CN102093604A - 可双重穿戴的手套 - Google Patents
可双重穿戴的手套 Download PDFInfo
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- CN102093604A CN102093604A CN2010105101335A CN201010510133A CN102093604A CN 102093604 A CN102093604 A CN 102093604A CN 2010105101335 A CN2010105101335 A CN 2010105101335A CN 201010510133 A CN201010510133 A CN 201010510133A CN 102093604 A CN102093604 A CN 102093604A
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- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 42
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Gloves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulding By Coating Moulds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
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Abstract
本发明涉及一种包含比聚氯丁二烯更容易氯化的聚合物的聚氯丁二烯制品。本发明还涉及一种使用聚氯丁二烯的水分散液或溶液来制造所述制品的方法,其特征在于在所述分散液或溶液中包含一种或多种比聚氯丁二烯更容易氯化的聚合物。优选所述制品是包含羧化丁腈橡胶、羧化苯乙烯丁二烯或聚异戊二烯的聚氯丁二烯手套。
Description
本申请是申请日为2003年5月14日,发明名称为“可双重穿戴的手套”,申请号为03816714.X的中国发明专利申请的分案申请。
本发明涉及聚氯丁二烯制品,更具体地涉及(但不限于)聚氯丁二烯外科手套。
因为在医学检查和外科手术期间越来越害怕感染的危险,通常医学工作者,特别是外科医生在一双手套上面再套上另一双橡胶手套(即双重穿戴(double-don))已经日益常见。穿戴两双手套提供了更好的安全性。但是,虽然某些橡胶手套可以较容易地双重穿戴,但是因为手套表面之间高度的摩擦,其它的手套即便可以,也会很难双重穿戴。已知有大量的方式可以降低摩擦,例如在手套上面使用润滑粉,或者对于无粉手套,可以氯化其表面。因此,当天然橡胶或丁腈橡胶手套被氯化时,摩擦降低,所以氯化的手套更容易双重穿戴。但是,由某些其它橡胶(例如聚氯丁二烯)制造的手套不容易氯化。为了在聚氯丁二烯表面的摩擦性质方面取得显著的降低,需要使用非常高的氯气浓度,例如2000ppm以上的有效氯,而在这么高的氯气浓度下聚氯丁二烯制品将变得不太适合其预期用途。另外,主要因为加工期间粘性的发展,在氯化聚氯丁二烯外科手套的过程中存在严重的生产困难。
我们现在已经发明了一种制造具有较低的表面摩擦的聚氯丁二烯手套的方法,所述手套更容易双重穿戴。
根据本发明的特征,制造例如手套的聚氯丁二烯制品,其包含少量的另一种更容易氯化的合成聚合物,并且氯化如此形成的手套。
因此,在其最广泛的方面,本发明提供了一种包含比聚氯丁二烯更容易氯化的聚合物的聚氯丁二烯制品。
在另一方面,本发明提供了一种制造具有容易氯化的表面的聚氯丁二烯制品(例如手套)的方法,所述方法包括由聚氯丁二烯的水分散液或溶液形成所述制品,适当地通过将前者浸入所述悬浮液或溶液中,其特征在于在所述分散液或溶液中包含一种或多种比聚氯丁二烯更容易氯化的聚合物。然后,氯化如此形成的制品。
在再一方面中,还提供了通过使用根据本发明的方法制造双重聚氯丁二烯制品(尤其是手套)的方法。
氯化是胶乳表面上化学官能团与氯气的反应。典型地,反应借助聚合物链的不饱和进行,但是化学上是非常复杂的。虽然有一些方法来测量表面氯化,但是这些方法很难实施,并且结果通常不可重复。已经发现表面摩擦或表面阻力(如实施例2中所述)的主观测量能够给出最终用户可接受的可靠结果。氯化的总体物理效应是外表面的***,并且形成导致表面粗糙的表面次微米裂缝。这些都会引起表面摩擦的改善(降低)。
术语“更容易氯化”意指某些聚合物具有活性更高的官能团,在聚合物化学环境中这些官能团比在聚氯丁二烯的官能团对氯气的反应活性高。一般来说,这将涉及聚合物骨架中C=C不饱和键的化学环境。因此,适当的聚合物包括那些具有不饱和基团(特别是C=C基团)的聚合物,它们比聚氯丁二烯中相应的基团对氯气更具有反应性。
聚氯丁二烯中存在弹性聚合物能够有效地通过标准氯化步骤提供可氯化的产品,以使氯化表面具有降低的摩擦。氯化过程可以使用在水中的氯气,或者酸化的次氯酸钠,或者使用氯气给体试剂来实施,所有情况中有效氯的浓度在200-1000ppm之间。所述浓度水平取决于所需的表面滑动(surface slip)。对于良好的滑动和双重穿戴性质,优选的有效氯浓度是400-600ppm。对于手套而言,其表面应该具有良好的滑动性质,即制品外表面的粘性通过氯化而降低,以至于最终的手套可以更容易地双重穿戴。
根据实施例,“标准”条件是每个待处理的手套用大约150毫升含有400-600ppm有效氯的溶液洗涤20分钟,然后用硫代硫酸钠溶液中和10分钟,尽管技术人员将理解还可以使用各种等价处理。
因此,本发明提供了一种制造聚氯丁二烯手套的方法,所述手套可以容易地双重穿戴,而不需用非常高的氯气强度进行预处理。因此不会损害根据本发明制造的聚氯丁二烯手套的性能。
我们优选通过将适当的成型模具浸入复合的聚氯丁二烯水分散液(即胶乳)中来制造聚氯丁二烯手套,但是如果需要也可以使用溶液。下文中,本发明参照胶乳来描述。
添加到聚氯丁二烯胶乳中的弹性聚合物必须自身是在标准氯化条件下可被氯化的材料。优选它们与聚氯丁二烯具有一定的不兼容程度,以至于添加的材料趋向于迁移到聚氯丁二烯薄膜的表面上,从而在薄膜表面上导致更高浓度的容易氯化的聚合物。如此,在聚氯丁二烯薄膜的表面上基本上可以形成可氯化材料的薄层。“不兼容程度”指在分子水平上与聚氯丁二烯不完全混溶的聚合物,以至于在干燥薄膜时至少有一定程度的相分离。
添加的聚合物原则上可以是聚合物链具有一定的不饱和度,比聚氯丁二烯更容易氯化,并且优选在标准条件下可氯化的任何聚合物。我们优选使用诸如羧化丁腈橡胶、羧化苯乙烯丁二烯和聚异戊二烯的聚合物。优选这些聚合物自身是胶乳形式,然后被加入主体胶乳中。
为了达到最好的结果,我们已经发现添加的聚合物应该以较小的量使用。优选向主体胶乳中添加4至15%(与主体胶乳的重量比)的聚合物胶乳。如果使用高于约15%,趋向于改变薄膜的性质,这通常是不可取的。更优选使用5至10%(与主体胶乳的重量比)的聚合物胶乳。
在使用羧化丁腈胶乳作为添加材料的情况中,聚合物优选包含(按重量比)3-6%的羧酸单元、20-40%的丙烯腈单元和60-80%的丁二烯单元。特别优选的级别包含4%羧酸单元、26%丙烯腈单元和70%丁二烯单元。
特别优选的材料是羧化苯乙烯丁二烯(SBR)胶乳,因为即使以较高水平使用时,它对最终的聚氯丁二烯手套的物理性质的不利影响也非常小。优选所用聚合物包含(按重量比)0-5%的羧酸单元、40-60%的苯乙烯单元和40-60%的丁二烯单元。最优选所用聚合物是苯乙烯单元:丁二烯单元的比例为40∶60的羧化苯乙烯丁二烯胶乳。羧酸单元的优选含量在1-3%(按重量比)之间。
另一个优选的材料是合成的顺1,4-聚异戊二烯胶乳,并且它可以按上述一般说明的量使用。
通过浸入复合胶乳中而形成成型橡胶制品(例如手套)的方法在本领域是公知的,在此不作进一步描述。实例包括Enichem的Europrene 5583,它是一种包含40%(重量比)的苯乙烯的羧化苯乙烯丁二烯;以及Synthomer 6000(Synthomer),一种包含20%(重量比)丙烯腈的羧化腈胶乳。
在优选实施方案中,通过将成型模具浸入包含羧化苯乙烯丁二烯的聚氯丁二烯胶乳中来制造聚氯丁二烯手套。用例如在EP-A-105613、EP-A-198514和EP 199318中公开的水凝胶聚合物材料涂布手套的内表面。优选的水凝胶聚合物是在我们的欧洲专利105613中描述的甲基丙烯酸-2-羟乙酯(HEMA)与甲基丙烯酸(MAA)和/或丙烯酸-2-乙基己酯(EHA)的共聚物。我们优选使用包含约68摩尔%HEMA、14摩尔%MAA和18摩尔%EHA的共聚物。水凝胶聚合物涂层优选通过将凝结的聚氯丁二烯手套浸入水凝胶聚合物的分散液中来实施。一旦水凝胶聚合物层已经涂布到橡胶上、结合并固化后,优选在表面活性剂溶液中翻动手套。优选的表面活性剂包括那些在US3,813,695(“Podell专利”)中描述的化合物。然后,在标准条件下氯化手套。可以在涂布任何水凝胶聚合物层之前,或者在涂布所述层之后进行氯化。令人惊奇地是我们发现当在涂布水凝胶层后进行氯化时,所述层的性质(提供了优异的干和湿滑动)不受氯化的影响。然后,由此制得的氯化的聚氯丁二烯手套在以相同方式制造的另一个聚氯丁二烯手套上容易地双重穿戴。
通常,复合胶乳包含:
典型地,所述胶乳固体是40-47%(组合物重量比),优选范围为45-46%。
为了更完全地理解本发明,仅通过举例说明方式给出下面的实施例。
实施例1(比较)
如下制造薄壁外科手套。手套成型模具被浸入硝酸钙(SG1.10-1.20)的溶液中,然后在90-110℃下干燥20-30秒。然后,将成型模具浸入复合胶乳中,其包含氯丁橡胶750(2-氯-1,3-丁二烯和2,3-二氯-1,3-丁二烯的共聚物;总固体含量(TSC)=40-46%),但不含有任何附加的可氯化聚合物。根据上述优选配方,胶乳包含Rhenocure,DPG(二苯胍)和锌BuD(二丁基二硫代氨基甲酸锌)作为促进剂,硫和氧化锌作为硫化剂,Dehydol和Arylan作为稳定剂,Wingstay L作为抗氧化剂,并且Colanyl蓝A2R作为颜料。
涂布的成型模具在约100℃下干燥约1分钟,然后成边(beaded),接着在55-60℃的水中浸提约3分钟,然后在空气中干燥约20秒。然后,浸入0.9-1.1%盐酸中,用水漂洗,然后在热空气流中干燥,以修整成型模具上胶乳的表面。然后,将涂布的成型模具浸入HydrocoteA(一种基本上由68摩尔%HEMA、14摩尔%MAA和18摩尔%EHA组成的三元共聚物)的工业用甲醇改性酒精(IMS)溶液中,珠化并在125-145℃下固化25-30分钟。然后,从成型模具上剥离手套,并用水洗涤,然后在含有0.25%CPC、0.075%聚硅氧烷的溶液中洗涤并干燥。然后,在0.05%的Darvan L(抗粘剂)中洗涤15-30分钟。在用水洗涤后,将手套在90℃下干燥120分钟。
实施例2
除了使用包含含有7.5重量%的羧化SBR胶乳的氯丁橡胶750(即氯丁橡胶750和羧化SBR的比例为92.5∶7.5)的胶乳外,根据实施例1制造外科手套。羧化SBR胶乳是购自Enichem的Europrene 5583,其包含40重量%的苯乙烯。还省去了在抗粘剂中的洗涤步骤,而是根据下面的步骤来氯化手套:
a)在水中洗涤手套,并将水排干。
b)在包含400-600ppm有效氯的溶液中翻动手套约20分钟。
c)然后,添加硫代硫酸钠中和剂,并且继续翻动手套10分钟。(根据需要可以使用其它中和剂,例如碳酸钠)
d)取出手套,然后在包含0.1%Rexanol的水洗涤,取出,在水中洗涤,最后取出并干燥。
然后,通过测量手套外表面的表面阻力来确定所述方法的有效性。这是一种主观试验,并且以下面方式进行。
试验人用肥皂和水洗净他们的手,然后淋洗掉肥皂,并且弄干手。用一只手把持手套的卷边(bead area)来进行评价。然后,试验人用另一只手的拇指和食指轻轻地握住手套,并轻轻地从手套的腕部向手套的指尖方向向下滑动这些手指。使用另外的三根手套手指重复同样的动作。
使用下面的等级,并且参照表面阻力试验的参考样品在每一步评价主观表面阻力。
1.0非常光滑
2.0相当光滑
3.0中等阻力
4.0高度阻力且没有粘性
根据实施例2制造的手套具有1-2级的表面阻力,而根据实施例1,单独用氯丁橡胶750制造的氯丁橡胶手套具有约3.0的等级。
1-2级的手套能够在以相同方式制造的另一个聚氯丁二烯手套上面容易地双重穿戴。
根据实施例2,使用下面给出的配方制造其它的手套。根据实施例2中描述的试验,发现这些手套具有1级的表面阻力。
实施例3
成分 | pphr |
氯丁橡胶750 | 100 |
胶乳稳定剂 | 1.0 |
羧化SBR胶乳 | 8.1 |
橡胶促进剂 | 1.5 |
硫化剂 | 12.0 |
抗氧化剂 | 1.0 |
颜料 | 1.0 |
实施例4
成分 | pphr |
氯丁橡胶750 | 100 |
胶乳稳定剂 | 1.0 |
羧化腈胶乳 | 8.1 |
橡胶促进剂 | 1.5 |
硫化剂 | 12.0 |
抗氧化剂 | 1.0 |
颜料 | 1.0 |
实施例5
成分 | pphr |
氯丁橡胶750 | 100 |
胶乳稳定剂 | 1.0 |
顺-1,4-聚异戊二烯胶乳 | 8.1 |
橡胶促进剂 | 1.5 |
硫化剂 | 12.0 |
抗氧化剂 | 1.0 |
颜料 | 1.0 |
根据实施例2至5制造的手套的外表面具有良好的滑动性质,非常适用于双重穿戴。
Claims (10)
1.聚氯丁二烯制品用于双重穿戴的用途,所述聚氯丁二烯制品由聚氯丁二烯胶乳形成,其中所述胶乳包含4-15重量%的聚合物胶乳,其中所述聚合物是包含3-6重量%的羧酸单元、20-40重量%的丙烯腈单元和60-80重量%的丁二烯单元的羧化丁腈橡胶,或者是羧化苯乙烯丁二烯,或聚异戊二烯,包括合成顺-1,4-聚异戊二烯。
2.制备用于根据权利要求1所述的用途的聚氯丁二烯制品的方法,该方法包括由聚氯丁二烯的含水分散液形成所述制品,所述含水分散液包含4-15重量%的聚合物胶乳,其中所述聚合物是包含3-6重量%的羧酸单元、20-40重量%的丙烯腈单元和60-80重量%的丁二烯单元的羧化丁腈橡胶,或者是羧化苯乙烯丁二烯,或聚异戊二烯,包括合成顺-1,4-聚异戊二烯;
并将所述制品双重穿戴。
3.根据权利要求2所述的制备聚氯丁二烯制品的方法,其还包括氯化所述制品的步骤。
4.根据权利要求1所述的用途或根据权利要求2或3所述的方法,其中所述制品是薄膜制品。
5.根据权利要求1或4所述的用途或根据权利要求2、3或4所述的方法,其中所述制品是手套,尤其是外科手套。
6.根据权利要求1、4或5所述的用途或根据权利要求2-5任一项所述的方法,其中所述聚合物是含有0-5重量%的羧酸单元、40-60重量%的苯乙烯单元和40-60重量%的丁二烯单元的羧化苯乙烯丁二烯。
7.根据权利要求4、5或6所述的用途或根据权利要求2-6任一项所述的方法,其中所述聚合物胶乳的量为聚氯丁二烯胶乳的5-10重量%。
8.根据权利要求1、4、5、6或7任一项所述的用途,其是在其接触使用者的内表面上包含水凝胶层的手套。
9.制备可双重穿戴的聚氯丁二烯制品,尤其是手套的方法,该方法为权利要求3-8任一项所述的方法。
10.聚异戊二烯,包括合成顺-1,4-聚异戊二烯用于制备由聚氯丁二烯胶乳形成的可双重穿戴的制品的用途,其中所述聚氯丁二烯胶乳包含4-15重量%的聚合物胶乳,所述聚合物胶乳包含聚异戊二烯或合成顺-1,4-聚异戊二烯。
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Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8110266B2 (en) | 2007-02-08 | 2012-02-07 | Allegiance Corporation | Glove coating and manufacturing process |
US7805773B2 (en) * | 2007-03-12 | 2010-10-05 | Joseph Di Lorenzo | Surgical glove |
US20100192295A1 (en) | 2007-06-01 | 2010-08-05 | Liquidbreaker Llc | Drain Cartridge Having Removable Valved System |
US7900288B2 (en) | 2007-06-01 | 2011-03-08 | Liquidbreaker, Llc | Drain cartridge having removable valved system |
US20080306200A1 (en) | 2007-06-11 | 2008-12-11 | Seong Fong Chen | Antistatic gloves and process for making same |
AU2009223247B2 (en) | 2008-03-14 | 2015-06-18 | Allegiance Corporation | Water-based resin composition and articles made therefrom |
CN102459972B (zh) | 2009-05-05 | 2015-09-23 | 李奎德布瑞科尔公司 | 具有可拆除的阀***的排水道滤芯 |
GB201021903D0 (en) * | 2010-12-23 | 2011-02-02 | Midas Safety Inc | Elastomeric films |
WO2012121135A1 (ja) * | 2011-03-10 | 2012-09-13 | 電気化学工業株式会社 | ポリクロロプレンラテックスの化学的安定性の評価方法 |
CN105358618B (zh) * | 2013-07-10 | 2017-04-26 | Ttk防护设备有限公司 | 一种用于制备浸渍胶乳制品的二元工艺 |
CN105492179B (zh) | 2013-07-16 | 2019-03-08 | 皮肤防护有限公司 | 形成弹性体膜的组合物和由所述弹性体膜制成的制品 |
US10253170B2 (en) | 2014-03-25 | 2019-04-09 | Ansell Limited | Polyisoprene/polychloroprene compositions |
ES2883225T3 (es) * | 2015-10-18 | 2021-12-07 | Allegiance Corp | Revestimiento de mezcla de hidrogel a base de agua y método de aplicación a artículos elastoméricos |
MY190526A (en) * | 2016-12-30 | 2022-04-27 | Skinprotect Corp Sdn Bhd | Elastomeric film-forming compositions and associated articles and methods |
US10479874B1 (en) * | 2018-02-15 | 2019-11-19 | Shimon Amdur | Latex compositions and antistatic articles manufactured therefrom |
KR102155169B1 (ko) * | 2018-10-19 | 2020-09-11 | 아주대학교산학협력단 | 의료용 이중 장갑 |
AU2022319176A1 (en) * | 2021-07-27 | 2024-03-07 | Ansell Limited | Accelerator free synthetic gloves with high tear resistance |
CN114316395B (zh) * | 2022-01-11 | 2023-06-02 | 星宇医疗科技股份有限公司 | 一种复合胶乳的制备方法和应用 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6503238A (zh) * | 1964-03-18 | 1965-09-20 | ||
US3813695A (en) | 1973-02-21 | 1974-06-04 | D Podell | Surgical glove |
US4102844A (en) * | 1973-09-22 | 1978-07-25 | Bayer Aktiengesellschaft | Dipped articles of rubber |
JPS53101036A (en) * | 1977-02-15 | 1978-09-04 | Kuraray Co Ltd | Manufacture of synthetic rubber molded product |
DE2922656A1 (de) | 1979-06-02 | 1980-12-04 | Wilfried Messerschmidt | Vorrichtung mit einem mahlwerk |
EP0084325B1 (en) | 1982-01-16 | 1988-04-20 | Kei Mori | Apparatus for photosynthesis |
PT77275B (en) | 1982-09-03 | 1986-02-04 | Lrc Products | Rubber article with a lubricating layer and a process for the production thereof by dipping means |
SU1288189A1 (ru) * | 1985-04-10 | 1987-02-07 | Научно-исследовательский институт резиновых и латексных изделий | Композици дл получени пленочных изделий |
US5351698A (en) | 1988-11-15 | 1994-10-04 | Family Health International | Bidirectionally donnable generally tubular sheath articles, and apparatus and method for making and using same |
US5084514A (en) * | 1990-11-14 | 1992-01-28 | Reichhold Chemicals, Inc. | Latex gloves with improved donnability |
GB9219658D0 (en) | 1992-09-17 | 1992-10-28 | Fraser Studios Ltd | Rubber gloves |
EP0643743B1 (en) * | 1993-03-01 | 1998-10-28 | Allegiance Corporation | Sequential copolymer based gloves |
GB2292384A (en) | 1994-08-11 | 1996-02-21 | Wembley Rubber Products | Coating composition, method of using it and article coated with same |
AU5866296A (en) * | 1995-06-07 | 1996-12-30 | Allegiance Corporation | Surgeon's gloves from neoprene copolymers |
AT409819B (de) * | 1996-09-12 | 2002-11-25 | Semperit Ag Holding | Gegenstand aus einem flexiblen gummi und/oder kunststoff |
AU741202B2 (en) * | 1997-11-07 | 2001-11-22 | Microflex Corporation | Elastomeric articles from a blend of polychloroprene and acrylonitrile |
CA2227645A1 (en) * | 1998-01-21 | 1999-07-21 | Eci Medical Technologies Inc. | Multi-layered thin-walled powder-free articles manufactured from styrene block copolymers |
US6195805B1 (en) * | 1998-02-27 | 2001-03-06 | Allegiance Corporation | Powder free neoprene surgical gloves |
US6329444B1 (en) * | 1998-10-14 | 2001-12-11 | Apex Medical Technologies, Inc. | Dip-molded medical devices from cis-1,4-polyisoprene |
US6347408B1 (en) * | 1998-11-05 | 2002-02-19 | Allegiance Corporation | Powder-free gloves having a coating containing cross-linked polyurethane and silicone and method of making the same |
US6000061A (en) | 1998-11-18 | 1999-12-14 | Pt. Irama Dinamika Latex | Glove made from a blend of chloroprene rubber and a carboxylated synthetic butadiene rubber |
NZ513955A (en) | 1999-02-12 | 2001-09-28 | Allegiance Corp | Powder-free nitrile-coated gloves with an intermediate rubber-nitrile layer between the glove and the coating |
US6391409B1 (en) * | 1999-02-12 | 2002-05-21 | Allegiance Corporation | Powder-free nitrile-coated gloves with an intermediate rubber-nitrile layer between the glove and the coating and method of making same |
GB0025777D0 (en) | 2000-10-20 | 2000-12-06 | S S L Internat | Neoprene glove |
US20080306200A1 (en) * | 2007-06-11 | 2008-12-11 | Seong Fong Chen | Antistatic gloves and process for making same |
-
2002
- 2002-05-14 GB GBGB0211027.8A patent/GB0211027D0/en not_active Ceased
-
2003
- 2003-05-14 CA CA2485746A patent/CA2485746C/en not_active Expired - Lifetime
- 2003-05-14 US US10/514,020 patent/US8187684B2/en not_active Expired - Fee Related
- 2003-05-14 DK DK03749958.9T patent/DK1511610T3/da active
- 2003-05-14 IL IL16515103A patent/IL165151A0/xx unknown
- 2003-05-14 WO PCT/GB2003/002083 patent/WO2003095172A1/en active Application Filing
- 2003-05-14 MX MXPA04011212A patent/MXPA04011212A/es active IP Right Grant
- 2003-05-14 JP JP2004503231A patent/JP2005529641A/ja not_active Withdrawn
- 2003-05-14 CN CN03816714XA patent/CN1668438B/zh not_active Expired - Lifetime
- 2003-05-14 RU RU2004136305/04A patent/RU2325278C2/ru not_active IP Right Cessation
- 2003-05-14 CN CN2010105101335A patent/CN102093604A/zh active Pending
- 2003-05-14 DE DE60334902T patent/DE60334902D1/de not_active Expired - Lifetime
- 2003-05-14 EP EP03749958A patent/EP1511610B1/en not_active Expired - Lifetime
- 2003-05-14 NZ NZ536724A patent/NZ536724A/en not_active IP Right Cessation
- 2003-05-14 AU AU2003242825A patent/AU2003242825C1/en not_active Ceased
- 2003-05-14 EP EP10184628A patent/EP2360001A1/en not_active Withdrawn
- 2003-05-14 BR BR0309984-9A patent/BR0309984A/pt not_active IP Right Cessation
- 2003-05-14 AT AT03749958T patent/ATE487582T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
GB0211027D0 (en) | 2002-06-26 |
US8187684B2 (en) | 2012-05-29 |
EP1511610B1 (en) | 2010-11-10 |
CN1668438B (zh) | 2010-12-15 |
DE60334902D1 (de) | 2010-12-23 |
EP2360001A1 (en) | 2011-08-24 |
EP1511610A1 (en) | 2005-03-09 |
DK1511610T3 (da) | 2011-02-21 |
RU2004136305A (ru) | 2005-05-10 |
ATE487582T1 (de) | 2010-11-15 |
MXPA04011212A (es) | 2005-11-17 |
CN1668438A (zh) | 2005-09-14 |
AU2003242825A1 (en) | 2003-11-11 |
WO2003095172A1 (en) | 2003-11-20 |
JP2005529641A (ja) | 2005-10-06 |
NZ536724A (en) | 2007-04-27 |
BR0309984A (pt) | 2005-03-01 |
CA2485746A1 (en) | 2003-11-20 |
CA2485746C (en) | 2011-08-02 |
US20060010565A1 (en) | 2006-01-19 |
RU2325278C2 (ru) | 2008-05-27 |
IL165151A0 (en) | 2005-12-18 |
AU2003242825C1 (en) | 2010-03-04 |
AU2003242825B2 (en) | 2009-10-29 |
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Application publication date: 20110615 |