CN107309421A - 射出成型用结合剂 - Google Patents
射出成型用结合剂 Download PDFInfo
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Abstract
本发明提出一种射出成型用结合剂,其包含占约3至约20%重量百分比的带有顺丁烯二酸酐基团的聚烯烃、占约30至约40%重量百分比的聚烯烃化合物、占约5至约20%重量百分比的聚甲醛、占约1至约5%重量百分比的硬脂酸及占约35至约60%重量百分比的蜡。本发明的射出成型用结合剂的特点为利用带有顺丁烯二酸酐基团的聚烯烃与聚烯烃化合物及聚甲醛键结,以提升结合剂成分间的兼容性,延长其热裂解时间,达到减少对象的缺陷,提高其尺寸的精确度及一致性的功效。
Description
技术领域
本发明是关于一种射出成型用结合剂,尤其是用于金属粉末或陶瓷粉末射出成型的结合剂。
背景技术
粉末射出成型为一种零件制造技术,其结合了塑料射出成型与粉末的技术,其中主要又可分为金属粉末射出成型(Metal Injection Molding,MIM)及陶瓷粉末射出成型(Ceramic Injection Molding,CIM)两大应用领域,这种技术具有表面状态良好、成型循环快、精密度高且质量均匀、适合大量生产复杂形状并可减少后续加工等等的优点,故受到工业界广泛的重视。粉末射出成型的基本步骤为将金属粉末或陶瓷粉末加入结合剂(binder)中,以结合剂为载体,于适当温度下混炼(blending)为待塑形材料,之后经射出机射出成型为生胚,再经脱脂过程脱除生胚中的结合剂,然后烧结成零件。以上过程中皆牵涉结合剂与粉末之间的相互作用,故结合剂的性质对对象能否成功成型,甚至进一步达成高精密度的要求有密切的关系。
结合剂主要的功能为提供载体,降低粉末间的摩擦力,使其具有流动性,且在脱脂时仍可维持生胚形状。而单一成分的结合剂不容易同时拥有多种特性,故结合剂通常为多成分设计,其带来的优点为在脱脂过程时,可逐渐移除各成分,避免瞬间脱去大量的结合剂而导致对象变形或崩解,同时,先被移除的成分(例如石蜡、微晶蜡等)亦可产生初期孔道,以利脱脂过程中产生的气体能顺利扩散至生胚外,避免胚体产生膨胀破裂。
优良的结合剂必须使混炼后的待塑形材料具有良好的流动性及成形性,且需具有分散粉体的作用,避免粉体颗粒结块,以及在脱脂后生胚不易崩塌,易于受热去除而不产生残碳等等的特性。然而,多成分的结合剂中所使用的高分子通常具有晶质(例如聚甲醛(Polyoxymethylene,POM))与非晶质(聚乙烯(Polyethylene,PE))的特性,因其性质的差异及结构的不同,影响彼此间的兼容性,导致组成的结合剂产生不均匀的现象。此种不均匀的情况会使得(1)待塑形材料缺乏良好的流动性,增加制程所需花费的时间,且在复杂的射出成型零件的状况下,甚至会造成不完全的铸模充填;以及(2)让射出成型生胚在后续的脱脂过程中,因受热分解的速率不一致而产生缺陷(例如变形)。以上所述即为产品尺寸、精密度不易控制的主要原因,因此有必要对于结合剂中各成分之间的兼容性进行加强,以满足对高质量粉末射出成型零件的市场需求。
发明内容
鉴于上述现有的问题,本发明的目的在于提供一种射出成型用结合剂,提升结合剂中各成分之间的兼容性以满足制造高质量的粉末射出成型品之需求。
根据上述目的,本发明提出一种射出成型用结合剂,其可包含:带有顺丁烯二酸酐(maleic anhydride)基团的聚烯烃、聚烯烃化合物、聚甲醛、硬脂酸(stearic acid)及蜡。其中,带有顺丁烯二酸酐基团的聚烯烃的平均分子量可为约90,000至约110,000。
进一步,其中聚烯烃化合物及聚甲醛可经由分别与带有顺丁烯二酸酐基团的聚烯烃形成键结而接合。
进一步,带有顺丁烯二酸酐基团的聚烯烃可占射出成型用结合剂约3至约20%的重量百分比;该聚烯烃化合物可占该射出成型用结合剂约30至约40%的重量百分比;聚甲醛可占该射出成型用结合剂约5至约20%的重量百分比;硬脂酸可占该射出成型用结合剂约1至约5%的重量百分比;以及该蜡可占该射出成型用结合剂约35至约60%的重量百分比。
进一步,其中聚烯烃化合物可包含密度为约0.950至约0.965g/cm3的高密度聚乙烯(high density polyethylene,HDPE)或密度为约0.915至约0.930g/cm3的低密度聚乙烯(low density polyethylene,LDPE);蜡可选自由石蜡、密蜡、巴西蜡、微结晶蜡及其组合所组成的群组中。
本发明亦提供一种用来制造成型对象的组合物,其可包含约30至约50体积%的本发明的射出成型用结合剂;以及约50至70体积%的可烧结粉末。其中,所述组合物可在约170至约190℃下将本发明的射出成型用结合剂与可烧结粉末混炼约90至约150分钟而得。
进一步,可烧结粉末可选自由金属粉末、金属合金粉末、金属羰基粉末、陶瓷粉末及其组合所组成的群组中。
综上所述,根据本发明的射出成型用结合剂能经由带有顺丁烯二酸酐基团的聚烯烃与聚烯烃化合物及聚甲醛形成键结,以达到提高结合剂本身的兼容性的功效,并藉此延长结合剂热分解的温度区间以降低烧结时产生缺陷的机率。此外,结合剂的兼容性提高亦有助于提升生胚的流动性,能避免射出成型时短射(shortshots),造成流痕(flowing mark)、结合线(welding line)等不美观表面。
附图说明
图1为本发明第二实施例的射出成型用结合剂、高密度聚乙烯、聚甲醛及第一对照例的热重分析(Thermogravimetric Analysis,TGA)结果图;
图2为本发明第三实施例的利用本发明的射出成型用结合剂制造射出成型对象的流程图;
图3为应用图2的流程所得的第二对照例的生胚烧结后照片;
图4为本发明第三实施例的生胚烧结后照片;
图5为本发明第四实施例与第三对照例的粘度与剪率(shear rate)的结果图。
附图标记
S1~S6:步骤。
具体实施方式
本发明的第一实施例提供了一种五成分系的结合剂组合物,以应用于射出成型,其可包含带有顺丁烯二酸酐基团的聚烯烃、聚烯烃化合物、聚甲醛、硬脂酸及蜡。在该实施例中,带有顺丁烯二酸酐基团的聚烯烃的平均分子量可为约90,000至约110,000,优选为约100,000。聚烯烃化合物可包含密度为约0.950至约0.965g/cm3的高密度聚乙烯(HDPE)或密度为约0.915至约0.930g/cm3的低密度聚乙烯(LDPE),较佳为高密度聚乙烯。蜡可选自由石蜡、密蜡、巴西蜡、微结晶蜡及其组合所组成的群组中,较佳为石蜡、微结晶蜡及其组合所组成的群组,但不限于此。
根据该第一实施例,将带有顺丁烯二酸酐基团的聚烯烃、聚烯烃化合物、聚甲醛、硬脂酸及蜡在约170至约190℃下均匀混合约90至约150分钟,优选为在约180℃下均匀混合约120分钟,可得到具有高兼容性的结合剂,其中带有顺丁烯二酸酐基团的聚烯烃可占射出成型用结合剂约3至约20%的重量百分比,优选为约3%;聚烯烃化合物可占射出成型用结合剂约30至约40%的重量百分比,优选为约33%;聚甲醛可占射出成型用结合剂约5至约20%的重量百分比,优选为约11%;硬脂酸可占射出成型用结合剂约1至约5%的重量百分比,优选为约3%;以及蜡可占射出成型用结合剂约35至约60%的重量百分比,优选为约50%。
请参照图1,其为本发明第二实施例的射出成型用结合剂、高密度聚乙烯、聚甲醛及第一对照例的热重分析结果图。在本发明第二实施例中,带有顺丁烯二酸酐基团的聚烯烃可为经顺丁烯二酸酐改质的线性低密度聚乙烯(maleicanhydride modified low-density polyethylene,18302N,密度为0.912g/cm3),占射出成型用结合剂约3%的重量百分比;聚烯烃化合物可为高密度聚乙烯,其密度为0.955g/cm3,占射出成型用结合剂约33%的重量百分比;聚甲醛占射出成型用结合剂约11%的重量百分比;硬脂酸,占射出成型用结合剂约3%的重量百分比;以及蜡,占射出成型用结合剂约50%的重量百分比,其中石蜡与微结晶蜡比例为2:1。将上述5种成分在约180℃下均匀混合约120分钟,即可得到本发明第二实施例的射出成型用结合剂。此外,另提供第一对照例,在第一对照例中,除了使用乙烯-醋酸乙烯共聚物(ethylene vinylacetatecopolymer,EVA)取代经顺丁烯二酸酐改质的线性低密度聚乙烯之外,其余的组成比例及混合方法皆与本发明第二实施例的射出成型用结合剂相同。经由热重分析仪分别对本发明第二实施例的射出成型用结合剂、高密度聚乙烯、聚甲醛及第一对照例做热重分析,可得到那些在不同温度下的重量烧失曲线。如图所示,可以悉知单一化合物,也就是聚甲醛的重量烧失曲线A及高密度聚乙烯的重量烧失曲线B从开始热分解至热分解结束的温度区间相当狭窄,都仅为约80℃的区间(聚甲醛为约320至约400℃;高密度聚乙烯为约380至约460℃)。而本实施例的射出成型用结合剂的重量烧失曲线C的热分解过程则有约290℃的广泛区间(约200至490℃)。相较之下,第一对照例的重量烧失曲线D仅有约265℃的温度区间(约200至465℃)。
上述结果显示,本发明第二实施例的射出成型用结合剂为一具有高兼容性的结合剂。其基本原理为带有顺丁烯二酸酐基团的聚烯烃与聚烯烃化合物及聚甲醛可形成键结,使原本兼容性不佳的聚烯烃化合物及聚甲醛经由化学键结合在一起,提升该结合剂的兼容性表现,从而使热裂解区间显著延长。此外,比起仅利用范德华力来提升结合剂成分之间兼容性的先前技术(例如乙烯-醋酸乙烯共聚物与聚乙烯),本案因具有化学键的存在,因此在生胚的强度上占有优势。
请参照图2,其为本发明第三实施例的利用本发明的射出成型用结合剂制造射出成型对象的流程图。在此实施例中,结合剂为本发明的射出成型用结合剂。可烧结粉末可选自金属粉末、金属合金粉末、金属羰基粉末、陶瓷粉末及其组合所组成的群组中,但不限于此。如图所示,其实施流程可包含下列步骤:
步骤S1:将本发明的射出成型用结合剂与可烧结粉末均匀混合。其中,本发明的射出成型用结合剂占体积百分比约30至约50%且可烧结粉末占体积百分比约50至约70%。
步骤S2:将步骤S1中所得的混合物在约180℃下混炼约120分钟,可得到组合物。
步骤S3:将步骤S2中所得的组合物冷却,接着进一步将其粉碎匀化后造粒,以利射出成型机给料。
步骤S4:利用射出成型机将步骤S3中所得的料粒射出成型为所需的物件生胚。
步骤S5:将对象生胚中放入脱脂炉,在约800℃下持温约120分钟以去除结合剂。
步骤S6:将脱脂后的对象生胚放入烧结炉,在约1,200至约1,360℃,优选为约1,360℃下持温约120至约240分钟,优选为约120分钟以烧结生胚,即可得到所需对象。
请参照图3,其为应用图2的流程所得的第二对照例的生胚烧结后照片。第二对照例与本发明第三实施例大致相同,且步骤S1中的射出成型用结合剂占体积百分比约40%且可烧结粉末占体积百分比约60%,不同之处仅在于第二对照例的射出成型用结合剂仅由经顺丁烯二酸酐改质的线性低密度聚乙烯、硬脂酸及蜡组成,其中,经顺丁烯二酸酐改质的线性低密度聚乙烯占射出成型用结合剂约47%的重量百分比;硬脂酸占射出成型用结合剂约3%的重量百分比;以及蜡占射出成型用结合剂约50%的重量百分比,且石蜡与微结晶蜡比例为2:1。如图所示,能够知道经顺丁烯二酸酐改质的线性低密度聚乙烯自身即可将可烧结粉末结合,并能形成具有一定强度的生胚,只是生胚烧结后的变形状况不甚理想,呈现大幅弯曲状态。
请参照图4,其为本发明第三实施例的生胚烧结后照片。在此实施例中,所用的结合剂为本发明第二实施例的射出成型用结合剂,且步骤S1中的射出成型用结合剂占体积百分比约40%且可烧结粉末占体积百分比约60%。对照第3图及第4图可知根据本发明第三实施例制得的对象的变形状况明显较根据第二对照例制得的对象为小,由此可证实本发明的结合剂除了能够解决聚甲醛与高密度聚乙烯之间的兼容性不良的问题,且能进一步改善烧结时产生缺陷或变形的状况。
请参照图5,其为本发明第四实施例的组合物与第三对照例的粘度与剪率的结果图。在本发明第四实施例中,组合物可依照图2中的步骤S1至S2制得,其中射出成型用结合剂可与本发明第二实施例的射出成型用结合剂相同,且可烧结粉末可为金属粉末(三菱17-4PH)。在第三对照例中,除了使用日本ATECT公司的M3结合剂取代本发明第二实施例的射出成型用结合剂之外,其余皆与本发明第四实施例相同。如图所示,第四实施例的组合物的粘度在测量的剪率范围内比第三对照例的粘度小或大致上相同。由此能够悉知,本发明第四实施例的组合物比起使用市售的结合剂而制得的组合物具有较高或大致上相同的流动性,可借此在之后的射出填模过程中达到较好或大致上相同的填充率。
综上所述,由本发明的射出成型用结合剂所组成的组合物,因结合剂中带有顺丁烯二酸酐基团的聚烯烃与聚烯烃化合物及聚甲醛形成键结,故能够解决聚甲醛与高密度聚乙烯之间的兼容性不良的问题,使其兼容性提高,从而使其热裂解区间比起使用乙烯-醋酸乙烯共聚物的结合剂的先前技术有显著的延长。利用此特点,可使生胚在脱脂及烧结的过程中,缓慢均匀地脱去结合剂,避免因短时间内脱去过多结合剂而导致对象变形或崩解,故能有效减少对象的缺陷,提高其尺寸的精确度及一致性。此外,结合剂的兼容性提高也有助于提升组合物的流动性,填模时能避免形成生胚内部气泡或因填模不完全而在模具角落产生孔洞或缺角。最后,由本发明的射出成型用结合剂所组成的组合物仅需高温烧结即可移除结合剂,不需要容易产生污染及造成后续废弃物处理问题的溶脱及酸脱制程。
以上所述仅为示例性的,并不用于限制本发明。任何未脱离本发明的精神与范畴,而对其进行的等效修改或变更,均应包含于随附的权利要求中。
Claims (6)
1.一种射出成型用结合剂,其特征在于,包含:
带有顺丁烯二酸酐基团的聚烯烃;
聚烯烃化合物;
聚甲醛;
硬脂酸;以及
蜡,
其中,所述带有顺丁烯二酸酐基团的聚烯烃的平均分子量为90,000至110,000。
2.根据权利要求1所述的射出成型用结合剂,其特征在于,所述聚烯烃化合物及所述聚甲醛经由分别与所述带有顺丁烯二酸酐基团的聚烯烃形成键结而接合。
3.根据权利要求1所述的射出成型用结合剂,其特征在于,所述带有顺丁烯二酸酐基团的聚烯烃占所述射出成型用结合剂3至20%的重量百分比;所述聚烯烃化合物占所述射出成型用结合剂30至40%的重量百分比;所述聚甲醛占所述射出成型用结合剂5至20%的重量百分比;所述硬脂酸占所述射出成型用结合剂1至5%的重量百分比;以及所述蜡占所述射出成型用结合剂35至60%的重量百分比。
4.根据权利要求1所述的射出成型用结合剂,其特征在于,所述聚烯烃化合物包含密度为0.950至0.965g/cm3的高密度聚乙烯或密度为0.915至0.930g/cm3的低密度聚乙烯;所述蜡选自由石蜡、密蜡、巴西蜡、微结晶蜡及其组合所组成的群组中。
5.一种用来制造成型对象的组合物,其特征在于,包含:
30至50体积%的根据权利要求1-4中任一项所述的射出成型用结合剂;以及50至70体积%之可烧结粉末,其中,所述组合物是在170℃至190℃下将根据权利要求1-4的任一项所述的射出成型用结合剂与所述可烧结粉末混炼约90至约150分钟而得。
6.根据权利要求5所述的组合物,其特征在于,所述可烧结粉末选自由金属粉末、金属合金粉末、金属羰基粉末、陶瓷粉末及其组合所组成的群组中。
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