CN1151935A - 模塑片材的生产方法、由该方法制备的纤维增强模塑片材及由其制成的安全鞋的鞋包头 - Google Patents
模塑片材的生产方法、由该方法制备的纤维增强模塑片材及由其制成的安全鞋的鞋包头 Download PDFInfo
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Abstract
一种模塑片材,其是通过组合粒料或片料并且在加热下压制所得到的粒料或片料而制备的,其中通过切割一种用树脂浸渍一束增强纤维单丝制备的棒状物从而得到粒料,通过切割一块用树脂浸渍机织织物制备的片材而得到片料。这种模塑片材由于它的增强纤维的含量提高而具有增进的强度,以及通过使用低分子量的树脂作为基体树脂而避免流动性和模塑性的降低。相应地,这种模塑片材能使制品具有极好的强度。
Description
本发明涉及一种用于制备模塑片材的方法,通过该方法制备的纤维增强模塑片材,以及由其制成的完全鞋的鞋包头。
长短玻璃纤维二者已经被作为增强纤维用于合成树脂的模塑制品。作为充填长玻璃纤维的模塑制品的例子有:已知的不规则编绕型模塑制品,其中长玻璃纤维随机地散布在合成树脂基体中;织物型模塑制品,其中长玻璃纤维以编织的状态包含在合成树脂基体中;以及单向编绕型模塑制品,其中长玻璃纤维以单向布置的状态包含在其中。
在这些模塑制品中,充填有短纤维的模塑制品和长纤维增强的不规则编绕型模塑制品在耐冲击强度方面太差而不能满足安全鞋的鞋包头的要求例如在日本工业标准(JIS)中的规定。另一方面,织物型和单向编绕型的长纤维增强模塑制品具有以下问题:由于复合材料差的流动性所以它在模塑性上也差,这样,即使这种材料能够模塑,但为了得到最终产品,常常不能省去导致生产成本提高的二次加工。
例如,在JIS中认可的并经常使用的用于树脂造安全鞋鞋包头的材料具有如图4所示的完整结构,其包括两个作为芯层的纤维层1和作为面层的不规则层(皮层)2用于达到所希望的模塑性和流动性。
(i)这里所用的L级(用于轻体力劳动)的鞋包头具有450kg或以上的抗压强度和S级(用于正常劳动)的鞋包头具有1100kg或以上的抗压强度。在生产树脂造安全鞋鞋包头中,所用材料必须根据最终鞋包头的级别进行正确选择,更精确地讲,在生产L级鞋包头中,必须使用上面所描述的含有2或3层纤维层的材料,而在生产S级的鞋包头中必须使用含有4或8层纤维层的材料。用于S级鞋包头的材料含有较多的纤维层,因此它的填模性能差和在模塑性和流动性方面不如用于L级鞋包头的材料以及表现出次品的比例提高,尽管材料本身的硬度有所提高。
(ii)必须根据最终鞋包头的级别是否是L或S正确选择用于生产鞋包头的材料。当然,用于S级鞋包头的材料比用于L级鞋包头的材料昂贵,因为它含有较多的增强纤维层。
(iii)如果显示出吸水性能和对于增强纤维有极好粘性的聚酰胺被用作基体;增强纤维含量高达48~54%;以及作为材料的填模原坯布不能被准确固定时,在模塑中会失去芯层和皮层之间的流动平衡性而使模塑产品具有焊接痕,而该焊接痕导致鞋包头制品的强度低。由于鞋包头的吸水性或不均匀的强度,在鞋包头的强度方面出现降低的形态。
本发明的目的在于提供一种可用于安全鞋鞋包头或诸如此类的模塑片材的生产方法、一种模塑片材以及使用该片材制成的安全鞋鞋包头,其中模塑片材具有极好的模塑性和能够使模型制品具有高的强度。
正如在权利要求中所限定的一样,解决上述问题的本发明涉及一种生产模塑片材的方法、一种通过该方法生产的纤维增强模塑片材和一种安全鞋的鞋包头。
换句话说,根据本发明生产模塑片材的方法包括组合含有在特定方向布置的增强纤维的复合模塑材料的切片,和在加热下压制所得到的切片以形成模塑片材,例如,通过切割用合成树脂浸渍单向布置的增强纤维而制备的复合材料从而生产粒料或通过切割用合成树脂浸渍的纤维织物从而得到片料。
通过上述方法生产的模塑片材含有55~80%(重量)的增强纤维。另外,要求构成该材料的树脂的分子量为10,000~25,000。树脂最好是从聚酰胺、聚对苯二甲酸丁二酯和聚对苯撑硫所组成的组中选择的至少一种热塑性树脂以及增强纤维最好是从玻璃纤维、碳纤维、芳族聚酰胺纤维和金属纤维所组成的组中选择的至少一种。
图1是用于图解说明本发明的模塑片材的生产步骤的视图。
图2是表示在安全鞋鞋包头中测量的吸水率和强度(抗压强度)之间关系的图。
图3是鞋包头的玻璃纤维含量和它的强度(抗压强度)之间的关系图。
图4是一种安全鞋鞋包头的例子的剖面图。
现在将通过参照图1详细地描述本发明的生产模塑片材的方法。单向布置的增强纤维束或纤维网用合成树脂浸渍以形成一块片材或一根方棒或圆柱棒(图1A)。
将棒或片材根据预定的尺寸切割成粒料或片料,例如它们的长为3~50mm、宽为1~40mm和厚度为0.1~10mm(图1B)。
将这些粒料或片料收集起来并按预定的厚度进行排列(图1C)。
所得到的粒料或片料在加热的条件下进行压制以形成模塑片材,其中以平放和无规形式布置增强纤维(图1D和1E)。
这种模塑片材含有大量的以平放和在所有方向(即无规)布置的增强纤维,这样通过使用这种材料制成的鞋包头在耐冲击强度和抗压强度方面极好。
通过将增强纤维无规则地和均匀地分散在合成树脂中而制备的现有技术的无规则编网确实可以被认为处在一个正如一个盒子一样的状态中,在盒子中线束(相当于增强纤维)无规则地放置和盒子的其余空间填充着合成树脂。另一方面,本发明的模塑片材能被比作一个盒子,在盒子中以单向布置的状态放置线束(相当于增强纤维),盒子的剩余空间充填着合成树脂,以及此后重新布置无规则的纤维。相应地,本发明的片材含有大量的增强纤维以及因此它应该具有差的流动性。然而,在本发明中,使用分子量为10,000~25,000的树脂作为基体树脂,借此材料的流动性和通过该材料生产的模塑制品的强度得到改善。如果树脂的分子量小于10000,本身用作增强纤维粘结剂的树脂将具有差的物理性能从而使复合材料具有差的强度,而它超过25000时,所得到的片材的流动性差。
如果模塑片材的增强纤维含量小于55%(重量)时,正如图3所示,达到公司标准强度1500kg(1100kg(JIS标准)×安全系数)将是困难的,而如果它超过80%(重量),树脂含量相对太低,则树脂对增强纤维的粘结效果差,这样,所得到的片材由于它过高的增强纤维含量而具有差的强度和表现出不好的模塑性。
构成这种复合模塑材料的基体树脂和增强纤维的例子如下:
树脂(基体树脂):热塑性树脂,例如:聚酰胺(如尼龙6、尼龙66和尼龙12)、聚丙烯(PP)、聚碳酸酯(PC)、聚对苯二甲酸丁二酯(PBT)、聚对苯撑硫(PPS)和聚醚醚酮(PEEK),其中,尼龙6、聚对苯二甲酸丁二酯(PBT)和PPS是优选的,因为它们的粘度低从而有极好的模塑性。
增强纤维:玻璃纤维(GF)、碳纤维(CF)、芳族聚酰胺纤维、金属纤维等。
在加热条件下通过压制上面的复合材料生产本发明的纤维增强片材中,所用的温度为210~350℃。如果温度低于210℃,熔融树脂将需要很长时间或者在某些程度视种类而定树脂将不能被熔融。相反,如果它高于350℃,由于树脂的热降解将在片材中间产生大的物理性能变化。
在上面的生产中所用的压力是10~80kg/cm2。如果压力小于10kg/cm2,那么,由于压力不足将产生含有空气的空穴(气泡),而如果压力超过80kg/cm2,由于向该处施加的压力过多片材产生内部应力从而具有翘曲或厚度不均的缺陷。
因此,所制备的模塑片材能够作为通用的材料均可用于L和S级的鞋包头,无需根据鞋包头的等级正确选择用于鞋包头的材料,但这种选择在现有技术中是无法避免的。另外,本发明的模塑片材能够可靠地使制品具有恒定的强度。
此外,使用本发明的模塑片材作为如图4所示的无规则(表皮)层2以及在这样的无规则层2之间放置织物(增强)层1能够生产一直具有较高强度的模塑片材。
实施例
检验通过使用充填有尼龙6的玻璃纤维生产的鞋包头并给出结果,其中使用充填有尼龙6的玻璃纤维作为复合材料用于安全鞋的鞋包头是最普遍的。
在表1中,术语“现有技术材料”是指如图4所示的一种材料,其中一种8层的含特殊玻璃布的聚酰胺片材的层压制品被用作织物层1和一种含45%的2英寸长的无规则玻璃纤维的复合尼龙6被用作表皮层2。
在表1中,术语“本发明材料是指由含70%(重量)的长度为25.4mm的玻璃纤维的尼龙6制成的模塑片材,以及片材的生产条件如下:
在片材生产中所使用的切片尺寸:10mm(宽)×25.4mm(长)×0.15(厚),单向增强的材料,
在片材生产中所使用的模子的尺寸和温度:150mm×300mm×3mm(厚),250℃,
在片材生产中的模塑压力:25(kg/cm2),
模塑时间:30(分)
表1
*JIS中要求的强度
正如表1中所给的结果显示的一样,本发明的材料具有极好的流动性和模塑性并且能使模塑制品具有恒定的强度。
上述鞋包头的抗压强度由于吸水例如脚汗而降低。吸水性越高使抗压强度降低得越多。结果在图2中给出。在每个的吸水率(%)下,通过比较本发明的材料制成的鞋包头和现有技术的材料制成的鞋包头的抗压强度能够清楚地看到具有低树脂含量和较高增强纤维含量的前一种鞋包头在抗压强度方面远远地优于后一种鞋包头。
图3表示使用玻璃纤维增强模塑片材制成的鞋包头的玻璃纤维含量和它的强度(抗压强度)之间的关系。
在生产鞋包头中所用的材料和模塑条件如下:
材料:玻璃纤维(25.4mm长)/PA6片3mm厚
模塑条件:片材预热:370℃×210秒
模塑温度、130
模塑压力:550kg/cm2
从图3可以看出,通过使用本发明的纤维增强模塑片材能够生产出在抗压强度上远远高于现有技术的鞋包头。
正如上面所描述的一样,通过本发明的方法生产的纤维增强模塑片材具有高的强度和极好的模塑性,这样通过使用这种模塑片材制成的安全鞋的鞋包头在抗压强度方面是极好的。
Claims (10)
1.一种用于生产模塑片材的方法,其包括将含有在特定方向布置的增强纤维的复合材料切成预定形状的片料,以平放的形式组合这些片料,并在加热下压制它们。
2.根据权利要求1的用于生产模塑片材的方法,其中在复合模塑材料中所含的增强纤维处于单向布置状态或一种织物状态。
3.根据权利要求1或2的用于生产模塑片材的方法,其中复合模塑材料以粒料或片材的形式存在。
4.根据权利要求1~3之一的用于生产模塑片材的方法,其中通过切割复合模塑材料得到的片料的长度是3~50mm、宽度为1~40mm和厚度为0.1~10mm。
5.根据权利要求1~4之一的用于生产模塑片材的方法,其中在生产模塑片材中所用的温度和压力分别是210~350℃和10~80kg/cm2。
6.一种包括树脂作为基体及增强纤维的纤维增强模塑片材,其中增强纤维的含量在55~80%(重量)的范围之内。
7.根据权利要求6的纤维增强模塑片材,其中树脂的分子量为10,000~25,000。
8.根据权利要求6或7的纤维增强模塑片材,其中树脂至少是一种从聚酰胺、聚对苯二甲酸丁二酯和聚对苯撑硫组成的组中选择的热塑性树脂以及增强纤维至少是一种从玻璃纤维、碳纤维和金属纤维组成的组中选择的纤维。
9.根据权利要求6~8之一的纤维增强模塑片材,其中增强纤维是以机织织物或针织物的形式存在。
10.一种通过在加热下加压模塑根据权利要求6~9之一的纤维增强模塑片材而生产的鞋包头。
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JP272632/95 | 1995-10-20 | ||
JP7272632A JPH09109310A (ja) | 1995-10-20 | 1995-10-20 | 成形シート材料の製造方法、その方法によって製造される繊維強化成形シート材料およびそれを用いた安全靴の先芯 |
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CN1989862B (zh) * | 2005-12-30 | 2010-05-05 | 上海杰事杰新材料股份有限公司 | 一种安全防护用鞋头及其制造方法 |
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CN108883548A (zh) * | 2016-03-24 | 2018-11-23 | 三菱化学株式会社 | 纤维增强树脂材料及其制造方法 |
CN109016556A (zh) * | 2018-06-08 | 2018-12-18 | 广州金发碳纤维新材料发展有限公司 | 一种短切纤维增强热塑性树脂板材及其制备方法 |
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JP2969518B2 (ja) * | 1997-06-11 | 1999-11-02 | 東洋紡績株式会社 | 安全靴用軽量先芯 |
JP2000238142A (ja) | 1999-02-22 | 2000-09-05 | Ykk Corp | 強化繊維入り成形用材料およびそれを用いた成形体の製造方法並びに安全靴先芯 |
FR2806425B1 (fr) * | 2000-03-16 | 2002-07-12 | Hexcel Composites | Produit intermediaire composite, procede de production d'un tel produit et utilisation a titre de materiau de moulage |
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GB0222753D0 (en) * | 2002-10-02 | 2002-11-06 | Carbon Fibre Technology Ltd | Method of production of advanced composite materials |
EP1908574A1 (en) * | 2006-10-05 | 2008-04-09 | Novameer B.V. | Method for producing self-reinforced polymeric three-dimensional products |
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WO2019168010A1 (ja) * | 2018-02-27 | 2019-09-06 | 国立大学法人名古屋大学 | 繊維強化熱可塑性樹脂の成形物及びその製造方法 |
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JPS56157433A (en) * | 1980-05-09 | 1981-12-04 | Toho Rayon Co Ltd | Sheetlike resin/fiber composite molding material and preparation thereof |
EP0100181A1 (en) * | 1982-07-28 | 1984-02-08 | Imperial Chemical Industries Plc | Protective toe caps |
JPH0330916A (ja) * | 1989-06-27 | 1991-02-08 | Kuraray Co Ltd | 繊維強化プラスチック成形物の製造方法 |
JP2567828B2 (ja) * | 1991-04-03 | 1996-12-25 | 日東紡績株式会社 | 成形用シート材料及び安全靴先芯 |
JPH05116228A (ja) * | 1991-08-13 | 1993-05-14 | Kawasaki Steel Corp | ガラス繊維強化プラスチツク再生シート、ガラス繊維強化プラスチツク再生成形品の製造方法 |
JPH06182761A (ja) * | 1992-12-15 | 1994-07-05 | Toyobo Co Ltd | 繊維強化樹脂ペレットおよびその成形品 |
-
1995
- 1995-10-20 JP JP7272632A patent/JPH09109310A/ja active Pending
-
1996
- 1996-10-16 FR FR9612603A patent/FR2740149B1/fr not_active Expired - Fee Related
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Cited By (5)
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CN108883548A (zh) * | 2016-03-24 | 2018-11-23 | 三菱化学株式会社 | 纤维增强树脂材料及其制造方法 |
CN109016556A (zh) * | 2018-06-08 | 2018-12-18 | 广州金发碳纤维新材料发展有限公司 | 一种短切纤维增强热塑性树脂板材及其制备方法 |
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Publication number | Publication date |
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FR2740149B1 (fr) | 1999-01-08 |
CN1084669C (zh) | 2002-05-15 |
JPH09109310A (ja) | 1997-04-28 |
FR2740149A1 (fr) | 1997-04-25 |
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