CN116323133A - 微压印 - Google Patents

微压印 Download PDF

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Publication number
CN116323133A
CN116323133A CN202180061108.XA CN202180061108A CN116323133A CN 116323133 A CN116323133 A CN 116323133A CN 202180061108 A CN202180061108 A CN 202180061108A CN 116323133 A CN116323133 A CN 116323133A
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CN
China
Prior art keywords
laminate
polymer
layer
thermoplastic
thickness
Prior art date
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Pending
Application number
CN202180061108.XA
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English (en)
Inventor
M·加农
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bixby International Co ltd
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Bixby International Co ltd
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Publication date
Application filed by Bixby International Co ltd filed Critical Bixby International Co ltd
Publication of CN116323133A publication Critical patent/CN116323133A/zh
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
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Abstract

一种聚合物压印‑工具垫片层压体，其包括具有固化在聚合阻隔体膜上的三维几何图案的微压印聚合表面纹理。该压印‑工具层压体使得生产表面具有微尺寸三维几何图案的聚合层压体的方法成为可能。

Description

微压印
相关申请的交叉引用
本申请要求2020年7月16日提交的美国临时专利申请号63/052554和2020年11月19日提交的美国临时专利申请号63/115859的权益，其均通过引用全文纳入本文。
背景技术
本发明一般涉及挤出(extrusion)，更具体地涉及微压印(micro embossing)。
通常，在典型的挤出制造过程中，加热塑料并通过螺杆将其输送通过加热的机筒。使塑料强制通过模具以形成部件的最终形状，并且对挤出的塑料进行冷却。
发明内容
以下是对创新的简化概述，以提供对本发明一些方面的基本了解。该概述不是对本发明的广泛描述。其目的既不是要确定本发明的主要或关键要素，也不是要划定本发明的范围。其唯一目的是以简化的形式介绍本发明的一些概念，作为后面更详细描述的前序。
通常，在一个方面，本发明的特征是一种层压体，其包括具有固化在聚合阻隔体(insulator)膜上的三维几何图案的微压印聚合物表面纹理。
在另一个方面，本发明的特征是一种热塑性聚合层压体，其包括具有三维几何图案的微压印表面纹理。
在另一个方面，本发明的特点是一种生产层压体的方法，该方法包括布置具有厚度小于10密耳的三维几何图案的金属微压印表面纹理，以及下方的热稳定粘合剂层，在下方提供厚度小于15密耳的至少一层热塑性阻隔体层，使得热挤出的热塑性熔体层在接触时立即加热金属微压印表面纹理，并在熔融的热塑性聚合物表面上形成冻结表皮(frozenskin)，通过设置熔融热塑性聚合物的熔体温度、厚度、辊冷却温度和生产线速度，使得与通过熔融热塑性聚合物阻隔体厚度的热传递速率相平衡，从而控制有效的传递，在下方提供热稳定的粘合层，以及在下方提供冷却作用的挤出冷却辊或金属套筒。
在另一个方面，本发明的特点是一种生产聚合物层压体的方法，该方法包括布置具有厚度小于10密耳的三维几何图案的聚合物压印工具-垫片层压体(polymericembossing tool-shim laminate)，其来自UV可固化的聚合物，在下方提供热稳定的粘合剂层，在下方提供至少一层厚度小于15密耳的热塑性阻隔体层，使得热挤出的热塑性熔体层在接触时立即加热聚合物微压印表面纹理层，并在热塑性熔体层上形成冻结表皮，通过设置聚合物的熔体温度、厚度、辊冷却温度和生产线速度，使得与通过聚合物膜阻隔体厚度的热传递速率相平衡，从而控制有效的传递，在下方提供热稳定的粘合层；以及在下方提供载体基材。
通过阅读下文的详细描述和对相关附图的概述，这些和其他的特征和优点将是显而易见的。应理解，前文的一般性描述和下面的详细描述都只是解释性的，并不是对所要求保护的方面的限制。
附图简要说明
参考以下描述、所附权利要求和附图，本发明的这些和其他特征、方面和优点将得到更好的理解，其中:
图1说明了示例性的挤出片材生产线。
图2说明了示例性的结构。
图3说明了用金属压印工具-垫片层压体冷却的截面图。
图4说明了示例性的铸造膜挤出系统。
图5说明了九种示例性的表面压印纹理。
图6说明了另一示例性的聚合物压印工具-垫片层压体。
图7说明了聚合物-垫片工具条带(belt)的替代实施方式。
具体实施方式
现参照附图来描述本发明的主题，其中相似的附图标记在全文中用于指代相似的元素。在下面的描述中，为了解释的目的，列出了许多具体的细节，以提供对本发明的全面理解。然而，显而易见的是，本发明可以在没有这些具体细节的情况下实施。在其他情况下，众所周知的结构和装置以框图形式显示，以便于描述本发明。
如图1所示，一个示例性的片材生产线10包括挤出机12、辊堆(roll stack)14、冷却段16、压/拉辊段18和卷机(winder)20。在该实施例中，该辊堆14包含三个辊，其通常被称为修饰辊(polishing roll)。其用于对片材施加压力，并将辊的表面状态赋予塑料片材。如果需要光滑的表面，就使用光滑的辊。如果需要有纹理的表面，则使用表面有纹理的辊。辊的纹理是片材上所需纹理的阴面(negative)。通过使用彼此相邻的光滑辊和纹理辊，有可能生产出一面有纹理、另一面光滑的片材。
在一个方面，本发明针对的是一种在连续铸造热塑性材料挤出过程中，在膜或片材的一个或两个表面上压印细微的三维几何图案细节的方法。
该方法与压印工具结构一起，使得能够利用大规模生产的挤出方法在各种热塑性材料上创建高度细节的微小尺寸的技术三维(3D)图案。在本发明之前，这样的图案制作只能使用一次性铸造热固性材料来实现。本发明通过连续辊压(nip-roll)铸造挤出法在膜上形成了需要高分辨率微压印表面的热塑性材料，解决了其固有的热力学和聚合物流变学挑战。
例如，本发明包括一种夹辊法，其利用薄金属(特别是镍)，通过化学或激光蚀刻来制造工具，或"金属工具垫片"，用于在其表面产生微观几何纹理，从而在挤出过程中将该微尺寸几何纹理原位转移到挤出的聚合物部件上。细微纹理的金属垫片和挤出过程的冷却辊都具有高导热性，可以在挤出过程中快速冷却熔融聚合物。因此，即使在工艺允许的情况下温度设置得很高，冷却辊也会使熔融的聚合物骤冷，形成固态表皮，导致无法复制精细的压印纹理。
本发明的辊压法利用薄(例如3-15密耳)的金属-工具垫片，通过热稳定的压敏胶(PSA)或其他固化胶将其粘附到热阻隔体上。该热阻隔体可以是热稳定固化或高温橡胶、弹性体或其他聚合物膜。例如，7密耳厚的聚酯(例如，聚对苯二甲酸乙二醇酯(PET))膜在压(nip)的过程中提供了良好的阻隔平衡，同时在压后仍允许热传导率以使挤出和压印的膜在足够的时间内冷却，从而在受控的稳态过程中设置压印图像从辊上转移、凝固和移出。粘附在PET阻隔体膜上的镍金属-工具垫片的层压体随后通过PSA或其他合适的热稳定粘合剂粘附在金属冷却辊表面。在我们的方法中，该压印工具垫片层压结构粘附在导热金属(如镍)套筒上，该套筒可以在冷却辊上滑动，便于添加和移走整个微压印结构。在制造过程中，这使得可以从一个微结构的压印图案快速更换到另一个。
如图2所示，示例性的结构100包括金属压印工具-垫片层压体102和挤出冷却辊104。该金属压印工具-垫片层压体102包括阻隔体膜106，金属-垫片工具108和微压印表面纹理几何图案110。热稳定的粘合剂112将阻隔体膜106粘合到挤出冷却辊104上，并将阻隔体膜106粘合到金属-垫片工具108上。
图3说明了冷却辊的截面图，如上文图2所述，金属压印工具-垫片层压体102粘附在辊表面104上。
该层压压印工具垫片的作用是使热挤出的热塑性熔体在接触时立即加热薄金属-工具垫片层。PET阻隔体层可防止冷却辊的低冷却温度使熔融聚合物表面迅速形成冻结表皮。因此，聚合物保持在低粘度，能够流入并完全浸润(wet out)蚀刻在金属垫片上的微观细节和几何图案。因为阻隔体层的厚度是由系统的热力学决定的，其度量允许设定的冷却辊温度通过层压体传递以最终冷却熔融的聚合物表皮，使得其在将垫片的压印几何图案和细节复制和转移到冻结的表皮层后固定和凝固。通过设置聚合物熔体温度、厚度、辊冷却温度和生产线速度，使得与通过PET膜阻隔体厚度的热传递速率相平衡，从而实现有效传递的控制。改变阻隔体的厚度可以使挤出过程温度和生产线速度达到不同的平衡，也可以使不同的热塑性化学品在该微压印过程中发挥作用。
如图4所示，示例性的铸造膜挤出系统200包括安装在冷却辊204上的金属压印-工具垫片层压体202。
图5说明了九种示例性的表面压印纹理。
在另一个实施方式中，如图6所示，聚合物压印工具-垫片层压体300在没有镍或金属垫片的情况下制成。在此，聚合物压印工具-垫片层压体300包括在铸造聚合物-垫片工具304上的微压印表面纹理几何形状302，阻隔体膜306，载体基材308和热稳定的粘合剂310。或者，阻隔体膜上的聚合物压印工具-垫片层压体可以如同金属垫片结构那样通过热稳定的粘合剂安装在冷却辊上，而不是安装在载体基材上做成条带。
聚合物-垫片层压工具，或"条带"，使得能够在膜挤出的辊压过程中快速、连续地进行复制。聚合物垫片工具由聚合物膜上的UV固化的丙烯酸酯聚合物制成，起到了热阻隔体的作用，减轻了上述导热金属辊和/或垫片发生的骤冷/结皮效应。由于非常热的挤出熔体幅材(web)的表面现在是阻隔的，不会骤冷和在冷却辊的冷金属上迅速结皮，挤出聚合物的粘度仍然很低，足以流入并浸润细微压印的固化丙烯酸酯垫片细节。事实上，挤出过程中最大的热量来自于挤出机筒中的塑料熔化，通常超过400°F。相对于其他外部热源，挤出的热熔体本身成为将热量引入辊压站(nip roll station)的有效手段。通过这种方式，可以将薄的聚合物熔体幅材挤出到聚合物工具-垫片表面，以连续制造微压印热塑性膜。其还可以制造UV固化的丙烯酸酯垫片胚料(stock)的长的、连续且柔软/可卷的"条带"。卷起的丙烯酸酯垫片条带通过压区展开在冷却辊上，使挤出的熔体与冷却辊隔绝，并将其表面压花转移到正在加工的挤出熔融聚合物上。该固化的丙烯酸酯条带垫片还可用于热/压/时间控制的层压工艺，如条带层压、压制层压等。由于丙烯酸酯聚合物垫片工具相对较薄，其在热熔体接触其表面的瞬间有效地进行阻隔，但最终允许较冷的辊温度转移到挤出熔体上。当熔体冷却时，其产生表皮，在围绕冷却辊时将压印固定化，并以固体压印膜的形式释出。为了使利用聚合物-垫片工具层压的微压印过程在连续生产中可持续进行，可以将聚合物-垫片工具制成的热塑性膜做成长卷，通过压站时展开，然后重新卷起，并在压区中作为成型工具重新使用。
如图7所示，另一个实施方式包括通过将确定长度的金属或聚合物垫片工具条带的两端拼接成连续的环来制作聚合物垫片工具条带400。这样，条带400的任何部分在高温和高压下在压区402的时间都大大减少，而且也有更长并且可控的冷却时间，供固体挤出幅材表皮形成、冷却，并从金属或聚合物垫片工具的微压印表面释出。熔体(或幅材)404被冷却，在一侧或两侧使用金属或聚合物工具垫片(例如，有光泽和/或有纹理的辊，条带，或热稳定的柔性膜，片材或压印纸)，将纹理从图案化的"工具"转移到热挤出聚合物幅材404。在铸造热塑性材料挤出过程中通过这样的工具挤出熔融聚合物幅材时，为了审美或功能性改善，施加这样的纹理是常见的做法。可以创建宏观尺寸的表面图案，以提供诸如有光泽的表面、"喷砂"哑光表面、皮革或木纹或任何其他定制图案等特性。这些图案可以从工具上转移到熔融的幅材上，并在挤出过程中连续原位冷却。同样，也可以在挤出后施加压印，其通过将聚合物表面预热到可成形状态，然后在后压印过程中将挤出的聚合物膜或片材通过加热和冷却的辊、条带、热稳定的成形片材或膜，或使用加热和加压进行层压压制。通过这些方法获得5密耳(0.005")以下的表面的准确的光学真实复制是不可能的，其速度和规模不适合大规模生产某些热塑性部件的成本需求。
所有热塑性聚合物成型和成形方法的独特之处在于，需要将聚合物材料提高到一定的温度，使其能够移动或流动，从而使其变形，随后被塑造成所期望的几何形状的"铸型"，或者在本例中，形成精细图案化的表面纹理。所有粘性、非牛顿的热塑性材料在成型过程中面临的一个挑战是施加和保持适当的热量和成型力，以避免聚合物特性或其成型工作的毁坏，同时也提供足够的时间在合理的周期内冷却和冻结所期望的成型形状或纹理。冷却时间要求将热量从熔融聚合物中移出，使得在从成型工具中移出时保持成型的固体，而不发生扭曲或变形。在非连续注射成型过程中，聚合物熔体温度、注射速度、工具温度和冷却时间可以单独设置和管理，以便密切控制聚合物的流变性和流动性——这反过来又能对成型的几何形状和纹理进行精细(fine)(甚至是微观(microscopic))的控制。在非常高的注射成型压力下(如20,000psi)控制聚合物熔体的流变性，可确保在聚合物开始冷却之前完全"浸润"所有几何细节和表面。一旦冷却，聚合物熔体的粘度就会迅速增加，并形成固态的坚硬表皮，如果不过度用力或重新加热，就不会与细微的纹理细节吻合。
在连续挤出过程中，所有这些热聚合物流动控制(例如，熔体温度、工具/辊的温度和粘性剪切稀化)与注射成型相比，联系更加复杂，更难以独立控制。例如，降低热塑性聚合物熔体粘度的最有效方法是通过剪切使材料的聚合物链结构定向，大大降低熔体对压力流动的阻力。在成型过程中，这很容易通过注射速度和压力实现，但在挤出过程中，剪切流动力量要小得多。因此，在挤出过程中，为了实现纹理的亲密(intimate)表面浸润，聚合物熔体所需的低粘度几乎完全由熔体温度决定。在较小的程度上，工具温度可用于减缓熔体的冷却速度。因此，较高的工具/辊温度将提高材料的流动和浸润纹理的能力。然而，在挤出过程中，夹辊(或辊上的条带)的作用是将聚合物熔体冷却到稳定的固体，然后再将挤出的幅材(现在是"成品"冷却膜或片材)从有纹理的辊上释出，当不再固定在辊纹理上时也不会变形、收缩或翘起。因此，辊的温度必须低于聚合物的熔融温度，以便熔体可以凝固成成型的膜。并且在实践中，其必须大大低于熔体温度，在该温度下聚合物熔体凝固并在最终形态和质地上保持稳定，因此其就不会被工艺拉力拉伸，在具有成本效益的工艺速度下也不会在从工具和拉紧状态移开时发生收缩和翘起。
这意味着，在挤出的幅材冷却到固体形态并从成型辊上移开之前，工具温度需要设置到有足够的时间将热量从聚合物熔体(熔体的温度明显较高，使得有良好的流动性并浸润到精细的工具纹理)中移出。与冷却辊或条带接触的"冷却时间"由挤出生产线的速度决定。放慢生产线的运行速度可以使操作人员有更多的时间来移出热量，从而有能力运行更热的辊，以实现更好的向辊纹理的流动。然而，降低速度会造成成本和效率方面的损失，而且如果速度太慢，还会失去工艺控制和稳定性。在实践中，该工艺的运行速度不能慢到不足以为图像转移提供超过几秒钟的充分冷却时间。更希望的做法是用热的、容易流动的聚合物熔体进行辊冷却，这样可以快速凝固，从而提高产量，并容易将稳定的成型膜或片材产品移出。
然而，运行热熔体和较冷的辊时，一旦聚合物熔体接触到冷却辊，其表面就会骤冷。聚合物熔体是由外向内冷却的，因此，一旦热的聚合物表面接触到低于其热软化点的较冷表面，其就会骤冷成固体，形成"聚合物表皮"。聚合物是优秀的热阻隔体。一旦形成固体聚合物表皮，剩余的聚合物质量就能有效地阻隔冷却辊的影响。此外，固体表皮不流动，其随后的骤冷熔体的粘度迅速增加，随着熔体表面的骤冷而变得更硬。
本发明的压印工具-垫片层压结构能够在使用常规的、生产规模的挤出工艺制造的膜表面上创造出可控的、微尺度的表面图案；其简单、经济、高效。
上文所述的本发明提供了温度、流动和冷却的适当平衡，从而能够从压印工具或辊上生产出在热塑性聚合物幅材的一侧或两侧的可控的、微观的、精细的几何形状。与本文所述不同的结构和材料无法实现温度、流量和冷却的适当平衡，因此无法可靠地生产出所需的微观的、精细的几何形状。在两个冷却/成型辊之间"夹"聚合物幅材之前，对压印辊或垫片进行"点"加热，这表明我们可以改善浸润和印迹从辊上到聚合物熔体的转移，但加工问题(例如，热聚合物粘附和包裹加工辊以及加工质量不稳定的膜)使该解决方案昂贵、复杂和低效。
相比于通过铸造聚合物(例如，有时带有各种固化硬和/或脱模涂料和添加剂的UV可固化的丙烯酸酯聚合物)并将其固化在蚀刻金属垫片上来用作压印工具以转移细微的压印图案，本发明也具有明显的优势。尽管热固性和UV铸造可用于制造聚合物微纹理膜和片材，但该方法是额外的步骤，速度慢且成本高。虽然这种方法解决了挤出过程中复杂的聚合物流变学和热动力学问题，但在夹区的高循环温度、压力、疲劳和剪切下，聚合物垫片会破坏。使用长的、紫外线固化的聚合物垫片条带可以允许更长的运行——但条带的长度最终是有限的，因此需要多个垫片条带轮流使用，以保持制造班次的连续挤出——再次增加了生产过程的复杂性和成本。
具有较低导热性的材料(如热稳定的固化橡胶和/或弹性体)的辊套的冷却辊被视为替代材料，但目前不存在蚀刻或以其他方式在其表面创造精细纹理的方法。橡胶辊的使用更加复杂，因为其主要作用是冷却聚合物熔体，但由于橡胶辊的导热性较差，如果可能的话在挤出过程中对夹区进行精确的热控制是很困难的——而且还因要求工艺运行得太慢而不实用。
本领域的技术人员可以理解，在不背离本发明精神的情况下，可以对图示的实施方式进行各种改变和修改。除了受所附权利要求书的范围限制外，所有这些修改和变化都在本发明的范围内。

Claims (20)

1.一种层压体，其包括：
具有固化在聚合阻隔体膜上的三维几何图案的微压印聚合表面纹理。
2.如权利要求1所述的层压体，所述层压体进一步包括：具有微压印表面纹理几何图案的聚合物薄涂层，其附接在涂层下方的厚度小于15密耳的阻隔体聚合物片材上。
3.如权利要求2所述的层压体，其中所述阻隔体聚合物片材在具有微压印表面纹理几何形状的聚合物涂层下方的厚度为10密耳或更小。
4.如权利要求3所述的层压体，其中所述阻隔体聚合物片材在具有微压印表面纹理几何形状的聚合物涂层下方的厚度优选为3至10密耳。
5.如权利要求2所述的层压体，其中所述层压体包括至少一层热塑性阻隔体膜层，其在固化的微压印聚合物表面下方的厚度小于15密耳，所述固化的微压印聚合物表面具有施加的金属化顶层薄涂层，或通过热稳定的粘合剂粘附在固化的聚合物上的微压印金属箔。
6.如权利要求5所述的层压体，其中所述层压体包括至少一层厚度小于10密耳的热塑性阻隔体膜层。
7.如权利要求6所述的层压体，其中所述层压体包括至少一层厚度优选为3至10密耳的热塑性阻隔体膜层。
8.如权利要求5所述的层压体，其中所述层压体包括在热塑性阻隔体膜层下方的热控挤出冷却辊。
9.如权利要求8所述的层压体，其中所述层压体包括在热塑性阻隔体膜层和挤出冷却辊之间的热稳定聚合粘合剂。
10.如权利要求5所述的层压体，其中所述热塑性阻隔体膜选自如下聚合物组:聚酯、聚酰胺、聚氨酯、聚碳酸酯、聚酯弹性体、聚酰胺弹性体、聚氨酯、聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、工程热塑性材料、PBT、聚砜、PEEK、聚酰亚胺、热塑性弹性体、热塑性硫化橡胶、烯烃均聚物和共聚物及其掺混物。
11.一种热塑性聚合物层压体，其包括：
具有三维几何图案的微压印表面纹理。
12.如权利要求11所述的热塑性聚合物层压体，其中所述微压印表面纹理包括紫外线(UV)可固化聚合物。
13.如权利要求12所述的层压体，其中所述紫外线可固化聚合物选自下组：紫外线可固化的丙烯酸酯或甲基丙烯酸酯或环氧树脂或硅氧烷或硅烷。
14.如权利要求12所述的层压体，其进一步包括在铸造聚合物垫片层下方的厚度小于15密耳的阻隔体膜层。
15.如权利要求12所述的层压体，其进一步包括由耐用热塑性膜或纺织织物形成的载体基材层压体层。
16.如权利要求12所述的层压体，其进一步包括：
微压印箔；
金属沉积涂层；
UV固化的3D微压印聚合表面；
底漆；
作为载体和阻隔体的PET挤出膜，其厚度为3-15密耳；
热稳定的粘合剂；以及
冷却辊或载体基材层压体。
17.如权利要求12所述的层压体，其进一步包括阻隔体膜层和载体基材层之间的热稳定粘合剂层。
18.如权利要求13所述的层压体，其进一步包括阻隔体膜层和载体基材层之间的热稳定粘合剂层。
19.一种生产层压体的方法，所述方法包括：
布置具有厚度小于10密耳的三维几何图案的金属微压印表面纹理，以及下方的热稳定粘合剂层；
在下方提供厚度小于15密耳的至少一层热塑性阻隔体层；
使得热挤出的热塑性熔体层在接触时立即加热金属微压印表面纹理，并在熔融的热塑性聚合物表面上形成冻结表皮；
通过设置熔融热塑性聚合物的熔体温度、厚度、辊冷却温度和生产线速度，使得与通过熔融热塑性聚合物阻隔体厚度的热传递速率相平衡，从而控制有效的传递；
在下方提供热稳定的粘合剂层；以及
在下方提供冷却作用的挤出冷却辊或金属套筒。
20.一种生产聚合物层压体的方法，所述方法包括：
布置具有厚度小于10密耳的三维几何图案的聚合物压印工具-垫片层压体，其来自UV可固化的聚合物；
在下方提供热稳定的粘合剂层；
在下方提供至少一层厚度小于15密耳的热塑性阻隔体层；
使得热挤出的热塑性熔体层在接触时立即加热聚合物微压印表面纹理层，并在热塑性熔体层上形成冻结表皮；
通过设置聚合物的熔体温度、厚度、辊冷却温度和生产线速度，使得与通过聚合物膜阻隔体厚度的热传递速率相平衡，从而控制有效的传递；
在下方提供热稳定的粘合剂层；以及
在下方提供载体基材。
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