CN1287497A - 带有用硅氧烷浸过的聚氨酯内涂层的无粉手套 - Google Patents
带有用硅氧烷浸过的聚氨酯内涂层的无粉手套 Download PDFInfo
- Publication number
- CN1287497A CN1287497A CN99802005A CN99802005A CN1287497A CN 1287497 A CN1287497 A CN 1287497A CN 99802005 A CN99802005 A CN 99802005A CN 99802005 A CN99802005 A CN 99802005A CN 1287497 A CN1287497 A CN 1287497A
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- Prior art keywords
- glove
- model
- goods
- layer
- powder
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Classifications
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Landscapes
- Health & Medical Sciences (AREA)
- Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Heart & Thoracic Surgery (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
本发明描述了带有用硅氧烷浸过的交联聚氨酯内涂层的无粉天然橡胶和合成弹性体手套和其制造方法。该手套具有良好的贴合性、由其湿和干摩擦系数测得的良好的穿戴性、拉伸强度、断裂伸长和在500%模量时的应力。
Description
本发明涉及含有用硅氧烷浸过的交联聚氨酯内涂层的无粉天然橡胶和合成弹性体手套及其制造方法。更具体地说，本发明涉及含有用硅氧烷浸过的交联聚氨酯内涂层的独特的医用、外科或工业用无粉手套，该手套易于戴上，它可以在脱线后处理(post-processing off-line)如氯化、酸洗或其它处理过程中无需手工翻转手套的步骤就可制得。另外，本发明的手套还具有良好的贴合性(grippability)、良好的穿戴性(donnability)、拉伸强度、断裂伸长和在500％模量时的应力。
发明的背景
商购无粉天然橡胶和合成弹性体手套一般是这样制得的，即采用常规的胶乳浸渍技术和制造技术先制造粉末手套。然后经氯化或酸处理再漂洗的步骤对手套进行脱线后处理以除去粉末。两个过程都除去在制造过程中沉积在手套上的粉末。氯化过程也会氧化手套的表面，提供穿戴特性改进的手套。
这些方法都有若干缺点。首先，它们费时和费力。例如，氯化是一个多步过程，它首先要求将手套从前一步中取下，把里面翻到外面来。然后该手套经若干氯化、中和、漂洗、翻转手套和干燥操作步骤的循环。在制造无粉手套的常规操作循环中，需要两步手工翻转手套的步骤。由于手套的内表面或穿戴面是待氯化的一面，故手套首先必须把里面翻到外面来，这样手套的内表面就暴露在外部。手套氯化后，接着必须手工再将手套翻回去，这样刚氯化的穿戴面就回复成手套的内表面。结果，氯化后处理也是昂贵的。
另一个与氯化有关的问题是氯化过程也可能会使施涂到手套表面上使手套无粉末的聚合物涂层发生降解。通常，与氯化有关的手套降解会导致手套穿戴性变差，在涂覆的一面上手套相互粘附，涂料粘合性差并且涂层剥落。因此，施涂到手套表面上随后氯化使手套无粉末的任何聚合物涂层必须具有优异的抗氯化降解性。
本发明的概述
本发明提供一种医用、外科和/或工业用途的具有良好穿戴性和良好贴合性(按穿戴和贴合表面的摩擦系数测量)的无粉、内涂覆的天然橡胶或合成弹性体手套。本发明的手套也具有良好的拉伸强度、500％模量时的应力和断裂伸长。该手套也可以在氯化后处理过程中无需昂贵的翻转手套步骤就可制得。
本发明手套上的内涂层是一种用硅氧烷浸过的交联聚氨酯。与在其内表面上用非交联聚氨酯涂覆的手套相比，本发明手套的穿戴性有了改进。与带有不含硅氧烷的交联聚氨酯内涂层的手套相比，本发明手套的穿戴性也有了改进。本发明手套的聚合物涂层也具有优异的与天然橡胶或合成弹性体橡胶的粘合性，并且也可被氯化，而不会发生由于氯化过程所引起的明显的降解。
本发明的较好实例
本发明的手套包含天然橡胶、腈、聚氯丁二烯、聚丁二烯、聚氯乙烯、聚氨酯、聚异戊二烯、苯乙烯二嵌段和三嵌段共聚物，或其它合成弹性体，还包括它们的共混物，在该手套的内表面上含有一层包含用硅氧烷浸过的交联聚氨酯的涂层。
天然橡胶可以与稳定剂、交联剂、硫化活化剂、硫化促进剂、抗氧化剂、抗臭氧剂和任选的白色颜料混合。
合适的稳定剂包括油酸盐、硬脂酸盐、藻酸盐、聚丙烯酸酯、黄原酸胶、酪蛋白酸盐或其它非离子型和离子型表面活性剂。配制配方所用的典型的交联剂包括硫或其它有机过氧化物。合适的硫化活化剂包括金属氧化物如氧化镁、氧化铅和较好的是氧化锌。硫化促进剂可以选自巯基苯并噻唑和其衍生物、二硫代氨基甲酸酯和其衍生物、硫给体、胍和醛-胺的反应产物。合适的抗氧化剂包括受阻芳胺或聚合受阻酚。配制配方所用的典型的抗臭氧剂包括石蜡、微晶蜡和中间型蜡(它是石蜡和微晶蜡的混合物)。可以使用的典型的白色颜料包括二氧化钛和氧化锌。
诸如聚丁二烯、聚异戊二烯、腈、聚氯丁二烯和它们混合物的合成二烯基的弹性体可与上述类似的混合成分(compounding ingredients)相混合。用作基体手套的其它合成热塑性弹性体材料(如聚氯乙烯、聚氨酯、苯乙烯二嵌段和三嵌段共聚物及其共混物)不需要交联就可制备具有所需物理性能的手套。因此，这些合成弹性体可与上述稳定剂、抗氧化剂、抗臭氧剂和彩色颜料混合。
本领域的技术熟练者可容易地改变浸渍配方中的混合成分，以使所用特定的弹性体适于形成基体手套和最终所需的制品。本领域的技术熟练者也将明白上述所列的特定化学物质或化合物是用于配制二烯基和热塑性弹性体所用的常规的代表性材料，它们是配方中各组分的非限制性例子。
用于涂覆成形手套内表面的聚氨酯分散体是一种可交联的阴离子型聚氨酯分散体，其粒度小于约0.5微米，较好小于约0.1微米，以合成聚氨酯所用的含羧酸材料的用量计，算得羧酸官能度的酸值大于约15(假定单体中所有的羧酸官能度都进入最终聚合物)。聚氨酯分散体较好是一种[A]和[B]的分散体混合物，所述[A]是一种Sward硬度约为74或更大(其中Sward硬度是使用ASTM D2134测得的)并且酸值约为24或更小的可交联的阴离子型聚酯基聚氨酯，所述[B]是一种Sward硬度约为38或更小并且酸值约为24或更大的可半交联的阴离子型聚酯基聚氨酯。本发明的可半交联的聚氨酯是一种具有在加热、辐射或化学手段下使用或不使用外交联剂的情况下易于交联的官能度的聚氨酯。聚氨酯分散体更好是一种约50份[A]和约50份[B]的分散体混合物，所述[A]是一种Sward硬度约为74或更大并且酸值约为24或更小的可交联的阴离子型聚酯基聚氨酯，所述[B]是一种Sward硬度约为38或更小并且酸值约为24或更大的可半交联的阴离子型聚酯基聚氨酯。
上述聚氨酯分散体和混合物通常是商用级别，它是加入表面活性剂和稳定剂制得的。分散体也可以包含残余溶剂和未反应的单体。为了用作本发明手套内部的部分涂层，聚氨酯分散体还可以与稳定剂、润湿剂、交联剂、乳化硅油(siliconeemulsion)和任选的白色颜料混合。
稳定剂可以是油酸盐、硬脂酸盐、藻酸盐、酪蛋白酸盐、黄原酸胶、聚丙烯酸酯或其它离子型和非离子型表面活性剂。稳定剂较好是非离子型表面活性剂。表面活性剂更好是支化的壬基苯氧基聚(乙烯氧基)乙醇。将稳定剂加到涂料分散体中，以改进其稳定性并防止由于沾污从胶乳手套沥滤到涂料分散体中的离子物质而使分散体凝结。若从制造商处得到的聚氨酯分散体包含加入足够量的稳定剂，从而在制造手套的过程中不会发生分散体的自凝结现象，则这些附加的稳定剂是可以忽略不计的。
润湿剂可以是非离子型或离子型表面活性剂。润湿剂较好是非离子型或离子型的硅氧烷基表面活性剂。润湿剂更好是非离子型的聚醚改性的硅氧烷表面活性剂。
乳化硅油是硅氧烷基的乳化硅油。硅氧烷较好是聚(烷基取代的硅氧烷)乳状液。乳化硅油最好是聚(二甲基硅氧烷)乳状液。
交联剂可以是通常用作阴离子型聚氨酯交联剂的锆、氮丙啶和蜜胺-甲醛基化合物。交联剂较好是锆基交联剂。交联剂更好是碳酸氧锆铵。分散体任选地可以包含金属氧化物如既可用作交联剂也可用作白色颜料的氧化锌和氧化镁。
用于制备聚氨酯基无粉分散体的混合成分和它们的相对比例列于下表1中。[A]和[B]的总量约为100份。
表1
| 分散体组分 | 以重量计的干或活性份数 |
| 聚氨酯分散体[A] | 约0-100 |
| 聚氨酯分散体[B] | 约100-0 |
| 润湿剂 | 约0.05-5 |
| 乳化硅油 | 约0.5-20 |
| 交联剂 | 约0.5-10 |
| 稳定性(任选的) | 约0.05-5 |
| 金属氧化物(任选的) | 约0.5-10 |
本领域的技术熟练者可容易地改变浸渍配方中的混合成分，以适合所需的最终合成或天然橡胶制品。本领域的技术熟练者也将明白上述所列的特定化学物质或化合物是制备配方所用的常规的代表性材料，它们仅是配方中各组分的非限制性例子。
聚氨酯基的无粉分散体可用于涂覆各种天然橡胶和合成弹性体制品的内部，所述制品包括外科和检查手套、工业手套、指套、管状物、保护性覆盖物、避孕套或类似的产品。
进行对比试验以评价在无粉涂料组合物中不同组分对手套穿戴性的影响(通过摩擦系数测量，摩擦系数越低，则穿戴性就越好)。按如下所述制备对比实施例中的手套。在约158°F的烘箱内预热手套模型约2分钟。然后将模型浸在保持在约122°F下的包含硝酸钙、碳酸钙、润湿剂和水的水基促凝剂中。带有促凝剂层的模型接着在158°F的烘箱内干燥约3分钟。将涂有促凝剂的模型浸到经混合的天然橡胶胶乳中，使其置于其中约2-10秒钟。然后将带有凝结胶乳膜的模型从胶乳内取出，在保持在约122°F的温水浴中沥滤约5分钟。而后将带有胶乳膜的模型浸到包含下表2所列各组分的无粉涂料分散体中。
接着将模型放在248°F的烘箱内约20分钟，以固化涂覆的胶乳膜。而后从模型上剥下手套，测试其粘合性和摩擦系数。
在这些实施例中的无粉涂料分散体包含如表2所列的聚氨酯混合物、润湿剂、乳化硅油和交联剂。在所有实施例中所用的聚氨酯混合物包含50干份Sward硬度约为74并且酸值约为21.6的阴离子型聚酯基聚氨酯[A]和50干份Sward硬度约为38并且酸值约为26.7的阴离子型聚酯基聚氨酯[B]。乳化硅油是11.1干份SM2140，一种购自General Electric的聚二甲基硅氧烷分散体。交联剂是3.3干份Bacote20，一种购自Magnesium Elektron Inc.，Flemington，New Jersey的碳酸氧锆铵，润湿剂是0.56份BYK348，一种购自BYK-Chemie的聚醚改性的硅氧烷。加入水将固体总量(TSC)调节到约2.5-3.0％。
除了湿COF测定外，按ASTM D 1894-95中所述的步骤测量摩擦系数(COF)。从各手套的手掌区域切下测试样品，使用粘合带将其粘贴到滑板上，使带不与固定物的摩擦表面接触。为了测量湿COF，在固定物的摩擦表面上倒入10-20毫升蒸馏水，将包有样品膜的滑板放到湿固定物上。将在滑移距离内承载力的平均值除以滑板重量来计算湿动COF。无粉分散体中的不同组分对摩擦系数的相对影响列于下表2中。
表2
| 无粉分散体 | PU混合物 | PU混合物/硅氧烷 | PU混合物-硅氧烷-润湿剂剂-Bacote 20 |
| TSC(重量％) | 2.5 | 2.5 | 2.5 |
| 干COF | 1.169 | 0.515 | 0.370 |
| 湿COF | 0.830 | 0.741 | 0.638 |
表2表明，本发明所揭示的用无粉涂料，即用硅氧烷浸过的交联聚氨酯涂覆的手套表面的摩擦系数明显优于仅用未交联聚氨酯混合物或未交联聚氨酯混合物/硅氧烷涂覆的对比例手套的摩擦系数。
对比试验也证实，当Bacote20用作交联剂时，可以使本发明手套的摩擦系数达到最低。这些结果概括于下表3中，其中各记录项目代表用聚氨酯分散体涂覆手套内部制得的手套，所述聚氨酯分散体包含聚氨酯混合物、润湿剂、硅氧烷和交联剂，其固体总量(TSC)为2.5％，这样就制得了带有含用硅氧烷浸过的交联聚氨酯的内涂层的手套。Cymel325是一种购自Cytec Industries，Inc.，的甲基化的蜜胺-甲醛，QZ-43是一种购自K.J.Quinn and Co，Inc.的多官能氮丙啶。
表3
| 交联剂 | Bacote 20 | Cymel 325 | QZ-43 |
| 干COF | 0.370 | 0.572 | 0.554 |
| 湿COF | 0.638 | 0.803 | 0.882 |
同样定性地评价涂层的粘合性。在此试验中，将涂覆的手套表面拉伸达大于500％，用拇指反复摩擦涂层。然后肉眼观察涂覆表面的涂层薄片和粉状物质。按1-5的等级定性地评价涂层的粘合性，1最差，即整个涂层从橡胶基材上剥落下来，5最好，即在手套表面上没有可见的粉状物质。采用这个试验，测得了本发明涂层的粘合性是相当好的，以5为尺度其等级在4-4.5(其中约4-4.5是商购手套涂层所具有的粘合性值)。
按本发明制造的手套可按下述方法制得。首先将手套轮廓形状的模具烘箱干燥，然后浸到包含硝酸钙、粉末(碳酸钙或玉米淀粉)、润湿剂和水或醇(用于醇基促凝剂分散体)的醇或水基促凝剂分散体中。而后干燥沉积在手套模型上的促凝剂层。接着将手套模型浸到经混合的天然橡胶或合成弹性体中，这样橡胶或合成弹性体膜就凝结在手套模型上。在其仍在模型上时，任选地可用水沥滤凝结的天然橡胶或合成弹性体层，然后浸到包含如上表1所列的聚氨酯分散体、润湿剂、乳化硅油、交联剂、稳定剂和水的无粉分散体中。接着在烘箱内固化载有聚氨酯分散体涂覆的天然橡胶或合成弹性体的模型。从烘箱内取出模型，而后从模型上剥下涂覆的手套。
然后使手套经氯化、酸处理或其它化学过程的后处理，以除去碳酸钙或玉米淀粉粉末。若手套是和珠粒制成的，则可以氯化或酸处理手套，而无需手工翻转手套的步骤。若氯化除去粉末，则可按下述过程处理手套。任选地用水预漂洗手套，浸在氯化水溶液(含200ppm氯)中约8分钟。在溶液中加入碱如氢氧化铵以中和氯化溶液，直到pH值约为7或更大。而后排出中和溶液，用水漂洗手套约2.5分钟。漂洗手套3次以上(每次约2.5分钟)，以除去痕量的氯化溶液和中和的碱。或者，可以省略中和步骤，用水洗涤手套以除去痕量的氯化溶液。然后将漂洗过的手套置于抽提器内以除去过量的水。从抽提器中取出手套，放在旋风干燥器内干燥。或者，用水漂洗手套后立刻对其进行干燥。手套完全干燥后，可以包装手套。
若用酸处理的方法除去粉末，则可按下述过程处理手套。使用可任选地包含防粘剂的酸溶液漂洗翻转的手套。然后用水漂洗手套，除去痕量的水，将其放在抽提器中以除去过量的水。从抽提器中取出手套，放在旋风干燥器中干燥。或者，用水漂洗手套后立刻对其进行干燥。手套完全干燥后，可以包装手套。
若粉末涂覆的手套不是和珠粒制成，则在上述固化步骤后采取下述附加的手套成形步骤。在各层和涂层固化并从烘箱内取出模型后，任选地将涂覆的手套浸到在水中包含碳酸钙或玉米淀粉的粉末浆料中。这种粉末施加步骤是需要的，因为在橡胶或合成弹性体浸渍范围的下面有一未被聚氨酯涂覆的区域(以使用聚氨酯涂料沾污模型降至最小)。这种未涂覆的区域是粘性的，并且更易涂上粉末。另一种方案是采用辊涂法用粉末选择性地对未涂覆的层或橡胶或合成弹性体进行施粉。然后从模型上剥下手套。
为了制造无粉的涂覆手套，开始时把手套的里面翻到外面来，如上所述对其进行处理以除去粉末，这样对手套进行后处理。干燥手套后，再次把手套的里面翻到外面来，使聚氨酯涂覆的表面在里面。接着进一步干燥手套，之后包装。
本发明手套的厚度至少约为0.003英寸。手套的厚度较好约为0.004英寸至0.010英寸。手套的厚度更好约为0.005至0.008英寸。
本发明手套的拉伸强度大于约1300psi，较好大于约2000psi，最好大于约2600psi。本发明手套在500％时的应力小于约3000psi，较好小于约2000psi，最好小于约1000psi。本发明手套的断裂伸长大于约200％，较好大于约400％，最好大于约500％。
本发明手套的穿戴(涂覆)内表面的干动COF小于约0.5，贴合(未涂覆)外表面的干动COF大于约0.5。较好是，穿戴表面的干动COF小于约0.4，贴合表面的干动COF大于约0.6。更好是，穿戴表面的干动COF小于约0.3，贴合表面的干动COF大于约0.7。
用本发明的聚氨酯涂层涂覆其内部的天然橡胶手套的拉伸强度大于约2000psi，较好大于约3000psi，最好大于约4000psi。本发明的聚氨酯涂覆的天然橡胶手套在500％时的应力小于约2000psi，较好小于约1000psi，最好小于约800psi。聚氨酯涂覆的天然橡胶手套的断裂伸长大于约200％，较好大于约500％，最好大于约800％。
聚氨酯涂覆的天然橡胶手套的穿戴表面的干动COF小于约0.5，贴合表面的干动COF大于约0.5。较好是，穿戴表面的干动COF小于约0.4，贴合表面的干动COF大于约0.6。更好是，穿戴表面的干动COF小于约0.3，贴合表面的干动COF大于约0.7。
用本发明的聚氨酯涂层涂覆其内部的丁腈橡胶手套的拉伸强度大于约2000psi，较好大于约2500psi，最好大于约3000psi。本发明聚氨酯涂覆的丁腈手套在500％时的应力小于约3000psi，较好小于约2000psi，最好小于约1000psi。聚氨酯涂覆的丁腈手套的断裂伸长大于约200％，较好大于约400％，最好大于约500％。
聚氨酯涂覆的丁腈橡胶手套的穿戴表面的干动COF小于约0.5，贴合表面的干动COF大于约0.4。较好是，穿戴表面的干动COF小于约0.4，贴合表面的干动COF大于约0.6。更好是，穿戴表面的干动COF小于约0.3，贴合表面的干动COF大于约0.7。
用本发明的聚氨酯涂层涂覆其内部的氯丁橡胶手套的拉伸强度大于约2000psi，较好大于约2400psi，最好大于约2600psi。本发明聚氨酯涂覆的氯丁橡胶手套在500％时的应力小于约2000psi，较好小于约1000psi，最好小于约800psi。聚氨酯涂覆的氯丁橡胶手套的断裂伸长大于约200％，较好大于约500％，最好大于约800％。
聚氨酯涂覆的氯丁橡胶手套的穿戴表面的干动COF小于约0.5，贴合表面的干动COF大于约0.5。较好是，穿戴表面的干动COF小于约0.4，贴合表面的干动COF大于约0.6。更好是，穿戴表面的干动COF小于约O.3，贴合表面的干动COF大于约0.7。
手套厚度是用数字式厚度仪测量的，它是在手掌区域上测得的三次测量值的平均。拉伸强度、在500％模量时的应力和断裂伸长按ASTM D412-92测量。干动COF和湿动COF按ASTM D1894-95测量，其过程如上所述。
本发明由下述实施例作进一步说明。应明白的是本领域的普通技术人员将理解如何按所制的制品、所用的特定弹性体或共混物以及所选的具体配方组分去改变过程的时间和温度。类似地，本领域的普通技术人员将知道如何所述吧。选择与其各手套生产线和设备相适应的后处理方法。
实施例1
在其内部用浸过硅氧烷的交联聚氨酯涂覆的无粉天然橡胶胶乳手套按下述过程制造，首先在约120-180°F的烘箱内预热手套模型。然后将手套模型浸到小于约140°F的醇或水基促凝剂分散体中，其时间足以使促凝剂涂覆模型。促凝剂分散体包含硝酸钙、碳酸钙粉末、润湿剂和水(或用于醇基促凝剂分散体的醇)。而后让沉积到手套模型上的促凝剂层干燥。
接着将带有干燥促凝剂层的手套模型浸在保持在约68-86°F的经混合的天然橡胶胶乳中。让手套模型置于胶乳配方物中，其时间足以使天然橡胶胶乳凝结在手套模型上达所需的厚度。然后从胶乳中取出手套模型，在保持在约100-160°F的水沥滤箱内沥滤凝结的胶乳约3-10分钟。
将载有凝结天然橡胶胶乳的手套模型浸在保持在约68-86°F的无粉聚氨酯涂料分散体中，时间少于约1分钟。
无粉聚氨酯涂料分散体包含约49.7干份Sward硬度约为74并且酸值约为21.6的阴离子型聚酯基聚氨酯[A]，约50.3干份Sward硬度约为38并且酸值约为26.7的阴离子型聚酯基聚氨酯[B]，约11.1干份GE SM2140，约0.5份IgepalCO-730(一种购自Rhone-Poulenc的支化壬基苯氧基聚(乙烯氧基)乙醇表面活性剂)，约0.5份BYK 348和约2.2份Bacote20。然后使用软水将固体总含量调节到约2.0％。
从分散体中取出手套，在保持在约248°F的烘箱内使仍在模型上的手套固化约10-20分钟。接着从烘箱内取出手套。而后将固化聚氨酯涂覆的天然橡胶胶乳手套浸在在水中含3％碳酸钙的粉末浆料中。然后从浆料中取出粉末涂覆的手套，在约248°F的烘箱内干燥约1-3分钟。接着从模型上剥下手套。
手套接着经氯化后处理，以除去碳酸钙粉末。由于手套浸渍线不包括卷边机，故必须采用手工翻转的方式后处理手套。首先用手工把手套的里面翻到外面来，用水预漂洗两次，时间约5分钟。然后将手套浸在包含约200ppm氯的氯化水溶液中约8分钟。在溶液中加入氢氧化铵来中和氯化溶液直到pH值约为7或更大。中和过程约需4分钟。然后从氯化器中排出中和溶液，用水漂洗手套约2.5分钟。重复洗涤步骤三次以上。接着将漂洗过的手套放在抽提器中约5分钟，以除去过量的水。取出手套置于干燥器内，加热到约140°F约40分钟。接着取出手套，手工翻转。再次将手套放在干燥器内，加热到140°F约15分钟，使其完全干燥。而后将手套准备包装。
实施例1所述制得的手套的平均厚度约为0.0078英寸，拉伸强度约为4300psi，500％时的应力约为350psi，伸长约为970％，涂覆的穿戴表面的干动COF约为0.21-0.24，未涂覆的贴合面的干动COF约为0.49-0.72。
实施例2
在其内部用浸过硅氧烷的交联聚氨酯涂覆的无粉天然橡胶胶乳手套按下述过程制造，首先在约120-180°F的烘箱内预热手套模型。然后将手套模型浸到保持在小于约140°F的醇或水基促凝剂分散体中，其时间足以使促凝剂涂覆模型。促凝剂分散体包含硝酸钙、碳酸钙粉末、润湿剂和水(或用于醇基促凝剂分散体的醇)。而后让沉积到手套模型上的促凝剂层干燥。
接着将带有干燥促凝剂层的手套模型浸在保持在约68-86°F的经混合的天然橡胶胶乳中。让手套模型置于胶乳配方物中，其时间足以使天然橡胶胶乳凝结在手套模型上达所需的厚度。然后从胶乳中取出手套模型，在保持在约100-160°F的水沥滤箱内沥滤凝结的胶乳约3-10分钟。
沥滤后，在约230°F的烘箱内干燥带有沥滤天然橡胶胶乳的手套模型约2分钟。从烘箱内取出载有天然橡胶胶乳的手套模型，然后浸在保持在约68-86°F的无粉聚氨酯涂料分散体中，时间少于约1分钟。
无粉聚氨酯涂料分散体包含约49.7干份Sward硬度约为74并且酸值约为21.6的阴离子型聚酯基聚氨酯[A]，约50.3干份Sward硬度约为38并且酸值约为26.7的阴离子型聚酯基聚氨酯[B]，约11.4干份GE SM2140，约0.5份IgepalCO-730(一种购自Rhone-Poulenc的支化壬基苯氧基聚(乙烯氧基)乙醇表面活性剂)，约0.5份BYK-348和约2.2份Bacote20。然后用水将固体总含量调节到约1.8-2.0％。
然后从分散体中取出涂覆的手套，用辊卷边机制成珠粒。在约230°F的烘箱内固化手套约10-20分钟。从烘箱内取出固化聚氨酯涂覆的天然橡胶胶乳手套，从模型上剥下来。
手套接着经氯化后处理，以除去碳酸钙粉末。将手套浸在包含约200ppm氯的氯化水溶液中约8分钟。中和氯化溶液直到PH值约为7或更大。然后从氯化器中排出中和溶液，用水漂洗手套。重复洗涤步骤三次以上。接着将漂洗过的手套放在抽提器中约5分钟，以除去过量的水。取出手套置于旋风干燥器内，加热到约140°F约60分钟。接着将手套置于旋风干燥器内约15分钟使其冷至环境温度，之后从干燥器中取出。将手套准备包装。
实施例2所述制得的手套的平均厚度约为0.0067英寸，拉伸强度约为3870psi，500％时的应力约为609psi，断裂伸长约为813％，涂覆的穿戴表面的干动COF约为0.4，未涂覆的贴合面的干动COF约为1.6。
实施例3
在其内部用浸过硅氧烷的交联聚氨酯涂覆的无粉丁腈橡胶手套按下述过程制造，首先在保持在约100-180°F的烘箱内预热手套模型。然后将手套模型浸到保持在小于约140°F的醇或水基促凝剂分散体中，其时间足以使促凝剂涂覆模型。促凝剂分散体包含硝酸钙、碳酸钙粉末、润湿剂和水(或用于醇基促凝剂分散体的醇)。而后让沉积到手套模型上的促凝剂层干燥。
接着将带有干燥促凝剂层的手套模型浸在保持在约68-86°F的经混合的丁腈胶乳中。让手套模型置于丁腈胶乳中，其时间足以使丁腈胶乳凝结在手套模型上达所需的厚度。然后从丁腈胶乳中取出手套模型，在保持在约78-110°F的水沥滤箱内沥滤凝结的胶乳约3-10分钟。
接着将载有凝结丁腈胶乳的手套模型浸在保持在约68-86°F的包含聚氨酯混合物、硅氧烷、交联剂、润湿剂、稳定剂和水的无粉聚氨酯分散体中，时间少于约1分钟。然后从分散体中取出手套，用辊折弯机(roller bender)制成珠粒。在约260°F的烘箱内固化手套约10-20分钟。从烘箱内取出固化聚氨酯涂覆的丁腈橡胶手套，从模型上剥下来。
手套接着经氯化后处理，以除去碳酸钙粉末。将手套浸在包含约50-100ppm氯的氯化水溶液中约8分钟。中和氯化溶液直到pH值约为7或更大。然后从氯化器中排出中和溶液，用水漂洗手套。重复洗涤步骤三次以上。接着将漂洗过的手套放在抽提器中约5分钟，以除去过量的水。取出手套置于旋风干燥器内，加热到约140°F，时间约60分钟。接着将手套置于旋风干燥器内约15分钟使其冷至环境温度，之后从干燥器中取出。将手套准备包装。
实施例3所述制得的手套的平均厚度约为0.005-0.006英寸，拉伸强度约为2200-3000psi，500％时的应力约为800-1000psi，断裂伸长约为600-750％，穿戴表面的干动COF约为0.2-0.4，贴合表面的干动COF约为0.5-0.7。
在不偏离下述权利要求书所定义的本发明精神和范围的情况下，在此可作出本发明上述仅涉及较好实例的描述和实施例以及多种改变和改进。
Claims (33)
1．一种在手套的内表面上带有涂层的无粉弹性体手套，该涂层包含用硅氧烷浸过的交联聚氨酯，其中手套的拉伸强度大于约1300psi，在手套内表面上的干动摩擦系数小于约0.5。
2．如权利要求1所述的手套，其中手套在500％时的应力小于约3000psi。
3．如权利要求2所述的手套，其中手套的断裂伸长大于约200％。
4．如权利要求3所述的手套，其中手套是天然橡胶手套。
5．如权利要求3所述的手套，其中手套是丁腈橡胶手套。
6．如权利要求3所述的手套，其中手套是氯丁橡胶手套。
7．如权利要求1所述的手套，其中涂层包含用硅氧烷浸过的交联阴离子型聚氨酯。
8．如权利要求7所述的手套，其中手套在500％时的应力小于约3000psi。
9．如权利要求8所述的手套，其中手套的断裂伸长大于约200％。
10．如权利要求9所述的手套，其中手套是天然橡胶手套。
11．如权利要求9所述的手套，其中手套是丁腈橡胶手套。
12．如权利要求9所述的手套，其中手套是氯丁橡胶手套。
13．如权利要求1所述的手套，其中涂层包含用硅氧烷浸过的Sward硬度约为74或更大并且酸值约为24或更小的交联阴离子型聚酯基聚氨酯和Sward硬度约为38或更小并且酸值约为24或更大的交联阴离子型聚酯基聚氨酯的混合物。
14．如权利要求13所述的手套，其中手套在500％时的应力小于约3000psi。
15．如权利要求14所述的手套，其中手套的断裂伸长大于约200％。
16．如权利要求15所述的手套，其中手套是天然橡胶手套。
17．如权利要求16所述的手套，其中手套是丁腈橡胶手套。
18．如权利要求17所述的手套，其中手套是氯丁橡胶手套。
19．一种制造在制品的内表面上带有包含用硅氧烷浸过的交联聚氨酯的涂层的无粉弹性体制品的方法，它包括下述步骤：
(a)将模型浸在促凝剂分散体中，以将促凝剂层沉积在模型上；
(b)干燥带有沉积促凝剂层的模型；
(c)将带有沉积促凝剂层的模型浸在弹性体中，在其上制得包含凝结弹性体的第二层；
(d)将凝结弹性体的第二层浸在包含聚氨酯分散体、润湿剂、乳化硅油、交联剂、稳定剂和水的无粉分散体中，以在第二层上形成涂层；
(e)固化模型上的各层和涂层；
(f)从模型上剥下制品；
(g)处理制品以除去粉末；和
(h)干燥制品。
20．如权利要求19所述的方法，其中处理制品以除去粉末的步骤包含将制品浸在氯化水溶液中而后漂洗制品的步骤。
21．如权利要求19所述的方法，其中处理制品以除去粉末的步骤包括用酸溶液处理制品而后漂洗制品的步骤。
22．如权利要求19所述的方法，它包括在水中沥滤制品的附加步骤，该附加步骤发生在将模型浸在弹性体中以在模型上制得含凝结弹性体的第二层之后。
23．如权利要求20所述的方法，它包括在水中沥滤制品的附加步骤，该附加步骤发生在将模型浸在弹性体中以在模型上制得含凝结弹性体的第二层之后。
24．如权利要求21所述的方法，它包括在水中沥滤制品的附加步骤，该附加步骤发生在将模型浸在弹性体中以在模型上制得含凝结弹性体的第二层之后。
25．一种制造在制品的内表面上带有包含用硅氧烷浸过的交联聚氨酯的涂层的无粉弹性体制品的方法，它包括下述步骤：
(a)将模型浸在促凝剂分散体中，以将促凝剂层沉积在模型上；
(b)干燥带有沉积促凝剂层的模型；
(c)将带有沉积促凝剂层的模型浸在弹性体中，在其上制得包含凝结弹性体的第二层；
(d)将凝结弹性体的第二层浸在包含聚氨酯分散体、润湿剂、乳化硅油、交联剂、稳定剂和水的无粉分散体中，以在第二层上形成涂层；
(e)固化模型上的各层和涂层；
(f)从模型上剥下制品；
(g)翻转制品，以将制品的涂覆面位于制品的外部；
(h)处理制品以除去粉末；
(i)干燥制品；
(j)翻转制品，以将制品的涂覆面位于制品的内部；和
(k)干燥制品。
26．如权利要求25所述的方法，其中处理制品以除去粉末的步骤包含将制品浸在氯化水溶液中而后漂洗制品的步骤。
27．如权利要求25所述的方法，其中处理制品以除去粉末的步骤包括用酸溶液处理制品而后漂洗制品的步骤。
28．如权利要求25所述的方法，它包括用粉末处理模型上的涂覆制品的附加步骤，该附加步骤发生在模型上的各层和涂层固化后。
29．如权利要求26所述的方法，它包括用粉末处理模型上的涂覆制品的附加步骤，该附加步骤发生在模型上的各层和涂层固化后。
30．如权利要求27所述的方法，它包括用粉末处理模型上的涂覆制品的附加步骤，该附加步骤发生在模型上的各层和涂层固化后。
31．如权利要求28所述的方法，它包括在水中沥滤制品的附加步骤，该附加步骤发生在将模型浸在弹性体中以在模型上制得含凝结弹性体的第二层之后。
32．如权利要求29所述的方法，它包括在水中沥滤制品的附加步骤，该附加步骤发生在将模型浸在弹性体中以在模型上制得含凝结弹性体的第二层之后。
33．如权利要求30所述的方法，它包括在水中沥滤制品的附加步骤，该附加步骤发生在将模型浸在弹性体中以在模型上制得含凝结弹性体的第二层之后。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/186,850 | 1998-11-05 | ||
| US09/186,850 US6347408B1 (en) | 1998-11-05 | 1998-11-05 | Powder-free gloves having a coating containing cross-linked polyurethane and silicone and method of making the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1287497A true CN1287497A (zh) | 2001-03-14 |
Family
ID=22686517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99802005A Pending CN1287497A (zh) | 1998-11-05 | 1999-11-05 | 带有用硅氧烷浸过的聚氨酯内涂层的无粉手套 |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US6347408B1 (zh) |
| EP (1) | EP1047461A1 (zh) |
| JP (1) | JP2002528659A (zh) |
| KR (1) | KR20010052139A (zh) |
| CN (1) | CN1287497A (zh) |
| AU (1) | AU760951B2 (zh) |
| WO (1) | WO2000025840A1 (zh) |
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-
1998
- 1998-11-05 US US09/186,850 patent/US6347408B1/en not_active Expired - Lifetime
-
1999
- 1999-11-05 AU AU13430/00A patent/AU760951B2/en not_active Ceased
- 1999-11-05 CN CN99802005A patent/CN1287497A/zh active Pending
- 1999-11-05 WO PCT/US1999/026122 patent/WO2000025840A1/en not_active Application Discontinuation
- 1999-11-05 JP JP2000579276A patent/JP2002528659A/ja active Pending
- 1999-11-05 KR KR1020007007425A patent/KR20010052139A/ko not_active Application Discontinuation
- 1999-11-05 EP EP99956929A patent/EP1047461A1/en not_active Withdrawn
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2001
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861175B (zh) * | 2007-08-07 | 2013-06-26 | 史密夫及内修公开有限公司 | 涂层 |
| US20200109256A1 (en) * | 2013-03-22 | 2020-04-09 | Honeywell International Inc. | Rubber-based elastomeric compositions and articles of manufacture produced therewith |
| US11639433B2 (en) * | 2013-03-22 | 2023-05-02 | Honeywell International Inc. | Method for fabricating a rubber-based elastomeric glove/material |
| CN106894239A (zh) * | 2017-03-16 | 2017-06-27 | 江苏工程职业技术学院 | 一种锦纶荧光黄乳胶手套浸胶时防褪色的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002528659A (ja) | 2002-09-03 |
| AU1343000A (en) | 2000-05-22 |
| US6582788B2 (en) | 2003-06-24 |
| EP1047461A1 (en) | 2000-11-02 |
| US6347408B1 (en) | 2002-02-19 |
| KR20010052139A (ko) | 2001-06-25 |
| US20020029402A1 (en) | 2002-03-14 |
| WO2000025840A1 (en) | 2000-05-11 |
| AU760951B2 (en) | 2003-05-22 |
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