CN1433879A - 具有聚合物涂层的外表面和氯化的内表面的橡胶制品 - Google Patents
具有聚合物涂层的外表面和氯化的内表面的橡胶制品 Download PDFInfo
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Classifications
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Abstract
本发明涉及具有含聚合物涂层的外表面和氯化的内表面的双面处理形成的橡胶制品。本发明还涉及一种手套的制备方法,该方法使用作为手套外表面的脱模剂和防粘剂的聚合物,并氯化手套内表面。该橡胶制品可成型为无粉手套。
Description
本发明涉及其外表面有聚合物涂层且内表面氯化的双面处理橡胶制品。本发明还涉及形成这种制品,尤其是形成乳胶手套的在线方法。
发明背景
橡胶制品为具有低玻璃化转化温度(Tg)的弹性材料。低Tg制品的表面容易互相粘合。尤其是在橡胶或乳胶手套中,手套内表面必需具有良好的donning,而手套外表面(在制造期间与模型接触)必需能很容易地与模型脱离,而且当其包装时不能与其他手套粘连(必需具有良好的防粘性能)。这些问题迄今都已通过用诸如淀粉、滑石或碳酸钙的粉末涂覆手套的内外表面来解决。
粉末涂料是公知的公害,因为散开的粉末能悬浮在空气中。粉末容易吸收天然橡胶乳胶中的蛋白质,而且粉末在donning和使用中容易移动,污染周围环境并造成过敏症和其他负面影响。此外,蛋白质/粉末配合物起到细菌的食物来源的作用,使细菌繁殖。近年来,对不使用松散粉末来donning和脱模的无粉天然和合成橡胶手套的需求日益增长。
对采用粉末的手套的一种替代物是采用氯化的内外表面,以降低橡胶粘性和摩擦力的无粉手套。该方法的另一个优点是降低了乳胶的蛋白质水平。其缺点是氯化过程使橡胶的柔韧性降低,并缩短了橡胶的储存寿命。手套的双面氯化是劳动强度很大的过程,因为必需将手套从模型上剥离,以氯化其外表面。
制备无粉手套的另一种方法是采用聚合物涂层。已发展了许多种聚合物涂层,主要是基于聚氨酯:美国专利5088125公开了通过离子型聚氨酯改性的手套;美国专利5272771公开了通过含有全反应异氰酸酯基团的离子型聚氨酯改性的手套;美国专利5534350公开了手套外涂层含有聚氨酯分散体和手套内涂层含有包含硅氧烷乳液的聚氨酯的手套。
已发展的其他涂料包括含有低表面能量单体和硬单体的乳液共聚物,尤其是核壳乳液共聚物,如美国专利5691069及5700585中公开的;或含有选自苯乙烯、丙烯酸甲酯或丙烯酸丁酯、甲基丙烯酸或丙烯酸和硅氧烷低聚物的两种单体的乳液共聚物,其玻璃化转化温度低于0℃,和分别为0~100℃,如美国专利5712346公开的。这些依次进行的乳液聚合反应实质上产生直链共聚物。同时待审的美国专利申请09/400488描述了用星形高聚物作为乳胶手套涂层的方法。同时待审的美国专利申请09/663468和09/882222描述了分别用于手套内涂层和外涂层的聚合物涂层和聚合物脱模组合物,此处参考引用。
现已发现用于涉及内表面的氯化和外表面的聚合物涂覆的双面处理橡胶制品的连续在线处理方法能有益地将两种技术的正面特性结合,制备无粉手套。在线外涂覆方法与离线的氯化过程结合,使氯化处理在其他时间内进行,而不受生产线速度限制;也能在封闭系统中进行氯化处理,以控制氯的排放。
本发明概述
本发明涉及其外表面有聚合物涂层且内表面氯化的双面处理橡胶制品。
本发明还涉及制备手套的方法,包括:
a)手套模型浸入含有包含聚合物的脱模组合物的助凝剂溶液中,制备带涂层的模型;
b)将带涂层的模型浸入橡胶乳胶中,用所述乳胶涂覆模型;
c)在带涂层的模型上氯化乳胶;
d)在带涂层的模型上固化己氯化的乳胶;和
e)从模型上脱出完成的手套。
本发明还涉及手套的制备方法,包括:
a)将手套模型浸入含有包含聚合物的脱模组合物的助凝剂溶液中,制备带涂层的模型;
b)将带涂层的模型浸入橡胶乳胶中,用所述乳胶涂覆模型;
c)在带涂层的模型上固化乳胶;
d)在带涂层的模型上氯化乳胶;和
e)从模型上脱出完成的手套。本发明详细描述
本发明涉及具有聚合物涂覆的外表面;和氯化的内表面的双面处理橡胶制品;和制备所述手套的方法。
本文所用的橡胶制品指用天然或合成的、低Tg的弹性聚合物或聚合物混合物制成的制品。这种聚合材料的实例包括(但不限于)丁基橡胶、天然乳胶橡胶、聚氯乙稀、氯丁橡胶、腈、合成橡胶、苯乙烯-丁二烯共聚物、聚氨酯或互穿聚合物网络乳液聚合物,或它们的结合。
橡胶制品外表面上的聚合物涂层既起到脱模剂的作用,也起到防粘剂的作用。本发明的聚合物优选的具有高于-10℃的Tg,优选的25-200℃,最优选的40-150℃。为了在手套制造过程中容易使用,聚合物应是水基的。
用于外涂层的优选聚合物是由至少一种疏水单体形成的共聚物。该聚合物还可以含有,并优选的确实含有至少一种亲水单体,尽管可用的聚合物可以不用亲水单体形成。可用于形成本发明的聚合物的单体为烯属不饱和单体或其混合物。
外涂层聚合物的优选制备方法描述在同时待审的美国专利申请09/882222中。
用作橡胶制品外涂层的聚合物可与其他非必需的成分如分散剂、表面活性剂、微球和流变改性剂一起配制。
优选的聚合物涂层不含硅氧烷,然而将硅氧烷加入组合物中也是有益的。组合物中含有硅化合物的问题是它们会残留在模具或模型上,使模具或模型更难清洗。
聚合物涂料组合物还可含有微球。微球在减小表面接触面积上是有益的,这样就降低了涂覆的橡胶制品与模具、模型或其他物体间的粘性。既改善了脱模性能,又提高了防粘性。
可非必需的加入分散剂,有助于将微球分散在含水聚合物组合物中。可用于本发明的分散剂包括(但不限于)表面活性剂和包括两亲直链共聚物和星形共聚物的聚合分散剂。
流变改性剂可非必需的存在于脱模组合物中。
外涂层聚合物组合物还可含有本领域公知的其他添加剂,如增粘剂、交联剂、生物杀伤剂、低表面能量化合物、填料和消泡剂。
用于橡胶制品外表面的聚合物组合物通过用本领域公知的方法将每种成分混和形成水性分散体来制备。
配制外涂层聚合物的优选方法描述在同时待审的专利申请09/882222中,此处参考引用。
橡胶制品内表面的氯化可通过本领域公知的任何方法进行,包括浸入氯水溶液中,或浸入随时间可释放亲电子的氯的溶液中。用于本发明的氯水溶液含有500-15000ppm的氯,优选的1000-10000ppm的氯。该溶液可用含有次氯酸钠的漂白液,并在使用前加入盐酸来制备。手套的氯化可在线或离线进行,但优选的是在线氯化,以减少制造步骤和降低成本。
作为任何双面处理橡胶制品的形成方法,将列举手套,尤其是天然乳胶手套的形成方法。
本发明的乳胶手套的形成方法由以下几个基本步骤构成:
a)用聚合物(外)涂料涂覆手形模型,
b)用助凝剂涂覆模型,
c)用乳胶涂覆模型,
d)氯化乳胶(手套内部),
e)固化乳胶,
f)从模型上脱出手套。该方法中可以有几种变化。在某些情况下,步骤a)和b)可用既含有聚合物又含有助凝剂的水浴合并为一步。在其他情况下,步骤d)和e)反过来进行,先固化乳胶,然后氯化乳胶。
一般通过将模型浸入装有水性聚合物分散体的容器中,将聚合物外涂层涂覆到手形模型或模具表面。模具和模型可以是本领域公知的任何材料,包括(但不限于)陶瓷、玻璃和不锈钢。然后将涂覆了聚合物的模型浸入含有乳胶助凝剂的助凝剂混合物中。可用的助凝剂包括(但不限于)硝酸钙和氯化钙。作为可选的方法,可在单一步骤中而不是在分开的两个步骤中,将干净的模型或模具浸入含有聚合物组合物的助凝剂中。
干燥后,可用涂覆了聚合物涂层和助凝剂的模具,通过本领域公知的方法制备手套。例如,将涂覆的模具浸入天然或合成橡胶乳胶中一段时间,使橡胶足以凝结,并形成要求厚度的橡胶涂层。然后非必需地用水清洗手套,以除去橡胶中的杂质。然后将形成的手套在烘箱中固化,冷却并氯化。作为选择,可在烘箱固化和冷却前氯化形成的手套。冷却后,同时将手套从模具剥离并翻面。手套模具或模型上的部分或全部聚合物涂层就转移成为手套的外表面。
手套的氯化也可以离线进行。该过程包括将天然橡胶乳胶沉积在涂覆的模型上,如上所述。然而,在乳胶固化前,将模型浸入含有脱模和防粘助剂,如淀粉或碳酸钙的溶液中。然后烘箱固化已涂覆的手套。冷却后,同时将手套从模具上剥离并翻面。然后手工翻面手套并氯化暴露的表面。在氯化期间或氯化后,可除去粉末状脱模和防粘助剂。然后再手工翻面手套,使氯化的表面变成donning侧,即内表面。作为选择,如果将手套自动剥离而不翻面,将手套直接氯化。就能得到具有氯化的donning表面的手套,而不需与翻面操作相关的额外劳动。
用本发明的方法形成的橡胶制品包括手套、避孕套、导管、轮胎、泳帽、气球、管子和薄膜。特别合适的最终应用是作为乳胶手套,包括外科医生手套、内科医生诊断手套和工人手套,更具体的是无粉乳胶手套生产中的脱模组合物。
以下实施例用于进一步描述和解释本发明,但并不限制本发明。实施例1:氯水的制备
将5L含有1000ppm次氯酸钠的漂白液装入6L容器中。
使用前将500ppm盐酸加入容器中。实施例2:在硫化前通过在线氯化制备乳胶手套
通过以下步骤制备手套:
(a)将手套模型浸入含有聚合物组合物的助凝剂溶液中,以制备带涂层的模型,所述聚合物组合物含有Tg大于-10℃、用至少一种疏水单体和至少一种亲水单体形成的水基聚合物;
(b)将带涂层的模具浸入天然橡胶乳胶中,用乳胶涂覆模型;
(c)在实施例1制备的氯水中漂洗乳胶涂覆的模型,除去橡胶中的杂质,并氯化手套内表面;
(d)在烘箱中固化乳胶;和
(e)将完成的手套从模型上脱出。
完成的手套两面都进行处理,其中内表面表现出非常好的donnability,而外表面表现出良好的防粘性。实施例3:在硫化后通过在线氯化制备乳胶手套
通过以下步骤制备手套:
(a)手套模型浸入含有聚合物组合物的助凝剂溶液中,以制备带涂层的模型,所述聚合物组合物含有Tg大于-10℃、用至少一种疏水单体和至少一种亲水单体形成的水基聚合物;
(b)将带涂层的模具浸入天然橡胶乳胶中,用乳胶涂覆模型;
(c)在水中漂洗乳胶涂覆的模型,除去橡胶的杂质;
(d)在烘箱中固化乳胶;
(e)将乳胶手套浸入实施例1的氯水中;和
(f)将完成的手套从模型上脱出。
完成的手套两面都进行处理,其中内表面表现出良好的donnability,而外表面表现出非常好的防粘性。实施例4:用较高的氯剂量硫化后通过在线氯化制备乳胶手套
如实施例3所述通过在线氯化制备双面处理乳胶手套,不同的是所用氯水含有3000ppm次氯酸钠和1500ppm盐酸。完成的手套两面都进行处理,其中内表面表现出非常好的donnability,而外表面也表现出非常好的防粘性。实施例5:用较高的氯剂量硫化后通过在线氯化制备乳胶手套
如实施例3所述通过在线氯化制备双面处理乳胶手套,不同的是所用氯水含有5000ppm次氯酸钠和2500ppm盐酸。完成的手套两面都进行处理,其中内表面表现出非常好的donnability,而外表面也表现出非常好的防粘性。实施例6:通过离线氯化制备乳胶手套
通过以下步骤制备手套:
(a)手套模型浸入含有聚合物组合物的助凝剂溶液中,以制备带涂层的模型,所述聚合物组合物含有Tg大于-10℃、用至少一种疏水单体和至少一种亲水单体形成的水基聚合物;
(b)将带涂层的模具浸入天然橡胶乳胶中,用乳胶涂覆模型;
(c)在烘箱中固化所述模型上的乳胶;
(d)将乳胶手套浸入含有~2%淀粉的分散体中;
(e)表面干燥后,将完成的手套从模型上脱出;
(f)在含有500ppm次氯化物和250ppm盐酸的氯水中漂洗内表面已暴露在外的完成的手套15分钟;
(g)用水冲洗手套并干燥手套表面;
(h)翻面手套,使氯化表面变成donning侧。
完成的手套两面都进行处理,其中内表面表现出良好的donnability,而外表面表现出非常好的防粘性。
Claims (24)
1、包含双面处理形成的橡胶制品的制品,具有:
a)在外表面的聚合物涂层组合物;和
b)氯化的内表面。
2、权利要求1的制品,其中所述橡胶制品用天然乳胶橡胶形成。
3、权利要求1的制品,其中所述橡胶制品用合成弹性聚合物形成。
4、权利要求1的制品,其中所述制品为无粉的。
5、权利要求1的制品,其中聚合物包含Tg大于-10℃、用至少一种疏水单体和至少一种亲水单体形成的水基聚合物。
6、权利要求1的制品,其中所述制品选自手套、避孕套、导管、轮胎、泳帽、气球、管子和薄膜。
7、手套的制备方法,包括:
a)将手套模型浸入水性聚合物组合物中;
b)将所述手套模型浸入助凝剂溶液中,制备带涂层的模型;
c)将带涂层的模型浸入橡胶乳胶中,用所述乳胶涂覆模型;
d)氯化所述带涂层模型上的乳胶;
e)固化所述带涂层模型上己氯化的乳胶;和
f)将完成的手套从模型上脱出。
8、权利要求7的方法,其中通过将手套模型浸入含有所述水性聚合物组合物的助凝剂溶液中,使a)和b)在同一步骤中进行。
9、权利要求7的方法,其中所述聚合物包含Tg大于-10℃、用至少一种疏水单体和至少一种亲水单体形成的水基聚合物。
10、权利要求7的方法,其中乳胶涂覆的模型的氯化包括将所述模型浸入含有氯和水的溶液中。
11、权利要求7的方法,其中所述氯水溶液含有500-15000ppm的氯。
12、权利要求11的方法,其中所述氯水溶液含有1000-10000ppm的氯。
13、权利要求7的方法,其中所述乳胶的氯化在线进行。
14、手套的制备方法,包括:
a)将手套模型浸入水性聚合物组合物中;
b)将所述手套模型浸入助凝剂溶液中,制备带涂层的模型;
c)将带涂层的模型浸入橡胶乳胶中,用所述乳胶涂覆模型;
d)固化所述带涂层模型上的乳胶;
e)氯化所述带涂层模型上的乳胶;和
f)将完成的手套从模型上脱出。
15、权利要求14的方法,其中通过将手套模型浸入含有所述水性聚合物组合物的助凝剂溶液中,使a)和b)在同一步骤中进行。
16、权利要求14的方法,其中所述聚合物包含Tg大于-10℃、用至少一种疏水单体和至少一种亲水单体形成的水基聚合物。
17、权利要求14的方法,其中乳胶涂覆的模型的氯化包括将所述模型浸入含有氯和水的溶液中。
18、权利要求14的方法,其中所述氯水溶液含有500-15000ppm的氯。
19、权利要求14的方法,其中乳胶的所述氯化在线进行。
20、手套的制备方法,包括:
a)将手套模型浸入水性聚合物组合物中;
b)将所述手套模型浸入助凝剂溶液中,制备带涂层的模型;
c)将带涂层的模型浸入橡胶乳胶中,用所述乳胶涂覆模型;
d)将所述橡胶乳胶涂覆的模型浸入含有脱模剂和防粘剂的溶液中;
e)固化所述带涂层模型上的乳胶;
f)将完成的手套从模型上脱出;
g)氯化暴露的手套内表面;
h)翻面手套,使其内表面处于已完成手套内侧。
21、权利要求20的方法,其中所述粉末状脱模剂和防粘剂在氯化期间或氯化后,但在翻面前,并正好在步骤h)前除去,以形成无粉手套。
22、权利要求20的方法,其中所述防粘剂包括淀粉或碳酸钙。
23、权利要求20的方法,其中所述在步骤f)中将已固化的手套从模型上脱出包括手套不翻面的机械脱出。
24、权利要求20的方法,其中所述在步骤f)中将已固化的手套从模型上脱出包括在脱出期间将手套翻面,使其内表面在手套内,然后再将手套翻面,使手套内表面在手套外侧,然后在步骤g)中氯化暴露的手套内表面。
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2003
- 2003-01-21 MY MYPI20030198A patent/MY127781A/en unknown
- 2003-01-22 CN CN03119858.9A patent/CN1433879A/zh active Pending
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CN113693319A (zh) * | 2021-08-20 | 2021-11-26 | 南京润京乳胶制品有限公司 | 一种易穿戴医用乳胶手套及其使用方法 |
CN115091672A (zh) * | 2022-02-22 | 2022-09-23 | 深圳市可信华成通信科技有限公司 | 一种无链式手套全自动生产设备 |
CN115091672B (zh) * | 2022-02-22 | 2024-03-15 | 广东可成智能技术有限公司 | 一种无链式手套全自动生产设备 |
Also Published As
Publication number | Publication date |
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US6764731B2 (en) | 2004-07-20 |
US20030138579A1 (en) | 2003-07-24 |
MY127781A (en) | 2006-12-29 |
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