CN1079724C - 使塑料增强的复合基材和使用该复合基材的纤维增强塑料 - Google Patents

使塑料增强的复合基材和使用该复合基材的纤维增强塑料 Download PDF

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CN1079724C
CN1079724C CN97116132A CN97116132A CN1079724C CN 1079724 C CN1079724 C CN 1079724C CN 97116132 A CN97116132 A CN 97116132A CN 97116132 A CN97116132 A CN 97116132A CN 1079724 C CN1079724 C CN 1079724C
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base material
plastics
composite base
foamed sheet
resin
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CN1176873A (zh
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伊藤晴康
荒木定男
安田义信
辻修也
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Asahi Fiber Glass Co Ltd
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Abstract

用于塑料增强的复合基材，它包含用针刺成一体的纤维薄毡和密闭泡孔的泡沫塑料片。

Description

使塑料增强的复合基材和使用该复合基材的纤维增强塑料
本发明涉及用于塑料增强的复合基材，以及使用这种复合基材的纤维增强塑料。
通常使用树脂泡沫塑料(resin foam)作为纤维增强塑料(下面简称为FRP)的内芯层材料，使得FRP产品的重量变轻并改善其刚度，或者进一步使之具有隔热性能。
作为用于这种FRP产品的模塑方法，目前常用将纤维薄毡和具有溶剂耐受性并对用于模塑FRP的树脂具有良好亲和性的树脂泡沫塑料交替层压的手工铺叠法(HLU法)；或者树脂转移模塑法(RTM法)，该方法使用被纤维薄毡所包裹或夹在中间的泡沫塑料。
但是，这种用于FRP产品的常规模塑方法具有下列缺点：
(1)将纤维薄毡和树脂泡沫塑料交替层压，或者用纤维薄毡包裹或夹心泡沫塑料需要耗费许多时间和劳动力；
(2)FRP层和树脂泡沫塑料之间的粘合仅依靠树脂的化学粘合力。因此，如果该粘合力是弱的，则由于外力或长时间内各种材料不同的膨胀或收缩而很可能发生剥离，从而使品质下降。因此存在着必须使用与模塑树脂高度相容的树脂泡沫塑料这一限制。另外，FRP产品的剪切强度是差的。
(3)作为解决上面缺点(2)的一种方法，提出了使用具有连续泡孔的树脂泡沫塑料片，使FRP模塑树脂渗入该连续泡孔的树脂泡沫塑料片中，以改善与FRP层的粘合力。但是，发现该方法存在着密度增加并同时使隔热性能下降的缺点。
本发明的目的是解决现有技术的上述问题，提供用于塑料增强的复合基材，该复合基材的重量轻并具有优良的刚度和隔热性能，适用于模塑纤维增强塑料，并提供使用该复合基材的纤维增强塑料。
为达到上述目的，本发明提供一种用于塑料增强的复合基材，它包括用针刺(needling)成一体的纤维薄毡和密闭泡孔的泡沫塑料片。
另外，为达到上述目的，本发明提供纤维增强塑料，它包括用于塑料增强的复合基材，该复合基材包含用针刺成一体的纤维薄毡和密闭泡孔的泡沫塑料片，和施加至该用于塑料增强的复合基材上并被固化的树脂，其中树脂借助于针刺穿部分渗入基材的另一侧并被固化。
下面，参照较好的实例对本发明进行详细的描述。
在附图中：
图1是用于塑料增强的本发明复合基材的制备方法的一个实例的示意图。
图2是用于塑料增强的本发明复合基材的侧视图，显示纤维薄毡的纤维穿过密闭泡孔的泡沫塑料片的针刺穿部分的状况。
图3是用于塑料增强的本发明复合基材的制备方法的另一个实例的示意图。
如上所述，用于塑料增强的本发明复合基材包括纤维薄毡和密闭泡孔的泡沫塑料片。所述纤维薄毡可以是例如表面平整薄毡、短切原丝薄毡、连续原丝薄毡或纸，其中可使用树脂粉或树脂乳液将单股纤维或绞合股纤维化学地粘合成片材，或者可以使用机械方法，如用针刺或机械缝纫将它们结合成片材。
这种纤维薄毡的单位重量最好为20-1200g/m2。另外，由所用纤维薄毡种类所决定的最好的单位重量是从经济效益的观点考虑的(它对应于可市售获得产品的范围)。
表面平面薄毡、纸：20-100g/m2
短切原丝薄毡、连续原丝薄毡：200-1200g/m2
用于构成这种纤维薄毡的纤维可以是，例如无机纤维如玻璃纤维、陶瓷纤维或碳纤维，或者是有机纤维如聚酯纤维。
另一方面，作为本发明中与上述纤维薄毡一起使用的密闭泡孔的泡沫塑料片，其厚度可以为1-50mm，最好为3-10mm。这种密闭泡孔的泡沫塑料片可由例如丙烯酸树脂、氯乙烯树脂、聚乙烯、聚丙烯、聚氨酯、聚乙烯/聚苯乙烯共聚物、丙烯腈/丁二烯/苯乙烯共聚物(ABS)或橡胶制成。即可使用任何材料，只要它是能形成密闭泡孔的泡沫塑料的树脂即可。但是，由于该树脂将在模塑FRP时使用，因此形成泡沫塑料的树脂需要具有溶剂耐受性(耐受溶剂的种类取决于所使用的模塑树脂)。
这种密闭泡孔的泡沫塑料片的发泡幅度常在5-50倍的范围内，最好为10-30倍。如果该发泡幅度较低，则重量下降及隔热效果会变差。另一方面，如果发泡幅度太高，则该泡沫塑料会在FRP形成过程中作为缓冲材料，从而会降低工作效率。
用于塑料增强的本发明复合基材可如下制得，例如，如图1所示，用缝纫机械3将纤维薄毡1和密闭泡孔的泡沫塑料片2刺成一体，以便例如如图2所示，纤维薄毡1的至少部分纤维4穿过密闭泡孔的泡沫塑料片2中的针刺穿的部分5。
另外，如图3所示，可将纤维薄毡1置于密闭泡孔的泡沫塑料片2的两侧，以便将薄毡1和泡沫片2用针刺成一体。可分别使用一种或多种纤维薄毡1和密闭泡孔的泡沫塑料片2进行针刺。在组合使用不同种类的纤维薄毡的情况下，最好使用如表面平整薄毡那样具有光滑表面的薄毡作为最外面一层进行针刺，使得模塑后FRP具有光滑的表面。
在上述针刺中，针孔数可以例如在1-100孔/cm2，最好在3-50孔/cm2的范围内，在需要考虑隔热性的情况下，针孔数应尽可能少。
另外，为了提高粘合性能，可将粘合剂置于纤维薄毡1和密闭泡孔的泡沫塑料片2之间，或者用合适的线将纤维薄毡1和密闭泡孔的泡沫塑料片2缝制在一起。在后面的情况中，缝纫线无需使用与纤维薄毡相同的纤维制成。
可在生产线上用缝纫机械预先针刺纤维薄毡1和密闭泡孔的泡沫塑料片2制得用于塑料增强具有所述结构的本发明复合基材，或者可使用上面装有针刺针的合适的辊在操作点上进行针刺制得该复合基材。可通过调节所述针的直径改变如此制得的用于塑料增强的本发明复合基材中针刺穿部分(针孔)的直径。针的直径通常为0.3-3mm，最好为0.7-2.5mm。
如上所述，用于塑料增强的本发明复合基材是一种纤维薄毡和密闭泡孔的泡沫塑料片用针刺成一体的复合基材。当使用这种用于塑料增强的复合基材模塑FRP或制造FRP产品时，可以获得下列效果。
即，可简单地将FRP模塑树脂施加在用于塑料增强的本发明复合基材上形成FRP或制造FRP产品。因此，由于在FRP形成过程中树脂通过针刺穿部分进行渗透，所以无需设置密闭泡孔的泡沫塑料和纤维薄毡的设置时间，并可缩短FRP的形成时间。结果，与单独使用纤维薄毡和密闭泡孔的泡沫塑料片的情况相比，操作可很快完成。
用于形成FRP或制造FRP产品的树脂可以是通常已知的液态热固性树脂。它最好是，例如不饱和的聚酯树脂、乙烯酯树脂、酚醛树脂(phenol resin)、甲基丙烯酸甲酯树脂、环氧树脂、二环戊二烯树脂或呋喃树脂。从浸渍性能和模塑性的观点看，其中的不饱和聚酯树脂是最好的。
如此得到的本发明纤维增强的塑料包含由针刺成一体的纤维薄毡和密闭泡孔的塑料片组成的用于塑料增强的复合基材，以及施加至该用于塑料增强的复合基材上并被固化的树脂，其中树脂通过针刺穿的部分渗透至另一侧并固化，使得密闭泡孔的泡沫塑料片与FRP层之间的粘合不仅依靠化学粘合力，还依靠在针刺穿部分用于模塑FRP的树脂的渗透和固化以及进入密闭泡孔的泡沫塑料片的树脂的渗透部分形成的固定作用，从而形成强的机械粘合。因此，就作为密闭泡孔的泡沫塑料片的材料而言，仅需考虑其溶剂耐受性，而无需考虑与FRP模塑树脂的化学粘合性能。
另外，在本发明纤维增强塑料中用于塑料增强的复合基材是通过将纤维薄毡和密闭泡孔的泡沫塑料片用针刺成一体获得的。因此，简单地将树脂施加在上层纤维薄毡上，树脂就会渗透针刺穿部分(在密闭泡孔的泡沫塑料片上由针刺形成的孔)进入下面一侧并被固化，从而可简化模塑生产。
另外，由于在上述用于塑料增强的复合基材中使用了密闭泡孔的泡沫塑料片，因此可获得与常规产品具有相同刚度级别的FRP产品，同时，通过改变针孔数，可任意地用树脂代替部分密闭泡孔的泡沫塑料片，从而可以任意地调节密闭泡孔的泡沫塑料片部分的密度，可获得具有任意刚度的FRP产品。
另外，在本发明纤维增强塑料中，纤维薄毡的部分纤维渗透过密闭泡孔的泡沫塑料片的针刺穿部分，并且向该处施加树脂以形成柱状的FRP，从而改进了压缩强度，即使受到冲击，也不会在FRP层和密闭泡孔的泡沫塑料片之间的界面上产生剥离。为了改善刚度和隔热性能，可使用多层用于塑料增强的本发明复合基材。
下面，参照实施例对本发明作更详细的描述。但是，应该理解本发明不受这些特殊实施例的限制。
实施例1
用于塑料增强的复合基材的制备
将单位重量为450g/m2的玻璃短切原丝薄毡(Asahi Fiber Glass Co.，Ltd制)置于厚度为3mm、用聚乙烯制成的30倍发泡的密闭泡孔的泡沫塑料片(商品名为Softron，Sekisui Chemical Co.，Ltd制)的两侧，用针将薄毡和泡沫片刺成一体，获得用于塑料增强的本发明复合基材。针孔数量为22孔/cm2。
FRP模塑
向上述用于塑料增强的复合基材上施加下列组成的树脂并进行FRP模塑。
原型(ortho-type)聚酯树脂    100份
(加有环烷酸钴)
过氧化甲基乙基酮            1份
实施例2
使用与实施例1相同的方法制备用于塑料增强的复合基材，但是30倍发泡的密闭泡孔的泡沫塑料片的厚度改成5mm，用相同的方式进行FRP模塑。
实施例3
使用与实施例1相同的方法制备用于塑料增强的复合基材，但是玻璃短切原丝薄毡仅置于30倍发泡的密闭泡孔泡沫塑料片的一侧，用相同的方式进行FRP模塑。
实施例4
使用与实施例1相同的方法制备用于塑料增强的复合基材，但是玻璃短切原丝薄毡仅置于30倍发泡的密闭泡孔泡沫塑料片的一侧，30倍发泡的密闭泡孔的泡沫塑料片的厚度改成5mm，用相同的方式进行FRP模塑。
实施例5
使用与实施例1相同的方法制备用于塑料增强的复合基材，但是针孔数改成6.5孔/cm2，用相同的方式进行FRP模塑。
比较例1
使用与实施例1相同的方法制备用于塑料增强的复合基材，但是不进行针刺，用相同的方式进行FRP模塑。
比较例2
使用与实施例3相同的方法制备用于塑料增强的复合基材，但是不进行针刺，用相同的方式进行FRP模塑。
比较例3
使用与实施例3相同的方法制备用于塑料增强的复合基材，但是不进行针刺，使用30倍发泡的连续泡孔泡沫塑料代替30倍发泡的密闭泡孔泡沫塑料，用相同的方式进行FRP模塑。
比较例4
不使用30倍发泡的密闭泡孔泡沫塑料片，将单位重量为450g/m2的玻璃短切原丝薄毡(Asahi Fiber Glass Co.，Ltd制)相互叠合，用相同于实施例1的方式进行FRP模塑。
比较例5和6
使用与比较例1(称为比较例5)和比较例2(称为比较例6)相同的方法制备用于塑料增强的复合基材，但是30倍发泡的密闭泡孔的泡沫塑料片的厚度改成5mm，用相同的方式讲行FRP模塑。
比较例7
使用与比较例3相同的方法制备用于塑料增强的复合基材，但是30倍发泡的连续泡孔的泡沫塑料片的厚度改成5mm，用相同的方式进行FRP模塑。
比较试验
对上面制得的FRP产品进行各种比较试验。结果见表1和表2。表1和表2中的空格表示未进行测量。
                                表1
  试验项目     实施例   1   2   3   4   5
泡沫塑料片厚度(mm)   3   5   3   5   3
    剪切强度(kg/25mm)   80.7   76.7   -   -   18.0
    压缩强度(kg/cm2)   83.2   84.0   89.5   91.2   29.5
    热耐受性(m2h℃/kcal)   0.085   0.135   0.080   0.130   0.092
    弯曲刚度(mm)   0.2   0.3   1.0
                                        表2
  试验项目     比较例   1   2   3   4   5   6   7
泡沫塑料片厚度(mm)   3   3   3   -   5   5   5
    剪切强度(kg/25mm)   6.5   -   -   -   6.3   -   -
    压缩强度(kg/cm2)   7.8   8.2   6.0   6.6
    热耐受性(m2h℃/kcal)   0.101   0.096   0.051   0.010   0.158   0.153   0.083
    弯曲刚度(mm)   7.7   2.2   8.1
从上面表1和2可见，与比较例1-7的FRP产品相比，实施例1-5的FRP产品具有优良的刚度并具有高的隔热性能。
试验方法如下。
剪切强度
从FRP产品制得宽25mm、长200mm的试样，在上层FRP层的中部沿宽度方向刻一道口子(notch)，在下层FRP层上距上层FRP层刻口25mm处沿宽度方向也刻一道口子，在距试条两端各50mm处用夹具夹住试样并沿纵向拉伸之，测量上层或下层FRP层从泡沫塑料片上剥落时的强度。
压缩强度
根据JIS K69115.19，用25mm直径的压缩头(compress head)压缩大平板状的FRP产品。
热耐受性
根据JIS A1412测量热导性，由热导性和测量的厚度来测定热耐受性。
弯曲试验的刚度
根据JIS K7055，用25mm宽的试样测量在10kg负荷下的挠曲。
如上所述，纤维薄毡和密闭泡孔泡沫塑料片被用针刺成一体的用于塑料增强的本发明复合基材解决了现有技术的问题，本发明基材的重量轻、具有优良的刚度以及优良的模塑FRP层和密闭泡孔片之间的粘性，因此适用于模塑具有隔热性能的纤维增强的塑料。
另外，就用于塑料增强的本发明复合基材而言，通过改变针孔的数量，可任意地用树脂代替部分密闭泡孔泡沫塑料片，从而可调节密闭泡孔泡沫塑料片部分的密度。因此，它具有可获得任意刚度的FRP产品的优点。

Claims (15)

1.用于塑料增强的复合基材，它包含用针刺成一体的无机纤维薄毡和密闭泡孔的泡沫塑料片。
2.如权利要求1所述的用于塑料增强的复合基材，其特征在于所述纤维薄毡是置于密闭泡孔的泡沫塑料片两侧的，并且纤维薄毡和密闭泡孔的泡沫塑料片是用针刺成一体的。
3.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于所述纤维薄毡是表面平整薄毡、短切原丝薄毡、连续原丝薄毡或纸。
4.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于所述纤维薄毡的单位重量为20-1200g/m2。
5.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于所述无机纤维薄毡的纤维是选自玻璃纤维、陶瓷纤维和碳纤维的无机纤维。
6.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于所述密闭泡孔的泡沫塑料片是由丙烯酸树脂、氯乙烯树脂、聚乙烯、聚丙烯、聚氨酯、聚乙烯/聚苯乙烯共聚物、丙烯腈/丁二烯/苯乙烯共聚物或橡胶制成的。
7.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于所述纤维薄毡的至少部分纤维穿透密闭泡孔的泡沫塑料片中的针刺穿部分。
8.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于针孔数为3-50孔/cm2。
9.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于将粘合剂置于纤维薄毡和密闭泡孔的泡沫塑料片之间。
10.如权利要求1或2所述的用于塑料增强的复合基材，其特征在于用合适的线缝纫纤维薄毡和密闭泡孔的泡沫塑料片。
11.纤维增强塑料，包含由针刺成一体的无机纤维薄毡和密闭泡孔的泡沫塑料片组成的用于塑料增强的复合基材，以及施加至该用于塑料增强的复合基材上并被固化的树脂，其特征在于树脂通过针刺穿的部分渗透至基材的另一侧并固化。
12.如权利要求11所述的纤维增强塑料，其特征在于用于塑料增强的复合基材中的纤维薄毡置于密闭泡孔的泡沫塑料片的两侧，并将纤维薄毡和密闭泡孔的泡沫塑料片用针刺成一体。
13.如权利要求11或12所述的纤维增强塑料，其特征在于树脂借助于纤维薄毡穿透针刺穿部分的纤维渗入基材的另一侧并被固化。
14.如权利要求11或12所述的纤维增强塑料，其特征在于加至用于塑料增强的复合基材中的树脂是不饱和的聚酯树脂。
15.如权利要求13所述的纤维增强塑料，其特征在于加至用于塑料增强的复合基材中的树脂是不饱和的聚酯树脂。
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DE69718572T2 (de) 2003-11-20
CN1176873A (zh) 1998-03-25
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EP0822062A1 (en) 1998-02-04
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US6030907A (en) 2000-02-29

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