CN107787274A - 层压聚合物产品的制造方法 - Google Patents

层压聚合物产品的制造方法 Download PDF

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Publication number
CN107787274A
CN107787274A CN201680036784.0A CN201680036784A CN107787274A CN 107787274 A CN107787274 A CN 107787274A CN 201680036784 A CN201680036784 A CN 201680036784A CN 107787274 A CN107787274 A CN 107787274A
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layer
acrylonitrile
abs
styrene
product
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CN201680036784.0A
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CN107787274B (zh
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E·特斯塔
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MAZZUCCHELLI 1849 SpA
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Individual
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Abstract

本发明公开了一种相对层压的聚合物半成品的制造方法，所述层压的聚合物半成品具有深度美学特征，包含至少两个通过加热和/或加压的层压处理相互熔接的层，其中所述层中的至少一个是热塑性材料，其中提供以下步骤：提供100～500微米厚的粘合层，其由热塑性聚氨酯组成，具有深度美学图案；提供聚合物片材，其具有软化温度高于所述粘合层的材料；通过加热和/或加压，将至少部分透明或半透明的至少一个所述聚合物片材与所述粘合层层压，所述加热和/或加压适合于达到具有美学图案的所述粘合层的软化。

Description

层压聚合物产品的制造方法
技术领域
本发明涉及由层压热塑性材料组成的片材或其它半成品形式的产品的制造方法，以及相关的眼镜框架。
背景技术
已知在眼镜领域中，塑料材料广泛用于制造眼镜框架，即支撑一对镜片的部件。
历史上，所述框架是通过加工金属丝或天然来源的动物材料如角、骨和龟甲获得的。随着硝酸纤维素(赛璐珞)的出现，天然和动物来源的材料逐渐被替代或越来越多地与赛璐珞类产品一起使用，即适合于复制与天然材料相似的美学效果的塑化热塑性聚合物。自20世纪20年代以来，赛璐珞慢慢被乙酸纤维素制成的类似物取代，后者具有较高的热稳定性。通过诸如本体处理(block process)、挤出处理、层压处理等不同技术加工的塑化乙酸纤维素成为更广泛用于高档眼镜的聚合物，这是由于其物理和机械性能适合特定用途，而且具有更多的感官特性(如温暖柔滑的手感)，以及重要的美学资质。无论是眼科眼镜还是太阳镜，眼镜实际上越来越被视为时尚配饰，而不仅仅是矫正或保护用品。
多年来，伴随通过打磨纤维素酯片材(其中最有代表性的是乙酸纤维素)获得眼镜的是通过注塑或通过各种聚合物的铸造技术获得的眼镜，在大多数情况下为热塑性聚合物，包括聚酰胺、丙酸纤维素、聚氨酯、聚酯和共聚酯、天然来源的聚合物如聚乳酸(PLA)和聚羟基链烷酸酯(PHA)等。
以上产品均根据成品所需的要求进行选择：一些聚合物根据其技术性能(强度、稳定性、硬度、轻量等)进行选择，而其它聚合物则主要考虑其美学品质。实际上，总是做出权衡的选择，因为高技术性能塑料使用的越多(例如，特别紧贴的运动眼镜或要求轮廓薄的眼镜)，其美学品质越不可能变得精致。
然而，市场的导向越来越追求成品的美学资质和美学效果造成的差异化：最终，生产者甚至以推出小批量收藏品的代价来满足其顾客的要求。
最能满足这些要求的眼镜是由通过本体处理(湿本体和干本体处理)、挤出处理和层压处理形成的片材获得的那些眼镜，然而，这些眼镜可以与在某些应用中对技术性能造成限制的材料一起使用。这些材料的独特之处在于它们可以包含非常复杂和不均匀的图案(甚至在深度上)，从而提供持久美感和非常有特色的外观。相反地，通过注塑或铸造处理获得的框架(其可与技术性能更高的材料一起使用)在美学上较不精致(因为材料必须是均匀的)并且经受诸如喷涂、印刷或各种表面颜色涂覆处理等表面修整处理，然而，它们不能确保同样多样的美学图案和深度美学图案。如上所述的那些表面修整最容易受磨损：这些处理的有限厚度实际上暴露于可加速其去除的物质(例如，汗液、遮光剂和美容霜)，和可能会刮伤表面的力，造成聚合物层以其原始形貌暴露(在修整处理之前)，从而导致产品失去美学品质。
可以看出，目前还不能以合理的价格提供能够满足市场要求(即同时满足美学品质和机械要求)的眼镜。
上述情况也适用于与眼镜领域不同的其它应用领域(例如人造珠宝、消费类电子产品、其它技术物品等)，其中有利的是，具有高品质的美学效果的技术有效材料还将具有优异的技术功能。
因此，除了不会因磨损而劣化的产品，还期望提供一种用于获得具有高度美学特征以及适合于更多技术用途的机械性能的片材、眼镜坯件、眼镜或其部件的方法。
在概念层面上已经提供的至少一种可能的解决方案是通过将具有互补特征的若干材料层层压在一起来制造片材或半成品，其中所述层中的至少一个具有出众的美学品质：例如，与通过本体处理制造的乙酸纤维素薄片(美学材料)结合的聚碳酸酯层(技术材料)。
这种技术提供了各层的相互热熔(例如超声波熔接)或相互之间的模制，或者甚至通过粘合剂(例如，所谓的热熔聚合物胶)的粘结。然而，使用如乙酸纤维素等高美学价值的材料也存在技术性能差的问题，因此层压体具有较高的厚度以确保足够的机械特性。此外，这些材料中的一些(例如乙酸纤维素)在与不同材料结合时具有固有的粘结问题。
然而，遭受上述问题的这些结合技术的一个实例由CN103624978代表，其也公布为WO2014029192。
US2004/0126587中描述了用于聚碳酸酯镜片的通用层压技术，其也采用聚氨酯层。在这种情况下，热塑性或热固性聚氨酯材料层包括均匀分散的光致变色颜料，以提供轻微的(因为它必须保持基本上透明的)光致变色着色。聚氨酯层优选通过铸造或注射获得，并且可能与相邻层粘合，因为它仍然需要均匀地分布在视野的前方。在这种情况下，两种材料都有技术功能。
发明内容
因此，本发明解决的问题是提供一种用于眼镜框架的片材或半成品的制造方法，其克服了现有技术的缺点。具体而言，本发明旨在提供既具有高化学和物理-机械性能又具有重要美学价值的产品，其能够具有减小的厚度和成本。
这些目的是通过所附的独立权利要求中所限定的方法及由其获得的产品(以其基本特征)来实现的。
在从属权利要求中描述了本发明的其它发明方面。
实际上，根据本发明的第一方面，提供了一种层合聚合物半成品的制造方法，所述产品具有深度美学特征，并且包含至少两个通过加热和/或加压的层压处理而相互粘结的层，其中所述层中的至少一个是热塑性材料，在所述方法中提供了以下步骤：
提供100～500微米厚的粘合层，其由热塑性聚氨酯组成，具有在深度上延伸的深度美学的图案，其通过共挤出或本体处理获得，
提供聚合物片材，其具有软化温度高于所述粘合层的软化温度的材料，
通过加热和/或加压，将至少部分透明或半透明的至少一个所述聚合物片材与所述粘合层层压，所述加热和/或加压适合于达到具有美学图案的所述粘合层的软化。
根据另一方面，所述聚合物片材基于由聚酰胺(PA)、聚氨酯(PU)、聚醚酰亚胺(PEI)、丙酸纤维素(CP)、聚氨酯-聚脲、热固性聚氨酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚乙烯(PE)、苯乙烯-丙烯腈(SAN)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚碳酸酯和丙烯腈-丁二烯-苯乙烯的混合物(PC/ABS)、PVC、聚对苯二甲酸丁二酯(PBT)、PBT/ASA、ASA/PC组成的组中的聚合物材料的一种。
根据第二方面，本发明提供了一种层合半成品聚合物产品，其具有深度美学图案，包括至少两个通过加热和/或加压的层压处理过程而相互粘结的层，其中与一个或多个聚合物片材粘合的至少一个粘合层由具有深度美学图案的热塑性聚氨酯组成，其软化温度低于所述聚合物片材的软化温度，并且与粘合层接触的所述聚合物片材中的至少一个是至少部分透明或半透明的。
与上述类似地，聚合物片材基于由聚酰胺(PA)、聚氨酯(PU)、聚醚酰亚胺(PEI)、丙酸纤维素(CP)、聚氨酯-聚脲、热固性聚氨酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚乙烯(PE)、苯乙烯-丙烯腈(SAN)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚碳酸酯和丙烯腈-丁二烯-苯乙烯的混合物(PC/ABS)、PVC、聚对苯二甲酸丁二酯(PBT)、PBT/ASA、ASA/PC组成的组中的聚合物材料的一种。
热塑性聚氨酯夹层的美学效果是通过本体处理或共挤出处理获得的。
还提供了用上述产品获得的眼镜用框架原型。
根据另一方面，本发明提供了一种通过加工由多层热塑性聚合物组成的片材而获得的眼镜坯件、眼镜成品或其部件，其中至少一个内部热塑性聚氨酯类夹层用作层压体的熔接元件。另一方面，本发明还涉及由不同层的热塑性聚合物组成的片材获得的眼镜坯件、眼镜成品或其部件，其中至少一层由热塑性聚氨酯箔组成，所述聚氨酯箔用作层压体的熔接元件，同时赋予层压体美学品质。聚氨酯的美学特征可以优选通过本体处理获得。通过共挤出处理、共成型处理以及通过诸如丝网印刷、热转印或数字印刷等印刷处理或者对片材赋予深度着色和图案的处理也可以实现具有深度美学图案的特征。所述片材可以含有一种或多种颜色，其选自透明、乳白、不透明、珠光或外来颜色。除了眼镜领域之外，如此构成的片材可以用于所有那些美学部件在其中起重要作用的领域，例如人造珠宝、餐具、托盘、覆盖物(盒子、包装、个人计算机外壳等)，涂料(家具、地板、照明、汽车内饰或游艇、乐器、运动用品等)和其它技术物品。
附图说明
本发明的方法和产品的进一步的特征和优点将从以下通过示例给出并在附图中示出的优选实施方式的详细描述中变得更加明显，附图中：
图1是由热塑性聚氨酯的中间层和两个透明外层组成的示例性层压体的示意性透视图；
图2是由热塑性聚氨酯的中间层和两个外层(其中仅有一个透明)组成的示例性层压体的示意性透视图；
图3是由热塑性聚氨酯的中间层和两个外层(其中一个半透明而另一个有阴影)组成的示例性层压体的示意性透视图；
具体实施方式
通过本身已知的方式，通过层压多个不同材料的平面层来制造塑料材料的片材。在本申请的背景下，层压是指适合于将由单个塑料材料箔形成的多个层粘接的任何处理，所述塑料材料可以是不同的或相同的，但是在技术性能或美学外观方面不同。
下面将描述获得层压体的一些优选方法，但通常所述方法利用加热和加压来熔化一个或多个组件层，以便获得与相邻层的紧密粘附或者甚至获得与相邻层的化学结合，并且产生稳定的片材，其中各层彼此永久地粘合，同时避免(至少在正常的操作条件下)各层之间的层离。
根据本发明，这些中间层F1中的至少一个是热塑性聚氨酯类半成品，其通过在热塑性材料上使用一种可行的处理而被赋予具有深度图案的美学价值，所述处理优选为本体加工、共挤出和共注射，其可使美学图案深入界定在材料中，从而给予材料耐久和非常注目的美学特征。
该热塑性聚氨酯(TPU)的中间层F1通过刚描述的方法之一制造，可能通过套印而施加美学特征，然后使其冷却并且可将其储存。该层的厚度优选为100～500微米。
根据本发明，利用热塑性聚氨酯的固有性质而构成美学图案的支撑，同时也是用于层压过程的有效的粘合剂元件，热塑性聚氨酯由于化学性质和相对低的熔点(80～220℃)而能够有效地用作多种不同塑料聚合物材料的粘合剂。因此，根据本发明，具有美学特征的这种热塑性聚氨酯层将构成与不同材料的其它层层压的参考元件，其它层仅仅凭借其技术性能来进行选择，只要它们具有足够的透明度(在半成品的整个区域上或在其自身适当选择的部分上)以允许热塑性聚氨酯中间层的美学特征能够外部可见。
本发明的层压方法随后使具有美学特征的塑料聚氨酯层与其它技术塑料材料的片材结合，或者在半成品塑料材料的两个膜/片FLl和FL2(FL1是指封装的上部顶片，而FL2是指封装的下部基片)之间结合，各片材的厚度优选为500微米～1厘米。
如果热塑性聚氨酯层F1特别薄(例如约100微米)，则可暂时将其供应到防粘纸上：在这种情况下，可以期望在移除防粘纸之前在第一片材FL1上进行层F1的轻度层压步骤，而后进行与另一片材FL2层压的第二步骤。
塑料片材FLl和FL2(其可以通过插入具有美学特征的中间TPU层来层压)优选地选自由诸如聚酰胺(PA)、聚氨酯(PU)、聚醚酰亚胺(PEI)、丙酸纤维素(CP)、聚氨酯-聚脲、热固性聚氨酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚乙烯(PE)、苯乙烯-丙烯腈(SAN)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚碳酸酯和丙烯腈-丁二烯-苯乙烯的混合物(PC/ABS)、PVC、聚对苯二甲酸丁二酯(PBT)、PBT/ASA、ASA/PC等聚合物组成的组。
还已知的是，施加在与热塑性聚氨酯片材接触的某些聚合物表面上的等离子体处理可以提高粘合性：例如，用一些聚酰胺(聚酰胺6.6)、PBT、PS、PP获得了有利的结果。
与具有美学特征的层压TPU的中间层粘附并相对的两个塑料片FL1和FL2可由相同的聚合物或由两种不同的聚合物(例如，丙酸纤维素片材和聚酰胺片材)形成。基于待获得的产品或结构体(例如眼镜用框架)的最终应用，两个片材FL1或FL2中的至少一个必须具有至少透明或半透明的特征(可能在其几何界定的部分上)，从而使TPU下面的中间层的美学图案明显；在一些情况下，为了改善并使TPU的层F1的美学含义更加明显，片材FL1和FL2(可选地至少部分)具有透明/半透明的特性。
片材FL1和FL2也可以具有美学特征或特征性多色特性，但是这在本文提供的教导中不是必需的。作为非限制性实例，在图2示出的层压体中，顶片FL1是透明的，而基片FL2是不透明的，例如其均匀着色，而在图3示出的层压体中，顶片FL1有阴影，而基片FL2为半透明且颜色均匀。最外部片材FL1和FL2上的阴影也可以通过挤出处理或通过插入颜料填料或通过使用染色处理(在眼镜领域中称为“浸渍”，即浸渍染色，其有阴影)获得。
根据第一实施方式，将由至少三个层FLl、FL2和Fl(以及可能的其它多个外层，无论是否包括具有美学特征的附加热塑性聚氨酯夹层)构成的“封装体”置于一个平面压机内，在此通过加压和加热获得最终厚度1050微米～2厘米的层压体。
层压热也可以通过其它技术来提供，例如高频或摩擦加热处理。
在此种压制过程中，温度通常低于构成外部片材FL1和FL2的材料的软化温度，但是适合于导致TPU中间层软化(不过度流化，如下文所述)。
因此，加热、冷却和压力条件以及各种加工循环的持续时间取决于诸如以下因素：
-聚氨酯层F1的类型和厚度；
-用于其它层FL1和FL2的聚合物的类型和厚度。
“封装体”的各层之间的粘结主要取决于聚氨酯层F1的软化温度，除了美学功能外，聚氨酯层F1还起到粘接剂(热熔粘合剂)的作用。为此，所述封装体必须包含一个聚氨酯层F1，其如上所述具有低于或等于用于其它包围层FL1和FL2的聚合物的软化温度；这样就保证了层压体的粘结，同时避免了各个部件的变形。所述软化必须足以获得难以层离的“封装体”(FL1，F1，FL2)，但避免达到会损害聚酯片材Fl美学图案的稳定性和一致性的过度流动性。
因此，应基于所选具体组成的折衷方案选择条件。
通常使用热塑性材料的温度为40～220℃，优选高于100℃，压力为约1kg/cm2～100kg/cm2，然而其与处理过程温度成反比(应避免过高的压力以及高温，以不损坏审美图案的连贯性)，并且减少的停留时间为约1分钟～10小时。
举例来说，下面报道了用于形成封装体的方法的实验测试，所述封装体由以下部件构成：
-聚酰胺(商品Trogamid TR90)的第一顶层FL1，厚度为2000微米；
-通过具有“锦缎”美学效应的本体处理获得的热塑性聚氨酯(例如，脂肪族聚氨酯)的中间层F1，厚度为200微米；
-聚酰胺(商品Trogamid TR 90)的第二基层FL2，厚度为2000微米。
基片FL2通过聚酰胺的注射成型获得，表面清洁且没有表面污染，并且水平置于平面上；在所述片材FL2上放置厚度为200微米的具有美学特征的热塑性聚氨酯中间层F1的片材，并且在其上面放置表面清洁且没有表面污染的聚酰胺顶片FL1。
将由此获得的“封装体”放置在压机平面内的两个镀铬板之间。其后，以下列规格施加压力和热：温度130℃，压力5kg/cm2，时间10分钟。
层压的产品一旦冷却，便通过任何眼镜制造商已知的条件将其切割并打磨为眼镜前框的形状。
由此获得的产品在技术性能和所达到的美学效果方面都是优异的。特别是，在确保通常的强度和刚性性能的同时，可以生产厚度低并具有典型的薄型轮廓的眼镜，在技术(轻量)和美观(新光线)方面获得有利的结果。
本发明的半成品不是仅通过如上所述的压制层压获得的。在替代性实施方式中，提供了用其它类型的熔接来进行层压：例如，如上所述，在某些情况下，可以使用超声波或振动/摩擦熔接。
在某些条件下，不推荐厚度大于500微米的热塑性聚氨酯(F1)的中间层，因为其可能是后续加工(例如抛光)的障碍。事实上，当TPU夹层(F1)的硬度低于其它相邻层的硬度时，对层压体边缘进行机械加工可导致材料的差异化磨损，使得在侧面上形成不期望的弯月面，其易于积聚加工材料(研磨膏)并且产生半成品可能层离的触发点。
本发明的半成品是非常有效的，并完全满足前文中所述的目的。通过生产具有深层装饰和美学效果(特别是能够通过本体处理获得)的热塑性聚氨酯片材，可以获得下述层压层，其在由各种聚合物材料片材组成的层压体中同时提供期望的美学效果和粘合剂功能，由此这赋予半成品所需的技术性能。
从基于热塑性聚氨酯的中间层的选择得到的另一个优点涉及如下事实，即不需要使用特定的胶和粘合剂来使层压层相互粘接。这意味着消除了额外的成本、实践上的困难，并且最重要的是不会对层压体的尺寸稳定性产生不利的影响：实际上，热塑性聚氨酯的尺寸变形接近0％，并且具有使其能够匹配并遵循由眼镜领域的所有传统处理(包括热成型处理)中的外部片材FL1和FL2赋予的曲率。
而且，在用TPU和非常高性能的聚合物(如尼龙)获得层压体的情况下，甚至在眼镜制造过程中可以避免用于界定结构芯，从而使层压眼镜的制造简化。
最后，在夹层中提供美学组件有利地保护了所有美学效果免受属于外部环境的任何磨损或化学侵蚀。
然而，应该理解的是，本发明不限于以上示出的特定实施方式(其仅代表本发明范围的非限制性实例)，在本领域技术人员可以实现的范围内许多变体都是可能的，而不偏离本发明的范围。
尽管上述的层压技术只是其中一些可行的技术，但是也可以有利地使用其它加工模式，其仍然利用热塑性聚氨酯的中间层的美学品质和粘接功能。此外，层压不仅可以在矩形片材之间进行，而且也可以在已经是半成品的片材之间进行，例如眼镜前框或模板的坯件。
而且，具有美学特征的热塑性聚氨酯片材还可以与其它支撑材料如纸、纸板或者木材或其它材料的薄片层压。
最后，如上所述，不排除层压处理可以制造下述半成品，其中具有美学特征的热塑性聚氨酯层保留在所述半成品的外部。

Claims (7)

1.一种层压聚合物半成品的制造方法，所述半成品具有深度美学特征，包含至少两个通过加热和/或加压的层压处理而相互熔接的层，其中，所述层中的至少一个是热塑性材料，所述方法的特征在于提供以下步骤：
提供100～500微米厚的粘合层，所述粘合层由热塑性聚氨酯组成，具有深度美学图案，
提供聚合物片材，所述聚合物片材具有软化温度高于所述粘合层的软化温度的材料，
通过加热和/或加压，将至少部分透明或半透明的至少一个所述聚合物片材与所述粘合层层压，所述加热和/或加压适合于达到具有美学图案的所述粘合层的软化。
2.如权利要求1所述的方法，其中，所述热塑性聚氨酯的粘合层通过本体或共挤出处理获得，并且具有在深度上延伸的美学图案。
3.如权利要求1或2所述的方法，其中，所述聚合物片材基于由聚酰胺(PA)、聚氨酯(PU)、聚醚酰亚胺(PEI)、丙酸纤维素(CP)、聚氨酯-聚脲、热固性聚氨酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚乙烯(PE)、苯乙烯-丙烯腈(SAN)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚碳酸酯和丙烯腈-丁二烯-苯乙烯的混合物(PC/ABS)、PVC、聚对苯二甲酸丁二酯(PBT)、PBT/ASA、ASA/PC组成的组中的聚合物材料的一种。
4.如权利要求1、2或3所述的方法，其中，所述加热和加压的层压步骤在40～220℃、优选高于100℃的温度和1kg/cm2～100kg/cm2的压力下进行。
5.一种层合半成品聚合物产品，所述产品具有深度美学图案，包含至少两个通过加热和/或加压的层压处理而相互熔接的层，其中，所述层中的至少一个是热塑性材料，所述产品的特征在于，与一个或多个聚合物片材(FLl,FL2)粘合的至少一个粘合层(Fl)由具有深度美学图案的热塑性聚氨酯组成，所述热塑性聚氨酯的软化温度低于所述聚合物片材(FLl,FL2)的软化温度，并且与所述粘合层(Fl)接触的所述聚合物片材中的至少一个是至少部分透明或半透明的。
6.如权利要求5所述的产品，其中，所述聚合物片材基于由聚酰胺、聚氨酯、丙酸纤维素、聚碳酸酯、聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚乙烯(PE)、苯乙烯-丙烯腈(SAN)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚碳酸酯和丙烯腈-丁二烯-苯乙烯的混合物(PC/ABS)、PVC、聚对苯二甲酸丁二酯(PBT)、PBT/ASA、ASA/PC组成的组中的聚合物材料的一种。
7.一种眼镜框架，其利用权利要求4或5所述的产品获得。
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