CN108049185A - 一种油性pu-丁腈双层复合橡胶手套及其制造方法 - Google Patents
一种油性pu-丁腈双层复合橡胶手套及其制造方法 Download PDFInfo
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Abstract
一种油性PU‑丁腈双层复合橡胶手套的制造方法,包括:步骤S1:浸渍油性PU树脂胶料:将手套胚浸渍油性PU树脂胶料,油性PU树脂胶料包含按质量份数计且混合调配的90‑120份油性PU树脂、250~800份DMF、0.2~1.5份消泡剂和0.2~2份流平剂;步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套,滴胶放置,后放入水中泡洗,取出后烘干;步骤S3:浸渍丁腈胶乳胶料:将经过步骤S2处理的手套,浸渍丁腈胶乳胶料,丁腈胶乳胶料包含按质量份数计且混合调配的90~120份丁腈胶乳,0.5~4份增稠剂,0~4份交联剂,5~10份水;步骤S4:硫化烘干:将经步骤S3处理的手套,经硫化烘干制得油性PU‑丁腈双层复合橡胶手套。由此方法制造的手套兼具丁腈橡胶的耐油耐化学品耐磨等特性和油性PU树脂橡胶的舒适柔软透气性。本发明还涉及油性PU‑丁腈双层复合橡胶手套。
Description
技术领域
本发明涉及一种油性PU-丁腈双层复合橡胶手套的制造方法。
背景技术
以往长筒劳保手套,大都是由单一种橡胶制作而成,例如天然乳胶类手套、丁腈类手套、氯丁类手套和丁基类手套等。采用单一橡胶制作的手套虽然制作工艺简单,但是功能性也相对单一,存在不少缺点。例如,天然乳胶类手套在耐油性、耐化学品、耐磨性方面较差;而丁腈类手套则在柔软舒适性方面较差等。另有一些橡胶手套,仅只对拇指和虎口部位进行加强,提高该部位的抗磨损性能,但未考虑整个手套的耐油性和耐化学品性能,尤其是未考虑透气性,导致整个产品的性能仍显不足。
发明内容
针对现有技术中的缺陷,本发明目的是提供一种油性PU-丁腈双层复合橡胶手套及其制造方法,使制造的手套兼顾丁腈橡胶耐油耐化学品耐磨等特性,同时兼顾油性PU的舒适贴合性等。
为达到以上目的,本发明提供一种油性PU-丁腈双层复合橡胶手套的制造方法,包括:
步骤S1:浸渍油性PU树脂胶料:将手套胚浸渍油性PU树脂胶料,所述油性PU树脂胶料包含按质量份数计且混合调配的90-120份油性PU树脂、250~800份DMF、0.2~1.5份消泡剂和0.2~2份流平剂;
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套滴胶放置,后放入水中泡洗,取出后烘干;
步骤S3:浸渍丁腈胶乳胶料:将经步骤S2处理的手套浸渍丁腈胶乳胶料,所述丁腈胶乳胶料包含包含按质量份数计且混合调配的90~120份丁腈胶乳,0.5~4份增稠剂,0~4份交联剂,5~10份水;
步骤S4:硫化烘干:将经步骤S3处理的手套,经硫化烘干制得油性PU-丁腈双层复合橡胶手套。
优选的,步骤S2中,所述油性PU树脂为固含量22%~33%的油性树脂胶乳,所述油性PU树脂为聚醚型PU树脂、聚酯型PU树脂或由聚醚型PU树脂和聚酯型PU树脂混合而成。
优选的,步骤S1中消泡剂为无硅型消泡剂、油性含硅消泡剂的一种或几种的组合。优选的,所述消泡剂选择为乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯、聚氧丙烯季戊四醇醚、聚氧乙烯、聚氧丙醇胺醚、聚氧丙烯甘油醚、聚氧丙烯聚氧乙烯甘油醚或聚二甲基硅氧烷。
无硅消泡剂由于完全不含有机硅成分,不会造成硅斑残留槽壁,易清洗设备。油性消泡剂是一种液体油性强效消泡剂,用于各种油水体系,具有突出的消抑泡、特别在油性体系分散性良好,在高温200度以上、20%左右的酸碱体系控泡理想。油性有机硅消泡剂DF-DF-899/834,具有如下特性:①极低的表面张力;②具有抑泡、脱泡和消泡功能,对粘度高的体系尤为有效;③可防止缩孔,对增进漆膜的光泽有优异的效果;④提高抗粘连性,增加表面滑爽,从而提高漆膜的抗划伤性和耐磨性;⑤可有效抑制与消除涂料在制造和施工时所产生的气泡和微泡。油性含硅消泡剂是指油性消泡剂中含硅的一类。非硅消泡剂,其成分醇类、脂肪酸类复合物。油性含硅消泡剂,优选可为一种油性氟硅消泡剂DF-10/80/16/803,具有突出的消抑泡特点,控泡作用,不受PH的影响。
优选的,步骤S1中,流平剂为有机硅类和氟碳化合物一种或两种以上的组合。优选的,所述流平剂选择为硅油,如聚二甲基硅氧烷和聚甲基苯基硅氧烷。
流平剂是一种常用的涂料助剂,它能促使涂料在干燥成膜过程中形成一个平整、光滑、均匀的涂膜。能有效降低涂饰液表面张力,提高其流平性和均匀性的一类物质。可改善涂饰液的渗透性,能减少刷涂时产生斑点和斑痕的可能性,增加覆盖性,使成膜均匀、自然。主要是表面活性剂,有机溶剂等。
优选的,步骤S2中滴胶放置时间为3~8分钟。
优选的,所述步骤S2水中泡洗包括三遍水洗,一遍水温25~35℃,时间10~15分钟;二遍水温35~50℃,时间20~35分钟;三遍水温50~65℃,时间25~35分钟。一遍水洗温度较低约为30℃上下,可让油性PU树脂快速充分与水反应和凝固;二遍和三遍水温略高于一遍水温,主要用于溶解去除DMF,避免DMF被大量残留在油性PU树脂橡胶与丁腈橡胶之间。因溶剂DMF对人体皮肤和人身健康有一定毒害作用,因此越低的DMF的含量所得到的手套越符合安全要求。
优选的,步骤S2水中泡洗完三遍后,手套烘干温度为95~105℃,时间40~55分钟。
优选的,步骤S3中使用的丁腈胶乳为预硫化丁腈胶乳。
优选的,步骤S3中使用的交联剂为氮丙啶类、多元醇类、多元胺类一种或前述各项的任意组合。多元胺类有丙二胺、MOCA(对二邻氯苯胺甲烷);多元醇类有聚乙二醇、聚丙二醇、三羟甲基丙烷。
优选的,步骤S3中增稠剂为聚丙烯酸钠、纤维素、纤维素钠、聚丙烯酸类增稠剂、干酪素及PVA(聚乙烯醇)一种或前述各项的任意组合。
优选的,步骤S3中调配制得丁腈胶乳胶料的粘度为1200~2500mpa.s,根据需要的厚度具体调节丁腈胶乳胶料的粘度。当外层的丁腈橡胶需要厚度较大时,可通过增稠剂等方式将粘度调节到1800~2500mpa.s,而若只需要在手套最外表面附着较薄一层丁腈橡胶时,则可将丁腈胶乳胶料的粘度调节到1200mpa.s~1800mpa.s。
优选的,所述步骤S4的硫化烘干包括先低温硫化烘干和后高温硫化烘干两个阶段。其中,低温硫化温度为60~85℃时间为35~45min;高温硫化温度为100~120℃时间为60~90min。其中,先低温硫化的目的是,由于胶乳成膜过程比较缓慢,要经过紧密堆积过程,如果开始就使用高温一次性硫化,很容易使得制品的表面快速形成较为致密的膜;而内部由于水汽分子较多,致密的膜会造成水汽无法排出,只能在制品表面形成若干个小鼓泡,鼓泡容易破裂,造成严重的产品缺陷,尤其是胶乳浸渍类厚制品,因此需要经过先低温硫化(≤90℃)30分钟左右,使制品加工更容易,避免缺陷产生;然后进行高温硫化(≧90℃)60分钟以上,达到制品使用性能和生产标准。
聚氨酯树脂是一类重要的合成树脂,简称PU树脂,由多异氰酸酯与多元醇经化学反应制成。-NCO与-OH的化学反应式:RNCO+R’-OH→RNHCOOR’。溶剂型(油性)树脂是指以溶剂为载体的聚氨酯树脂,比如甲苯,丁酯等溶剂等。水性树脂是指以水为载体的聚氨酯树脂。
DMF即N,N-二甲基甲酰胺,N,N-Dimethylformamide是一种化学物品,无色透明液体,既是一种用途极广的化工原料,也是一种用途很广的优良的溶剂、极性惰性溶剂。除卤化烃以外能与水及多数有机溶剂任意混合。对多种有机化合物和无机化合物均有良好的溶解能力和化学稳定性。DMF作为油性PU的溶剂,其功用除作为合成的介质外,还起到调节树脂固含、粘度及调整干速的作用。
本发明还提供一种油性PU-丁腈双层复合橡胶手套,其包含手套胚、附着于该手套胚外表面的油性PU树脂胶层,以及覆盖于所述油性PU树脂胶层全部外表面的丁腈橡胶层。
本发明的有益技术效果在于:
本发明将手套胚先后经过两次浸渍胶料程序,第一次浸渍油性PU树脂胶料,第二次浸渍丁腈胶乳胶料,且在两次浸胶处理之间还包含滴胶(放置滴胶使多余的胶滴下去)过程,进一步使手套胚表面的油性PU树脂胶料附着得更均匀,保证成品手套材料各处的一致性;而水泡洗的操作,通过水泡洗一方面促进油性PU树脂充分快速反应和凝固,另一方面去除DMF,降低DMF的残留量,提高产品安全性能。其中油性PU树脂可与水反应,产生二氧化碳气体,所以油性PU树脂胶层含有微小泡孔结构且透气性好,泡孔的存在又使其柔软度优于其他树脂(包括非油性PU树脂),用油性PU树脂附着在手套胚最接近皮肤的一层,能够有效改善手套制品的舒适度。由此方法制造的手套,最外表面的丁腈橡胶能提供手套的耐油耐化学品耐磨等特性,内层的油性PU树脂橡胶更接近人手皮肤,可提供使用者手部舒适贴合、柔软透气等特性,且由于柔软性较好,故穿戴更方便,手指灵活,用棉毛布手套胚制作的手套EN388(工业手套防护欧洲标准)测试等级为4131。
本发明的这些目的、特点和优点将会在下面的具体实施方式和权利要求中详细的揭露。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
步骤S1:浸渍油性PU树脂胶料:按质量份数计将100份聚酯型油性PU树脂(固含量28%)、600份DMF、0.5份消泡剂(高碳醇脂肪酸酯复合物)和0.5份流平剂聚二甲基硅氧烷混合调配制得油性PU树脂胶料,将棉毛手套胚浸渍前述过程制备的油性PU树脂胶料。
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套,滴胶放置3~8分钟,然后浸泡一遍水,温度为30℃,时间15分钟,使油性PU树脂充分与水反应完全并凝固;而后浸泡二遍水,温度为45℃,时间30分钟,一方面再次促进PU树脂反应更彻底,另一方面用于去除DMF;然后浸泡三遍水,温度65℃,时间30分钟,再次去除DMF,减少手套中DMF的含量;最后烘箱烘干,温度为105℃,时间50分钟。
步骤S3:浸渍丁腈胶乳胶料:将步骤S2中烘干的手套,浸渍调配好粘度为2000mpa.s的丁腈胶乳胶料,所述丁腈胶乳胶料包含100份的丁腈胶乳、3份CMC(质量分数1.5%)、1.5份氮丙啶交联剂和8份的水等混合调配。
步骤S4、先在75℃时间为40min预硫化烘干,最后在高温硫化温度为110~120℃时间为80min下制得所述油性PU-丁腈双层复合橡胶手套。
相较于一个高温的硫化烘干处理而言,本实施例优选将硫化烘干步骤处理成低温硫化和高温硫化两个阶段。经过低温硫化其原因是胶乳成膜过程比较缓慢,要经过紧密堆积过程,如果开始就使用高温硫化,很容易使得制品表面,成膜致密;而内部由于水分较多,形成表面的鼓泡,造成制品缺陷,尤其是胶乳浸渍类厚制品,因此需要经过低温硫化(≤90℃)30分钟左右,使制品加工更容易,避免缺陷产生;然后进行高温硫化(≧90℃)60分钟以上,达到产品的使用性能。
实施例2
步骤S1:浸渍油性PU树脂胶料:按质量份数计将120份聚醚型油性PU树脂(固含量22%)、800份DMF、1.5份消泡剂(聚氧乙烯聚氧丙烯季戊四醇醚)和2份流平剂(聚甲基苯基硅氧烷)混合调配制得油性PU树脂胶料,将针织手套胚浸渍前述过程制备的油性PU树脂胶料。
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套,滴胶放置2~6分钟,然后浸泡一遍水,温度为35℃,时间15分钟,使油性PU树脂充分与水反应完全并凝固;而后浸泡二遍水,温度为50℃,时间30分钟,一方面再次促进PU树脂反应更彻底,另一方面用于去除DMF;再浸泡三遍水,温度65℃,时间35分钟,再次去除DMF,最大限度减少手套中DMF的含量;最后烘箱烘干,温度为100℃,时间50分钟。
步骤S3:浸渍丁腈胶乳胶料:将步骤S2中烘干的手套,浸渍调配好粘度为2500mpa.s的丁腈胶乳胶料,所述丁腈胶乳胶料包含120份的预硫化丁腈胶乳、4份干酪素、4份丙二胺交联剂和10份的水等混合调配。
步骤S4、先在85℃时间为35min预硫化烘干,最后在高温硫化温度为120℃时间为90min下制得所述油性PU-丁腈双层复合橡胶手套。
实施例3
步骤S1:浸渍油性PU树脂胶料:按质量份数计将90份聚醚型油性PU树脂(固含量质量百分数33%)、250份DMF、0.2份消泡剂(主要成分聚氧乙烯聚氧丙醇胺醚)和0.2份流平剂(主要成分聚甲基苯基硅氧烷)混合调配制得油性PU树脂胶料,将棉毛针织手套胚或棉毛手套胚浸渍于前述过程制备的油性PU树脂胶料。
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套,滴胶放置4~8分钟,然后浸泡一遍水,温度为25℃,时间15分钟,使油性PU树脂充分与水反应完全并凝固;而后浸泡二遍水,温度为35℃,时间35分钟;再浸泡三遍水,温度60℃,时间35分钟,最大限度减少手套中DMF的含量;最后烘箱烘干,温度为110℃,时间40分钟。
步骤S3:浸渍丁腈胶乳胶料:将步骤S2中烘干的手套,浸渍调配好粘度为1200mpa.s的丁腈胶乳胶料,所述丁腈胶乳胶料包含90份的预硫化丁腈胶乳、0.5份PVA、0.5份聚丙二醇交联剂和10份的水等混合调配。
步骤S4、先在60℃时间为45min预硫化烘干,最后在高温硫化温度为110℃时间为90min下制得所述油性PU-丁腈双层复合橡胶手套。
实施例4
步骤S1:浸渍油性PU树脂胶料:按质量份数计将100份聚醚型油性PU树脂(固含量30%)、400份DMF、1份消泡剂(主要成分聚氧丙烯季戊四醇醚)和1份流平剂(主要成分聚二甲基硅氧烷)混合调配制得油性PU树脂胶料,将棉毛手套胚浸渍前述过程制备的油性PU树脂胶料。
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套,滴胶放置3~7分钟,然后浸泡一遍水,温度为30℃,时间15分钟;而后浸泡二遍水,温度为45℃,时间32分钟;最后浸泡三遍水,温度60℃,时间32分钟,经二遍水洗和三遍水洗去除DMF,最大限度减少手套中DMF的含量;最后烘箱烘干,温度为95℃,时间50分钟。
步骤S3:浸渍丁腈胶乳胶料:将步骤S2中烘干的手套,浸渍调配好粘度为1900mpa.s的丁腈胶乳胶料,所述丁腈胶乳胶料包含110份的预硫化丁腈胶乳、3.5份聚丙烯酸钠、2份三羟甲基丙烷交联剂和10份的水等混合调配。
步骤S4、先在75℃~80℃时间为30min预硫化烘干,最后在高温硫化温度为100℃~110℃时间为80min下制得所述油性PU-丁腈双层复合橡胶手套。
实施例5
步骤S1:浸渍油性PU树脂胶料:按质量份数计将110份聚醚型油性PU树脂(固含量28%)、500份DMF、1.5份消泡剂(主要成分聚氧丙烯甘油醚)和1份流平剂(主要成分聚二甲基硅氧烷)混合调配制得油性PU树脂胶料,将棉毛手套胚浸渍前述过程制备的油性PU树脂胶料。
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套,滴胶放置3~8分钟,然后浸泡一遍水,温度为35℃,时间15分钟;而后浸泡二遍水,温度为50℃,时间32分钟;最后浸泡三遍水,温度65℃,时间30分钟,经二遍水洗和三遍水洗去除DMF,最大限度减少手套中DMF的含量;最后烘箱烘干,温度为105℃,时间45分钟。
步骤S3:浸渍丁腈胶乳胶料:将步骤S2中烘干的手套,浸渍调配好粘度为1700mpa.s的丁腈胶乳胶料,所述丁腈胶乳胶料包含110份的丁腈胶乳、3份PVA和10份的水等混合调配。
步骤S4、先在85℃时间为30min预硫化烘干,最后在高温硫化温度为100℃时间为80min下制得所述油性PU-丁腈双层复合橡胶手套。
按照上述实施例1-5制备的油性PU-丁腈双层复合橡胶手套,透气较好,经透气性检测仪检测,手套透气率在10Mpa下接近0.04,与纯丁腈橡胶手套相比,本发明的双层复合橡胶手套,手感明显舒适贴合、柔软,穿戴更方便,手指活动灵活不紧绷,制作的手套按照EN388(工业手套防护欧洲标准)测试标准,等级达到4131。
Claims (10)
1.一种油性PU-丁腈双层复合橡胶手套的制造方法,其特征在于,包括:
步骤S1:浸渍油性PU树脂胶料:将手套胚浸渍油性PU树脂胶料,所述油性PU树脂胶料包含按质量份数计且混合调配的90-120份油性PU树脂、250~800份DMF、0.2~1.5份消泡剂和0.2~2份流平剂;
步骤S2:滴胶及水洗:将步骤S1经油性PU树脂浸渍后的手套滴胶放置,后放入水中泡洗,取出后烘干;
步骤S3:浸渍丁腈胶乳胶料:将经步骤S2处理的手套浸渍丁腈胶乳胶料,所述丁腈胶乳胶料包含按质量份数计且混合调配的90~120份丁腈胶乳,0.5~4份增稠剂,0~4份交联剂,5~10份水;
步骤S4:硫化烘干:将经步骤S3处理的手套,经硫化烘干制得油性PU-丁腈双层复合橡胶手套。
2.根据权利要求1所述的制造方法,其特征在于,步骤S2中,所述油性PU树脂为固含量为22%~33%的油性树脂胶乳;所述油性PU树脂为聚醚型PU树脂、聚酯型PU树脂或聚醚型PU树脂和聚酯型PU树脂混合。
3.根据权利要求1所述的制造方法,其特征在于,步骤S1中消泡剂为无硅型消泡剂、油性含硅消泡剂的一种或几种的组合。
4.根据权利要求1所述的制造方法,其特征在于,步骤S1中,所述流平剂选择为聚二甲基硅氧烷或聚甲基苯基硅氧烷。
5.根据权利要求1所述的制造方法,其特征在于,所述步骤S2水中泡洗包括三遍水洗,一遍水温25~35℃,时间10~15分钟;二遍水温35~50℃,时间20~35分钟;三遍水温50~65℃,时间25~35分钟。
6.根据权利要求1所述的制造方法,其特征在于,步骤S3中使用的丁腈胶乳为预硫化丁腈胶乳。
7.根据权利要求1所述的制造方法,其特征在于,步骤S3中使用的交联剂为氮丙啶类、多元醇类、多元胺类一种或前述各项的任意组合;所述多元胺类包含丙二胺、对二邻氯苯胺甲烷;所述多元醇类包含聚乙二醇、聚丙二醇、三羟甲基丙烷;步骤S3中增稠剂为聚丙烯酸钠、纤维素、纤维素钠、聚丙烯酸类增稠剂、干酪素及聚乙烯醇中的一种或前述各项的任意组合。
8.根据权利要求1所述的制造方法,其特征在于,步骤S3中调配制得丁腈胶乳胶料的粘度为1200~2500mpa.s。
9.根据权利要求1所述的制造方法,其特征在于,所述步骤S4的硫化烘干包括先低温硫化烘干和后高温硫化烘干两个阶段;其中低温硫化温度为60~85℃时间为35~45min;高温硫化温度为100~120℃时间为60~90min。
10.一种油性PU-丁腈双层复合橡胶手套,其特征在于,包含:手套胚、附着于该该手套胚外表面的油性PU树脂胶层、以及覆盖于所述油性PU树脂胶层全部外表面的丁腈橡胶层。
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CN114957819B (zh) * | 2022-01-19 | 2024-01-30 | 山东景元记劳保用品有限公司 | 一种长袖化学防护手套及其制备方法 |
CN114316392A (zh) * | 2022-02-25 | 2022-04-12 | 天津市橡胶工业研究所有限公司 | 含内衬长袖丁腈防护手套及制备方法 |
CN114316392B (zh) * | 2022-02-25 | 2023-09-05 | 天津市橡胶工业研究所有限公司 | 含内衬长袖丁腈防护手套及制备方法 |
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