CN1937967A - 无粉末橡胶手套的在线制备 - Google Patents
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Abstract
一种具有无粉末凝结剂的第一表面和有聚合物涂料的第二表面以使穿用容易的无粉末医用手套。第一表面上的无粉末凝结剂包括微粉化高密度聚乙烯,氨基硅氧烷的微乳液,二甲聚硅氧烷乳液,钙盐,乙氧基化炔二醇表面活性剂和纤维素增稠剂。医用手套以制备胶乳制品的在线方法制备,该方法包括将手形模型浸入凝结剂,然后将模型浸入胶乳之中。此后在从模型脱除之前将手套采用聚合物涂覆以改进穿用性。新颖的凝结剂配制剂允许制品从模型的容易脱除,使手套的双-穿用容易和消除离线加工的需求。
Description
发明领域
本发明涉及医用手套和通过浸渍制备无粉末合成和天然橡胶胶乳手套的在线方法和涉及用于制造这些手套的方法和材料。本发明特别涉及在制造期间采用无粉末凝结剂的合成和天然胶乳医用手套和其它胶乳制品。
发明背景
从弹性体材料如天然橡胶胶乳和合成胶乳制造的手套遇到各种问题。医用手套的重要标准在于它们拉紧地与穿用者的手一致。天然橡胶,具有它的固有高摩擦系数,使手套穿用困难。为解决此问题,常规医用手套在内表面上使用润滑剂以使手套穿用容易。此润滑剂也用于使手套从用于制造的手形模型的脱除容易。通常,润滑剂为粉末形式和通常具有吸收剂本质;例如,通常使用淀粉粉末。然而,关于在用于手术过程的手套中使用疏松起尘粉末在医疗公众中存在疑问。结果是,进行了许多尝试以通过开发各种无粉末方法来改进穿用性能,从而降低或消除疏松粉末的使用以利于医用手套的穿用。
合成胶乳和天然橡胶手套通常由如下步骤的方法制造:首先将手形模型,或芯模浸入粉状凝结剂浴,将模型浸入胶乳或天然橡胶浴,和采用泡洗和干燥工艺进行表面修饰。经常,由此方法制备的手套得到在干燥之后倾向于粘附到模型的手套。在从模型剥离手套时,由此方法制造的手套通常撕裂和粘附在一起。
在商业制备的手套中,凝结剂浴包括矿物质来源的粉末以在模型表面上提供防粘连性能。防粘连粉末防止手套的两个层彼此粘附。粉末通常是碳酸钙或滑石,这是由于这些粉末可承受用于胶乳手套制造的高温度(100-130℃)。在外表面上,通过将具有硫化胶乳手套的模型浸入淀粉浆料浴施加淀粉或其它粉末层。或者,硫化胶乳手套可以由合成聚合物涂料涂覆以赋予防粘连性能。
也有关于制备无粉末医用手套的离线氯化,洗涤和硅化工艺的公开。这些方法脱除滑石和玉米淀粉粉末残余物,降低粘性和改进手套穿用性。然而,这些方法通常是劳动密集的和使用大量水,使它们非常昂贵。另外,氯化可导致手套的物理性能低劣,变色和老化特性差。在一些状况下,氯化可带来贮存和环境危害。
使用氯化工艺,聚合物涂料方法,或两者组合的无粉末医用手套制备公开于U.S.专利Nos.6,195,805;5,674,818;5,612,083;5,570,475;5,284,607;5,088,125;4,597,108和4,143,109。然而,描述没有后加工,或离线步骤如氯化,洗涤和/或硅化的无粉末手套的制备的公开内容较少。这些较少的公开内容是U.S.专利Nos.6,075,081;5,534,350和4,310,928。
Nile的U.S.专利No.6,075,081公开了用于胶乳浸渍工艺包括聚氯丁二烯橡胶和无机金属盐的盐稳定分散体的无粉末凝结剂。此公开内容的凝结剂也可包含无粉末脱模剂,该脱模剂包括聚丙烯蜡乳液和阳离子表面活性剂以协助浸渍制品从模型的脱除。
Liou的U.S.专利No.5,534,350公开了在凝结剂中使用聚氨酯聚合物制备无粉末医用手套的在线方法,该凝结剂用作防水润滑层以使手套从陶瓷模型的剥离容易。聚氨酯聚合物在手套内侧上的涂层改进穿用。
Joung的U.S.专利No.4,310,928公开了采用分散体形式的包含脂肪化合物和表面活性剂的凝结剂涂覆手套模型。在手套从模型剥离之后这些材料与手套在一起,因此提供手套的脱模表面。
另外,Hassan等人的U.S.专利No.6,378,137公开了无粉末医用手套的制备,该制备使用与微粉化高密度聚乙烯材料和蜡混合的聚合物或共聚物的防粘连组合物。此组合物使手套更容易穿用。然而,手套在最终产品中仅基本没有粉末和要求在离线加工中采用硅氧烷乳液/蜡混合物的处理。Hassan等人的U.S.专利No.6,019,922公开了制备无粉末医用手套的另外方法,该方法包括在手套外表面上的硅氧烷处理和在手套内表面上的防粘连组合物处理。此参考文献的防粘连组合物包含聚合物或共聚物,微粉化高密度聚乙烯材料和蜡。然而为制造此参考文献的手套,制造商必须清洗完成的手套以脱除存留的凝结剂粉末。此清洗工艺不完美和得到仅基本没有粉末,而不是完全没有粉末的手套。此公开内容的手套工艺也要求离线加工,包括由硅氧烷溶液的手套处理以生产成品。
因此需要具有穿用性能良好的无粉末、非粘性手套,它可以在制造之后容易地从手套模型剥离。也需要此无粉末手套仅要求最小数目的加工步骤,最优选不要求离线加工。因此需要提供生产无粉末合成胶乳或天然橡胶浸渍手套的新颖方式,该方式解决离线加工的上述问题。本发明的实施方案提供一种新颖凝结剂组合物,由于不使用碳酸钙该组合物消除离线加工和结果是,消除离线氯化,洗涤和硅化。获得的方法降低生产成本和得到完全无粉末手套。
发明概述
根据本发明的一个实施方案,将无粉末凝结剂组合物与合成聚氯丁二烯胶乳一起用于在线方法以制备无粉末和不要求任何离线加工的手套。特别地,用于制备这些手套的方法在一个实施方案中包括:在将手形模型浸入天然橡胶或合成胶乳组合物之前,将该模型浸入新颖凝结剂组合物,该组合物包括微粉化高密度聚乙烯,氨基硅氧烷的微乳液,二甲聚硅氧烷乳液,钙盐,表面活性剂和纤维素增稠剂。
在一个实施方案中,制备本发明的制品的方法包括如下步骤:将预热的、成某种形状的模型浸入含水无粉末溶液,该溶液包括由微粉化高密度聚乙烯、氨基硅氧烷的微乳液、二甲聚硅氧烷乳液、炔二醇表面活性剂和无机金属盐的含水、盐稳定溶液;将模型浸入聚氯丁二烯胶乳的分散体以形成胶凝化胶乳膜和形成制品的无粘性表面;泡洗胶凝化胶乳膜;将胶凝化胶乳膜采用低盐溶液打底;将胶凝化胶乳膜浸入聚合物涂料;干燥聚合物涂料;在模型上硫化形成的橡胶制品;和从模型剥离硫化的无粘性制品。
在手套内部上的聚合物涂料可以是丙烯酸类-或聚氨酯类和要在硫化之前涂布。此涂料可以由如下方式进一步增强:在将手套从模型脱除之前将硫化的手套浸入硅氧烷浸渍浴。此聚合物涂料与任选的硅氧烷浸渍用于促进手套的穿用。
根据本发明的原理,提供生产无粉末橡胶或胶乳制品,特别地由常规浸渍方法生产的制品,如医用和手术手套,避孕套和导流管的方法。
附图简述
图1说明根据本发明的实施方案的无粉末手套在线制备的浸渍方法的流程图。
发明详述
本发明的实施方案根据引入新颖凝结剂配制剂的二甲聚硅氧烷乳液的组成数量,提供变化合成胶乳或天然橡胶制品,特别地医用手套的紧箍性能的能力。在一个实施方案中,新颖的凝结剂配制剂在制造工艺结束时在手套的外表面上,产生滑性表面,该滑性表面改进一个在另一个上部的手套双穿用的能力,即,穿用两对手套的能力。
通过将加热的手形模型(平滑,有图案或有纹理)浸入新颖凝结剂组合物形成根据本发明实施方案生产的制品,特别地医用手套。新颖凝结剂组合物包括微粉化高密度聚乙烯,氨基硅氧烷的微乳液,二甲聚硅氧烷乳液,钙盐,乙氧基化炔二醇表面活性剂和纤维素增稠剂。然后将凝结剂涂覆的模型从凝结剂罐取出和浸入合成或天然弹性体胶乳分散体以形成胶凝化胶乳膜。优选,胶乳是聚氯丁二烯胶乳。然后将胶凝化胶乳膜泡洗和浸入聚合物涂料。
根据本发明的一个实施方案,然后在将硫化的无粘性制品从模型剥离之前,将胶凝化胶乳手套在模型上硫化。在本发明的另一个实施方案中,在从模型脱除手套之前将胶凝化胶乳手套在模型上硫化和然后浸入硅氧烷浸渍浴。在本发明的此实施方案中描述的聚合物涂料与硅氧烷浸渍进一步使手套的穿用容易。
优选,二甲聚硅氧烷类硅氧烷乳液从25℃下的粘度为约10,000-约100,000厘沲和平均分子量为约62,700-约116,500的聚二甲基硅氧烷流体制备。
从以上粘度范围内的二甲聚硅氧烷流体制备的乳液,当引入到新颖凝结剂配制剂时,在宽温度范围内提供相对小的粘度波动。乳液提供良好的热/氧化稳定性,化学惰性和在机械剪切下的耐破乳的性能。它们也呈现对与新颖凝结剂接触的手套的曝露弹性体表面的良好防摩擦性能,使制造期间手套从模型的脱除容易。
从二甲聚硅氧烷流体制备的几种乳液和流体是市售的。例如,从粘度为约10,000厘沲的二甲聚硅氧烷流体制备的乳液由GESilicones,USA,以商品名SM 2140销售。从相同基础材料制备的流体由GE Silicones,USA,以商品名VISCASIL 10M销售。从粘度为约100,000厘沲的二甲聚硅氧烷流体制备的乳液由GE ToshibaSilicones Co.Ltd,日本,以商品名XS65-135891销售。从相同基础材料制备的流体由GE Toshiba Silicones Co.Ltd,日本,以商品名TSF451-10M销售。约10,000-约100,000厘沲的二甲聚硅氧烷流体分类为高粘度流体和以商品名200 FLUID由Dow Corning Corporation销售。乳液也可以从二甲聚硅氧烷和环二甲基硅氧烷的混合物制备;这样乳液的例子由Dow Corning Corporation以商品名DOWCORNING Q2-1803销售。
设计使用氨基硅氧烷的微乳液以在手套表面上产生丝状纹理和增强手套的柔软性。氨基硅氧烷的微乳液以商品名SOFTEX 5850,由Kao Industrial(泰国)Company Ltd销售。
微粉化高密度聚乙烯的使用可用作固定物以增强凝结剂膜覆盖以及促进手套从手形模型的剥离。微粉化高密度聚乙烯也提供防摩擦和防粘连性能到手套外表面(手套的内部在浸渍工艺期间与凝结剂接触)。高密度聚乙烯的有效熔点典型地为约100-约130℃。微粉化高密度聚乙烯的平均粒度典型地为约3-约12微米。
非离子炔二醇表面活性剂正常用作凝结剂的润湿剂和纤维素增稠剂优选增稠凝结剂。
本发明的实施方案现在进一步描述于如下实施例和由根据本发明实施方案的这样制品的生产流程图(图1)伴随。
实施例1
将陶瓷素瓷模型加热到60-70℃和然后浸入25-35℃防粘连凝结剂分散体大约5-10秒。凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 1% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 79.5% |
在实施例1的配制剂中,将微粉化HDPE作为20%分散体加入,将氨基硅氧烷的微乳液作为20-22%乳液提供,将纤维素增稠剂稀释到1%溶液和将炔二醇表面活性剂如提供时那样加入。陶瓷模型,在浸入凝结剂分散体之后,缓慢从凝结剂分散体拉出和旋转以均匀在模型表面上分布凝结剂。然后将模型移动到加热到90℃的烘箱约90秒以干燥凝结剂。在干燥之后,将陶瓷模型浸入聚氯丁二烯胶乳分散体约20-30秒。此聚氯丁二烯胶乳分散体包含40%干燥聚合物和保持在25℃。在将聚氯丁二烯胶乳在模型上沉积之后,将它转动和提升,和然后在烘箱中在75℃下加热约60秒。然后将胶凝化聚氯丁二烯胶乳在40-60℃下泡洗约180秒。然后将陶瓷模型上的聚氯丁二烯聚合物凝胶在浸入聚氨酯或丙烯酸类涂料溶液之前,浸入盐溶液的1-2%打底料。然后将陶瓷模型在110-140℃下逐渐干燥35分钟。然后在将手套从模型剥离之前冷却模型。通过在酸中和然后在水中清洗模型,模型可再用于进一步的生产循环。模型也容易地由用于手套浸渍的标准清洁剂清洁。
使用实施例1的无粉末凝结剂配制剂浸渍的手套没有薄斑和容易地从陶瓷模型剥离。手套握感是令人满意的和与相同类型和尺寸手套的双穿用是令人满意的。聚氯丁二烯手套具有无粉末属性及粉末水平小于2mg每个手套。
实施例2
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 1% |
二甲聚硅氧烷/环二甲基硅氧烷乳液 | 0.1% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 79.4% |
在此实施例中,将加入的二甲聚硅氧烷/环二甲基硅氧烷共混物乳液作为60%乳液提供。在此实施例中生产的手套浸渍良好及没有薄斑和容易地从陶瓷模型剥离。手套握感不如实施例1中所生产的手套那样紧箍,和使用相同类型和尺寸手套戴双手套情况良好。聚氯丁二烯手套具有无粉末属性及粉末水平小于2mg每个手套。
实施例3
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 1% |
二甲聚硅氧烷/环二甲基硅氧烷乳液(100,000厘沲) | 0.1% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 79.4% |
在此实施例中,提供的二甲聚硅氧烷/环二甲基硅氧烷共混物乳液从25℃下测量的粘度为100,000厘沲的聚二甲基硅氧烷流体制备。手套浸渍良好及没有薄斑和容易地从陶瓷模型剥离。手套握感比任何先前实施例更滑,和使用相同类型和尺寸手套戴双手套情况优异。聚氯丁二烯手套具有无粉末属性及粉末水平小于2mg每个手套。
实施例4
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 2% |
二甲聚硅氧烷乳液(10,000厘沲) | 0.2% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 78.3% |
在此实施例中,提供的二甲聚硅氧烷乳液从25℃下测量的粘度为10,000厘沲的聚二甲基硅氧烷流体制备。手套浸渍良好及没有薄斑和容易地从陶瓷模型剥离。手套握感没有实施例3中生产的手套滑和不如实施例1和2中的手套那样紧箍。使用相同尺寸和类型手套戴双手套情况优异。聚氯丁二烯手套具有无粉末属性及粉末水平小于2mg每个手套。
实施例5
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 2% |
二甲聚硅氧烷乳液(10,000厘沲) | 0% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 78.5% |
实施例6
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 2% |
二甲聚硅氧烷乳液(10,000厘沲) | 0.2% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 78.3% |
实施例7
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 1% |
氨基硅氧烷的微乳液 | 2% |
二甲聚硅氧烷乳液(10,000厘沲) | 0.4% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 78.1% |
通过在实施例5-7中使用不同水平二甲聚硅氧烷产生的握感性能在表1中列表。以由RJ Harvey Instrument Corporation,USA制备的摩擦系数测试仪测定握感性能。
表1
在凝结剂侧测量的橡胶摩擦性能 | 二甲聚硅氧烷水平 | |||||
实施例50%二甲聚硅氧烷 | 实施例60.2%二甲聚硅氧烷 | 实施例70.4%二甲聚硅氧烷 | ||||
克力(gmf) | 摩擦系数(COF) | 克力(gmf) | 摩擦系数(COF) | 克力(gmf) | 摩擦系数(COF) | |
金属在橡胶上 | 229182-318 | 1.150.91-1.59 | 187142-242 | 0.940.71-1.21 | 144115-208 | 0.720.58-1.04 |
橡胶在橡胶上 | 152157-266 | 0.760.79-1.33 | 135119-162 | 0.680.60-0.81 | 121112-145 | 0.610.56-0.73 |
如可以在表1中看出的那样,通过变化凝结剂的二甲聚硅氧烷水平,可以根据握感性能要求变化在聚氯丁二烯橡胶表面的凝结剂侧上的摩擦性能。实施例5-7中的所有聚氯丁二烯手套具有无粉末属性及粉末水平小于2mg每个手套。
实施例8
根据实施例1,采用相似的过程生产手套及区别在于防粘连凝结剂的组成和以天然橡胶胶乳替代实施例1的聚氯丁二烯胶乳分散体。此实施例的防粘连凝结剂分散体与用于实施例4的相同。
天然橡胶手套浸渍良好及没有薄斑和容易地从陶瓷模型剥离。手套握感比实施例1-7的任何手套更紧箍。使用R J Harvey Instrument测量的橡胶摩擦性能显示金属在橡胶(MR)上数值大约为250gmf,对应于COF值1.26。天然橡胶手套具有无粉末属性及粉末水平小于2mg每个手套。
实施例9
凝结剂的制备和手套生产的过程与实施例8相似及区别在于凝结剂组成。此实施例的防粘连凝结剂分散体包含:
Wt% | |
硝酸钙 | 18% |
微粉化HDPE | 2.5% |
氨基硅氧烷的微乳液 | 2.5% |
二甲聚硅氧烷乳液(10,000或100,000厘沲) | 0.4% |
纤维素增稠剂 | 0.2% |
炔二醇表面活性剂 | 0.3% |
水 | 76.1% |
从此实施例的配制剂生产的天然橡胶手套浸渍良好及没有薄斑和容易地从陶瓷模型剥离。手套握感不如使用实施例7的配制剂生产的手套那样紧箍。相同尺寸和类型手套戴双手套是令人满意的。使用R J Harvey Instrument测量的橡胶摩擦性能显示MR值为大约135gmf或COF值为0.68。来自此实施例的天然橡胶手套具有无粉末属性及粉末水平小于2mg每个手套。
尽管结合其具体的实施方案描述了本发明,显然的是,按照以上描述,替代,改进和变化对本领域技术人员是显然的。因此,指出在所附权利要求的精神和宽范围内包括所有这样的替代,改进和变化。
Claims (16)
1.一种无粉末弹性体制品,制品包括:
具有第一表面和第二表面的弹性体材料;
弹性体材料的第一表面由无粉末凝结剂涂料涂覆;
无粉末凝结剂组合物包括:
微粉化高密度聚乙烯;
氨基硅氧烷的微乳液;
二甲聚硅氧烷乳液;
乙氧基化炔二醇表面活性剂;和
纤维素增稠剂;和
弹性体材料的第二表面由聚合物涂料涂覆。
2.权利要求1的制品,其中该制品是手套。
3.权利要求2的制品,其中弹性体材料选自聚氯丁二烯、天然橡胶、合成聚异戊二烯、羧基化丙烯腈丁二烯和聚氨酯。
4.权利要求3的制品,其中弹性体材料是与标准硫化剂配混的。
5.权利要求4的制品,其中第二表面是卤代的。
6.一种用于制备无粉末弹性体制品的防粘连凝结剂组合物,凝结剂包括:
微粉化高密度聚乙烯;
氨基硅氧烷的微乳液;
二甲聚硅氧烷乳液;
钙盐;
乙氧基化炔二醇表面活性剂;和
纤维素增稠剂。
7.权利要求6的防粘连凝结剂组合物,其中微粉化高密度聚乙烯的平均熔点为约100-约130℃和平均粒度为约2-约12微米。
8.权利要求6的防粘连凝结剂组合物,其中氨基硅氧烷的微乳液包括粒度为约1-约100微米的混合颗粒。
9.权利要求6的防粘连凝结剂组合物,其中二甲聚硅氧烷从粘度为约10,000-约100,000厘沲的聚二甲基硅氧烷流体源乳化。
10.权利要求6的防粘连凝结剂组合物,进一步包括环二甲基硅氧烷。
11.权利要求10的防粘连凝结剂组合物,其中与环二甲基硅氧烷组合的二甲聚硅氧烷从粘度为约10,000-约100,000厘沲的聚二甲基硅氧烷流体源乳化。
12.权利要求6的防粘连凝结剂组合物,进一步包括如下总固体含量:
约10%-约30%钙盐;
约0.1%-约3%微粉化HDPE;
约0.1%-约3%氨基硅氧烷的微乳液;
约0%-约1%二甲聚硅氧烷乳液;
约0%-约0.5%纤维素增稠剂;和
约0.1%-约0.5%非离子炔二醇表面活性剂。
13.一种制备无粉末制品的方法,包括如下步骤:
通过将模型浸入权利要求6的防粘连凝结剂的浴形成该制品的第一层;
通过将模型浸入改性弹性体材料在第一层上形成第二层;
胶凝化第二层;
泡洗胶凝化层以脱除溶解性非橡胶或非胶乳组分;
采用具有低盐浓度的溶液将第二层打底;
通过将模型浸入聚合物涂料在第二层上形成第三层;
干燥第三层;
使形成的层经受约120-约160℃的加热;和
后泡洗硫化的形成的层。
14.权利要求13的方法,其中在约20-约40℃的温度下将模型浸入防粘连凝结剂。
15.一种由权利要求13的方法制备的无粉末弹性体制品。
16.权利要求15的制品,其中该制品是手套。
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MX (1) | MXPA06011951A (zh) |
PE (1) | PE20051080A1 (zh) |
TW (1) | TW200534826A (zh) |
WO (1) | WO2005110749A1 (zh) |
Cited By (4)
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CN102762164A (zh) * | 2009-12-21 | 2012-10-31 | 安塞尔有限公司 | 具有稳定及快速作用的抗菌涂层的无粉手套 |
CN104448415A (zh) * | 2014-11-27 | 2015-03-25 | 苏州市贝克生物科技有限公司 | 透气性医用手套用复合材料及其制备方法 |
CN104619206A (zh) * | 2012-02-22 | 2015-05-13 | 保罗·安斯蒂 | 抗疲劳且在人体工程学上改进的医用/牙科/多用途手套 |
CN112867640A (zh) * | 2018-10-17 | 2021-05-28 | 陶氏环球技术有限责任公司 | 涂料组合物、经涂布织物、制造经涂布织物的方法以及由经涂布织物制成的制品 |
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US8499363B2 (en) | 2006-07-28 | 2013-08-06 | Shen Wei (Usa) Inc. | Elastomeric flexible article with absorbent polymer and manufacturing method |
CA3015590C (en) * | 2008-08-27 | 2020-12-22 | O&M Halyard International Unlimited Company | Thin, smooth nitrile rubber gloves |
US9730477B2 (en) | 2013-12-13 | 2017-08-15 | Covco Ltd. | Ambidextrous fish scale-textured glove |
US11241051B2 (en) | 2014-07-08 | 2022-02-08 | Covco (H.K.) Limited | Ambidextrous fish scale-textured glove |
BR112014014354A2 (pt) | 2013-12-13 | 2020-02-27 | Joseph Furlong John | luva com textura de escama de peixe, ambidestra |
US11819303B2 (en) | 2017-01-24 | 2023-11-21 | Smarterials Technology Gmbh | Damage-resistant gloves with breach-indicator function |
US10966475B2 (en) | 2017-04-27 | 2021-04-06 | Inteplast Group Corporation | Fixture, system, and method for coating plastic glove |
CN107955429A (zh) * | 2017-12-13 | 2018-04-24 | 安徽新胜塑料科技有限公司 | 一种耐高温硅胶板表面耐热涂层的制备方法 |
KR102368982B1 (ko) * | 2020-03-24 | 2022-03-03 | 유한회사 에스에이치켐텍 | 특수 합성 고무로 코팅된 작업용 장갑 및 이의 제조방법 |
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US5742943A (en) * | 1996-06-28 | 1998-04-28 | Johnson & Johnson Medical, Inc. | Slip-coated elastomeric flexible articles and their method of manufacture |
EP0906731B1 (en) * | 1997-10-01 | 2003-08-06 | Ansell Shah Alam Sdn. Bhd. | Powder-free medical glove and manufacture thereof |
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US6638587B1 (en) * | 2000-04-18 | 2003-10-28 | Allegiance Corporation | Elastomeric article having silicone-based composite coating |
-
2004
- 2004-04-16 CA CA 2557821 patent/CA2557821A1/en not_active Abandoned
- 2004-04-16 MX MXPA06011951A patent/MXPA06011951A/es active IP Right Grant
- 2004-04-16 EP EP20040821994 patent/EP1742786B1/en not_active Expired - Fee Related
- 2004-04-16 WO PCT/US2004/011799 patent/WO2005110749A1/en active Application Filing
- 2004-04-16 BR BRPI0418675-3A patent/BRPI0418675A/pt not_active IP Right Cessation
- 2004-04-16 CN CNB2004800427459A patent/CN100479780C/zh not_active Expired - Fee Related
- 2004-04-16 AU AU2004319695A patent/AU2004319695B2/en not_active Ceased
- 2004-04-16 JP JP2007508318A patent/JP4464441B2/ja not_active Expired - Fee Related
- 2004-04-16 US US10/599,348 patent/US7678435B2/en not_active Expired - Fee Related
-
2005
- 2005-03-22 TW TW94108761A patent/TW200534826A/zh unknown
- 2005-04-15 PE PE2005000424A patent/PE20051080A1/es not_active Application Discontinuation
- 2005-04-15 AR ARP050101509 patent/AR048868A1/es unknown
-
2006
- 2006-08-21 IL IL177600A patent/IL177600A/en not_active IP Right Cessation
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102762164A (zh) * | 2009-12-21 | 2012-10-31 | 安塞尔有限公司 | 具有稳定及快速作用的抗菌涂层的无粉手套 |
CN102762164B (zh) * | 2009-12-21 | 2015-10-21 | 安塞尔有限公司 | 具有稳定及快速作用的抗菌涂层的无粉手套 |
CN104619206A (zh) * | 2012-02-22 | 2015-05-13 | 保罗·安斯蒂 | 抗疲劳且在人体工程学上改进的医用/牙科/多用途手套 |
CN109512058A (zh) * | 2012-02-22 | 2019-03-26 | 保罗·安斯蒂 | 抗疲劳且在人体工程学上改进的医用/牙科/多用途手套 |
US11311064B2 (en) | 2012-02-22 | 2022-04-26 | Paul Anstey | Medical/dental/utility glove with anti-fatigue and ergonomic improvement |
US11844383B2 (en) | 2012-02-22 | 2023-12-19 | Paul Anstey | Medical/dental/utility glove with anti-fatigue and ergonomic improvement |
CN104448415A (zh) * | 2014-11-27 | 2015-03-25 | 苏州市贝克生物科技有限公司 | 透气性医用手套用复合材料及其制备方法 |
CN112867640A (zh) * | 2018-10-17 | 2021-05-28 | 陶氏环球技术有限责任公司 | 涂料组合物、经涂布织物、制造经涂布织物的方法以及由经涂布织物制成的制品 |
CN112867640B (zh) * | 2018-10-17 | 2024-03-29 | 陶氏环球技术有限责任公司 | 涂料组合物、经涂布织物、制造经涂布织物的方法以及由经涂布织物制成的制品 |
Also Published As
Publication number | Publication date |
---|---|
JP4464441B2 (ja) | 2010-05-19 |
CA2557821A1 (en) | 2005-11-24 |
US7678435B2 (en) | 2010-03-16 |
AR048868A1 (es) | 2006-06-07 |
IL177600A (en) | 2010-05-31 |
JP2007532794A (ja) | 2007-11-15 |
WO2005110749A9 (en) | 2006-03-30 |
TW200534826A (en) | 2005-11-01 |
AU2004319695A1 (en) | 2005-11-24 |
EP1742786A1 (en) | 2007-01-17 |
CN100479780C (zh) | 2009-04-22 |
MXPA06011951A (es) | 2007-01-26 |
EP1742786A4 (en) | 2009-05-20 |
BRPI0418675A (pt) | 2007-06-05 |
IL177600A0 (en) | 2008-03-20 |
EP1742786B1 (en) | 2011-10-05 |
WO2005110749A1 (en) | 2005-11-24 |
AU2004319695B2 (en) | 2010-01-28 |
US20090139012A1 (en) | 2009-06-04 |
PE20051080A1 (es) | 2005-12-17 |
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