CN102639305A - 长纤维增强热塑性树脂颗粒的制造方法 - Google Patents
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Abstract
本发明是一种长纤维增强热塑性树脂颗粒的制造方法,是一边使多条增强纤维束彼此捻合在一起,一边在热塑性树脂浴抽丝,从而形成在增强纤维的周围被覆有所述热塑性树脂的线束,将该线束切断成规定长度而得到颗粒的长纤维增强热塑性树脂颗粒的制造方法,其中,将所述热塑性树脂的熔融粘度调整到熔体流动速率=500~1500g/10min,使增强纤维束相对于所述线束的抽丝方向的加捻角度θ为0°<θ≤50°而对所述线束进行抽丝。由此,根据长纤维增强热塑性树脂颗粒的制造方法,能够以优良生产率制造出这样的颗粒,即,在颗粒熔化时,增强纤维容易释放,能够使增强纤维均等地分散在成形品中。
Description
技术领域
本发明涉及长纤维增强热塑性树脂颗粒的制造方法。
背景技术
纤维增强热塑性树脂(FRTP)因为轻量且强度优异,所以经常被用于车辆和船舶的外装等。特别是在纤维增强热塑性树脂之中含有纤维长度长的增强纤维的长纤维增强热塑性树脂(LFRTP),因为耐冲击性和刚性优异,所以近年来被大量用于汽车的保险杆和车体。
这样的长纤维增强热塑性树脂的成形品,由使颗粒熔化了的树脂材料制造,在颗粒中分散调配有纤维长度长的增强纤维。例如在专利文献1中,公开有一种颗粒的制造方法,其是对于浸渍在熔融的热塑性树脂浴中的多个玻璃粗纱(glass roving)这样的增强纤维束,一边使增强纤维束彼此捻合在一起,一边从热塑性树脂浴中将其拉出,从而形成在增强纤维的周围被覆有热塑性树脂的线束,将线束切断成规定长度而得到颗粒。
在该颗粒的制造方法中,在热塑性树脂浴的下游侧配备有一对牵拉辊,该牵拉辊其配备方式为,彼此相对于线束的抽丝方向朝着互不相同的方向倾斜。因此,在专利文献1的颗粒的制造方法中,是在该辊间夹入增强纤维束,对于增强纤维束施加了搓捻的线束被作为中间体制造。
如此抽丝的中间体的线束,通过捻合,增强纤维束彼此牢固缔结,在线束的中央侧,增强纤维束聚拢。然后,以在中央侧的增强纤维的周围包围热塑性树脂的方式将其被覆。因此,从硬模拉出线束时,热塑性树脂承担着润滑的作用并协助线束的抽丝,另外,增强纤维与硬模接触,线束也没有抽丝的阻抗。其结果是,与平行抽丝增强纤维束的现有的制造方法相比,能够以更小的力抽丝线束,因为线束的抽丝阻抗小,所以具有能够加快颗粒的生产速度这样的优点。
另外,在施加搓捻而进行制造的专利文献1的制造方法中,增强纤维束捻合而被压缩,体积减小,因此能够容易使增强纤维的含量增加,与平行抽丝增强纤维的现有的制造方法相比,具有能够提高增强纤维的含有率这样的优点。
先行技术文献
专利文献
专利文献1:日本特开2008-221574号公报
可是,如果被覆在增强纤维的表面的热塑性树脂的熔融粘度降低,则存在其越低,热塑性树脂越难以浸透至被搓捻的增强纤维束的内部的倾向。因此,若热塑性树脂使用的是熔融粘度低的,则热塑性树脂未浸透到增强纤维束的内部的部分容易残留。而且,热塑性树脂未浸透部分在冷却后的线束和颗粒的内部作为空隙残留,若使颗粒熔化,则容易在母料(master batch)中发生气泡。其结果是,若使用熔融粘度低的热塑性材树脂,则存在成形品容易发生外观不良的问题。
另外,在捻合增强纤维束的方法中还存在的问题是,若提高线束的抽丝速度,则增强纤维在线束的内部紧紧纠缠。如此紧紧纠缠的增强纤维,即使颗粒熔化也难以释放,在成形品中增强纤维无法很好地分散,从而使成形品的机械特性恶化。
发明内容
本发明鉴于上述的问题而做,其目的在于,提供一种长纤维增强热塑性树脂颗粒的制造方法,其能够以优良的生产率制造增强纤维以高含有率被含有的颗粒,同时在颗粒熔化时,增强纤维会容易地释放,从而能够使增强纤维均匀地分散在成形品中,不会损害成形品的机械特性和外观。
为了达成前述目的,本发明采取了以下的技术手段。
即,本发明的长纤维增强热塑性树脂颗粒的制造方法,是对于浸渍在熔融的热塑性树脂浴中的多个增强纤维束,一边使该增强纤维束彼此捻合在一起,一边从熔融的热塑性树脂浴中对其进行抽丝,从而形成在增强纤维的周围被覆有所述热塑性树脂的线束,将该线束切断成规定长度,从而得到颗粒的长纤维增强热塑性树脂颗粒的制造方法,其中,将所述热塑性树脂的熔体流动速率调整到500~1500g/10min,使增强纤维束相对于所述线束的抽丝方向的加捻角度θ为0°<θ≤50°而对所述线束进行抽丝。
还有,所谓长纤维增强热塑性树脂,是使用在增强纤维之中还具有长的树脂的增强纤维,使热塑性树脂强化的意思,在本发明的情况下是使用具有3~25mm的纤维长度的增强纤维。
发明者们考虑,即便使用浸透到增强纤维束的内部十分困难的这种熔体流动速率(熔融粘度)低达500~1500g/10min的热塑性树脂,如果调整使增强纤维束捻合时的加捻角度,则也会使增强纤维紧紧纠缠在一起。于是发现,通过使加捻角度θ为0°<θ≤50°而使增强纤维束捻合,便不会损害成形品的机械特性和外观,能够以优良的生产率制造以高含有率含有增强纤维的颗粒,从而完成了本发明。
根据上述这种方法,能够容易地制造所述增强纤维含有50~90重量%这样的增强纤维的含有率高的颗粒。另外,可以使所述线束对于所述抽丝方向,以60~80m/min这样高的生产速度进行抽丝。
还有,优选所述热塑性树脂为聚丙烯系树脂,所述增强纤维束为玻璃粗纱。
根据本发明的长纤维增强热塑性树脂颗粒的制造方法,能够以优良的生产率制造增强纤维以高含有率被含有的颗粒,同时在颗粒熔化时,增强纤维会容易地释放,从而能够使增强纤维均匀地分散在成形品中,不会损害成形品的机械特性和外观。
附图说明
图1是用于本发明的制造方法的制造装置的立体图。
图2是牵拉装置的放大平面图。
图3是使加捻角度变化时的线束的正视图和剖面图。
图4是熔体流动速率和增强纤维的加捻角度的相关图。
具体实施方式
以下,基于附图详细地说明本发明的长纤维增强热塑性树脂颗粒1的制造方法。首先,对于用于长纤维增强热塑性树脂颗粒1的制造方法的颗粒制造装置2进行说明。
如图1所示,颗粒制造装置2具有:缠绕有增强纤维束3的多个线卷4;使作为原料的热塑性树脂(以下称为树脂5)混匀熔化的混炼压出机6;用通过混炼压出机6塑化的树脂5被覆盖从线卷4送出的增强纤维束3的树脂浸渍头7。另外,颗粒制造装置2还具有:冷却装置9,其对于由树脂浸渍头7被覆盖了树脂5的增强纤维束3(线束8)进行冷却;牵拉装置10,其配备在冷却装置9的下游侧而牵拉线束8;切割机11,其将冷却的线束8切断为规定长度。
线卷4是增强纤维束3的线材缠绕而成的卷。作为增强纤维,能够使用玻璃纤维、碳纤维、芳族聚酰胺等的有机合成树脂、钢线等金属纤维,在本实施方式中,作为该增强纤维束3使用玻璃粗纱12。玻璃粗纱12是使粗纱支数为1000~4000tex而将直径4~30μm的玻璃单丝(glassmonofilament)多条会聚,缠绕成圆筒状而成,在本实施方式中,该玻璃粗纱12有3卷。
混炼压出机6,在内部被认为是空洞的室13内具有可自由旋转的螺杆轴(screw shaft)(未图示),该螺杆轴具有混炼叶片,混炼压出机6使从漏斗14投入的树脂5的原料熔化塑化。塑化的树脂5被送至树脂浸渍头7。
作为供给到混炼压出机6的树脂5(被覆增强纤维的树脂5),有聚丙烯和聚乙烯这样的聚烯烃系树脂,聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯这样的聚酯系树脂,尼龙这样的聚酰胺系树脂,聚碳酸酯系树脂,聚缩醛或聚苯硫醚等热塑性的树脂,在本实施方式中使用的是聚丙烯系树脂。
在树脂5中,也能够适宜添加氨基硅烷偶合剂(对于增强纤维的粘接性)、活性稀释剂(改善耐冲击性等颗粒的机械的特性的添加剂)、抗氧化剂、紫外线吸收剂、光稳定剂、阻燃剂、填充剂或着色用颜料等。
树脂浸渍头7为如下构造:在沿着上下方向的轴心周围形成为圆筒状,在其中空的内部储存有由混炼压出机6进行了塑化的树脂5。树脂浸渍头7的上端朝向上方开口,从该开口将增强纤维束3引入储存的树脂5内。在树脂浸渍头7的内部,在上下方向上间隔设有多个(在本实施方式中为5个)浸渍辊(未图示),在顺序通过这些浸渍辊期间,从上端的开口引入的增强纤维束3释放,在内部浸渍塑化的树脂5。在树脂浸渍头7的下端侧,形成有将浸渍了树脂5的增强纤维束3抽丝到外部的出口16,在该出口16上设有硬模17,其在增强纤维的周围赋予树脂5以形状,形成线束8。
冷却装置9冷却从树脂浸渍头7中抽丝的线束8,配备在树脂浸渍头7的下游侧。冷却装置9是在内部储存有冷却水18的水槽,能够将被覆在线束8的表面、处于可塑状态的树脂5导入冷却水18中进行冷却。由冷却装置9冷却的线束8被送至牵拉装置10。
牵拉装置10具有在外周面相互接触的上下一对牵拉辊19U、19D。此上下一对牵拉辊19U、19D,以夹住线束8而使之向下游侧送出的方式朝向互不相同的旋转方向旋转。
如图2所示,上下一对牵拉辊19U、19D,朝向相对于线束的抽丝方向倾斜的方向而配备,上下牵拉辊19U、19D之间为彼此相等的角度,并且朝向不同的方向。即,上侧的牵拉辊19U相对于牵拉方向从上方看时,逆时针旋转倾斜倾角θ时,下侧牵拉辊19D相对于牵拉方向,顺时针旋转倾斜倾角θ。因此,若在牵拉辊19间夹入线束8,则对于线束8在轴心周围施加扭转方向的力,对于线束8施加相当于牵拉牵拉辊19的倾角θ的加捻角度θ的搓捻。
由该牵拉辊19施加的搓捻,被施加到配备在树脂浸渍头7的内部的最下侧的浸渍辊的更下游侧的线束8整体,因此,对于通过最下侧的浸渍辊的增强纤维束3来说,在直至其通过硬模17的期间也会发生搓捻。其结果是,从硬模17拉出的线束8成为在树脂浸渍头7内搓捻的增强纤维的周围被覆有热塑性树脂5的线束。
切割机11配备在牵拉装置10的下游侧,将由冷却装置9冷却的线束8切断成规定长度(例如3~10mm)。切割机11,在沿轴心周围旋转的圆筒状的主体20的外周面,具有多个相对于切线方向倾斜的刃部21,刃部21在周向保持规定的间隔。因此,若一边使线束8碰到刃部21一边使切割机11旋转,则线束8被切割机11切断成与刃部21间隔对应的规定长度。
如此得到的颗粒1,在注射成形前使之熔化,并且根据需要以稀释用的树脂5稀释,作为注射成形用的母料使用。
本发明的制造方法,其特征在于,将树脂5的熔融粘度调整到熔体流动速率=500~1500g/10min,使增强纤维束3相对于线束8的抽丝方向的加捻角度θ为0°<θ≤50°而对线束8进行抽丝。
熔体流动速率(树脂5的熔融粘度)是表示树脂5的可塑状态的流动性的指标,由JISK 7210(塑料-热塑性塑料的熔体流动速率)规定。
在本发明的制造方法中,调整树脂5的熔体流动速率,使之达到500~1500g/10min。若熔体流动速率低于500g/10min,则树脂5的流动性差,树脂5难以浸透至增强纤维束3的内部。另一方面,若熔体流动速率比1500g/10min高,则树脂5的粘度过低,树脂5难以附着(难以被覆)在增强纤维上。
可是,该树脂5的熔体流动速率,作为长纤维增强热塑性树脂颗粒1所使用的树脂5的值被设定在很高的范围,作为被覆增强纤维的表面的树脂5的熔融粘度低。
若使用熔融粘度如此低的树脂5,则难以充分浸透到搓捻的增强纤维束3的内部,因此在增强纤维束3的内部残留有未浸渍树脂5的部分,在此状态下线束8被冷却。其结果是存在如下问题:未浸渍树脂5的部分在颗粒1的内部作为空隙残留,下次使颗粒1熔化时,在熔融的树脂5中容易发生气泡,成形品容易发生外观不良。
因此在本发明中,不仅要把树脂5的熔体流动速率调整为500~1500g/10min,还要如上述使增强纤维束3相对于线束8的抽丝方向的加捻角度θ为0°<θ≤50°,优选为10°≤θ≤40°而对于线束8进行抽丝。
之所以如此调整增强纤维束3相对于线束8的抽丝方向的加捻角度θ,是出于以下的理由。
即,如图3(c)所示,若使增强纤维束3的加捻角度θ为0°,则对增强纤维没有施加扭转,因此增强纤维成为沿着线束8的牵拉方向平行对齐的状态。其结果如图3(f)所示,在线束8的表面附近也存在增强纤维,从硬模17抽丝线束8时,表面邻域的增强纤维勾挂在硬模17上,线束8的抽丝阻抗变大。其结果是,若提高颗粒1的生产速度,则容易发生线束8的断裂,不能在加大生产速度的状态下稳定地生产。
可是,若如图3(a)所示这样使增强纤维束3的加捻角度θ为0°~50°,优选为10°~40°,则对增强纤维施加扭转,因此增强纤维容易聚集到线束8的内部。其结果如图3(d)所示,从硬模17抽丝线束8时,被覆在增强纤维3的周围的树脂5承担着润滑的作用并协助线束8的抽丝,因此,线束8的抽丝阻抗变小,能够加大颗粒1的生产速度。另外,因为增强纤维聚集在线束8的内部,所以增强纤维很难碰到硬模17,也不会发生线束8的断裂。
另一方面,如图3(b)所示,若使增强纤维3的加捻角度θ比50°大,则对增强纤维施加很强的扭转。其结果如图3(e)所示,增强纤维被使劲压缩,以紧紧纠缠在一起的状态聚集在线束8的内部,在使颗粒1熔化时,增强纤维难以从颗粒1释放并分散。其结果是,增强纤维无法很好地分散在成形品中,成形品的机械特性降低。
因此,如果使增强纤维束3相对于线束8的抽丝方向的加捻角度θ为0°<θ≤50°,优选为10°≤θ≤40°,则在保存被覆在增强纤维的周围的树脂5的润滑作用的状态下,能够使增强纤维不会在线束8的内部过紧地纠缠。若是如此,则使颗粒1熔化时,能够使增强纤维良好地分散在母料中。另外,即使对于抽丝方向提高线束8的抽丝速度达60~80m/min,也不会发生线束8的断裂,可以稳定地生产颗粒1。
此外,如此制造的颗粒1,是以将增强纤维聚集在线束8的内部的方式使之捻在一起,因此与不进行搓捻的增强纤维的情况相比,能够将更多的增强纤维调配在树脂5中。其结果是,即使是增强纤维的含有率高达50~90重量%的颗粒1,也可以稳定地制造。
实施例
接下来,运用实施例和比较例,对于本发明的长纤维增强热塑性树脂颗粒1的制造方法进行说明。
实施例和比较例,其实施是对于以如下方式制造的长纤维增强热塑性树脂颗粒,按照规定的评价进行评价。
在颗粒1的制造中,准备2个~3个会聚有直径17μm(比重2.5g/cm3)的单丝的玻璃粗纱12(粗纱支数:2310tex)的线卷4,从这些线卷4向树脂浸渍头7供给玻璃粗纱12。还有,线卷4为2个时,制造的是纤维含有率为55wt%的颗粒1,线卷4为3个时,制造的是纤维含有率为69wt%的颗粒1。在树脂浸渍头7中,由混炼压出机6供给处于可塑状态的树脂5。该树脂5为比重0.9g/cm3的聚丙烯(PP)。在树脂浸渍头7的树脂5中使玻璃粗纱12浸渍后,从口径形成为3.0mm的硬模17的开口,以60~80m/min的牵拉速度抽丝线束8,得到直径3.0mm的线束8。然后,将线束8切断成5mm的长度而制造颗粒1。
还有,实施例的颗粒1,是将熔体流动速率调整为500g/10min、800g/10min、1500g/10min的树脂5,被覆在施加了加捻角度θ为0°、10°、40°、50°的搓捻的玻璃单丝上。
另外,比较例的颗粒1,使用熔体流动速率调整为300g/10min的树脂5,使加捻角度θ为15°而施加搓捻,或者使用熔体流动速率调整为800g/min的树脂5,使加捻角度θ为5°或60°而施加搓捻。
对于以上述方式得到的实施例和比较例的颗粒1,遵循以下的评价项目进行评价。
·运转稳定性:根据在硬模上因勾挂玻璃单丝而发生的绒毛、牵拉装置10在线束8的滑动或线束8有无断裂,判断是否可以在60~80m/min的牵拉速度下连续运转。评价结果以○×△三个等级进行评价。×是发生线束8的断裂的情况,△是在硬模中发生绒毛或是在牵拉装置10中发生线束8的滑动的情况,○是这些以外的情况(可以在规定速度下稳定的连续运转的情况)。
·树脂向增强纤维中的浸渍性:判断树脂5未浸渍的玻璃单丝是否从颗粒1游离。评价结果以○×两个等级进行评价。×是确认到有树脂5未浸渍的玻璃单丝游离的情况,○是未确认到有游离的情况。
·成形品的外观:判断是否确认到未分散在颗粒1中,呈不均匀的状态的玻璃单丝。评价结果以○×两个等级进行评价。×是在颗粒1中确认到不均匀状态的玻璃单丝的情况,○是未确认到玻璃单丝的情况。
评价结果显示在表1中。
[表1]
若观看表1的结果可知,在使用了熔体流动速率调整到比500g/10min小的300g/10min的树脂5的比较例1中,确认到树脂未浸渍的玻璃单丝的游离,因此“树脂向增强纤维中的浸渍性”不良,另外在颗粒1中确认到不均匀状态的玻璃单丝,因此“成形品外观”也差。
另外,在使用熔体流动速率调整到处于500~1500g/10min范围的800g/10min的树脂5,对于线束加捻角度为低于10°的5°的玻璃粗纱12进行被覆的比较例2中,不仅“树脂向增强纤维中的浸渍性”和“成形品外观”不良,而且发生线束8的断裂,“运转稳定性”也差。
此外,在对于线束加捻角度超过50°的60°的玻璃粗纱12进行被覆的比较例3中,虽然“运转稳定性”和“树脂向增强纤维中的浸渍性”良好,但在颗粒1中确认到不均匀状态的玻璃单丝,因此“成形品外观”不良。
相对于这些比较例,在将熔体流动速率调整到500~1500g/10min的树脂5,被覆到施加了加捻角度θ为0°~50°这样搓捻的玻璃粗纱12上的实施例1~5中,“运转稳定性”、“树脂向增强纤维中的浸渍性”、“成形品外观”均良好。
因此如图4所示,如果使熔体流动速率为500~1500g/10min,并且使加捻角度θ处于10~50°的恰当范围内而进行生产,则即使是增强纤维含有50~90重量%这样的增强纤维的含有率高的颗粒1,也可以使增强纤维均等地分散在成形品中,同时还不会损害成形品的机械特性和外观,判断为可以稳定地进行颗粒的生产。
本发明并不限定为上述各实施方式,在不改变本发明的本质的范围内,可以适宜改变各构件的形状、构造、材质、组合等。
在上述实施方式中,玻璃粗纱12例示的是2个或3个,但玻璃粗纱12的个数也可以是1个,也可以是4个以上。
在上述实施方式中,作为树脂5例示的是聚丙烯树脂,但在树脂5中也可以使用聚乙烯、尼龙、聚对苯二甲酸乙二醇酯、聚碳酸酯等。
在上述实施方式中,以制造增强纤维含有50~90重量%的颗粒的情况,和相对于抽丝方向以80~100m/min抽丝线束8的情况为例进行列举,但本发明的制造方法也可以用于制造增强纤维只含有低于50重量%的颗粒1的情况,和相对于抽丝方向以80m/min抽丝线束8的情况。
详细并参照特定的实施方式说明了本发明,但不脱离本发明的精神和范围可以施加各种变更和修改,从业者应该清楚。
本申请基于2009年9月18日申请的日本专利申请(专利申请2009-217032),其内容在此作为参照并援引。
产业上的可利用性
本发明的长纤维增强热塑性树脂颗粒,例如能够作为汽车的保险杠和车体的成形材料加以利用。
符号的说明
1 颗粒(长纤维增强热塑性树脂颗粒)
2 颗粒制造装置
3 增强纤维束
4 线卷
5 热塑性树脂(树脂)
6 混炼压出机
7 树脂浸渍头
8 线束
9 冷却装置
10 牵拉装置
11 切割机
12 玻璃粗纱
13 室
14 漏斗
16 出口
17 硬模
18 冷却水
19U 上侧牵拉辊
19D 下侧牵拉辊
20 主体
21 刃部
θ 增强纤维束的加捻角度(牵拉辊的倾角)
Claims (4)
1.一种长纤维增强热塑性树脂颗粒的制造方法,其特征在于,一边使多条增强纤维束彼此捻合在一起,一边在熔融的热塑性树脂中抽丝,从而形成在增强纤维的周围被覆有所述热塑性树脂的线束,将该线束切断成规定长度而得到颗粒,其中,
将所述热塑性树脂的熔融粘度调整到熔体流动速率=500~1500g/10min,
使增强纤维束相对于所述线束的抽丝方向的加捻角度θ为0°<θ≤50°而对所述线束进行抽丝。
2.根据权利要求1所述的长纤维增强热塑性树脂颗粒的制造方法,其特征在于,在所述颗粒中含有50~90重量%的所述增强纤维。
3.根据权利要求1或2所述的长纤维增强热塑性树脂颗粒的制造方法,其特征在于,相对于所述抽丝方向,以60~80m/min抽丝所述线束。
4.根据权利要求1~3中任一项所述的长纤维增强热塑性树脂颗粒的制造方法,其特征在于,所述热塑性树脂为聚丙烯系树脂,所述增强纤维束为玻璃粗纱。
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JP2009217032A JP5467828B2 (ja) | 2009-09-18 | 2009-09-18 | 長繊維強化熱可塑性樹脂ペレットの製造方法 |
PCT/JP2010/066258 WO2011034187A1 (ja) | 2009-09-18 | 2010-09-17 | 長繊維強化熱可塑性樹脂ペレットの製造方法 |
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CN105940045A (zh) * | 2014-01-29 | 2016-09-14 | 住友电木株式会社 | 成型品的制造方法、成型品、背板和制动块 |
CN108602208A (zh) * | 2016-02-25 | 2018-09-28 | 东丽株式会社 | 不连续纤维增强复合材料 |
CN108948429A (zh) * | 2018-07-23 | 2018-12-07 | 合肥市丽红塑胶材料有限公司 | 一种预分散塑料专用玻璃纤维生产方法及加捻设备 |
CN114641523A (zh) * | 2019-11-11 | 2022-06-17 | 东丽株式会社 | 成型材料及成型品 |
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CN107322844A (zh) * | 2016-04-28 | 2017-11-07 | 全球能源互联网研究院 | 一种热塑性复合芯棒拉挤成型模具 |
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