CN1260814A - 用于橡胶制品的高弹材料 - Google Patents
用于橡胶制品的高弹材料 Download PDFInfo
- Publication number
- CN1260814A CN1260814A CN98806248A CN98806248A CN1260814A CN 1260814 A CN1260814 A CN 1260814A CN 98806248 A CN98806248 A CN 98806248A CN 98806248 A CN98806248 A CN 98806248A CN 1260814 A CN1260814 A CN 1260814A
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- China
- Prior art keywords
- monomer
- polymer latex
- latex composition
- gloves
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
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Abstract
适用于制备橡胶制品的聚合物胶乳组合物包含约5wt%至约65wt%的芳香乙烯基单体,约35wt%至约90wt%的共轭二烯单体,和约0.5wt%至约10wt%的选自不饱和羧酸单体、不饱和多元羧酸的偏酯及其混合物的组分。聚合物胶乳组合物的胶体含量不高于约85%。
Description
发明领域
本发明涉及可用于制备橡胶制品的聚合物胶乳组合物。更具体地,本发明涉及能够形成具有各种物理性质的材料的聚合物胶乳组合物。
发明背景
橡胶制品如手套、避孕套、袋子等等由胶乳聚合材料形成,并广泛用于如医疗、工业和家庭用品等应用中。这些聚合材料一般为水基聚合物,利用商业上已知的方法很容易形成。在这样的方法中,重要的是胶乳材料能够在模具表面形成薄膜。这样的用途的例子之一为胶乳手套的制造。由于可将其制成轻、薄、柔韧、紧合及基本上不透液体和不透气,这些手套是合乎需要的。常常要求这些手套具有适当的物理性质如抗拉强度和伸长率。
要求手套戴起来柔软舒适,并防止细菌侵入。优选同时具有高抗拉强度和伸长率及低模量。较低的模量和高伸长率通常意谓着更柔韧、更舒适的手套。另外,手套必须有足够的弹性恢复能力。
由于天然橡胶的回弹能力和适当的物理性质,传统的胶乳手套典型地由天然橡胶制成。但是,许多戴这种手套的人对在天然橡胶内发现的蛋白质过敏。这些人难于使用这种手套。因此,已有人努力开发由舒适程度和物理性质可与天然橡胶手套相比的合成材料制成的手套。一种可供选择的合成方法集中于使用聚氯乙烯(PVC)。PVC通常需要增塑处理,以便足够柔软可用于制造手套。由PVC制成的手套在许多方面不合意,例如,这些手套通常很硬,戴者感到不舒适。而且,当与溶剂接触时,增塑剂可由PVC内迁移并析出。由于薄膜内的缺陷,由乙烯基材料制成的合成手套也可能不足以隔绝细菌。
Tillotson等人的美国专利No.5014362描述了另一种可能替代天然橡胶制成的手套的方法,Tillotson等人的专利建议以据说具有适当的与流体渗透性、强度和回弹能力有关的物理性质的高弹性材料制造手套。手套由含腈橡胶制成,更具体地是含羧酸化腈的丁二烯橡胶。含腈橡胶手套典型地适用于苛求的最终应用,如那些经常要求优越性质如抗溶剂和抗刺穿性的应用。不过,对于更一般的、不太苛求的应用,常常不需要手套表现出这样的性质。
由苯乙烯和丁二烯形成的胶乳聚合物已被用于制造合成手套。但这些材料大部分不成功,因为它们通常不能有效地“浸涂(dip)”,也就是不能凝聚形成薄、均一、无缺陷的薄膜。而且,薄的薄膜通常没有足以单独作为手套使用的物理性质。最重要的是,希望提供使用起来舒适并充分防止细菌和化学品进入的薄膜手套。相应地,手套应具有高抗拉强度、高伸长率和低模量。由于抗拉强度高的薄膜倾向于具有低伸长率和高模量,因此一般难于同时具有这些性质。
本领域仍需要适合形成不含天然橡胶蛋白质,并能提供宽范围所需要的与强度、伸长率和模量有关的物理性质,以及可向使用者提供适当舒适性的橡胶制品的合成胶乳材料。也有必要以成本可与天然橡胶竞争的材料生产用于一般性应用的手套。
本发明概述
考虑上述情况,提供适宜形成橡胶制品、不含天然橡胶并能赋予由其制造的制品以所需要的物理性质的的聚合物胶乳是本发明的目标。
为了达到这一目的和其它目的,一方面,本发明提供适宜制造橡胶制品的聚合物胶乳组合物。该组合物包含从约5wt%至约65wt%的芳香乙烯基单体,从约35wt%至约90wt%的共轭二烯单体和约0.5wt%至约10wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、或其混合物的组分。重量百分数以单体的总重量为基准。优选的芳基乙烯基单体为苯乙烯,优选的共轭二烯单体为1,3-丁二烯,优选的组分为不饱和单元或二元羧酸单体。
另一方面,本发明提供由聚合物胶乳组合物形成的交联薄膜。优选地,交联薄膜的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不高于约500psi。
还有一方面,本发明提供由本发明的聚合物胶乳组合物制成的手套。优选地,手套的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不高于约500psi。
本发明详述
本发明将在下文中得到更充分地说明,本发明的优选实施方案也将在下文给出。但是,本发明可以不同方式实施,不应受到其中所给实施方案的限制。相反地,提供这些实施方案是为了充分、完全地公开本发明,并将本发明范围完全地传达给本领域普通技术人员。
本发明涉及适宜制造橡胶制品的聚合物胶乳组合物。该聚合物胶乳组合物包含从约5wt%至约65wt%的芳香乙烯基单体,从约35wt%至约90wt%的共轭二烯单体和约0.5wt%至约10wt%的选自不饱和酸单体、不饱和多元羧酸偏酯、或其混合物的组分。重量百分数以单体的总重量为基准。
对于本发明的目的,“芳香乙烯基单体”一词可广义地解释,其包括,例如,芳基和杂环单体。可用于聚合物胶乳组合物的芳香乙烯基单体的例子包括,例如,苯乙烯和苯乙烯衍生物如α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、乙基苯乙烯、叔丁基苯乙烯、单氯代苯乙烯、二氯苯乙烯、乙烯基苄基氯、乙烯基吡啶、氟代苯乙烯、烷氧基苯乙烯(例如,对甲氧基苯乙烯)等等,以及共混物和它们的混合物。除在此陈述的组成范围外,芳香乙烯基单体的用量优选为从约5wt%至约50wt%,最优选为从约10wt%至约40wt%。此处所给的重量百分数以单体的总重量为基准。尤其优选的芳香乙烯基单体为苯乙烯。
可使用的适宜共轭二烯单体包括,但不局限于C4-C9二烯烃如,例如,丁二烯单体如1,3-丁二烯、2-甲基-1,3-丁二烯、2-氯-1,3-丁二烯等等。也可使用二烯烃单体的共混物或共聚物。除在此给出的组成范围外,共轭二烯烃单体的用量优选为从约40wt%至约90wt%,更优选为从约55wt%至约80wt%。此处所给的重量百分数以单体的总重量为基准。对于感觉更柔软的手套材料来说,尤其希望共轭二烯烃单体的用量从约60wt%至约95wt%。尤其优选的共轭二烯烃单体为1,3-丁二烯。
许多不饱和酸单体可用于聚合物胶乳组合物。这类单体的例子包括,但不局限于不饱和单元或二元羧酸单体如丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸等等。也可使用上述单体的衍生物、共混物或混合物。优选使用甲基丙烯酸。
可加入聚合物胶乳组合物内的适宜不饱和多元羧酸的偏酯很多。这些单体典型地包括不饱和二元或高于二元的羧酸单体,其中至少一个羧酸基团被酯化。这类单体的一个例子的分子式为ROOC-CH=CH-COOH的单体,其中R为C1-C12烷基,例如,马来酸单甲酯、马来酸单丁酯和马来酸单辛酯。也可使用含有C1-C12烷基的衣康酸半酯如衣康酸单甲酯。也可使用其它半酯,如上述分子式内的R为烷氧基链,而不是烷基的那些半酯。也可使用不饱和多元羧酸单体偏酯的共混物或共聚物。
除上述给出的组成范围外,不饱和酸单体或不饱和多元羧酸偏酯单体或其混合物的用量可在占单体总量约1.5%至约5%的范围内变化。
本发明的聚合物胶乳组合物可使用许多其它组分,例如含氮单体。例如,可使用丙烯酰胺基单体,其包括,例如,丙烯酰胺、N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、甲基丙烯酰胺、N-异丙基丙烯酰胺、N-叔丁基丙烯酰胺、N-N’-亚甲基-双-丙烯酰胺,烷基化N-羟甲基丙烯酰胺如N-甲氧基甲基丙烯酰胺和N-丁氧基甲基丙烯酰胺,腈类如丙烯腈和甲基丙烯腈。可使用上述化合物的共混物和混合物。
聚合物胶乳组合物也可包括非芳香不饱和单羧酸酯单体,例如,丙烯酸酯和甲基丙烯酸酯。丙烯酸酯和甲基丙烯酸酯可包括功能基团如氨基、羟基、环氧基等。丙烯酸酯和甲基丙烯酸酯的例子包括丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、甲基丙烯酸异丁酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、甲基丙烯酸3-氯-2-羟丁酯、甲基丙烯酸正丙酯等等。氨基官能化的甲基丙烯酸酯的例子包括甲基丙烯酸叔丁基氨基乙酯和甲基丙烯酸二甲氨基乙酯。也可使用适宜的非芳香二元羧酸酯单体,例如,富马酸、衣康酸和马来酸的烷基和二烷基酯,烷基含1至8个碳原子,有或无官能团均可。具体的单体包括富马酸、衣康酸和马来酸的二乙酯和二甲酯。其它适宜的非芳香二元羧酸酯单体包括马来酸二(乙二醇)酯、衣康酸二(乙二醇)酯、马来酸双(2-羟乙基)酯、富马酸2-羟乙基·甲基酯,等等。单和二元羧酸酯单体可互相共混或共聚。也可使用其它单体如乙烯基酯、卤乙烯和1,2-二卤乙烯。
聚合物胶乳组合物也可包括其它组分,例如,氨基甲酸乙酯树脂、环氧树脂、三聚氰胺-甲醛树脂和共轭二烯聚合物(如聚丁二烯、聚异戊二烯和聚氯丁二烯)。也可使用它们的共混物、衍生物和混合物。
聚合物胶乳组合物内可使用传统的表面活性剂和乳化剂。也可使用可掺入胶乳中的可聚合表面活性剂。例如,阴离子表面活性剂可广泛地选自磺酸盐、硫酸盐、醚硫酸盐、磺基琥珀酸盐、二苯醚二磺酸盐等,其选择对本领域的任何普通技术人员都是显而易见的。也可使用非离子表面活性剂改进薄膜和手套的特性,其可选自烷基苯氧基聚(亚乙基氧)乙醇系列,其中烷基典型地在C7-C18之间变化,环氧乙烷单元在4-100摩尔之间变化。各种优选的这类表面活性剂包括乙氧基化的辛基酚和壬基酚。乙氧基化醇也是所希望的表面活性剂。典型的阴离子表面活性剂选自二苯醚二磺酸盐系列,如十二烷氧基二苯磺酸的二钠盐。
促进胶乳组合物聚合的引发剂例如可包括,过硫酸盐、有机过氧化物、过酸酯,以及偶氮化合物,如偶氮双异丁腈(AIBN)。常见的引发剂例如包括,异丙苯基过氧化氢、二异丙基苯过氧化氢和叔丁基过氧化氢。优选的引发剂为过硫酸盐引发剂,例如,过硫酸铵和过硫酸钾。也可使用本领域普通技术人员熟知的氧化还原引发剂。
聚合物可包括交联剂和其它添加剂,其选择对本领域普通技术人员是显而易见的。交联剂的例子包括乙烯类化合物(例如,二乙烯基苯)、烯丙基化合物(例如,甲基丙烯酸烯丙酯、马来酸二烯丙酯)、多丙烯酸酯(例如,二、三和四(甲基)丙烯酸酯)、硫和金属氧化物(例如,氧化锌)。也可使用过氧化物。可使用的其它成分包括,但不局限于螯合剂(例如,乙二胺四乙酸)、分散剂(例如,缩合萘磺酸盐)、缓冲剂(例如,氢氧化胺)和阻聚剂(例如,氢醌)。本发明也可使用链转移剂(例如,叔十二烷基硫醇),其用量优选少于单体重量的约2%。更优选地,链转移剂的用量从约0.3wt%至约1.5wt%,最优选地,从约0.3wt%至约1.0wt%。
形成本发明聚合物胶乳组合物所用的单体可以本领域普通技术人员熟知的方式聚合。例如,单体可在优选约40°F至200°F,更优选约50°F至150°F的温度下聚合。
根据本发明,聚合物胶乳组合物的胶体含量不超过约85%,优选不超过约75%,更优选不超过约50%。最优选地,聚合物胶乳组合物的胶体含量不超过30%。对于本发明的目的,“胶体含量”一词指聚合物胶乳组合物内部交联的程度(百分数)。更具体地说,胶体含量可被认为是聚合物胶乳组合物的不溶百分数。可以被认可的技术测定胶体含量,一种技术是使胶乳组合物在异丙醇内凝结,然后干燥。将干燥组合物在甲苯内的不溶百分数定义为百分胶体含量。
虽然申请人不希望被任何理论所限制,但仍认为几种因素如温度、转化程度、反应速率、反应时间、催化剂浓度、链转移剂浓度和交联剂浓度可能影响百分胶体含量。
本发明的聚合物胶乳组合物也可具有不同的聚苯乙烯等当重均分子量。聚苯乙烯等当重均分子量一词指聚合物在四氢呋喃(THF)中可溶部分的分子量。测定该值的过程为本领域普通技术人员所熟知。典型地,使用凝胶渗透色谱(GPC)测定聚合物可溶部分的分子量。优选地,聚合物胶乳组合物的聚苯乙烯等当重均分子量在约40000至约500000之间,更优选从约70000至约400000。
本发明也涉及由在此所述的聚合物胶乳组合物形成的交联薄膜。根据本发明,许多制品可由交联薄膜和聚合物胶乳组合物制成。这样的胶乳制品一般包括那些典型地由天然橡胶形成的与人体接触的制品。制品的例子包括,但不局限于手套、避孕套、医疗设备、导液管、气球和血压袋。技术示例在Szczechura等人的美国专利No.5084514中有所描述,其中的公开内容在此通过引用将其全部并入并文。典型地,聚合物胶乳组合物与一种或多种交联剂(例如,金属氧化物如氧化锌、硫和过氧化物),及抗氧剂、填料及其它组分配混。配混或混合过程可以任何适宜的方式进行。将适宜的手形模子或模具在加热炉内加热,然后浸入或没入促凝剂内。适宜的促凝剂例如包括,金属盐溶液,优选硝酸钙水溶液或醇溶液。然后将模子由促凝剂内取出,使过量液体干燥,因此在模子上留下促凝剂的残留涂层。
然后将涂有促凝剂层的模子浸入或没入本发明的聚合物胶乳组合物内,胶乳在模子上凝结形成薄膜。模子在胶乳内浸没的时间常常决定薄膜的厚度,停留时间越长,薄膜越厚。
将模子由胶乳内取出,浸入水浴内除去促凝剂和部分表面活性剂。然后将涂有胶乳的模子放入干燥炉内去除薄膜内的水分,干燥炉的温度优选在约60℃至约100C之间。当薄膜干燥后,将模具放入整理炉内约5分钟至约30分钟,整理炉的温度优选在约100℃至约170℃之间。若有必要,干燥和整理过程可使用相同的炉子,炉的温度可随时间提高。
将整理的手套由模子上取下,为了易于取下和戴上,可对其进行粉化处理或后加工。优选的手套厚度为从3密耳(mil)至约20密耳。
根据本发明形成的交联薄膜和手套可有各种物理性质。优选地,上述材料的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不超过约500psi。更优选地,这些材料的抗拉强度至少约1500psi,伸长率至少约450%,100%伸长率下的模量不超过约450psi。最优选地,这些材料的抗拉强度至少约2000psi,伸长率至少约500%,100%伸长率下的模量不超过约400psi。
本发明的交联薄膜或手套可有各种百分面积膨胀值。百分面积膨胀通常根据ASTM试验方法No.D-471在二甲苯内测定,其为交联薄膜交联密度的指数。优选地,交联薄膜的百分面积膨胀大于约300%。
除以上所述外,根据本发明的交联薄膜和手套可含有与之相接触的附加(至少第二种)聚合物薄膜,以便形成复合结构。附加聚合物薄膜的施用可通过本领域熟知的技术实现,例如,聚合物膜可通过涂膜、喷涂或“过度浸醮”等方式在交联膜和手套上形成。然后,根据已知且被认可的技术将所得的材料干燥、整理。附加聚合物膜可由各种材料形成,其包括但不局限于氯丁橡胶、腈类树脂、氨基甲酸乙酯树脂、丙烯酸树脂、聚丁二烯、聚异戊二烯等等。也可使用上述材料的混合物。附加聚合物膜可以各种构型存在。例如,在一个实施方案中,附加膜位于交联膜的上面;在第二个实施方案中,附加膜位于交联膜的下面;在第三个实施方案中,交联膜位于两层附加膜之间。不同薄膜的构型可根据技术人员的需要选择。
下列实施例仅为本发明的示意,并不局限于此。
实施例1
向1加仑的反应器内加入150phm(每100份单体中的份数)的软化水,在搅拌下再加入61phm丁二烯、34phm苯乙烯和5phm甲基丙烯酸,以及0.05phm乙二胺四乙酸(EDTA)、2phm表面活性剂(即,十二烷氧基二苯磺酸的二钠盐)、0.6phm叔十二烷基硫醇、0.05phm过硫酸钾和0.3phm缩合萘磺酸钠盐。将上述混合物边搅拌边升温至120°F。温度逐渐提高至140℃。12.5小时后,加入氢醌停止反应。测定的转化率为91.5%。用氢氧化胺将胶乳的pH提高至7-7.5。然后将胶乳浓缩至总固体含量为44.9%,粘度为130cps。胶乳的胶体含量为9%。
将胶乳与0.5phm十二烷基苯磺酸钠混合,用NH4OH将其pH提高至8.5。将胶乳进一步与0.25phr二丁基二硫代氨基甲酸锌、0.5phr硫和1phr ZnO混合。
实施例2
如下述方式将实施例1制备的配混胶乳凝结在模子上,并使薄膜交联。在70℃下,将模子浸入促凝剂(35%的硝酸钙水溶液)内,部分干燥,然后在胶乳内浸没5-60秒。5-10mil的聚合物膜沉积在模子上。将膜在模子上干燥2-5分钟,在热水内洗涤,然后在70℃的加热炉内干燥20分钟。最后将膜在132℃下整理10分钟。
以ASTM D-412方法测量的膜的拉伸性质如下:
M100 | M200 | M300 | M400 | M500 | Tb | e% |
227 | 323 | 432 | 580 | 790 | 1309 | 661 |
M100-M150:模量(psi)
Tb:抗拉强度(psi)
e%:百分伸长率
以ASTM D-471测定,膜在二甲苯中的面积膨胀大于500%。
实施例3
与实施例1相似的胶乳组合物用62phm丁二烯、34phm苯乙烯和4phm甲基丙烯酸制得,然后将胶乳浓缩至总固体含量为43.8%,粘度为90cps。胶乳的胶体含量为6%。测定可溶部分的聚苯乙烯等当重均分子量为215000。以实施例2中描述的过程将胶乳制成凝聚膜,不同的是,使用2.5phr氧化锌、1phr硫和0.5phr丁基二硫代氨基甲酸锌。
以ASTM D-412方法测量的膜的拉伸性质如下:
M100 | M200 | M300 | M400 | M500 | Tb | e% |
365 | 592 | 862 | 1268 | 1861 | 2507 | 576 |
以ASTM D-471测定,膜在二甲苯中的面积膨胀大于500%。
实施例4
与实施例1相似的胶乳组合物用63phm丁二烯、34phm苯乙烯和3phm甲基丙烯酸制得,然后将胶乳浓缩至总固体含量为44.5%,粘度为100cps。胶乳的胶体含量为8%。测定可溶部分的聚苯乙烯等当重均分子量为225000。以实施例2中描述的过程将胶乳制成凝聚膜,不同的是,使用1.5phr氧化锌。
以ASTM D-412方法测量的膜的拉伸性质如下:
M100 | M200 | M300 | M400 | M500 | Tb | e% |
186 | 279 | 383 | 523 | 758 | 1705 | 693 |
以ASTM D-471测定,膜在二甲苯中的面积膨胀大于300%。
实施例5
与实施例1相似的胶乳组合物用61phm丁二烯、34phm苯乙烯和5phm甲基丙烯酸制得,然后将胶乳浓缩至总固体含量为43.4%,粘度为80cps。胶乳的胶体含量为78%。将胶乳与0.5phm十二烷基苯磺酸钠混合,以NH4OH将其pH提高至8.5。将胶乳进一步与1phr氧化锌、0.5phr硫和0.25phr丁基二硫代氨基甲酸锌混合。
按下述方式将配混胶乳凝结于金属平板上,并使薄膜交联。在70℃下,将金属平板浸入促凝剂(35%的硝酸钙乙醇溶液)内,部分干燥,然后在胶乳内浸没60秒。8-14mil的聚合物膜沉积在平板上。将膜在热水内洗涤,然后在70℃的加热炉内干燥2小时。最后将膜在132℃下整理15分钟。
以ASTM D-412方法测量的膜的拉伸性质如下:
M100 | M200 | M300 | M400 | M500 | Tb | e% |
308 | 443 | 595 | 818 | 1194 | 2187 | 632 |
在说明书和实施例内,已公开了本发明的典型优选实施方案,虽然使用了特定术语,但它们仅以通用叙述意义使用,并不限制下列权利要求书给出的本发明范围。
Claims (33)
1.适宜制造橡胶制品的聚合物胶乳组合物,所述的组合物包括:
约5wt%至约65wt%的芳香乙烯基单体;
约35wt%至约90wt%的共轭二烯单体;和
约0.5wt%至约10wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;
其中所述的聚合物胶乳组合物的胶体含量不高于85%。
2.根据权利要求1的聚合物胶乳组合物,其中所述的聚合物胶乳组合物的聚苯乙烯等当重均分子量处于约40000至约500000之间。
3.根据权利要求1的聚合物胶乳组合物,其中所述的芳香乙烯基单体为苯乙烯。
4.根据权利要求1的聚合物胶乳组合物,其中所述的共轭二烯单体为丁二烯。
5.根据权利要求1的聚合物胶乳组合物,其中所述的组分为不饱和酸单体。
6.根据权利要求1的聚合物胶乳组合物,其中所述的组合物进一步包含选自氨基甲酸乙酯树脂、环氧树脂、三聚氰胺-甲醛树脂、共轭二烯聚合物、及其共混物的组分。
7.根据权利要求1的聚合物胶乳组合物,所述的聚合物胶乳组合物包括:
约10wt%至约40wt%的芳香乙烯基单体;
约55wt%至约80wt%的共轭二烯单体;和
约1.5wt%至约5wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;
8.由聚合物胶乳组合物形成的交联薄膜,所述的聚合物胶乳组合物包含:
约5wt%至约65wt%的芳香乙烯基单体;
约35wt%至约90wt%的共轭二烯单体;和
约0.5wt%至约10wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;
其中所述交联薄膜的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不高于约500psi。
9.根据权利要求8的交联薄膜,其中所述交联薄膜的百分面积膨胀高于约300%。
10.根据权利要求8的交联薄膜,其中所述聚合物胶乳组合物的胶体含量不高于约85%。
11.根据权利要求8的交联薄膜,其中所述的芳香乙烯基单体为苯乙烯。
12.根据权利要求8的交联薄膜,其中所述的共轭二烯单体为丁二烯。
13.根据权利要求8的交联薄膜,其中所述的组分为不饱和酸单体。
14.根据权利要求8的交联薄膜,其中所述的聚合物胶乳组合物进一步包含选自氨基甲酸乙酯树脂、环氧树脂、三聚氰胺-甲醛树脂、共轭二烯聚合物、及其共混物的组分。
15.根据权利要求8的交联薄膜,所述的聚合物胶乳组合物包含:
约10wt%至约40wt%的芳香乙烯基单体;
约55wt%至约80wt%的共轭二烯单体;和
约1.5wt%至约5wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;
16.根据权利要求8的交联薄膜,进一步包含与所述交联薄膜相接触形成复合膜结构的第二种聚合物膜。
17.包含由聚合物胶乳组合物形成的交联薄膜的手套,聚合物胶乳组合物包含约5wt%至约65wt%的芳香乙烯基单体,约35wt%至约90wt%的共轭二烯单体,和约0.5wt%至约10wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;其中所述手套的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不高于约500psi。
18.根据权利要求17的手套,其中所述交联薄膜的百分面积膨胀高于约300%。
19.根据权利要求17的手套,其中聚合物胶乳组合物的胶体含量不高于85%。
20.根据权利要求17的手套,其中所述手套进一步包含与所述手套相接触形成复合结构的第二种聚合物膜。
21.根据权利要求17的手套,其中所述手套的厚度处于约3mil至约20mil之间。
22.根据权利要求17的手套,其中所述的芳香乙烯基单体为苯乙烯。
23.根据权利要求17的手套,其中所述的共轭二烯单体为丁二烯。
24.根据权利要求17的手套,其中所述的组分为不饱和酸单体。
25.根据权利要求17的手套,其中所述的聚合物胶乳组合物进一步包含选自氨基甲酸乙酯树脂、环氧树脂、三聚氰胺-甲醛树脂、共轭二烯聚合物、及其共混物的组分。
26.包含由聚合物胶乳组合物形成的交联薄膜的手套,聚合物胶乳组合物包含约10wt%至约40wt%的芳香乙烯基单体,约55wt%至约80wt%的共轭二烯单体,和约1.5wt%至约5wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;其中所述手套的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不高于约500psi;其中聚合物胶乳组合物的胶体含量不高于约85%。
27.制造手套的方法,其包括:
将手套形模具与促凝剂接触;
将含有促凝剂的模子与聚合物胶乳组合物接触,聚合物胶乳组合物包含约5wt%至约65wt%的芳香乙烯基单体,约35wt%至约90wt%的共轭二烯单体,和约0.5wt%至约10wt%的选自不饱和酸单体、不饱和多元羧酸偏酯单体、及其混合物的组分;聚合物胶乳组合物的胶体含量不高于约85%,其中聚合物胶乳组合物粘附于模具上;
从聚合物胶乳组合物中除去促凝剂;和
将存在于模具上的聚合物胶乳组合物固化,形成由组合物形成的手套。
28.根据权利要求27的方法,其中所述聚合物胶乳组合物的苯乙烯等当重均分子量处于约40000至约500000之间。
29.根据权利要求27的方法,其中所述芳香乙烯基单体为苯乙烯。
30.根据权利要求27的方法,其中所述共轭二烯单体为丁二烯。
31.根据权利要求27的方法,其中所述组分为不饱和酸单体。
32.根据权利要求27的方法,其中所述的组合物进一步包含选自氨基甲酸乙酯树脂、环氧树脂、三聚氰胺-甲醛树脂、共轭二烯聚合物、及其共混物的组分。
33.根据权利要求27的方法,其中所述手套的抗拉强度至少约1000psi,伸长率至少约400%,100%伸长率下的模量不高于约500psi。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US86471897A | 1997-05-28 | 1997-05-28 | |
US08/864,718 | 1997-05-28 |
Publications (1)
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CN1260814A true CN1260814A (zh) | 2000-07-19 |
Family
ID=25343908
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Application Number | Title | Priority Date | Filing Date |
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CN98806248A Pending CN1260814A (zh) | 1997-05-28 | 1998-05-27 | 用于橡胶制品的高弹材料 |
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US (1) | US6627325B1 (zh) |
EP (1) | EP0986608B1 (zh) |
JP (1) | JP2002500696A (zh) |
KR (1) | KR100559930B1 (zh) |
CN (1) | CN1260814A (zh) |
AT (1) | ATE272092T1 (zh) |
AU (1) | AU741891B2 (zh) |
BR (1) | BR9809700A (zh) |
CA (1) | CA2290998A1 (zh) |
DE (1) | DE69825277T2 (zh) |
WO (1) | WO1998054250A1 (zh) |
Cited By (4)
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US7662890B2 (en) | 2004-03-31 | 2010-02-16 | Zeon Corporation | Composition for dip forming and molding obtained by dip forming |
CN102408639A (zh) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | 抗冲聚苯乙烯树脂组合物及其制备方法 |
CN103096742A (zh) * | 2010-06-22 | 2013-05-08 | 维健股份有限公司 | 聚乳酸手套及其制造方法 |
CN103781803A (zh) * | 2011-09-07 | 2014-05-07 | 思迪隆欧洲有限公司 | 具有改进机械性质的聚合物胶乳和制备所述聚合物胶乳的方法 |
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EP1634899B1 (en) | 2000-06-07 | 2009-07-29 | Zeon Corporation | Conjugated diene rubber gel, rubber compositions containing the same and process for production of conjugated diene rubber |
US6673871B2 (en) | 2000-12-21 | 2004-01-06 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles made from a synthetic polymer |
US6780937B2 (en) * | 2002-08-29 | 2004-08-24 | The Goodyear Tire & Rubber Company | Emulsion particles as reinforcing fillers |
EP1686153B1 (en) * | 2003-11-21 | 2011-01-26 | Zeon Corporation | Dip forming composition and dip formed article |
EP1709879A3 (en) * | 2005-04-04 | 2008-06-04 | Medline Industries, Inc., | Disposable gloves |
WO2007026704A1 (ja) * | 2005-08-31 | 2007-03-08 | Zeon Corporation | ディップ成形用組成物およびディップ成形品 |
AT518307B1 (de) * | 2016-03-04 | 2020-04-15 | Semperit Ag Holding | Verfahren zum Herstellen eines Prophylaxeartikels |
EP3594284A4 (en) * | 2017-03-08 | 2020-12-02 | Zeon Corporation | COMPOSITION OF LATEX |
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- 1998-05-27 JP JP50084999A patent/JP2002500696A/ja not_active Ceased
- 1998-05-27 AT AT98923801T patent/ATE272092T1/de not_active IP Right Cessation
- 1998-05-27 CN CN98806248A patent/CN1260814A/zh active Pending
- 1998-05-27 DE DE1998625277 patent/DE69825277T2/de not_active Revoked
- 1998-05-27 BR BR9809700A patent/BR9809700A/pt not_active Application Discontinuation
- 1998-05-27 AU AU76009/98A patent/AU741891B2/en not_active Ceased
- 1998-05-27 EP EP19980923801 patent/EP0986608B1/en not_active Revoked
- 1998-05-27 CA CA 2290998 patent/CA2290998A1/en not_active Abandoned
- 1998-05-27 KR KR1019997010826A patent/KR100559930B1/ko not_active IP Right Cessation
- 1998-05-27 WO PCT/US1998/010748 patent/WO1998054250A1/en active IP Right Grant
- 1998-08-04 US US09/128,912 patent/US6627325B1/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US7662890B2 (en) | 2004-03-31 | 2010-02-16 | Zeon Corporation | Composition for dip forming and molding obtained by dip forming |
CN103096742A (zh) * | 2010-06-22 | 2013-05-08 | 维健股份有限公司 | 聚乳酸手套及其制造方法 |
CN102408639A (zh) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | 抗冲聚苯乙烯树脂组合物及其制备方法 |
CN102408639B (zh) * | 2010-09-21 | 2014-08-06 | 中国石油天然气股份有限公司 | 抗冲聚苯乙烯树脂组合物及其制备方法 |
CN103781803A (zh) * | 2011-09-07 | 2014-05-07 | 思迪隆欧洲有限公司 | 具有改进机械性质的聚合物胶乳和制备所述聚合物胶乳的方法 |
CN103781803B (zh) * | 2011-09-07 | 2016-06-08 | 盛禧奥欧洲有限责任公司 | 具有改进机械性质的聚合物胶乳和制备所述聚合物胶乳的方法 |
Also Published As
Publication number | Publication date |
---|---|
US6627325B1 (en) | 2003-09-30 |
ATE272092T1 (de) | 2004-08-15 |
AU7600998A (en) | 1998-12-30 |
KR100559930B1 (ko) | 2006-03-13 |
DE69825277D1 (de) | 2004-09-02 |
EP0986608B1 (en) | 2004-07-28 |
DE69825277T2 (de) | 2004-12-09 |
CA2290998A1 (en) | 1998-12-03 |
JP2002500696A (ja) | 2002-01-08 |
AU741891B2 (en) | 2001-12-13 |
WO1998054250A1 (en) | 1998-12-03 |
KR20010012860A (ko) | 2001-02-26 |
BR9809700A (pt) | 2000-07-11 |
EP0986608A1 (en) | 2000-03-22 |
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