CN117402480A - 一种组合物和使用该组合物制备水性聚氨酯手套的方法 - Google Patents
一种组合物和使用该组合物制备水性聚氨酯手套的方法 Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
本发明提供一种组合物和使用该组合物制备水性聚氨酯手套的方法。该组合物包含:(1)胶液原料,其包含水性聚氨酯树脂、钛白浆、消泡剂、金属盐类或金属氢氧化物和水;(2)絮凝剂/脱模剂混合溶液原料,其包含脱模剂、絮凝剂和水。使用本发明组合物得到的聚氨酯手套易脱模、不结皮,同时所得水性聚氨酯手套力学性能好。
Description
技术领域
本发明涉及聚氨酯手套技术领域,具体涉及一种组合物和使用该组合物制备水性聚氨酯手套的方法。
背景技术
一次性防护手套与我们的生产生活息息相关,其中丁腈手套、乳胶手套和PVC手套为目前主流三大一次性手套产品,这些手套各具特色,根据其性能优势应用在各个领域。丁腈和乳胶手套制备需要进行硫化,这一过程中会加入各种硫化剂等助剂,导致手套存在异味,且硫化需要在较高的温度下进行,能耗较高;丁腈手套因其没有弹性,导致手感偏硬不能用于较为精密的操作,如外科手术;乳胶手套因为含有残留的蛋白质会导致部分人群存在过敏的现象,因此在有些领域的应用受到限制。
水性聚氨酯手套具有无毒无味、生产工艺简单的优点,是当今一次性手套研究的热点。因为水性聚氨酯的制备方法与丁腈乳液、乳胶的制备方法有差异,因此决定了水性聚氨酯手套的制备工艺与其也有较大差别。丁腈乳液的合成采用类似丙烯酸乳液的合成方法,是乳液聚合法,颗粒表面被非离子乳化剂、阴离子乳化剂等外乳化剂包覆,因此对金属离子的容忍性高,而水性聚氨酯采用自乳化工艺,表面的亲水基团连接在聚合物链段上,没有外乳化剂包覆,因此对金属离子的容忍性低于丁腈乳液,另外如果使用外乳化剂,反而会影响正常的絮凝,无法制备手套。因此,减少或消除金属离子进入胶液,避免影响胶液的离子稳定性是水性聚氨酯絮凝法制备手套的关键所在。
发明内容
本发明的目的在于提供一种可以稳定生产水性聚氨酯手套的工艺方法,以解决金属盐类絮凝剂中的高价态金属离子迁移到胶液中,造成胶液不稳定而产生结皮甚至破乳的问题,同时也能增强手套的力学性能。
为实现以上目的,本发明采用如下技术方案:
本发明的一个方面,涉及一种组合物,其包含:
(1)胶液原料,按重量计,包含水性聚氨酯树脂(纯固体份)15-22份,钛白浆1-5份,消泡剂0.02-0.08份,金属盐类或金属氢氧化物0.2-3份,补加水至整体100份;
(2)絮凝剂/脱模剂混合溶液原料,按重量计,包含脱模剂5-12份,絮凝剂5-12份,补加水至整体100份。
进一步的,胶液原料,按重量计,包含水性聚氨酯树脂(纯固体份)18-20份,钛白浆1-2份,消泡剂0.02-0.04份,金属盐类或金属氢氧化物0.2-2份,补加水至整体100份;絮凝剂/脱模剂混合溶液原料,基于100份的絮凝剂/脱模剂混合溶液原料,其中脱模剂5-8份,絮凝剂8-10份。
进一步的,本发明中,所述水性聚氨酯树脂为离子型树脂或离子型与非离子型复配树脂,所带有的离子基为羧酸的铵盐或碱金属盐、磺酸钠盐等,其中,羧酸的铵盐或碱金属盐如羧酸与叔胺成的盐、羧酸与碱金属成的盐;其中,磺酸钠盐是通过乙二氨基乙基磺酸钠引入的;进一步的,所述水性聚氨酯树脂的离子基优选为二羟甲基丙酸与三乙胺的铵盐;
本发明中,对于离子型水性聚氨酯树脂,其制备原料包括异氰酸酯、多元醇、亲水扩链剂;对于离子型与非离子型复配水性聚氨酯树脂,其制备原料包括异氰酸酯、多元醇、小分子醇和小分子胺扩链剂以及非离子醇(如如聚乙二醇类或聚乙二醇单烷基醚),其中:
异氰酸酯组分选自官能度大于等于2的多异氰酸酯,优选官能度为2的二异氰酸酯,如甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯等,特别优选六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯的一种或多种;
制备所述水性聚氨酯树脂的多元醇选自数均分子量为500~6000的二元醇和/或三元醇和/或四元醇;更优选数均分子量为500~5000、官能度为2~3的聚酯多元醇(包括聚碳酸酯多元醇)、聚醚多元醇或其组合物;
制备所述水性聚氨酯树脂的亲水扩链剂选自二羟甲基丙酸、二羟甲基丁酸、乙二氨基乙基磺酸钠中的一种或多种;当所述水性聚氨酯树脂为离子型与非离子型复配树脂时,原料中含有占原料总质量0.2-1.5%的非离子醇。
本发明中,所述消泡剂选自聚醚改性有机硅消泡剂,如毕克化学的BYK028。
本发明中,所述金属盐类或金属氢氧化物为锂、钠、钾等的盐或氢氧化物;
进一步的,所述金属盐类或金属氢氧化物包括但不限于碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、海藻酸钠、氢氧化钾、氢氧化锂。
本发明中,所述脱模剂选自硬脂酸钙悬浊液,质量浓度为30-50%,优选50%;所述絮凝剂选自四水合硝酸钙。
本发明的另一方面,涉及一种水性聚氨酯手套的制备方法,其包括如下步骤:
A:手套胶液配置:将水性聚氨酯树脂用去离子水稀释,在200-400r/min、优选250-350r/min机械搅拌下加入钛白浆,消泡剂,和金属盐类或金属氢氧化物,机械搅匀10-30min,静置待用;
B:絮凝剂/脱模剂混合溶液配置:用去离子水配置含有脱模剂、絮凝剂的絮凝剂/脱模剂混合溶液,使用前保持200-400r/min机械搅拌搅匀;
C:将清洗干燥后的手模浸入絮凝剂/脱模剂混合溶液中保持5-15s,取出后放入95-110℃烘箱中烘干,保持手模温度在50-70℃下浸入手套胶液中保持5-15s,取出后放入100-120℃的烘箱中烘烤至表干,然后放入去离子水中浸泡约2-5min,取出后放入100-120℃烘箱中烘烤15-40min后脱模。
本发明的有益效果在于:
通过引入能够与金属盐类絮凝剂(通常为二价或三价的金属盐类)反应的金属盐类或金属氢氧化物,将高价态的金属离子(如钙离子)以不溶或者低水溶性的化合物形式固定在手套内部,避免其迁移到手套胶液中造成胶液不稳定而产生结皮甚至破乳,反应产生的化合物因具有低水溶性还可以起到填料的作用,同时金属离子(如钙离子)在手套内部还能够与树脂中的亲水基团形成离子键,提高手套的力学性能。
具体实施方式
为便于理解本发明,下面将结合实施例对本发明作进一步的说明。应当理解,下述实施例仅是为了更好的理解本发明,并不意味着本发明仅局限于以下实施例。
原料
脱模剂:液体硬脂酸钙类脱模剂,无锡田鑫化工有限公司,固含量为50%;
絮凝剂:四水合硝酸钙,国药化学试剂有限公司;
消泡剂:BYK028,聚醚改性有机硅类消泡剂,毕克化学;
水性聚氨酯:
万华化学7351,阴非离子磺酸钠盐型水性聚氨酯,固含量为55%;
万华化学7566,阴离子二羟甲基丙酸与三乙胺的铵盐型水性聚氨酯,固含量为35%;
钛白浆:世铭钛白浆,固含量为75%;
本文中出现的其他原料若无特别说明,均为常规市售原料。
测试方法
拉伸强度、延伸率:按照ASTM D412标准进行测试;
合格率:制作100只手套样本,对其进行充气处理,浸入水中观察有无漏气情况。
胶液中钙离子含量:使用离子色谱法标定;制作200只手套样本后检测胶液中钙离子的含量。
表面结皮现象:制作200只手套样本后观察胶液表面及容器壁上有无结皮、观察手模从胶液中提取出来时手套表面有没有粘附结皮。
手套的制备方法:
将清洗干燥后的手模浸入絮凝剂/脱模剂混合溶液中保持10s,取出后放入105℃烘箱中烘干,保持模具温度在60℃下浸入手套胶液中保持10s,取出后放入110℃的烘箱中烘烤至表干,然后放入去离子水中浸泡约3.5min,取出后放入110℃烘箱中烘烤25min后脱模。
其中,絮凝剂/脱模剂混合溶液原料、胶液原料的组成如下:
絮凝剂/脱模剂混合溶液原料配料表(单位:重量份):
脱模剂 | 8 |
絮凝剂 | 10 |
水 | 82 |
合计 | 100 |
胶液原料配料表(单位:重量份):
性能测试结果如下:
从上表可以看出,随着金属盐类或金属氢氧化物的加入,手套的合格率有明显的提升,手模上的钙离子往胶液的迁移也受到明显的抑制,结皮现象得到明显改善,随着手套合格率的提高,手套的缺陷减少,力学性能也得到了提升。
Claims (10)
1.一种组合物,其特征在于,其包含:按重量计,(1)胶液原料,基于100份的胶液原料,其中水性聚氨酯树脂(纯固体份)15-22份,钛白浆1-5份,消泡剂0.02-0.08份,金属盐类或金属氢氧化物0.2-3份;(2)絮凝剂/脱模剂混合溶液原料,基于100份的絮凝剂/脱模剂混合溶液原料,其中脱模剂5-12份,絮凝剂5-12份。
2.根据权利要求1所述的组合物,其特征在于,其包含:按重量计,(1)胶液原料,基于100份的胶液原料,其中水性聚氨酯树脂(纯固体份)18-20份,钛白浆1-2份,消泡剂0.02-0.04份,金属盐类或金属氢氧化物0.2-2份;(2)絮凝剂/脱模剂混合溶液原料,基于100份的絮凝剂/脱模剂混合溶液原料,其中脱模剂5-8份,絮凝剂8-10份。
3.根据权利要求1或2所述的组合物,其特征在于,金属盐类或金属氢氧化物为锂、钠、钾的盐或氢氧化物。
4.根据权利要求1-3任一项所述的组合物,其特征在于,所述金属盐类或金属氢氧化物包括碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、海藻酸钠、氢氧化钾、氢氧化锂。
5.根据权利要求1-4任一项所述的组合物,其特征在于,所述水性聚氨酯树脂为离子型树脂或离子型与非离子型复配树脂。
6.根据权利要求1-5任一项所述的组合物,其特征在于,消泡剂为聚醚改性有机硅消泡剂;和/或絮凝剂为四水合硝酸钙。
7.根据权利要求1-6任一项所述的组合物,其特征在于,脱模剂为硬脂酸钙悬浊液。
8.根据权利要求1-7任一项所述的组合物在制备手套中的用途。
9.一种水性聚氨酯手套的制备方法,其特征在于,包括如下步骤:
A:将权利要求1-7任一项所述的组合物中的胶料原料搅拌混合;
B:将权利要求1-7任一项所述的组合物中的絮凝剂/脱模剂混合溶液原料搅拌混合;
C:将清洗干燥后的手模浸入絮凝剂/脱模剂混合溶液中,取出后放入烘箱中烘干,然后将手模浸入手套胶液中,取出后放入烘箱中烘烤至表干,然后放入去离子水中浸泡,取出后放入烘箱中烘烤后脱模。
10.根据权利要求9所述的制备方法,其特征在于,步骤C中手模浸入絮凝剂/脱模剂混合溶液中保持5-15s,取出后在95-110℃烘箱中烘干,保持手模温度在50-70℃下浸入手套胶液中保持5-15s,取出后放入100-120℃的烘箱中烘烤至表干,然后放入去离子水中浸泡2-5min,取出后放入100-120℃烘箱中烘烤15-40min后脱模。
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