CN113773446B - 用于真空成型的可紫外固化的树脂组合物和包含其的真实材料的复制膜 - Google Patents

用于真空成型的可紫外固化的树脂组合物和包含其的真实材料的复制膜 Download PDF

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Publication number
CN113773446B
CN113773446B CN202011389721.8A CN202011389721A CN113773446B CN 113773446 B CN113773446 B CN 113773446B CN 202011389721 A CN202011389721 A CN 202011389721A CN 113773446 B CN113773446 B CN 113773446B
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resin composition
curable resin
acrylate
diisocyanate
ultraviolet
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CN113773446A (zh
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徐载植
金贤贞
权贤炅
金成度
姜昌昊
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Hyundai Motor Co
Kia Corp
SK Microworks Solutions Co Ltd
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Hyundai Motor Co
Kia Motors Corp
SKC Hi Tech and Marketing Co Ltd
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Abstract

本发明涉及一种用于真空成型的可紫外固化的树脂组合物和包含其的真实材料的复制膜。可紫外固化的树脂组合物包含预聚物、丙烯酸酯单体和光引发剂，所述预聚物包含含氨基甲酸酯的低聚物。

Description

用于真空成型的可紫外固化的树脂组合物和包含其的真实材 料的复制膜
技术领域
本发明涉及一种用于真空成型的可紫外固化的树脂组合物和包含其的真实材料的复制膜。
背景技术
通常将采用超高价的真实机织碳纤维织物的内部和外部材料应用于尤其是高性能的车辆，以提升车辆的内部和外部材料。但是，真实的碳材料非常昂贵，并且需要复杂的加工来制成部件。
因此，已经进行了各种尝试来模拟真实碳，例如将形状与真实碳的表面图案相似的膜注塑成型为模制品，在其上进行表面涂布，而后将所得物施用于部件。
这些方法具有成本降低的优点，但是具有外观明显变差的限制。特别地，常规模拟方法在技术上有如下限制：不能实现真实碳的线宽以及碳的独特三维质感和光泽。
为了克服这些缺点和限制，已经尝试将模拟方法与紫外压印相结合，但是由于硬质紫外树脂层的性质，无法形成具有复杂形状而不是平坦形状的车辆部件。
公开于该背景部分的以上信息仅用于增强对本发明的背景的理解，因此其可以包含不构成已为该国家中本领域普通技术人员所知的现有技术的信息。
发明内容
在优选的方面，提供一种复制膜和形成所述复制膜的可紫外固化的树脂组合物，所述复制膜可以具有真实材料的质感以实现其独特的特征。此外，提供一种复制膜和包含在所述复制膜中的可紫外固化的树脂组合物，所述复制膜由于优良的成型性而可以施用于具有复杂形状而不是平坦表面的车辆部件。
本发明的目的不限于上述目的。从以下描述中将清楚地理解本发明的目的，并且本发明的目的可以通过权利要求中限定的手段及其组合来实现。
在一方面，本发明提供一种的可紫外固化的树脂组合物，其包含预聚物、丙烯酸酯单体和光引发剂，所述预聚物包含含氨基甲酸酯的低聚物。
如在本文所用的术语“可紫外固化的树脂”或“可紫外聚合的树脂”是指通过在10nm至400nm的波长内的紫外(UV)光或通过紫外光辐射设备辐射出的能量来聚合、硬化和固化的聚合物材料。如在本文所用的术语“预聚物”或“聚合物前体”是指未反应或未固化的单体的混合物，其经由单体中的反应性基团进一步聚合。
如在本文所用的术语“含氨基甲酸酯的低聚物”或“聚氨基甲酸酯”是指通过将连接有氨基甲酸酯(-NH-(C＝O)-O-)的有机基团(例如环氧基、不饱和酯和酚基)连接起来而形成的聚合物。含氨基甲酸酯的低聚物的氨基甲酸酯键可以优选地通过使异氰酸酯基(-N＝C＝O)与具有多个羟基的多元醇反应来形成。
术语“丙烯酸酯单体”是指包含一个或多个(-CH2＝CHCOO-)基团的单体，其可以易于经由乙烯基聚合并且提供羧酸酯官能团。
如在本文所用的术语“光引发剂”是指可以在紫外或可见光辐射下产生反应性物质(例如自由基、阳离子或阴离子)的分子。在包含在可紫外固化的树脂组合物中时，光引发剂引发紫外固化或紫外聚合。
含氨基甲酸酯的低聚物可以是通过使异氰酸酯、多元醇和反应性单体反应来获得或可获得的，所述异氰酸酯包含选自甲苯二异氰酸酯(TDI)、萘-1,5-二异氰酸酯、对苯二异氰酸酯、联甲苯胺二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、4,4'-亚甲基二环己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或多种，所述多元醇包含选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇和丙烯酰基多元醇中的一种或多种。
反应性单体可以适当地包含选自丙烯酸2-羟乙酯、丙烯酸4-羟丁酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯和季戊四醇三丙烯酸酯中的一种或多种。
含氨基甲酸酯的低聚物可以适当地具有约2000g/mol至5000g/mol的重均分子量。
丙烯酸酯单体可以适当地包含选自丙烯酸异冰片酯、丙烯酸2-羟丙酯和羟基新戊酸新戊二醇二丙烯酸酯(hydroxyl pivalic acid neopentyl glycol diacrylate)中的一种或多种。
丙烯酸酯单体可以适当地包含丙烯酸异冰片酯、丙烯酸2-羟丙酯和羟基新戊酸新戊二醇二丙烯酸酯。
光引发剂可以包含选自短波长光引发剂和长波长光引发剂中的一种或多种。
优选地，短波长光引发剂可以包含1-羟基环己基苯基酮，长波长光引发剂可以包含二苯基(2,4,6-三甲基苯甲酰基)氧化膦(TPO)。
可紫外固化的树脂组合物可以进一步包含选自紫外稳定剂、耐热稳定剂及其组合的添加剂。
以可紫外固化的树脂组合物的总重量计，预聚物可以以约20至50重量％的量存在。
以可紫外固化的树脂组合物的总重量计，丙烯酸酯单体可以包含约15至30重量％的量的丙烯酸异冰片酯、约15至30重量％的量的丙烯酸2-羟丙酯和约1至10重量％的量的羟基新戊酸新戊二醇二丙烯酸酯。
以可紫外固化的树脂组合物的总重量计，光引发剂可以包含约1重量％至5重量％的量的短波长光引发剂和约0.5重量％至1重量％的量的长波长光引发剂。
在另一方面，提供一种具有真实材料(例如碳材料)的质感的复制膜，其包括：基层；以及树脂层，其设置在所述基层上，包括与所述基层相邻的第一表面和与所述第一表面相对的第二表面，并且包含根据本发明的可紫外固化的组合物。
树脂层可以优选地包括表面图案，例如具有与碳材料的三维质感相同或相似的图案。
复制膜可以具有与约1mm至10mm的曲率半径和约200％或更大的伸长率相对应的弯曲性。
在另一方面，本发明提供一种制备复制膜的方法。所述方法可以包括：在基层上形成树脂层，所述树脂层包含如本文所述的可紫外固化的树脂组合物；在树脂层的表面上形成表面图案；以及形成包括树脂层和基层的层压体。
如在本文所用的术语“层压体”是指包括两个或更多个层的物质，并且这些层可以彼此相同或不同。优选地，层压体至少包括基层和树脂层。
树脂层可以适当地具有约100至250μm的厚度。
可以通过在约130至150℃的温度下施加真空来形成层压体。
复制膜可以具有与约1mm至10mm的曲率半径和约200％或更大的伸长率相对应的弯曲性。
还提供一种车辆部件，其包括本文所述的复制膜。
下面讨论本发明的其它方面。
附图说明
现在将参考示于附图中的某些示例性实施方案来详细描述本发明的上述特征和其它特征，所述附图在下文中仅以举例说明的方式给出，因此对本发明是非限制性的，其中：
图1所示的横截面图示意性地示出根据本发明示例性实施方案的真实材料的示例性复制膜；
图2所示的流程图示出根据本发明示例性实施方案的制备具有真实材料的质感的示例性复制膜的示例性方法；以及
图3A示出根据本发明示例性实施方案的实施例中可紫外固化的树脂组合物的真空成型性的评价结果，并且图3B至图3E分别示出比较例1至4中可紫外固化的树脂组合物的真空成型性的评价结果。
具体实施方式
将参考附图通过以下优选实施方案来清楚地理解上述目的以及其它目的、特征和优点。然而，本发明并不限于这些实施方案，而是可以以不同的形式实施。推荐这些实施方案仅用以提供对所公开的上下文的完整和充分的理解，并且将本发明的技术构思充分地传达给本领域技术人员。
在整个说明书中，同样的附图标记指代同样的元件。在附图中，结构的尺寸可以为清楚起见而放大。将理解的是，虽然在本文会使用术语“第一”、“第二”等描述各个元件，但是这些元件不应该解释为由这些术语来限制，这些术语仅用于将一个元件与另一个元件区分。例如，在本发明限定的范围内，“第一”元件可以被称为“第二”元件，并且类似地，“第二”元件可以被称为“第一”元件。单数形式旨在也包括复数形式，除非上下文另有明确说明。
将进一步理解的是，当在本说明书中使用时，术语“包含/包括”或“具有”指明存在所述的特征、数值、步骤、操作、元件、组分或它们的组合，但是不排除存在或加入一种或多种其它的特征、数值、步骤、操作、元件、组分或它们的组合。此外，将理解的是，当诸如层、膜、区域或基底的元件被称为在另一元件“上面”时，它可以是直接在另一元件上面，或者也可以存在介入中间的元件。还将理解的是，当诸如层、膜、区域或基底的元件被称为在另一元件“下面”时，它可以是直接在另一元件下面，或者也可以存在介入中间的元件。
除非上下文另有明确说明，否则在本说明书中使用的表示组分、反应条件、聚合物组合物和混合物的量的所有数字、数值和/或表述均为这样的近似值，即其反映了除其它方面外在获得这些数值时固有地存在的各种测量不确定性。出于该原因，在所有情况中，术语“约”应理解为修饰所有此类数字、数值和/或表述。除非特别声明或者从上下文显而易见，否则如在本文所用的术语“约”理解为在本领域的正常公差范围内，例如在平均值的两个标准差内。“约”可理解为在所述值的10％、9％、8％、7％、6％、5％、4％、3％、2％、1％、0.5％、0.1％、0.05％或0.01％内。除非上下文另外明确表明，否则在本文提供的所有数值均用术语“约”修饰。
此外，当在本说明书中公开数值范围时，除非另外定义，否则这些范围是连续的并且包括从最小值到最大值的所有数字，包括所述范围内的最大值。而且，当范围是指整数时，除非另外定义，否则它包括从最小值到最大值的所有整数，包括所述范围内的最大值。
在下文将详细地描述根据本发明的真实材料的复制膜。
图1所示的横截面图示意性地示出根据本发明示例性实施方案的示例性真实材料的示例性复制膜1。如在图1中所示，复制膜1可以包括：基层10；树脂层20，其设置在基层10上并且包括与基层10相邻的第一表面21和与第一表面21相对的第二表面22；以及印刷层30，其设置在树脂层20上。
任何材料都可以用作真实材料，没有特别限制，只要其具有独特的表面质感即可。例如，真实材料可以选自真实的碳、真实木材、天然软木、真实石材、薄膜金属、韩国传统纸及其组合。优选地，真实材料可以是真实的碳材料。根据本发明，可以获得这样一种复制膜，即其中与真实材料的表面图案相同的表面图案暴露于外部。
基层10可以包含透明材料。例如，用于基层10的材料可以选自聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚对苯二甲酸乙二醇酯(PET)及其组合，但不限于此。
基层10可以具有约0.3mm至0.5mm的厚度。当厚度小于约0.3mm时，不能实现复制膜1的深度连续性，而当厚度大于约0.5mm时，成形性(成型性)会变差。
树脂层20可以包括第二表面22，所述第二表面22具有与真实材料的表面图案相同的表面图案。尽管在图1中将第二表面22的表面图案显示为不规则结构，但是表面图案并不限于此，而应被解释为根据需要与所选择的真实材料的表面图案相同。
第二表面22的表面图案可以包括多个凹陷部22a和多个凸出部22b。每个凹陷部22a可以嵌入至距第二表面22约100μm至250μm的深度。用于测量凹陷部22a的深度的基准可以是第二表面22的凸出部22b的平坦表面。当厚度小于约100μm时，三维效果会不尽人意，而当厚度大于约250μm时，成形性(成型性)会变差并且来自印刷层30的隐蔽性会变差。
在第二表面22的表面图案中，凹陷部22a和凸出部22b可以重复地彼此交叉。然而，相对应的凹陷部和凸出部之间的间隔可以是规则的或不规则的。此外，凹陷部22a可以相对于凸出部22b成直角或大致成直角地嵌入(如在图1中所示)，或者凹陷部22a可以以预定角度倾斜地嵌入。
树脂层20可以包含可紫外固化的树脂组合物，以便使用具有特定组成和含量的可紫外固化的树脂组合物来改进树脂层20的断裂负荷和伸长率。因此，复制膜1可以形成为具有约1mm或更大的曲率半径或者约1mm至10mm的弯曲性，以及约200％或更大的伸长率。优选地，可以获得这样一种复制膜1，即其也可以施用于具有复杂形状的车辆部件。
印刷层30可以是设置在树脂层20上以将整体颜色赋予复制膜1并保护树脂层20的组成部分。
可以通过在树脂层20上以预定的频率印刷选自含氨基甲酸酯的油墨、含聚氯乙烯的油墨及其组合的油墨来形成印刷层30，但不限于此。
油墨可以是一种液体类型或两种液体类型的油墨。例如，对于两种液体类型的油墨，固化剂可以是含异氰酸酯的固化剂，例如HDI、MDI、TDI或IPDI，并且其含量可以为以油墨组合物的总重量计的约10重量％至20重量％的量。当固化剂的含量小于约10重量％时，印刷层30的物理性能会变差并且油墨会洗掉，而当含量大于约20重量％时，印刷适性会变差。
在形成印刷层30时，频率没有特别限制，但优选为4或更大。当以小于约4的频率进行印刷时，在将复制膜1施用于车辆部件时油墨会洗掉。
在下文将详细地描述根据本发明的可紫外固化的树脂组合物。
可紫外固化的树脂组合物可以包含预聚物(A)、丙烯酸酯单体(B)和光引发剂(C)，所述预聚物(A)包含含氨基甲酸酯的低聚物。
所述预聚物可以包含具有相对较低分子量的聚合物，获得的所述聚合物具有中等聚合度，从而在制造最终模制品时易于成型。预聚物可以在未经任何处理的情况下或在与另一种可聚合的化合物反应之后成型，并且可以通过例如用异氰酸酯化合物、多元醇等反应来制得。
含氨基甲酸酯的低聚物可以包含丙烯酸酯端基。例如，含氨基甲酸酯的低聚物可以包含具有两个或更多个官能团的脂族氨基甲酸酯丙烯酸酯。
含氨基甲酸酯的低聚物可以是用于改进耐变黄性、对基底的粘合性和伸长率的组分。含氨基甲酸酯的低聚物可以通过使异氰酸酯和多元醇的聚合物与反应性单体反应来获得。
异氰酸酯可以适当地包含选自甲苯二异氰酸酯(TDI)、萘-1,5-二异氰酸酯、对苯二异氰酸酯、联甲苯胺二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、4,4'-亚甲基二环己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或多种。
多元醇没有特别限制，例如可以包含选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇和丙烯酰基多元醇中的一种或多种，且多元醇可以包含聚酯多元醇。
反应性单体可以包含可交联的单体，并且由光引发剂产生的自由基引起反应性单体中的双键的交联聚合，从而进行固化。反应性单体可以包含选自丙烯酸2-羟乙酯、丙烯酸4-羟丁酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯和季戊四醇三丙烯酸酯中的一种或多种。
含氨基甲酸酯的低聚物可以具有约2000g/mol至5000g/mol或者约3000g/mol至4000g/mol的重均分子量。
含氨基甲酸酯的低聚物例如是通过使聚酯多元醇和4,4'-亚甲基二环己基二异氰酸酯(其作为异氰酸酯)的聚合物与丙烯酸2-羟乙酯(其作为反应性单体)反应而获得或可获得的，并且具有约3000g/mol的重均分子量。
预聚物的含量可以为约20至50重量％。当预聚物的含量小于约20重量％时，树脂层的伸长率和对基底的粘合性会变差，而当含量大于约50重量％时，固化性会不足，脱模性会变差，并且由于其粘度增加而会使涂布性能变差。
丙烯酸酯单体(B)可以改进树脂层的物理性能，并且通过利用光引发剂产生的自由基在丙烯酸酯单体中的双键之间进行交联聚合而引起固化。
丙烯酸酯单体(B)可以包含选自丙烯酸异冰片酯、丙烯酸2-羟丙酯和羟基新戊酸新戊二醇二丙烯酸酯中的一种或多种。
优选地，丙烯酸酯单体(B)可以包含适当量的丙烯酸异冰片酯、丙烯酸2-羟丙酯和羟基新戊酸新戊二醇二丙烯酸酯。
优选地，以100重量％的可紫外固化的树脂组合物计，丙烯酸酯单体(B)可以包含约15至30重量％的量的丙烯酸异冰片酯、约15至30重量％的量的丙烯酸2-羟丙酯和约1至10重量％的量的羟基新戊酸新戊二醇二丙烯酸酯。
当丙烯酸异冰片酯的含量小于约15重量％时，与基底的粘合性会变差并且耐化学性会不足。另一方面，当该含量大于约30重量％时，固化性会变差并且未反应的残留物会继续存在。
当丙烯酸2-羟丙酯的含量小于约15重量％时，由于差的弯曲性(挠性)而无法保持图案，并且由于例如剥离而会使外观变差。
当羟基新戊酸新戊二醇二丙烯酸酯的含量大于约10重量％时，伸长率会变差。
光引发剂(C)可以吸收紫外光，因此被光降解以产生自由基。自由基可以使预聚物、丙烯酸酯单体等的双键交联聚合，从而引起固化。
光引发剂(C)可以包含选自短波长光引发剂和长波长光引发剂中的一种或多种，并且优选短波长光引发剂和长波长光引发剂的组合。
短波长光引发剂可以包含1-羟基环己基苯基酮等。
以可紫外固化的树脂组合物的总重量计，短波长光引发剂的含量可以为约1重量％至5重量％的量。当含量小于约1重量％时，表面无法固化，而当含量大于约5重量％时，会发生过度的固化。
长波长光引发剂可以包含二苯基(2,4,6-三甲基苯甲酰基)氧化膦(TPO)等。
以可紫外固化的树脂组合物的总重量计，长波长光引发剂的含量可以为约0.5重量％至1重量％的量。当含量小于约0.5重量％时，固化会不足，而当含量大于约1重量％时，变黄的可能性很大。
可紫外固化的树脂组合物可以进一步包含选自紫外稳定剂、热稳定剂、分散剂、消光剂、消泡剂及其组合的添加剂。
在下文中，将详细描述使用可紫外固化的树脂组合物来制备真实材料的复制膜的方法。
图2所示的流程图示意性地示出根据本发明示例性实施方案的制备示例性复制膜的示例性方法。如在图2中所示，制备真实材料的复制膜的方法可以包括：在基层上形成树脂层(S10)，所述树脂层包含可紫外固化的树脂组合物；在树脂层的第二表面上形成表面图案(S20)；以及形成包括树脂层的层压体(S30)。
形成表面图案的方法没有特别限制，可以通过例如压印等来形成。
该方法可以在形成表面图案之后进一步向树脂层发射紫外光。
真空成型是一种通过以下方式来形成膜的方法：使用用以实现所需形状的模具或框架来压制经热软化的膜，并且真空抽取在膜与模具或框架之间的空气。真空成型的方法没有特别限制，可以使用适当的装置进行。
通过施加真空来形成层压体可以通过以下方式来进行：通过将层压体的表面温度加热至约130至150℃的温度来真空模制层压体。
当真空成型的条件与上述条件相同并且使用上述可紫外固化的树脂组合物时，可以防止树脂层起皱或弯曲部分破裂。特别地，层压体可以确保约0.5mm或更大的曲率半径或者约0.5mm至10mm的弯曲性，以及约200％或更大的伸长率。
实施例
在下文，将参考具体实施例来更详细地描述本发明。然而，提供的以下实施例仅用于说明本发明，不应解释为限制本发明的范围。
实施例、比较例1至4
根据下表1中所示的组成和含量来制备可紫外固化的树脂组合物，并对其进行紫外压印以形成树脂层。以供参考，表1中的值以重量％表示。
表1
1)使用通过使4,4'-亚甲基二环己基二异氰酸酯和聚酯多元醇的聚合物与丙烯酸2-羟乙酯反应而获得的产物。其重均分子量为约3000g/mol。
2)使用通过使(2,4,6-三氧代三嗪-1,3,5-三基)三(六亚甲基)异氰酸酯((2,4,6-trioxotriazine-1,3,5-triyl)tris(hexamethylene)isocyanate)和聚酯多元醇的聚合物与季戊四醇三丙烯酸酯反应而获得的产物。其重均分子量为约2000g/mol。
3)使用重均分子量为约50000g/mol的丙烯酸丙烯酸酯。
4)1-羟基环己基苯基酮
5)二苯基(2,4,6-三甲基苯甲酰基)氧化膦
6)1010
7)292。
测量根据实施例和比较例1至4的树脂层的真空成型性、伸长率、断裂负荷、脱模性和粘度。
通过以下方式来评价真空成型性：在施加有压印树脂的基层(PC/PMMA)上形成树脂层，在320℃的加热器温度和80mm的距离下加热树脂层约30秒，然后对此施加真空之后，目视观察是否产生了具有所需形状(外曲率半径为2.5mm，内曲率半径为1mm，并且在深度方向上的伸长率为约210％)的复制膜。
根据ASTM D 882测量伸长率和断裂负荷，具体地，在130℃的温度下以200mm/min的速率评价尺寸为15mm×125mm的样品的伸长率和断裂。
使用粘度计在60RPM和25℃温度的条件下持续30秒来测量粘度，并且300cps或更小的粘度被认为是优良的(O)。
使用剥离强度测试仪以900mm/min的剥离强度和150mm的测量截面在尺寸为25.4mm×200mm的样品上测量脱模性，并且用肉眼观察不到残留物的情况被标记为优良的(O)。
实施例和比较例1至4的真空成型性的评价结果示于图3A至图3E中，并且伸长率、断裂负荷、脱模性和粘度的测量结果示于下表2中。
表2
项目 比较例1 比较例2 比较例3 比较例4 实施例
伸长率[％] 72 69 99 103 200或更大
断裂负荷[kgf] 0.158 0.156 0.154 0.193 0.036
脱模性[gf] 175 177 188 149 300或更大
粘度[cps] 161 206 233 250 389
图3A示出根据本发明实施例的复制膜的真空成型性的评价结果。如在图3A中所示，在曲率半径为2.5mm(外径)和1mm(内径)的弯曲部分中，图案得到恰当地维护而未被压碎或损坏。在另一方面，如在图3B、图3C、图3D和图3E中所示，它们示出了比较例1、比较例2、比较例3和比较例4的结果，在弯曲部分中的图案变形并且破裂。
此外，如在表2中所示，上述实施例的树脂层由于200％或更大的高伸长率和高粘度而具有优良的成型性，而比较例1至4具有低的伸长率和粘度。
根据本发明的各种示例性实施方案，复制膜可以基本上或精确地复制真实材料，从而实现其独特的特征。进一步提供这样一种复制膜，即由于其优良的成型性，其可用于具有复杂形状而不是平坦表面的车辆部件。
还提供这样一种复制膜，即其可以以真实材料的约1/10的成本制得，同时具有相同的外观水平，从而传递出优良的价格竞争力。
本发明的效果不限于以上提及的那些效果。应当理解，本发明的效果包括可以从本发明的描述中推断出的所有效果。
已经参考示例性实施方案详细描述本发明。然而，本领域技术人员将理解可以在这些实施方案中做出改变而不偏离本发明的原理和精神，本发明的范围在所附权利要求及其等效形式中限定。

Claims (12)

1.一种可紫外固化的树脂组合物，其包含：
预聚物，其包含含氨基甲酸酯的低聚物；
丙烯酸酯单体；以及
光引发剂；
其中，所述光引发剂包含短波长光引发剂和长波长光引发剂，所述短波长光引发剂包含1-羟基环己基苯基酮，所述长波长光引发剂包含二苯基(2,4,6-三甲基苯甲酰基)氧化膦，
其中，所述预聚物以20至50重量％的量存在，
所述丙烯酸酯单体包含15至30重量％的量的丙烯酸异冰片酯、15至30重量％的量的丙烯酸2-羟丙酯和1至10重量％的量的羟基新戊酸新戊二醇二丙烯酸酯，以及
所述光引发剂包含1重量％至5重量％的量的短波长光引发剂和0.5重量％至1重量％的量的长波长光引发剂，
其中，在每一种情况中重量百分比，即重量％，均是以可紫外固化的树脂组合物的总重量计的。
2.根据权利要求1所述的可紫外固化的树脂组合物，其中，所述含氨基甲酸酯的低聚物是通过或能够通过使异氰酸酯、多元醇和反应性单体反应来获得，
所述异氰酸酯包含选自甲苯二异氰酸酯、萘-1,5-二异氰酸酯、对苯二异氰酸酯、联甲苯胺二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、4,4'-亚甲基二环己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种或多种，
所述多元醇包含选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇和丙烯酰基多元醇中的一种或多种。
3.根据权利要求2所述的可紫外固化的树脂组合物，其中，所述反应性单体包含选自丙烯酸2-羟乙酯、丙烯酸4-羟丁酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯和季戊四醇三丙烯酸酯中的一种或多种。
4.根据权利要求1所述的可紫外固化的树脂组合物，其中，所述含氨基甲酸酯的低聚物具有2000g/mol至5000g/mol的重均分子量。
5.根据权利要求1所述的可紫外固化的树脂组合物，其中，所述丙烯酸酯单体包含选自丙烯酸异冰片酯、丙烯酸2-羟丙酯和羟基新戊酸新戊二醇二丙烯酸酯中的一种或多种。
6.根据权利要求1所述的可紫外固化的树脂组合物，其中，所述丙烯酸酯单体包含丙烯酸异冰片酯、丙烯酸2-羟丙酯和羟基新戊酸新戊二醇二丙烯酸酯。
7.根据权利要求1所述的可紫外固化的树脂组合物，其进一步包含选自紫外稳定剂、耐热稳定剂及其组合的添加剂。
8.根据权利要求1所述的可紫外固化的树脂组合物用于真实材料的复制膜的用途。
9.一种制备真实材料的复制膜的方法，其包括：
在基层上形成树脂层，所述树脂层包含根据权利要求1所述的可紫外固化的树脂组合物；
在树脂层的表面上形成表面图案；以及
形成具有树脂层的层压体。
10.根据权利要求9所述的方法，其中，所述树脂层具有100至250μm的厚度。
11.根据权利要求9所述的方法，其中，通过在130至150℃的温度下施加真空来形成所述层压体。
12.根据权利要求9所述的方法，其中，所述复制膜具有与1mm至10mm的曲率半径和200％或更大的伸长率相对应的弯曲性。
CN202011389721.8A 2020-06-10 2020-12-01 用于真空成型的可紫外固化的树脂组合物和包含其的真实材料的复制膜 Active CN113773446B (zh)

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