CN106608979B - 一种仿金属生物基复合基材 - Google Patents
一种仿金属生物基复合基材 Download PDFInfo
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Abstract
一种仿金属生物基复合基材,包含一生物基复合材料,一修补涂层设于该生物基复合材料的表面,一底层设于该修补涂层之上,一复合镀膜设于该底层之上,以及一表层设于该复合镀膜之上。仿金属生物基复合基材表面光亮如镜、无橘皮纹,且生物基材料/金属/修补涂层间结合力好,具有较佳的抗腐蚀性,可耐冷热冲击、高抗水性,在诸多外力影响下不会出现离层或变形等异常。
Description
技术领域
本发明是关于一种复合材料,尤其是一种仿金属高分子复合材料。
背景技术
石油基塑胶(例如:ABS、PP、PC、PBT等)因为具有良好的加工成型性、抗腐蚀性强且成本低廉,故有机会用来取代金属。当其表面施以金属化手段(例如电镀或镀膜)后,则外观便与金属几乎没有区别。但是石油基塑胶机械强度不足、耐热温度不够高,而且比重太低。因此往往采取添加纤维以及金属粉、矿物粉等改性,提高其机械强度与耐热性,然后再做表面金属化处理。此种改性后的塑胶较能符合相关产业对于外观的高标准要求。然而添加纤维以及金属粉改性的塑胶,经射出成型出来的胚件,表面呈粗糙或波浪纹、橘皮纹等缺陷,也无法透过后制程序将其表面金属化处理得出镜面高光的产品,因此,其在商业上的应用范围有限。如果以植物基或生物高分子替代石油基塑胶,也会面临相同困境,而且难度更大,因为植物基或生物高分子的强度、耐水性及耐热性常比石油基塑胶低。
生物基高分子材料的开发与应用愈来愈重要,并受到各界高度重视。因为石油基合成材料已被大量制造与使用,使得有限的石油资源被大量耗用,同时塑胶废弃物也造成环境污染。为了节能减碳,以生物基、可分解的材料取代石油基塑胶或金属,已成为本领域急需开发的技术。
发明内容
本发明针对前述生物基高分子的缺点,提供一种仿金属生物基复合基材。本发明的仿金属生物基复合基材可达到成品表面光亮如镜、无橘皮纹,且生物基材料/金属修补涂层间结合力好,具有较佳的抗腐蚀性,可耐冷热冲击、高抗水性,在诸多外力影响下不会出现离层或变形等异常。
根据本发明部分实施例,仿金属生物基复合基材包含一生物基复合基材,一修补涂层设于该生物基复合基材的表面,一底层设于该修补涂层之上,一复合镀膜设于该底层之上,以及一表层设于该复合镀膜之上。
根据本发明部分实施例,生物基复合材料包含纤维占10-60重量百分比、生物基材料占20-50重量百分比、金属添加物占1-30重量百分比、改质剂占1-20重量百分比以及助剂占1-5重量百分比。
根据本发明部分实施例,纤维是一玻璃纤维,且该纤维的表面覆盖一生物基尼龙。
根据本发明部分实施例,修补涂层包含分子量大于100,000的甲基丙烯酸甲酯树脂以及分子量大于12,000的聚氨酯丙烯酸树脂。
根据本发明部分实施例,修补涂层还包含云母占3-20重量百分比、二氧化硅占2-5重量百分比、有机硅树脂占2-8重量百分比以及黏结剂占5-10重量百分比。
根据本发明部分实施例,复合镀膜还包含一第一复合层,设于该底层之上,一第二复合层,设于该第一复合层,以及一第三复合层,设于该第二复合层之上。
根据本发明部分实施例,第一复合层包含铬,该第二复合层包含硅铬合金,且该第三复合层包含铬。
根据本发明部分实施例,第一复合层包含铬,该第二复合层包含硅铬合金,且该第三复合层包含氮化锆。
根据本发明部分实施例,底层是一光固性漆,且具有一厚度约5-15微米。
根据本发明部分实施例,表层是一光固性漆,且具有一厚度约10-20微米。
附图说明
本发明的上述和其他态样、特征及其他优点参照说明书内容并配合附加附图得到更清楚的了解,其中:
图1是依照本发明一实施例的仿金属生物基复合基材示意图。
具体实施方式
为了使本揭示内容的叙述更加详尽与完备,下文针对了本发明的实施态样与具体实施例提出了说明性的描述;但这并非实施或运用本发明具体实施例的唯一形式。以下所揭露的各实施例,在有益的情形下可相互组合或取代,也可在一实施例中附加其他的实施例,而无须进一步的记载或说明。在以下描述中,将详细叙述许多特定细节以使读者能够充分理解以下的实施例。然而,可在无此等特定细节的情况下实践本发明的实施例。
请参考图1。根据本发明部分实施例仿金属生物基复合基材10包含一生物基复合材料100,一修补涂层110设于该生物基复合材料100的表面,一底层120设于该修补涂层110之上,一复合镀膜130设于该底层120之上,以及一表层140设于该复合镀膜130之上。
生物基复合材料100经过多道程序后,不同材料覆盖其表面,除了增强生物基复合材料的强度,也利于生物基复合材料100与修补涂层110之间的结合。生物基复合材料100包含纤维占10-60重量百分比、生物基材料占20-50重量百分比、金属添加物占1-30重量百分比、改质剂占1-20重量百分比与助剂占1-5重量百分比。以下将详述生物基复合材料100的组成。
首先,浸润纤维于第一溶液。纤维可以为玻璃纤维,洋麻纤维或碳纤维。第一溶液是一硅烷溶液,纤维浸泡在硅烷溶液中,使得硅烷化合物沉积在纤维表面,增强纤维与其他材料之间的结合力。根据本发明部分实施例该硅烷溶液包含硅烷偶联剂以及碘化合物,其中硅烷偶联剂(silane coupling agent)占约20重量百分比,碘化合物占5-10重量百分比,碘化合物可以是,例如碘化钾以及碘化亚铜,且硅烷溶液可包含一种以上的碘化合物。溶液温度维持在约40℃。
接下来,浸润纤维于一第二溶液。纤维浸润于第一溶液后,无需经过冲洗,直接浸润于第二溶液中。第二溶液为一匀相生物基尼龙溶液,生物基尼龙溶液包含生物基尼龙、造孔剂以及水溶性高分子。根据本发明部分实施例,第二溶液包含生物基尼龙占约20-30重量百分比,苯酚占约25-35重量百分比,聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)占约10-20重量百分比,以及氯仿占约5-15重量百分比。由于纤维表面附有第一溶液中的硅烷化合物,纤维在第二溶液中可更容易与生物基尼龙结合。纤维浸润于第一与第二溶液之后,静置于一相转换溶液中,透过浓度梯度的原理,吸附于纤维上、原本属于第一溶液或第二溶液的溶剂将自然析出。根据本发明部分实施例,相转换溶液包含纯水占约60-80重量百分比、苯酚占约15-30重量百分比以及氯仿占约0-5重量百分比。相转换溶液维持在50-70℃之间。由于经过溶剂析出的程序,纤维表面呈现不规则裂纹、布满突出纤维或细小微孔。被纤维吸附的溶剂析出后,再将纤维以高温清水冲洗并烘干。
表面覆盖有生物基尼龙的纤维与生物基材料混合形成生物基复合材料100,如图1所示。将适当可反应大小的纤维与生物基材料混合。生物基材料为改质后的生物基高分子,生物基高分子可选自植物基树脂(例如植物基尼龙、植物基聚乙烯、耐热级聚乳酸等)、生物尼龙、生物基聚对苯二甲酸乙二酯(PET)、可降解生物高分子(包含聚乳酸树脂、聚羟基脂肪酸酯与聚丁二酸丁二醋等)、微生物产生聚酯(例如PHA、PHB、PHBV、P34HB等)或上述各种生物基高分子的混合物。生物基材料与金属添加物、改质剂以及助剂等依适当比例调配,再进行造粒。金属添加物可选自铜粉、铁粉、不锈钢粉、镍粉、锌粉、氧化铁粉、氧化锌粉、氧化钡铁粉等。改质剂包含矿物粉、接枝耐冲剂、纤维以及偶联剂。矿物粉例如滑石粉、云母粉、黏土或硅灰石粉等。接枝耐冲剂可以是马来酸酐接枝PLA、马来酸酐接枝P34HB、马来酸酐接枝植物基PE或马来酸酐接枝植物基聚丙烯等。偶联剂可选自钛酸酯偶联剂或硅烷偶联剂等。助剂可选自超细石墨粉、氧化石墨烯粉、PTFE粉、EBS粉、硬酯酸镁、硬酯酸锌、PE蜡、PP蜡等。上述金属添加物、改质剂以及助剂可选用其中一种或多种的不同组合,本发明并不以此为限。
改质后的生物基高分子即为生物基材料,与上述纤维透过适当反应大小,例如颗粒状,以10-50比1(生物基材料:纤维)的比例混合形成生物基复合材料。由于纤维经过上述第一与第二溶液处理后,表面覆盖生物基尼龙,因此可提高与生物基材料(主要成分为生物基高分子)的相容性。再加上生物基尼龙具有粗糙表面,当生物基材料与纤维结合时,两者之间的摩擦力减少表面之间的流动性,也降低收缩率差异,可明显减少甚至消除产物表面的浮纤情形。如图1所示,生物基复合材料100透过射出成型,依实际需求预先设计的外型形成胚件,例如版状或块状。
修补涂层110涂覆于生物基复合材料100的表面。修补涂层110包含热塑性的超高分子量甲基丙烯酸甲脂及大分子量聚氨酯丙烯酸树脂,为一双固化填平漆。所用的甲基丙烯酸甲酯为分子量大于100,000以上者。所用的聚氨酯丙烯酸为分子量在12,000以上者。根据本发明部分实施例,修补涂层110还包含云母占3-20重量百分比,二氧化硅占2-5重量百分比,有机硅树脂占2-8重量百分比,光固化剂(联苯甲酰类或α-羟基酮类或酰基磷氧化物)占0.5至1.0重量百分比,热固化剂(聚异氰酸脂)占0.5至1.0重量百分比,以及黏结剂占5-10重量百分比。黏结剂可以为氯化聚丙烯。上述原料(树脂与无机填充粉、黏结剂、固化剂等)依比例秤重后投于混合溶剂中搅拌均匀,得到固形份为15-35重量百分比的涂料。所指的混合溶剂由丁酯、丁酮、甲苯依70:20:10比例组成。
修补涂层110透过喷涂的方式形成在生物基复合材料100的表面。修补涂层110的厚度介于3-15微米,本身对于温度变化收缩率小,不仅可填补生物基尼龙的粗糙表面,且可阻隔水气。修补涂层110覆盖生物基复合材料100的表面后,再经过加热及光照交联固化成型。
底层120设置于修补涂层110之上。先喷涂一光固型底漆,例如紫外线光固化底漆,于修补涂层110表面,底漆厚度介于5-15微米之间,平坦化之后,烘干底漆,再暴露于可固化光线下,以紫外线光固化底漆为例,则暴露于紫外线下固化,达成光固化交联目的,使得底层120附着于修补涂层110上。
复合镀膜130设置于底层120之上。复合镀膜130具有第一复合层131、第二复合层133以及第三复合层135。第一复合层131以物理气相沉积〈PVD〉电弧的方式形成于底层120的表面,第二复合层133以溅镀的方式形成于第一复合层131上,第三复合层135以间歇性电弧的方式形成于第二复合层133上。更详细地说,形成第三复合层135的时候需中断电弧程序,停滞数分钟后,再继续电弧程序,并重复此间歇性步骤至少三次。第一复合层131、第二复合层133与第三复合层135三层所使用的金属材料并不完全相同。举例来说,根据本发明部分实施例,第一复合层131可以是铬(Cr),第二复合层133为硅铬合金(CrSi),第三复合层135与第一复合层131同为铬。又,根据本发明部分实施例,第一复合层131与第二复合层133分别为铬与硅铬合金,第三复合层135则为氮化锆(ZrN)。第一复合层131的金属材料选择会影响复合镀膜130与底层120的结合力,而第一复合层131与第二复合层133两者的金属材料选择则会影响复合镀膜130的抗腐蚀能力,第三复合层135金属材料的选择会影响产物的颜色。以铬为例,其与底层120结合力佳,且硅铬合金中的硅可有效填补第二复合层133甚至是第一复合层131的空隙,因此可以抵抗外来物的入侵,像是灰尘、水气等。当第三复合层135使用铬,会使得生物基复合基材10呈现银色外观,当第三复合层135使用氮化锆,外观将呈现金黄色。其他金属材料还包含铜以及铝等。复合镀膜130的厚度约为0.1-0.2微米之间。
表层140设置于复合镀膜130之上。如图1所示,表层140为光固化表漆,以喷涂方式形成于复合镀膜130上,厚度介于10-20微米之间,经过烘干以及平坦化的程序,再暴露于可固化表漆的光线下固化交联成型。表层140可当作一保护层。
另外,还可以在表层140添加氟硅化合物,提高表层140的接触角,改善疏水性。抑或于表层140上蒸镀氟硅烷薄膜,厚度介于0.02-0.1微米之间,同样可以提高表面疏水性。
经实验证明,生物基材料不包含经过上述改质步骤的纤维、不包含修补涂层、仅具有单一铬膜,其表层橘皮纹严重、各层之间的附着力也较差、抗水性不佳、在高温下易变形。增加改质纤维可改善表面橘皮纹。增加改质纤维以及修补涂层的基材,其表面橘皮纹明显减少、各层之间的附着力也增强。而使用了改质纤维、修补涂层以及复合镀膜的生物基复合基材则几近无橘皮纹,各层之间附着力〈经过冷热循环测试〉增强,抗水性加倍(从-6.4%到-3.2%),长时间暴露在高温(60℃)下无形变产生,且通过CASS抗腐蚀测试。
本发明的仿金属生物基复合基材机械强度高、耐水性佳、层间结合力优良、抗腐蚀性高。而且外观可依不同复合镀膜金属搭配呈现类似金属质感以及色泽,表面高光如镜(没有波浪纹或橘皮纹),成为一种高强度、高耐水性、仿金属生物基复合基材。本发明透过添加改质纤维以及其他辅助剂将生物基尼龙改性成为可以取代石油基工程塑料的高强度复合材料。更进一步使用多重喷镀程序,使产品外观接近金属,故可以取代传统的水电镀制程,适合作为家电、汽车与电子产品的零件,商业价值性高,而且生产方法清洁又环保。
虽然本发明已以实施方式揭露如上,然其并非用以限定本发明,任何熟悉此技艺者,在不脱离本发明的精神和范围内,当可作各种的更动与润饰,因此本发明的保护范围当视所附的权利要求书所界定的范围为准。
Claims (10)
1.一种仿金属生物基复合基材,其特征在于,包含:
生物基复合材料,其包含纤维,所述的纤维表面覆盖生物基尼龙;
修补涂层,设于所述的生物基复合材料上;
底层,设于所述的修补涂层上;
复合镀膜,设于所述的底层上;以及
表层,设于所述的复合镀膜上。
2.如权利要求1所述的仿金属生物基复合基材,其特征在于,所述的生物基复合材料包含:
纤维占10-60重量百分比;
生物基材料占20-50重量百分比;
金属添加物占1-30重量百分比;
改质剂占1-20重量百分比;以及
助剂占1-5重量百分比。
3.如权利要求2所述的仿金属生物基复合基材,其特征在于,所述的纤维是玻璃纤维、洋麻纤维或碳纤维。
4.如权利要求1所述的仿金属生物基复合基材,其特征在于,所述的修补涂层包含分子量大于100,000的甲基丙烯酸甲酯树脂以及分子量大于12,000的聚氨酯丙烯酸树脂。
5.如权利要求4所述的仿金属生物基复合基材,其特征在于,所述的修补涂层还包含:
云母占3-20重量百分比;
二氧化硅占2-5重量百分比;
有机硅树脂占2-8重量百分比;以及
黏结剂占5-10重量百分比。
6.如权利要求1所述的仿金属生物基复合基材,其特征在于,所述的复合镀膜还包含:
第一复合层,设于所述的底层之上;
第二复合层,设于所述的第一复合层;以及
第三复合层,设于所述的第二复合层之上。
7.如权利要求6所述的仿金属生物基复合基材,其特征在于,所述的第一复合层包含铬,所述的第二复合层包含硅铬合金,且所述的第三复合层包含铬。
8.如权利要求6所述的仿金属生物基复合基材,其特征在于,所述的第一复合层包含铬,所述的第二复合层包含硅铬合金,且所述的第三复合层包含氮化锆。
9.如权利要求1所述的仿金属生物基复合基材,其特征在于,所述的底层是光固性漆,且具有厚度5-15微米。
10.如权利要求1所述的仿金属生物基复合基材,其特征在于,所述的表层是光固性漆,且具有厚度10-20微米。
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TW201714969A (zh) | 2017-05-01 |
CN106608979A (zh) | 2017-05-03 |
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