CN114787247A - 复合材料的制造方法 - Google Patents

复合材料的制造方法 Download PDF

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CN114787247A
CN114787247A CN202080081678.0A CN202080081678A CN114787247A CN 114787247 A CN114787247 A CN 114787247A CN 202080081678 A CN202080081678 A CN 202080081678A CN 114787247 A CN114787247 A CN 114787247A
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fluororesin
prepreg
melt
composite material
film
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CN114787247B (zh
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村上真司
汤川宏和
羽仪圭祐
金森尚哲
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Daikin Industries Ltd
Fukuvi Chemical Industry Co Ltd
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Fukuvi Chemical Industry Co Ltd
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Abstract

本发明提供在预浸料制作时氟树脂膜不容易沿宽度方向收缩的氟树脂/碳纤维复合材料的制造方法。一种包含碳纤维和能熔融加工的氟树脂的复合材料的制造方法，其包括下述工序：工序(1)，在使开纤后的碳纤维与反张力为3.0N/cm2以下的能熔融加工的氟树脂的膜重叠的状态下，加热至上述氟树脂的熔点以上的温度并进行加压，由此得到预浸料；以及工序(2)，在将上述预浸料沿厚度方向重叠1片以上的状态下，加热至上述氟树脂的熔点以上并进行加压，由此得到上述复合材料。

Description

复合材料的制造方法
技术领域
本公开涉及复合材料的制造方法。
背景技术
近年来，已经开发出并市售有多种的纤维增强复合材料，该材料是在合成树脂等基体中混入或夹入有作为增强材料的碳纤维、玻璃纤维、芳香族聚酰胺纤维等而成的。这些纤维增强复合材料可以根据基体和增强材料的选择而在强度、耐热性、耐蚀性、电学特性、轻质性等诸方面获得符合目的的优异性能，因此被用于航空宇宙、陆上运输、船舶、建筑、土木、工业用部件、运动用品等广泛领域中，具有广大的社会需求。
作为增强纤维的使用形态，有将多根长丝排列成所需宽度而成的形态、将长丝切割成特定尺寸而成的形态、织物等制成了布状的形态等。作为复合材料，可以举出：使这些增强纤维通过基体直接进行复合化而成的复合材料；或者如下得到的复合材料：使合成树脂浸渗到长丝规则地排列而成的片或织物等中，制造被称为预浸料的半制品，将该预浸料根据需要重叠适当的片数，利用高压釜等装置制成作为目标物的最终产品；等等。
这些增强纤维以进行并丝并利用上胶剂结合的复丝的形态提供，若为加工时的粘度高的热塑性树脂，则树脂难以充分浸渗到增强纤维束中，因此对于将增强纤维开纤使树脂容易浸渗的技术进行了研究(例如参见专利文献1)。
另外，专利文献2和3中记载了使用已被开纤的碳纤维和尼龙、聚丙烯等非氟系基体树脂而成的纤维增强热塑性树脂片。
现有技术文献
专利文献
专利文献1：国际公开第97/41285号
专利文献2：日本特开2003-165851号公报
专利文献3：日本特开2012-148568号公报
发明内容
发明所要解决的课题
本公开的目的在于提供在预浸料制作时氟树脂膜不容易沿宽度方向收缩的氟树脂/碳纤维复合材料的制造方法。
用于解决课题的手段
本公开涉及一种包含碳纤维和能熔融加工的氟树脂的复合材料的制造方法，其包括下述工序：
工序(1)，在使开纤后的碳纤维与反张力为3.0N/cm2以下的能熔融加工的氟树脂的膜重叠的状态下，加热至上述氟树脂的熔点以上的温度并进行加压，由此得到预浸料；以及
工序(2)，在将上述预浸料沿厚度方向重叠1片以上的状态下，加热至上述氟树脂的熔点以上并进行加压，由此得到上述复合材料。
上述能熔融加工的氟树脂优选为选自由四氟乙烯/全氟(烷基乙烯基醚)共聚物、四氟乙烯/六氟丙烯共聚物、乙烯/四氟乙烯共聚物、聚三氟氯乙烯以及聚偏二氟乙烯组成的组中的至少一种。
上述能熔融加工的氟树脂优选熔体流动速率为0.1～100g/10分钟、熔点为272～323℃。
上述能熔融加工的氟树脂优选为四氟乙烯/全氟(烷基乙烯基醚)共聚物。
发明的效果
根据本公开，能够提供在预浸料制作时氟树脂膜不容易沿宽度方向收缩的氟树脂/碳纤维复合材料的制造方法。
具体实施方式
氟树脂具有耐热性、耐化学药品性、滑动性、低介电常数等多种优异的特性，可用于汽车、飞行器、半导体、电气、电子、化学等多种领域，但与其他树脂相比，其也存在强度低、线膨胀系数大等问题。作为其解决方法之一，可以举出与碳纤维等增强纤维进行复合化，但若在与使用尼龙等非氟系基体树脂的情况相同的条件下制作预浸料，则会产生氟树脂膜沿宽度方向收缩的问题。本发明人进行了深入研究，结果发现，氟树脂的弹性模量低，若以与非氟系树脂相同的反张力将氟树脂膜送出，则氟树脂膜会由于反张力和热的作用而沿宽度方向收缩。并且发现，通过将反张力控制在特定的范围内，可解决上述收缩的问题。
下面对本公开进行具体说明。
本公开涉及一种包含碳纤维和能熔融加工的氟树脂的复合材料的制造方法，其包括下述工序：工序(1)，在使开纤后的碳纤维与反张力为3.0N/cm2以下的能熔融加工的氟树脂的膜重叠的状态下，加热至上述氟树脂的熔点以上的温度并进行加压，由此得到预浸料；以及工序(2)，在将上述预浸料沿厚度方向重叠1片以上的状态下，加热至上述氟树脂的熔点以上并进行加压，由此得到上述复合材料。
本公开的制造方法中，在制作预浸料的工序(1)中，上述能熔融加工的氟树脂的膜不容易沿宽度方向收缩。其结果，能够提高连续生产上述复合材料时的品质稳定性。
工序(1)中使用的碳纤维已被开纤。由此，上述氟树脂充分浸渗到上述碳纤维中。
开纤的方法没有特别限定，可以采用使凹凸辊交替地通过的方法、使用大鼓型辊的方法、对轴向振动施加张力变动的方法、通过垂直地往返运动的2个摩擦体使碳纤维束的张力变动的方法、向碳纤维束吹送空气的方法等。另外，也可以采用日本专利第3064019号公报和日本专利第3146200号公报中记载的开纤方法。
上述碳纤维的基重优选为100g/m2以下、更优选为80g/m2以下、进一步优选为50g/m2以下，并且优选为10g/m2以上。基重越低，氟树脂越容易浸渗到碳纤维中。另外，上述基重可以为30g/m2以上。
作为上述碳纤维，可以举出聚丙烯腈系、沥青系、人造丝系、纤维素系、木质素系、酚系、气相生长系等。其中优选聚丙烯腈系、沥青系或人造丝系的碳纤维，更优选聚丙烯腈系的碳纤维。
上述碳纤维可以进行表面处理，可以使用处理剂，也可以使用上胶剂。
工序(1)中使用的氟树脂是能熔融加工的氟树脂。本说明书中，能熔融加工是指能够使用挤出机和注射成型机等现有的加工设备将聚合物熔融来进行加工。
上述能熔融加工的氟树脂的熔体流动速率(MFR)优选为0.1～100g/10分钟、更优选为0.5～50g/10分钟。
本说明书中，MFR是如下得到的值：依据ASTM D1238，使用熔体流动指数测定仪，在根据氟树脂的种类确定的测定温度(例如，PFA、FEP的情况下为372℃，ETFE的情况下为297℃)下、在负荷(例如，PFA、FEP和ETFE的情况下为5kg)下，求出每10分钟从内径2mm、长度8mm的喷嘴流出的聚合物的质量(g/10分钟)，将所得到的值作为该MFR。
上述氟树脂的熔点优选为150～323℃、更优选为200～323℃、进一步优选为250～323℃、进一步更优选为272℃～323℃、特别优选为280～320℃。
上述熔点是使用差示扫描量热计[DSC]以10℃/分钟的速度升温时的熔解热曲线中的极大值所对应的温度。
作为上述氟树脂，优选为选自由四氟乙烯[TFE]/全氟(烷基乙烯基醚)[PAVE]共聚物[PFA]、TFE/六氟丙烯[HFP]共聚物[FEP]、乙烯[Et]/TFE共聚物[ETFE]、聚三氟氯乙烯[PCTFE]以及聚偏二氟乙烯[PVDF]组成的组中的至少一种，更优选为选自由PFA、FEP以及ETFE组成的组中的至少一种，进一步优选为PFA。
上述PFA具有基于四氟乙烯(TFE)的聚合单元(TFE单元)和基于全氟(烷基乙烯基醚)(PAVE)的聚合单元(PAVE单元)。
作为上述PAVE没有特别限定，例如可以举出下述通式(1)
CF2＝CF-ORf1 (1)
(式中，Rf1表示碳原子数1～10、优选碳原子数1～5的全氟烷基)所表示的物质，其中优选全氟(甲基乙烯基醚)[PMVE]、全氟(乙基乙烯基醚)[PEVE]、全氟(丙基乙烯基醚)[PPVE]。
作为上述PFA没有特别限定，优选TFE单元相对于TFE单元和PAVE单元的合计的比例为70摩尔％以上且小于99.5摩尔％的共聚物，更优选该比例为70摩尔％以上98.9摩尔％以下的共聚物，进一步优选该比例为80摩尔％以上98.7摩尔％以下的共聚物。上述PFA可以为仅由TFE单元和PAVE单元构成的共聚物，还优选为相对于全部单体单元，来自能够与TFE和PAVE共聚的单体的单体单元为0.1～10摩尔％、TFE单元和PAVE单元合计为90～99.9摩尔％的共聚物。作为能够与TFE和PAVE共聚的单体，可以举出HFP、CZ1Z2＝CZ3(CF2)nZ4(式中，Z1、Z2和Z3相同或不同，表示氢原子或氟原子，Z4表示氢原子、氟原子或氯原子，n表示2～10的整数)所表示的乙烯基单体、以及CF2＝CF-OCH2-Rf11(式中，Rf11表示碳原子数1～5的全氟烷基)所表示的烷基全氟乙烯基醚衍生物等。
本说明书中，构成PFA的各单体单元的含量可以通过根据单体的种类将NMR、FT-IR、元素分析、荧光X射线分析适宜地组合而计算出。
上述能熔融加工的氟树脂的膜的厚度优选为0.01～2mm、更优选为0.01～1mm。
工序(1)中，将上述碳纤维和上述氟树脂的膜重叠时，使上述膜的反张力为3.0N/cm2以下。通过使反张力为上述范围内，能够抑制在预浸料的制作时上述膜沿宽度方向的收缩。
上述反张力优选为2.5N/cm2以下、更优选为2.0N/cm2以下、进一步优选为1.0N/cm2以下、特别优选为0.8N/cm2以下，并且优选为0.05N/cm2以上、更优选为0.1N/cm2以上。
上述反张力是沿着与上述膜的传送方向相反的方向对上述膜施加的张力，可以通过控制设备的输出进行调整。作为控制设备，例如可以举出三菱电机制ZKB-0.6AM/YK等。
在工序(1)中，优选将上述碳纤维和上述氟树脂的膜连续地传送。
工序(1)中，在将上述碳纤维与反张力为上述范围内的上述膜重叠的状态下，加热至上述氟树脂的熔点以上的温度并进行加压，由此得到预浸料。通过进行加热、加压，上述氟树脂浸渗到上述碳纤维中。
上述加热的温度为上述氟树脂的熔点以上即可，优选为310℃以上、更优选为340℃以上，并且优选为400℃以下。
上述加压的压力优选为0.01～5.0MPa、更优选为0.1～1.0MPa。
上述加热和加压优选通过利用加热至上述氟树脂的熔点以上的温度的辊施加压力来实施。
上述预浸料可以是上述碳纤维与上述氟树脂进行热熔接而成的。上述预浸料中，优选上述氟树脂浸渗到上述碳纤维中。
上述预浸料中，相对于上述碳纤维和上述氟树脂的总量，上述碳纤维优选为5～70体积％。上述碳纤维更优选为10体积％以上、进一步优选为15体积％以上，并且更优选为60体积％以下、进一步优选为50体积％以下。
本公开的制造方法可以进一步包括通过将工序(1)中得到的预浸料切断而得到短切材料的工序。上述短切材料可以作为工序(2)中的预浸料使用。
上述短切材料可以沿二维方向无规取向而进行层积，因此可以使碳纤维准各向同性地进行取向，所得到的复合材料基于方向的强度差减少。另外，还能够容易地成型出复杂的形状。
本公开的制造方法可以进一步包括通过将2片以上的上述短切材料以沿厚度方向重叠的状态进行加热而得到短切片的工序。上述短切片可以作为工序(2)中的预浸料使用。
工序(2)中，将上述预浸料以沿厚度方向重叠1片以上的状态加热至上述氟树脂的熔点以上并进行加压，由此得到包含碳纤维和能熔融加工的氟树脂的复合材料。
工序(2)中，优选将上述预浸料沿厚度方向重叠2片以上。这种情况下，构成各预浸料的碳纤维的取向可以相同、也可以不同。在重叠的预浸料为上述短切材料的情况下，优选沿二维方向无规取向。
工序(2)中的加热的温度为上述氟树脂的熔点以上即可，优选为310℃以上、更优选为340℃以上，并且优选为400℃以下。
工序(2)中的加压的压力优选为0.05～10MPa、更优选为2～5MPa。
工序(2)中，可以同时进行成型，得到包含上述碳纤维和上述氟树脂的复合成型品。这种情况下，例如使用压缩成型机进行上述加热和加压即可。
由本公开的制造方法得到的复合材料由2片以上的上述预浸料得到的情况下，优选将2片以上的上述预浸料进行了一体化。此处，一体化是指上述预浸料彼此热熔接，构成1个材料。热熔接后的上述预浸料彼此的界面不一定是明确的。
上述复合材料中，相对于上述碳纤维和上述氟树脂的总量，上述碳纤维优选为5～70体积％。上述碳纤维更优选为10体积％以上、进一步优选为15体积％以上，并且更优选为60体积％以下、进一步优选为50体积％以下。
上述复合材料可以通过压缩成型等公知的成型方法进行成型而制成成型品。另外，如上所述，也可以在工序(2)中进行成型。
上述复合材料可用于航空宇宙、陆上运输、船舶、建筑、土木、工业用部件、运动用品等广泛领域中。其中，能够适当地用于半导体清洗装置用的构件。
实施例
接着举出实施例更详细地说明本公开，但本公开并不仅限于这些实施例。
实施例的各数值通过下述方法进行测定。
(1)MFR
依据ASTM D3307，在测定温度372℃、载荷5kg下测定每10分钟从喷嘴流出的聚合物的质量。
实施例1
<UD片(预浸料)的制作>
使用下述材料制作UD片。
碳纤维束(东丽公司制造T700SC-12000-60E)
PFA膜(MFR14g/10分钟、熔点306℃、厚度0.05mm)
使用公知的开纤方法将5根上述碳纤维束分别开纤成宽度42mm，沿宽度方向排列成片状，制作宽度210mm的开纤碳纤维片(基重38.1g/m2)。通过使控制设备(三菱电机制ZKB-0.6AM/YK)的输出为5％以下而使上述PFA膜的反张力为0.6N/cm2，将该开纤碳纤维片与上述PFA膜进行层积，使其在设定为360℃的加热温度的加热加压辊间移动(线速度：10m/min)，制作UD片。得到了上述PFA膜在宽度方向不收缩、Vf(碳纤维体积含量)为29.7％、厚度为0.072mm的UD片。
实施例2
除了使PFA膜的厚度为0.025mm、使反张力为0.25N/cm2以外，与实施例1同样地制作UD片。得到了上述PFA膜在宽度方向不收缩、Vf为45.8％、厚度为0.046mm的UD片。
实施例3
除了使PFA膜的厚度为0.050mm、使反张力为2.5N/cm2以外，与实施例1同样地制作UD片。得到了上述PFA膜在宽度方向收缩了2～3mm左右、Vf为29.7％、厚度为0.072mm的UD片。
实施例4
将3根上述碳纤维束分别开纤成宽度75mm，沿宽度方向排列成片状，制作宽225mm的开纤碳纤维片(基重26.7g/m2)，除此以外与实施例1同样地制作UD片。得到了上述PFA膜在宽度方向收缩了2～3mm左右、Vf为22.7％、厚度为0.064mm的UD片。
<短切材料的制作>
使用上述UD片，通过公知的供给机构和切割机构，沿纤维方向切割成宽度5mm、沿与纤维方向正交的方向切割成长度20mm，制作短切材料。
<短切片的制作>
使用上述UD片，通过日本特开2016-27956号公报记载的方法制作短切片。该方法中使用了UD片切割机构、短切材料传送机构、片一体化机构、片卷取机构。
首先，利用UD片切割机构将UD片沿纤维方向切割成宽度5mm，沿与纤维方向正交的方向切割成长度20mm，制作短切材料。
接着，使所得到的宽度5mm×长度20mm的短切材料自然下落在传送带上使其分散。在带上重叠的短切材料沿厚度方向重叠了2片以上。
接着，利用设定为360℃的加热温度的加热辊使短切材料熔融而进行一体化(线速度：0.6m/min)，制作短切片。所得到的短切片的基重为500g/m2、厚度为0.6mm。
<复合材料的制作>
使用公知的模压成型机由上述UD片、短切材料、短切片分别制作复合材料。
关于由UD片的制作，将UD片按照宽度298mm×长度298mm的方式进行组合，层积940片使成型品厚度达到40mm，将模具设定为360℃的加热温度，在5MPa的压力下加热加压5分钟。其后将模具设定为30℃的温度，在7MPa的压力下加压20分钟。
比较例1
除了使上述PFA膜的反张力为5.0N/cm2将上述开纤碳纤维片和上述PFA膜进行层积以外，与实施例2同样地制作UD片，但在加热加压辊间移动时，上述PFA膜沿长度方向拉伸，沿宽度方向收缩20mm以上，厚度也发生了变化，因此未能以所设定的规格得到UD片。

Claims (4)

1.一种复合材料的制造方法，该复合材料包含碳纤维和能熔融加工的氟树脂，该制造方法包括下述工序：
工序(1)，在使开纤后的碳纤维与反张力为3.0N/cm2以下的能熔融加工的氟树脂的膜重叠的状态下，加热至所述氟树脂的熔点以上的温度并进行加压，由此得到预浸料；以及
工序(2)，在将所述预浸料沿厚度方向重叠1片以上的状态下，加热至所述氟树脂的熔点以上并进行加压，由此得到所述复合材料。
2.如权利要求1所述的制造方法，其中，所述能熔融加工的氟树脂为选自由四氟乙烯/全氟(烷基乙烯基醚)共聚物、四氟乙烯/六氟丙烯共聚物、乙烯/四氟乙烯共聚物、聚三氟氯乙烯以及聚偏二氟乙烯组成的组中的至少一种。
3.如权利要求1或2所述的制造方法，其中，所述能熔融加工的氟树脂的熔体流动速率为0.1g/10分钟～100g/10分钟，熔点为272℃～323℃。
4.如权利要求1～3中任一项所述的制造方法，其中，所述能熔融加工的氟树脂为四氟乙烯/全氟(烷基乙烯基醚)共聚物。
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