CN1693067A - 层合片材及其生产方法 - Google Patents

层合片材及其生产方法 Download PDF

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CN1693067A
CN1693067A CNA2005100640564A CN200510064056A CN1693067A CN 1693067 A CN1693067 A CN 1693067A CN A2005100640564 A CNA2005100640564 A CN A2005100640564A CN 200510064056 A CN200510064056 A CN 200510064056A CN 1693067 A CN1693067 A CN 1693067A
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acrylonitrile
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CN1693072B (zh
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D·波胡森
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Covestro Deutschland AG
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Abstract

公开了一种生产具有橘皮效应的、按照BYKGardner装置测定的波扫描DOI值为5～80的层合材料的方法。该方法包括a)得到其第一表面具有特别调节的糙度值的载体层和b)施加密封层于第一表面，防护层位于远离载体薄膜的那侧。本发明层合材料特别适用于汽车领域。

Description

层合片材及其生产方法
                技术领域
本发明涉及一种层合材料，更具体地说，涉及包含聚合物薄膜的层合材料及其生产方法。
                背景技术
本发明涉及一种具有所谓“橘皮”效应的层合片材及一种其生产工艺。
现在塑料制品广泛应用于汽车工业。在车身外部零件方面，塑料制品正与涂漆的金属或塑料结构件竞争。为了开辟在该领域中的新用途，除了涂漆的金属或塑料结构件之外，必须开发具有诸如抗刮性等机械性能和耐化学药品性以及光学规格的塑料结构件。特别是，对于塑料结构件而言，然后还必须模拟在涂漆结构零件中经常优选的所谓“橘皮”效应，这是一种复杂的方法。
在屋顶模件部分，需要应用高刚度和低屏蔽效应(良好空中信号接受性)的轻质材料。PU(聚氨酯)硬质泡沫塑料系统如所谓的LFI(长纤维注塑)或S-RIM系统(结构反应注塑或还有结构树脂注塑，比竞争系统如SMC(片状模塑料)，具有较多的优点。LFI或S-RIM结构件的结构表面自片材形成。另外，这些片材在预成形之后衬里发泡(back-foam)时必须对例如PU系统具有非常好的粘合性。
片材衬里发泡工艺由Haberstroh、Wirtz和Schlumm详述在journal FAPU，Issure No 21(2003年11月/12月)第66～99页。
关于成品结构件，片材必须具有，特别是，屋顶模件所需要的高耐热性。已经证明，基于聚碳酸酯的片材特别适于此目的。另外的表面强度和耐化学药品性借助于密封层实现，密封层在层合过程中施加到载体薄膜上。然后借此得到的层合片材必须，在随后的衬里发泡或衬里注塑(back-inject-ion molding)工艺中，得到类似于车体漆的所需橘皮结构。该结构通过模具的表面结构产生。
EP 0 320 925 B1叙述了一种生产具有装潢压花表面涂层的塑料模塑件的方法。为此，将未压花的可热成形片材置于模具中，模具内表面至少部分区域具有结构表面(具有图案的表面，具有纹理的表面)，然后进行衬里注塑。
在DE 10064520 A1中，叙述了相似的方法，其中还生产的纳米结构(具有尺寸为纳米级图案(纹理)的压花表面)。
现旨在通过一种可靠的生产方法提供一种费用效益经济的车体片材材料，该材料具有高的耐化学药品性、高的抗刮性、良好的可热成型性、对载体材料的非常高的粘性和，特别是，似漆的表面结构(“橘皮效应”)，以及提供一种简单的生产它的方法。
                发明内容
公开了一种生产层合材料的方法，该材料具有波扫描DOI(涂层的影像清晰度)值5～60，其采用BYK Gardner装置测定。该方法包括a)得到其第一表面具有特别调节的糙度值的载体层和b)向第一表面施加密封层，防护层位于远离载体薄膜的那一侧。本发明层合材料特别适用于汽车领域。
                具体实施方式
通过按照本发明方法达到了上述目的。
本发明提供一种生产层合材料的方法，优选片材材料，其一个表面具有DOI(涂层的影象清晰度)5～60(采用自BYK Gardner公司(Geretsried，德国)的“波扫描DOI”测定装置测定)，该方法包括
a)得到温度50℃～150℃的载体层(薄膜或复合材料)，其中两表面之一(第一表面)的表面糙度Rz为1μm～6μm，按照DIN EN ISO 4288测定；
b)施加温度80℃～180℃的密封层(含有防护层的薄膜或包含至少一个有色层和防护层的复合材料)到第一表面，使得密封层的防护层位于远离载体层的那侧；
c)使b)步骤产品经过两个反转辊，借此至少一个辊温度为80～180℃并且借此将产品加压，从而得到层合材料。
在其生产期间通过使用具有相应表面结构的转辊将层表面压花通过挤压得到载体层表面糙度Rz。转辊表面结构决定载体层(薄膜)的表面糙度Rz。
借助于层合所述密封层到具有规定表面糙度的载体层上，以简单方法令人惊异地产生了所谓的橘皮效应，这样相应结构件的光学效果相当于油漆车体件的光学效果。
优选密封层厚度为20～250μm，特别优选为50～200μm。
然后可以将按照本发明生产的层合材料置于生产结构件(模塑件)的模具中，任选在预成型后，和可以与塑料材料一起进行衬里注塑或衬里发泡。在这方面，可以使用完全传统的模具，其表面不需要结构化(表面平整光滑，任选经磨光)。
令人惊奇地，载体层表面或者经密封层层合其上或者经随后在模具中衬里注塑均不受损失。
载体层的表面糙度也可以借助所谓R3z值来限定。这是DaimlerBenz factory标准(DB N 31007，1983)。在按照本发明的方法中使用的载体层的R3z值优选为10μm～25μm。
对于具有消光表面或结构表面的载体层，已经证明，按照DaimlerBenz factory标准测定表面糙度，即以R3z值代替Rz值，是方便的，是现在执行的标准。
优选载体层是聚碳酸酯或聚碳酸酯共混物薄膜。优选该薄膜含有至少一种选自下述的物质：聚碳酸酯、丙烯腈/丁二烯/苯乙烯、聚甲基丙烯酸甲酯、苯乙烯/丙烯腈、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二酯、聚酰胺、聚酯以及丙烯酸系/苯乙烯/丙烯腈。
作为密封层，可以有，例如，叙述在EP-A 949120中的所用薄膜，在此引入其全部内容供作参考。该薄膜可以以商品名FluorexPaintfilm得自Soliant公司。
按照本发明生产的层合材料可以用作结构件的片材，特别是车体件，以及轻质模塑件的抗刮片材。它们可以用来生产模塑件，特别是屋顶模塑件。层合材料可以，例如，以热成形工艺成形。在成形之后，可以将它们应用在采用热塑性材料的衬里注塑工艺中。它们也可以经衬里发泡或者经粘合层施加到结构件上。
本发明还提供一种层合材料，其表面的通过BYK Gardner装置测定的波扫描DOI值为5～60，其包含：
A)载体层，载体层的第一表面的糙度值Rz为1μm～6μm，按照DIN ISO 4288测定，
B)在所述第一表面上的密封层，防护层位于远离载体薄膜的那侧，
所述载体层包含至少一层至少一种选自下述物质的薄膜：聚碳酸酯、ABS、聚甲基丙烯酸甲酯、苯乙烯/丙烯腈、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二酯、聚酰胺、聚酯、丙烯酸系/苯乙烯/丙烯腈，所述密封层包含防护层和任选至少一个着色层。
R3z值描述按照Daimler Benz factory标准DB N 31007(1983)的基础糙度深度(basic roughness depths)，它是5个连续的单个测定段的各个糙度深度R3zi的平均值。单个糙度深度R3zi是在单个测定段中从糙度分布的第三个最高的外观峰到第三个最低的外观谷的垂直距离。详述参见Mahr公司出版物，1/09/99版，题目“PerthometerOberflchenmessgrβen”[Perthometer表面测定定量]，在此引入供作参考。
漆的表面结构评定，所谓的“橘皮”效应评定常常以目测进行。将橘皮效应视作波形图案和光泽表面上的暗区。它采用例如DOI测定。
DOI(涂层的影象清晰度)用作油漆表面(对于橘皮效应而言)的测定值，对于理想平滑表面(无橘皮效应)而言，该值为100。正规漆的值为10左右。
关于DOI和其测定方法的详述参见自BYK Gardner的小册子“Qualittskontrolle für Lacke und Kunststoffe”[油漆和塑料的质量控制]2003/2004，在此引入供作参考。DOI测定采用自BYK Gardner(Geretsried，德国)的波扫描DOI仪。
糙度深度Rz是连续单个测定段的各个糙度深度Rzi的算术平均值。单个糙度深度Rzi是在单个测定段中的最大外观峰与最大外观谷深之和。糙度深度Rz按照DIN EN ISO 4288测定。
借助如下实施例更详述地叙述本发明。
                实施例
两层总厚度为1000μm的载体薄膜(薄膜复合材料)由共挤塑工艺生产。下层由CP/ABS共混物(BayblendT45，得彼Bayer MaterialScience公司)组成，厚度为200μm；上层由PC(Makrolon3103，得自Bayer Material Science公司)组成，厚度为800μm。离开喷嘴的熔体采用抛光块(polishing stack)冷却，PC层的表面糙度通过采用表面结构辊调节。然后，该载体薄膜在层合工艺中以10m/min速度与自Soliant公司的密封薄膜(FluorexISF 2010-Paintfilm)层合到结构聚碳酸酯侧上。所用的该密封层包括厚度为20μm的底层、厚度为50μm的有色层和厚度为50μm的防护层。易剥离的和可形成的防护薄膜位于防护层上。如此生产的层合片材具有相当于任选涂漆构件表面的表面结构。然后该层合片材在190℃下热成形工艺中成形，和与PUR硬质整体泡沫塑料(Baydur0768 C/Desmoder44 V10，得自BayerMaterial Science公司)一起衬里发泡，用作机动车顶模塑件的结构件。
测定结果：
载体薄膜：
结构侧的R值：3μm
结构侧的R3z值：15μm
按照BYK Gardner的DOI：在技术上不能进行测定，因为结构表面薄膜光泽对DOI测定而言太低。
层合片材：
按照BYK Gardner的DOI：54.0[采用自BYK Gardener公司(Geretsried，德国)的波扫描DOI测定装置进行测定]。
虽然上文为了举例说明详述了本发明，但要理解的是，这些详述仅仅出于所述目的，本领域技术人员可以对其进行若干变更，而不会偏离本发明范围和精神，只要这些变更受限于权利要求书。

Claims (8)

1.一种生产表面具有用BYK Gardner装置测定的波扫描DOI值为5～60的层合材料的方法，包括：
a)得到温度为50℃～150℃的载体层，其第一表面的糙度值，Rz，为1μm～6μm，按照DIN EN ISO 4288测定，
b)施加温度80℃～180℃的密封层到所述第一表面，防护层位于远离载体层的那侧，
c)使b)步骤产品经过两个反转辊，借此至少一个辊温度为80～180℃，并且借此将产品加压，从而得到层合材料，
所述载体层包含至少一层至少一种选自下述物质的薄膜：聚碳酸酯、丙烯腈/丁二烯/苯乙烯、聚甲基丙烯酸甲酯、苯乙烯/丙烯腈、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二酯、聚酰胺、聚酯、丙烯酸系/苯乙烯/丙烯腈，所述密封层包括防护层和任选至少一个着色层。
2.权利要求1的方法，其中载体层是包含聚碳酸酯的薄膜。
3.权利要求1的方法，其中载体层是选自聚碳酸酯和聚碳酸酯/ABS共混物的薄膜。
4.权利要求1的方法，其中载体层是共挤塑层合材料。
5.权利要求2的方法，其中载体层的表面糙度R3z为10μm～35μm，按照Daimler Benz factory标准DB N 31007(1983)测定。
6.按照权利要求1的方法制备的层合材料。
7.一种层合材料，其表面用BYK Gardner装置测定的波扫描DOI/值为5～60，包括：
A)载体层，其第一表面的糙度值，Rz，为1μm～6μm，按照DINISO 4288测定，
B)在所述第一表面上的密封层，防护层位于远离载体薄膜的那侧，
所述载体层包括至少一层至少一种选自下述物质的薄膜：聚碳酸酯、丙烯腈/丁二烯/苯乙烯、聚甲基丙烯酸甲酯、苯乙烯/丙烯腈、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二酯、聚酰胺、聚酯、丙烯酸系/苯乙烯/丙烯腈，所述密封层包括防护层和任选至少一个着色层。
8.一种模塑制品，包含权利要求6的层合材料。
CN2005100640564A 2004-04-06 2005-04-06 层合片材及其生产方法 Expired - Fee Related CN1693072B (zh)

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