均匀倒水后,测试其在倒水5min后的断裂强度的下降率,水与医用绷带的重量比为5g/kg。
对对比例1~2、实施例1~6制得的绷带进行上述测试,结果如表2所示:
表2断裂强度下降率
测试样 下降率(%)
对比例1 7.4
对比例2 10.3
实施例1 5.1
实施例2 6.3
实施例3 5.8
实施例4 6.4
实施例5 0.32
实施例6 0.76
从表2中可以看出,实施例1制得绷带的断裂强度的下降率稍低于对比例1~2,表明采用N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉对绷带耐水性影响不太明显;实施例5的效果显著高于实施例1,实施例6的效果好于实施例4,表明松脂醇二葡萄糖苷的存在可有效提升绷带的耐水性。
试验例3:
以市售某公司生产的医用绷带作为对照组对本发明制得的改性聚氨酯预聚体医用绷带和对照组中的医用绷带进行检测。
将本发明对比例1~2、实施例1~6所制得的绷带和对照组医用绷带进行杀菌、止痒功能效果验证,连续4天,在4所医院筛选270例绷带使用者。随机分为9组,每组30例,两组患者性别、年龄、绷带使用前状况等一般资料无显著性差异,具有可比性。观察使用后皮肤红肿、瘙痒情况。参照《医用包扎敷料救护绷带》(YY/T1467-2016)标准进行测试。
测试结果如表3所示:
表3性能测试结果
从表3中分析可知,本发明实施例1制得绷带的断裂强度和水蒸气透过率明显好于对照组和对比例1~2,表明采用N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉后制得绷带,可显著提升绷带的力学性能,改善绷带透气性;实施例5的效果好于实施例1,实施例6与效果与实施例5相当,实施例4效果与实施例1相当,表明松脂醇二葡萄糖苷的存在对绷带力学性能及透气性能的提升具有协同增强的作用。除此之外,实施例1制得绷带的防护时间明显长于对照组和对比例1~2,表明采用N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉后制得绷带,可有效增加绷带的使用时间,改善绷带产品质量;实施例4的效果明显好于实施例1,实施例6的效果明显好于实施例5,实施例5的效果与实施例1相当,表明丁氧羰基-D-二氨基二酸羟基的存在对绷带防护时间的延长具有增强的效果。从红肿例和感染例数据可以看出,本发明制得的改性聚氨酯预聚体医用绷带,无毒副作用,且对人体无不良刺激,可以有效杀灭皮肤表面的细菌,防止皮肤红肿瘙痒,防止伤口感染,为患者提供干燥舒适的康复环境,使用方便,可广泛用于临床治疗中。
试验例4:
绷带X光片的透光度测定
测试方法参照“王宁等:差示分光光度法测定淀粉聚氨酯绷带X光的透光度(广东药学院学报,1995,011(003):156-158)”。以X光照片最透明处,即包绷带处骨密质集中处为零点,测定包绷带处软组织相对于未包绷带处的透光度的定量结果。
绷带包绕内软组织相对于正常软组织透光度计算:
人射光强为IO,正常骨透射光强为ING,绷带内骨透射光强为IBG,绷带内软组织透射光强为IBR
相对于绷带内骨的软组织吸光度差为:
△ABR=lg(IO/IBR)-lg(IO/IBG)=lg(IBG/IBR)
相对于绷带内骨的正常软组织吸光度差为:
△ANR=lg(IO/INR)-lg(IO/IBG)=lg(IBG/INR)
相对于X光片正常软组织的绷带内软组织透光度为(后者透明度高):
TNB=TNR/TBR=(INR/IBG)/(IBR/IBG)=lg-1(△ANR)/lg-1(△ABR)
相对于荧光屏上正常软组织的绷带内软组织透光度为TBN=1/TNB
对对比例1~2、实施例1、实施例4~6制得的绷带进行上述测试,结果如表4所示:
表4 X光透光度的测试结果
测试样 TBN
石膏绷带 0.437
对比例1 0.821
对比例2 0.632
实施例1 0.854
实施例4 0.843
实施例5 0.864
实施例6 0.988
从表4中分析可知,实施例1制得绷带的透光度远高于石膏绷带,而与对比例1的效果相当,但好于对比例2,表明淀粉衍生物的存在使得绷带的透光度明显提升。实施例5的效果好于实施例1、实施例6的效果好于实施例4和实施例5,表明松脂醇二葡萄糖苷和丁氧羰基-D-二氨基二酸羟基复配使用,协同作用,显著增强了绷带的透光度。
上述实施例中的常规技术为本领域技术人员所知晓的现有技术,故在此不再详细赘述。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。

Claims (8)

1.一种淀粉衍生物,其为N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸改性淀粉;
所述的淀粉衍生物的制备方法,包括,N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸与淀粉发生酯化反应制得淀粉衍生物;
所述淀粉与N-叔丁氧羰基-氨基-(4-羟基环己基)羧酸的质量比为1:3~5。
2.根据权利要求1所述的淀粉衍生物,其特征在于:所述淀粉衍生物在制备医用绷带中的用途。
3.一种医用矫形绷带涂覆用改性聚氨酯预聚体,包括,权利要求1所述的淀粉衍生物。
4.根据权利要求3所述的一种医用矫形绷带涂覆用改性聚氨酯预聚体,其特征在于:所述预聚体的原料组份包括,按重量计,50~66份多异氰酸酯、40~60份聚醚多元醇、35~50份淀粉衍生物、10~20份丁氧羰基-D-二氨基二酸羟基、4~8份纳米碳酸钙、1~5份硅油、1~4份丙酮、1~2份DMDEE、0.2~2份甲苯磺酸。
5.权利要求3所述的改性聚氨酯预聚体的制备方法,包括:
将淀粉衍生物、松脂醇二葡萄糖苷与聚醚多元醇在恒温70~80℃下混合搅拌1~2h,升温至105~120℃,高真空度下脱水1~2h,然后冷却至45~55℃,加入DMDEE、硅油、甲苯磺酸、丙酮、纳米碳酸钙和多异氰酸酯的混合体系中,搅拌均匀反应30~40min后,缓慢加热到70~85℃,保温反应1.5~2.5h,脱泡即得改性聚氨酯预聚体。
6.一种医用矫形绷带,包括:
绷带基材,所述基材为涤纶网眼织带或专用PU无纺布;
涂覆材料,包括权利要求3所述的改性聚氨酯预聚体。
7.权利要求6所述的医用矫形绷带的制备方法,包括:
将涂覆材料加热至50℃后,在氮气环境中采用双滚筒涂覆法,将改性聚氨酯预聚体均匀涂覆在基材上,经送布、辊压后,再经成卷、剪切、氮封、封口工序,制得成品。
8.根据权利要求7所述的医用矫形绷带的制备方法,其特征在于:所述涂覆材料在基材表面的涂覆量为560~700g/m2
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Publication number Priority date Publication date Assignee Title
CN103405802A (zh) * 2012-07-12 2013-11-27 绍兴立德生物科技有限公司 杀菌止痒聚氨酯绷带的制备方法及该方法制得的绷带
CN104264485A (zh) * 2014-09-18 2015-01-07 张伟 一种涂覆有聚氨酯树脂预聚体的医用绷带的制备方法
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CN109880052A (zh) * 2019-03-20 2019-06-14 亳州科蔚科技服务有限公司 一种医用绷带涂覆用聚氨酯树脂复合料的制备方法

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CN103405802A (zh) * 2012-07-12 2013-11-27 绍兴立德生物科技有限公司 杀菌止痒聚氨酯绷带的制备方法及该方法制得的绷带
CN104264485A (zh) * 2014-09-18 2015-01-07 张伟 一种涂覆有聚氨酯树脂预聚体的医用绷带的制备方法
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