CN1426891A - 用外层和聚氨酯夹芯材料制成的层压零件及其生产方法 - Google Patents
用外层和聚氨酯夹芯材料制成的层压零件及其生产方法 Download PDFInfo
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Abstract
本发明涉及包含外层和聚氨酯夹芯材料的层压零件,也涉及这些层压零件的生产方法,还涉及它们在汽车工业中的用途。
Description
技术领域
本发明涉及包含外层和聚氨酯夹芯材料的层压零件,涉及其制造方法,也涉及其在汽车工业零件生产中的用途。
背景技术
外部汽车工业中有A级表面和特殊机械功能的零件通常是用金属制成的。使用金属的缺点是零件沉重的重量。A级表面零件的主要表面质量基准是表面短波长和长波长数值低的已知波扫描工艺。
在采用聚氨酯模塑品的情况下,一般使用有增强物质的较致密材料,以期改善专门的机械性能,例如挠曲强度。这样的增强聚氨酯已经在外部汽车工业中用来作为裙板、底板、轮缘或门覆盖物和挡泥板。相对显著的膨胀行为是所使用材料的特征,就是说,非常不同于通常所来用的金属的高度线性热膨胀系数(α值),和较高的密度。这些物品的主要目标是用已知波扫描法测定的、短波长和长波长数值低的表面质量。
为了在这种情况下得到具有低的长波长值和短波长值的优异表面质量,这些物品可能不得不遭遇表面后处理。
为了避免以上所有缺点,现已开发了有整体A级外层的层压PUR(聚氨酯)零件。这些层压PUR零件显示出非常高的挠曲强度水平、低的膨胀行为(α值在1~15×10-6m·K-1·m-1范围内)、低的密度、和高的表面质量。类似的层压零件已有描述,可参阅拜耳公司题为“Structhan,一种有前景的复合纤维材料“的现状报告,订货号PU52231,和拜耳公司题为“车辆内壁轻质建造用复合纤维PUR材料”的重印本,订货号PU52248。
已经发现,这些PUR粘结的复合材料在低于所使用外层的密度时有较大的挠曲强度。
发明内容
本发明涉及一种层压零件,包含
A)一个芯,
B)排列在该芯两侧并浸渍了一种聚氨酯树脂(P)的纤维层,
C)在该纤维层之一上一个有A级表面质量的外层,和,任选地
D)在第二纤维层上一个装饰层。
本发明也涉及一种有一个按照本发明的层压零件用外部可装饰层的层压零件的一步法生产工艺。可用于生产有以上所述增强物质的物品的加工方法是NafpurTec工艺、LFI-/FipurTec或Interwet工艺和层压工艺。该复合材料是在60~140℃的模塑温度生产的。
更具体地说,如上所述层压零件的本发明制作方法包含
(I)把一种浸渍了聚氨酯树脂(P)的组分的纤维层B)施用到一种芯A)的两侧,
(II)把一种外层C)和任选地一种装饰层D)定位在一种开放式模型的内表面上,
(III)把在(I)中形成的复合材料放进含有该外层C)和任选地该装饰层D)的开放式模型中,
(IV)将该模型闭合,和
(V)通过使该聚氨酯树脂(P)成分的各组分完全反应,使该外层和存在时的装饰层粘结到该复合材料上。
适用于浸渍按照本发明的层压零件的纤维层的聚氨酯树脂(P)可以通过使下列物料反应得到:
(1)至少一种多异氰酸酯;
(2)至少一种平均OH值300~700、含有至少一条短链和一条长链多元醇的多元醇组分,该初始多元醇有2~6的官能度;
(3)水;
(4)活化剂;
(5)稳定剂;和任选地
(6)其它辅助材料、脱模剂和添加剂。
适用的多元醇组分是有至少两个能与异氰酸酯基团反应的氢原子的多元醇。较好使用聚酯多元醇和聚醚多元醇。
按照本发明,较好使用二苯甲烷二异氰酸酯系列(pMDI型)的聚合物异氰酸酯、其预聚物、或粗MDI。
水是以该多元醇配方每100份对0.1~3.0、较好0.3~2.0份的数量采用的。
通常的发泡和交联反应用活化剂例如胺或金属盐用于催化。
适用的泡沫稳定剂主要是聚醚硅氧烷、尤其是水溶性的。这些化合物一般有与聚二甲基硅氧烷残基结合的环氧乙烷和环氧丙烷的共聚物。这种类型的泡沫稳定剂在诸如美国专利2,834,748,2,917,480和3,629,308中有描述,其公开内容列为本文参考文献。往往具有特殊意义的是按照据信对应于美国专利4,096,162和4,163,830的DE-OS2558523用脲基甲酸根基团支化的聚硅氧烷-聚氧化烯共聚物,这些专利的公开内容列为本文参考文献。其它有机聚硅氧烷、氧乙基化烷基苯酚、氧乙基化脂肪醇、石蜡油、蓖麻油或蓖麻酸的酯、土耳其红油和花生油以及泡孔调节剂例如石蜡、脂肪醇和二甲基聚硅氧烷也是适用的。有聚氧化烯和氟烷残基作为侧基的低聚物聚丙烯酸酯进一步适用于改善和/或稳定乳化作用、填料分散、和泡孔结构。表面活性剂通常以每100重量份多元醇对0.01~5重量份的数量采用。
其它辅助材料、脱模剂和添加剂可以任选地掺入该聚氨酯树脂制备用反应混合物中。例如,该反应混合物可以包括表面活性添加剂如乳化剂、阻燃剂、核化剂、阻氧化剂、润滑剂和脱模剂、染料、分散助剂和颜料。
各组分以如此数量反应,使得多异氰酸酯组分(1)中的NCO基团与组分(2)和(3)以及可能(5)中能与异氰酸酯基团反应的氢的总和的当量比是0.8∶1~1.4∶1、较好0.9∶1~1.3∶1。
可热成形的PUR泡沫体、或纸、金属或塑料蜂窝体可以用来作为按照本发明的层压零件的芯A)用材料。
玻璃纤维垫、短玻璃纤维股垫、无规玻璃纤维层、玻璃纤维织物、切断或研磨的玻璃或矿物纤维、天然纤维垫和针织织物、切断的天然纤维和纤维垫,基于聚合物纤维、碳纤维或芳族聚酰胺纤维及其混合物的非织造织物和针织织物,可以采用来作为纤维材料B)。这些纤维层被排列在或施用到该芯的两侧,并浸渍聚氨酯树脂。适用的聚氨酯树脂如以上所述。
本发明的一些适用外层C)包括,例如,金属箔或片材,以及诸如PMMA(聚甲基丙烯酸甲酯)、ASA(丙烯酸酯改性苯乙烯-丙烯腈三元共聚物)、PC(聚碳酸酯)、PA(聚酰胺)、PBT(聚对苯二甲酸丁二醇酯)和/或PPO(聚苯醚)制成、供外部施用的致密热塑性复合材料。该外层可以涂漆、使之可涂漆或着色。
有TPU(热塑性聚氨酯)片材阻透层以防止泡沫体通过的纺织品材料,致密或发泡的塑料片材和喷射或RIM(反应注塑)聚氨酯皮层可以用来作为装饰层D)。
纤维层B)的纤维组分可以作为一种织物置于芯A)上,或者,在切断或磨碎纤维的情况下,可以与该聚氨酯组分一起导入或喷射,或喷射到聚氨酯组分(P)上。
按照本发明的层压零件的生产工艺最初包含:把一种纤维层B)施用到芯A)的两侧,和把初始聚氨酯组分施用到层B)上。在一种替代实施方案中,可以使用一种适用混合头技术,经由原聚氨酯材料流,把增强物质(即纤维组分)导入到芯A)上。该聚氨酯树脂可以用文献上所述工艺例如一步法或预聚物法,借助于业内人士基本上都知道的加工装置生产。它们较好是用一步法生产的。
把这样生产的毛坯(即层压芯)转移到一种含有外层C)和任选地一个装饰层D)的模型中。通过该模型的闭合并使该原PUR材料组分反应,使这种毛坯粘结或结合到该外层C)和该装饰层D)(当存在时)上。该毛坯同样可以用适用方法以实际模型生产。
按照本发明的层压材料的特征在于:在约400~700kg/m3范围内的低密度,在约0.5~5.2×107N·mm2范围内的高挠曲强度,和优异表面质量(即一面上一个A级表面)。具体地说,当本发明的层压材料与在外部应用范围内使用的传统塑料和金属例如PC/ABS(聚碳酸酯/丙烯腈-丁二烯-苯乙烯)、聚丙烯、Noryl(聚苯醚和降酰胺的共混物,商标,GE公司)、SMC(片状模塑料)或者铝或钢片材比较时,它们有颇低的GSM(克/平方米)和可比的挠曲强度。
按照本发明的层压材料在汽车工业内的一些适当应用包括,例如,车顶、引擎顶盖、后挡泥板、门板或底板组件。
以下实施例进一步说明本发明工艺的细节。以上公开文书中提出的本发明,在精神或范围上不会受这些实施例限制。业内人士将会容易地理解,以下程序的条件的已知变化均可使用。除非另有说明,否则所有温度都是摄氏度,所有百分率都是重量百分率。
具体实施方式
在以下工作实施例中使用了下列起始原料。多元醇1: 一种三(羟甲基)丙烷引发的环氧丙烷聚醚多元醇,
其OH值约865,其官能度约3多元醇2: 一种三(羟甲基)丙烷引发的环氧丙烷聚醚多元醇,
其OH值约1000,其官能度约3多元醇3: 一种丙二醇引发的环氧丙烷/环氧乙烷
(PO∶PE=86wt%∶14wt%)聚醚多元醇,其OH值约
42,其官能度约2多异氰酸酯: 一种多亚甲基多(苯基异氰酸酯),其异氰酸酯含
量为31.5wt%(由拜耳公司以商品名Desmodur
44V20L销售)稳定剂: 一种硅稳定剂,由Osi Crompton Witco
Specialities公司(D-60318 Frankfrut,
Humboldtstr、12)以商品名PolyuraxSR242销
售催化剂: 一种氨基催化剂,由Air Products公司(D-45527
Hattingen)以商品名Thancat销售染料: Baydur黑色糊状物DN,拜耳公司聚氨酯配方1:
多元醇1 30重量份
多元醇2 20重量份
多元醇3 33重量份
催化剂 2.8重量份
稳定剂 1.3重量份
乙酸 0.3重量份
水 1.4重量份
染料 3.3重量份
多异氰酸酯 140重量份
以上包含多元醇1~3的多元醇混合物的平均OH值为568mgKOH/g。
实施例1
把GSM(克/平方米)为450的短玻璃纤维股垫B)放在一种芯(A)的两侧上,该芯包含一种5/5瓦楞纸板型、厚度12mm、GSM为960的纸蜂窝,在常温下把总共1150g聚氨酯配方1(P)喷到其上。把这种夹芯结构插入一个模型中,其中在下部预先放置了一种涂布了标准底漆、厚度0.85mm、密度2,640kg/m3、初始挠曲强度为2.18×105N·mm2的铝片材作为外层C),并在上部预先放置一种用PUR片材形成一种泡沫体渗透阻挡层的装饰性纺织品作为一个GSM约180的装饰层D)。然后,这种粘结的织物在该模型中压成11.7mm的壁厚并加热到110℃。在240秒的加压时间之后,将模型打开,取出成品层压零件。该层压零件有444kg/m3的密度和5.20×107N·mm2的挠曲强度。
与作为外层C)使用的材料相比,本发明的层压零件显示出挠曲强度增加200多倍,且平均密度从2640kg/m3降低到444kg/m3。
实施例2
所使用的生产方法类似于以上实施例1中所述的那种。在本实施例中,使用一种有5mm厚度、GSM(克/平方米)为395、5/5瓦楞纸板型的纸蜂窝作为芯A),并将1000g聚氨酯配方1(P)施用到置于该芯A)两侧的短玻璃纤维股垫B)上。作为外层C)使用的铝片材的厚度是0.35mm、密度是2540kg/m3、初始挠曲强度是1.5×104N·mm2。使用一种GSM为180并有一个能防止泡沫体渗透的阻挡层的纺织品作为装饰材料D)。在110℃加压后得到的4.9mm厚层压零件有654kg/m3的密度和8.56×106N·mm2的挠曲强度。外层C)的初始挠曲强度提高了560倍。
实施例3
所使用的生产方法类似于以上实施例1中所述的那种。在本实施例中,使用一种厚度为7mm、GSM(克/平方米)为560、5/5瓦楞纸板型的纸蜂窝作为芯A),并施用900g聚氨酯配方1(P)到置于该芯A)两侧的短玻璃股垫上。使用一种ASA(丙烯酸酯改性苯乙烯-丙烯腈三元共聚物)与PMMA(聚甲基丙烯酸甲酯的共混物的、厚度为1.40mm、初始挠曲强度为3.43×104N·mm2的致密热成形多层热塑性薄膜作为外层C)。使用一种GSM为180并有一个能防止泡沫体渗透的阻挡层的纺织品作为装饰材料D)。加压操作期间的模具温度是外层侧约60℃、装饰层侧约90℃。所得到的7.2mm厚的层压零件有517kg/m3的密度和5.71×106N·mm2挠曲强度。
作为有PUR粘结的复合材料结构的结果,外层C)的挠曲强度可观地提高了,即使之提高了166倍。
尽管为了说明之目的,已经在上述详细描述了本发明,但要理解的是,这样的细节仅仅是为了该目的,而且业内人士只要不背离本发明的精神和范围就可以对此加以改变,除了它可能受到权利要求的限制外。
Claims (18)
1.一种层压零件,包含
A)一个芯,
B)排列在该芯两侧并浸渍了一种聚氨酯树脂(P)的纤维层,
C)在该纤维层之一上一个有A级表面质量的外层,和,任选地
D)在所述第二纤维层上一个装饰层。
2.权利要求1的层压零件,其中,所述聚氨酯树脂包含:
(1)至少一种多异氰酸酯成分;
(2)至少一种平均OH值300~700、含有至少一条短链和一条长链多元醇的多元醇组分,该初始多元醇有2~6的官能度;
(3)水;
(4)活化剂;
(5)稳定剂;和任选地
(6)其它辅助材料、脱模剂和添加剂。
3.权利要求1的层压零件,其中,A)所述芯包含一种选自下列组成的一组的材料:可热成形PUR泡沫体、纸蜂窝、金属蜂窝、和塑料蜂窝。
4.权利要求1的层压零件,其中,B)所述纤维选自下列组成的一组中一种或多种:玻璃纤维垫,短玻璃纤维股垫,无规玻璃纤维层,玻璃纤维织物,切断玻璃纤维,研磨玻璃纤维,矿物纤维,天然纤维垫,天然针织织物,切段天然纤维,切段天然纤维垫,基于聚合物纤维、碳纤维或芳族聚酰胺纤维的非织造织物,和基于聚合物纤维、碳纤维或芳族聚酰胺纤维的针织织物。
5.权利要求1的层压零件,其中,C)所述外层包含一种选自下列组成的一组的材料:金属箔,金属片材,和致密热塑性复合材料。
6.权利要求1的层压零件,其中,D)所述装饰层包含一种选自下列组成的一组的材料:有一个热塑性聚氨酯片材阻挡层的纺织品材料,致密片材,泡沫化塑料片材,喷射聚氨酯皮层,和RIM(反应注塑)聚氨酯皮层。
7.按照权利要求1的层压零件的制造方法,包含
(I)把一种浸渍了聚氨酯树脂(P)的组分的纤维层B)施用到一种芯A)的两侧,
(II)把一种外层C)和任选地一种装饰层D)定位在一种开放式模型的内表面上,
(III)把在(I)中形成的复合材料放进含有该外层C)和任选地该装饰层D)的开放式模型中,
(IV)将该模型闭合,和
(V)通过使该聚氨酯树脂(P)成分的各组分完全反应,使该外层和存在时的装饰层粘结到该复合材料上。
8.权利要求7的方法,其中,所述聚氨酯树脂包含
(1)至少一种多异氰酸酯成分;
(2)至少一种平均OH值300~700、含有至少一条短链和一条长链多元醇的多元醇组分,该初始多元醇有2~6的官能度;
(3)水;
(4)活化剂;
(5)稳定剂;和任选地
(6)其它辅助材料、脱模剂和添加剂。
9.权利要求7的方法,其中,A)所述芯包含一种选自下列组成的一组的材料:可热成形PUR泡沫体、纸蜂窝、金属蜂窝、和塑料蜂窝。
10.权利要求7的方法,其中,B)所述纤维选自下列组成的一组中一种或多种:玻璃纤维垫,短玻璃纤维股垫,无规玻璃纤维层,玻璃纤维织物,切断玻璃纤维,研磨玻璃纤维,矿物纤维,天然纤维垫,天然针织织物,切段天然纤维,切段天然纤维垫,基于聚合物纤维、碳纤维或芳族聚酰胺纤维的非织造织物,和基于聚合物纤维、碳纤维或芳族聚酰胺纤维的针织织物。
11.权利要求7的方法,其中,C)所述外层包含一种选自下列组成的一组的材料:金属箔,金属片材,和致密热塑性复合材料。
12.权利要求7的方法,其中,D)所述装饰层包含一种选自下列组成的一组的材料:有一个热塑性聚氨酯片材阻挡层的纺织品材料,致密片材,泡沫化塑料片材,喷射聚氨酯皮层,和RIM(反应注塑)聚氨酯皮层。
13.按照权利要求1的层压零件的制造方法,包含
(I)把还包含纤维组分的一种聚氨酯树脂(P)的组分施用到一种芯A)的两侧,
(II)把一种外层C)和任选地一种装饰层D)定位在一种开放式模型的内表面上,
(III)把在(I)中形成的复合材料放进含有该外层C)和任选地该装饰层D)的开放式模型中,
(IV)将该模型闭合,和
(V)通过使该聚氨酯树脂(P)成分的各组分完全反应,使该外层和存在时的装饰层粘结到该复合材料上。
14.权利要求13的方法,其中,所述聚氨酯树脂包含:
(1)至少一种多异氰酸酯成分;
(2)至少一种平均OH值300~700、含有至少一条短链和一条长链多元醇的多元醇组分,该初始多元醇有2~6的官能度;
(3)水;
(4)活化剂;
(5)稳定剂;和任选地
(6)其它辅助材料、脱模剂和添加剂。
15.权利要求13的方法,其中,A)所述芯包含一种选自下列组成的一组的材料:可热成形PUR泡沫体、纸蜂窝、金属蜂窝、和塑料蜂窝。
16.权利要求13的方法,其中,B)所述纤维选自下列组成的一组中一种或多种:玻璃纤维垫,短玻璃纤维股垫,无规玻璃纤维层,玻璃纤维织物,切断玻璃纤维,研磨玻璃纤维,矿物纤维,天然纤维垫,天然针织织物,切段天然纤维,切段天然纤维垫,基于聚合物纤维、碳纤维或芳族聚酰胺纤维的非织造织物,和基于聚合物纤维、碳纤维或芳族聚酰胺纤维的针织织物。
17.权利要求13的方法,其中,C)所述外层包含一种选自下列组成的一组的材料:金属箔,金属片材,和致密热塑性复合材料。
18.权利要求13的方法,其中,D)所述装饰层包含一种选自下列组成的一组的材料:有一个热塑性聚氨酯片材阻挡层的纺织品材料,致密片材,泡沫化塑料片材,喷射聚氨酯皮层,和RIM(反应注塑)聚氨酯皮层。
Applications Claiming Priority (4)
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DE10161980 | 2001-12-17 | ||
DE10161980.4 | 2001-12-17 | ||
DE10229473A DE10229473A1 (de) | 2001-12-17 | 2002-07-01 | Verbundteile aus Deckschichten und Polyurethan-Sandwichmaterialien und ihre Herstellung |
DE10229473.9 | 2002-07-01 |
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US (1) | US6761953B2 (zh) |
EP (1) | EP1319503A1 (zh) |
JP (1) | JP4369114B2 (zh) |
KR (1) | KR20030051340A (zh) |
CN (1) | CN1321816C (zh) |
BR (1) | BR0205263A (zh) |
CA (1) | CA2414313A1 (zh) |
DE (1) | DE20211026U1 (zh) |
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2002
- 2002-07-22 DE DE20211026U patent/DE20211026U1/de not_active Expired - Lifetime
- 2002-12-04 EP EP20020026972 patent/EP1319503A1/de not_active Withdrawn
- 2002-12-10 US US10/315,452 patent/US6761953B2/en not_active Expired - Lifetime
- 2002-12-13 BR BR0205263A patent/BR0205263A/pt not_active Application Discontinuation
- 2002-12-13 JP JP2002362146A patent/JP4369114B2/ja not_active Expired - Fee Related
- 2002-12-13 CA CA 2414313 patent/CA2414313A1/en not_active Abandoned
- 2002-12-13 MX MXPA02012427A patent/MXPA02012427A/es active IP Right Grant
- 2002-12-13 HU HU0204332A patent/HUP0204332A2/hu unknown
- 2002-12-16 KR KR1020020080192A patent/KR20030051340A/ko not_active Application Discontinuation
- 2002-12-17 CN CNB021563926A patent/CN1321816C/zh not_active Expired - Lifetime
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CN109666123B (zh) * | 2018-11-20 | 2021-11-19 | 黎明化工研究设计院有限责任公司 | 一种玻纤增强蜂窝夹芯板用聚氨酯组合物及其使用方法 |
CN113382853A (zh) * | 2018-12-03 | 2021-09-10 | 大陆结构塑料有限公司 | 具有车辆外表面光泽的中空结构夹芯结构组件 |
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Also Published As
Publication number | Publication date |
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DE20211026U1 (de) | 2002-10-02 |
EP1319503A1 (de) | 2003-06-18 |
JP2003220661A (ja) | 2003-08-05 |
CA2414313A1 (en) | 2003-06-17 |
CN1321816C (zh) | 2007-06-20 |
HUP0204332A2 (hu) | 2004-04-28 |
US6761953B2 (en) | 2004-07-13 |
MXPA02012427A (es) | 2004-12-13 |
BR0205263A (pt) | 2004-07-20 |
HU0204332D0 (en) | 2003-02-28 |
JP4369114B2 (ja) | 2009-11-18 |
KR20030051340A (ko) | 2003-06-25 |
US20030134085A1 (en) | 2003-07-17 |
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