CN102939330A - 激光诱导的聚合物发泡 - Google Patents
激光诱导的聚合物发泡 Download PDFInfo
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- CN102939330A CN102939330A CN2011800151491A CN201180015149A CN102939330A CN 102939330 A CN102939330 A CN 102939330A CN 2011800151491 A CN2011800151491 A CN 2011800151491A CN 201180015149 A CN201180015149 A CN 201180015149A CN 102939330 A CN102939330 A CN 102939330A
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- oxide
- phosphate
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Abstract
由聚合物，优选为热塑性聚合物或者涂覆材料组成的基质材料，所述基质材料含有0.01至50重量%的添加剂，用于使得所述基质材料发泡，通过用激光或者IR光照射引发该发泡，其中所述添加剂至少包含以下组分：a)至少一种吸收剂材料，该吸收剂材料嵌入或者溶解在基质材料中，吸收激光或者IR光并导致基质材料中激光或IR光照射位点的局部加热，以及b)至少一种发泡剂，当由于激光或者IR光的照射导致被加热到超过50°C的温度时，所述发泡剂通过分解、化学转化或反应形成使得基质材料发泡的气体。
Description
技术领域
本发明涉及由塑料，优选地由热塑性聚合物或者涂料、清漆或者天然漆制备的基质材料，该基质材料含有添加剂，使得可以通过激光照射或者IR光照射来引发所述基质材料的发泡。此外，本发明涉及所述添加剂的组成及其应用。
背景技术
已知通过物理方法或者化学方法使得塑料部件发泡。将发泡剂与塑料混合或者溶解在塑料中，以保证在塑料中产生或者释放气体。然而，就以定点的、受控制的并且局部受限制的方式引发发泡的可能性而言，所述方法受到了限制。目前为止，还不能通过发泡产生不连续的图案化表面结构。
塑料部件的发泡可以起各种作用，例如，降低部件的重量，制备绝热部件，制备海绵以及其他吸收泡沫，制备漂浮物或者创作艺术元素、装饰物或图案。
现在对各种发泡方法加以区分：
1.物理方法，将气体物理引入到熔融的塑性物料中，并发生膨胀。形成的气泡导致了塑料的发泡。该方法的一个缺点是设备以及控制工程的昂贵费用。需要以昂贵的花费通过气体供给装置将塑料加工机器，例如，挤出机改造成用于发泡。结合塑料熔融特性对气体供给和控制的调整表现出进一步的问题。
2.在所谓的溶出方法中，通过合适的溶剂使得塑料组分从固体塑料材料中释放出来。这产生室和腔，导致所希望的重量降低。然而，正是由于环保的原因，该方法是可质疑并且有问题的，因为所使用的溶剂中含有塑料组分，造成了处置或者再加工的显著问题。
3.在过去，在化学发泡方法中主要使用含CFC的产品作为发泡剂。然而出于环境相容性的原因，应避免使用这些发泡剂并用其他发泡剂取代。越来越多地使用偶氮化合物、N-亚硝基化合物、磺酰肼、尿素衍生物、胍衍生物、硼氢化物/水体系、碳酸盐以及碳酸氢盐。偶氮化合物的一个缺点是在降解和泡沫形成时产生了大量的氨，这引起了可能的健康风险的问题。当达到分解温度时，许多碳酸盐和碳酸氢盐无需其他添加剂即以不受控制的方式发生分解。这导致了不受控制的发泡，并且可能导致不合乎希望的变色和/或气味。
4.以泡沫橡胶等著称的聚氨酯（PUR）非常容易产生泡沫，并用作清洁海绵、床垫材料或者垫子，还用于大楼、冰箱、储热单元和蓄冷单元以及绝热管道系统的绝热。一段时间以来，还发展起了聚氨酯泡沫在其他领域的应用，例如用于车辆构建中。为绝热而提供的聚氨酯泡沫具有闭孔结构，从而在泡沫孔中保留了具有低导热性的孔气体。过去，三氯氟甲烷常用作孔气体。然而，由于该卤代烃的臭氧消耗特性，其首先被二氧化碳取代，然后被环戊烷取代，作为结果，如今的泡沫孔通常含有约10至30%的环戊烷以及余量的二氧化碳的混合物。
大多数的发泡剂和发泡系统自身或者它们的反应产物通常对环境或者健康有害，和/或在加工或者处理过程中引起问题。所述处理问题可以是，例如不可控制地快速形成气体，形成气体时放热，或者过于缓慢地形成气体，这会导致在塑料部件中完全没有正确地形成泡沫，或者例如由于形成了不均匀的孔或者不合乎希望的孔径（太大或太小）等导致泡沫结构不符合所希望的要求。
在已知系统中，通常在整个塑料材料中进行发泡。对于制作图案、文字或者其他设计元素，希望能够以定点的、受控制的并且局部受限制的方式引发发泡。
在塑料加工或者操作领域中，已知通过激光或者其他辐射源的方法来使用NIR/IR辐射（热辐射）。该辐射用于塑料焊接并用于对塑料做标志和贴标签。NIR/IR辐射源还用于塑料材料的目标加热，例如用于PET瓶制备工艺（称作PET制瓶）或者用于制备杯子的拉膜或者所谓的深拉工艺中。使用NIR/IR辐射来产热是非常有效率的，因为可以以高度定点的方式施加热能，且比例如传统对流烘箱的热损失小。从而可以实现较短的加工时间和定点更好的能源利用。在改变要加热的工件的材料厚度的情况下，NIR/IR辐射源提供了明显更好的加热可能性，因为可以更好且更快地对其输出进行调整。
发明目的
本发明的目的是提供由塑料或涂料、清漆或天然漆制备的可发泡基质材料，相比于现有系统，可以对该可发泡基质材料中的发泡和气体形成进行更好的控制，且可以以定点的、受控制的并且局部受限制的方式引发发泡，从而例如产生离散图案化表面结构、装饰件或者书写件。
发明描述
通过由塑料，优选地由热塑性聚合物或者涂料、清漆或者天然漆制备的基质材料来实现本发明的目的，所述基质材料含有0.01至50重量%的添加剂，用于基质材料的发泡，可以通过用激光或者IR光进行照射来引发所述发泡，其中所述添加剂至少包含以下组分：
a)至少一种吸收剂材料，该吸收剂材料嵌入或者溶解在基质材料中，吸收激光或者IR光并导致基质材料中激光或IR光照射位点的局部加热，以及
b)至少一种发泡剂，当由于激光或者IR光的照射导致被加热到超过50°C的温度时，所述发泡剂通过分解、化学转化或反应产生使得基质材料发泡的气体。
本发明的一个重要方面是吸收剂材料与发泡剂的结合，所述吸收剂材料吸收激光或者IR光，从而使得能量局部集中并因此导致基质材料在照射位点的局部加热，当由于激光或者IR光的照射被加热时，所述发泡剂产生使得基质材料发泡的气体。除了发泡剂引起发泡之外，激光或者IR光照射位点的基质材料的局部加热还具有使得热塑性基质材料软化的额外作用，从而才允许材料发泡。根据基质材料的稳定性和产生气体的强度，如果发泡剂开始在固体基质材料中产生气体，气体要么不会发生膨胀并仍被截留在基质材料中，要么通过气体膨胀使得固体基质材料破裂并被部分破坏。然而，通过在照射位点加热发生的基质材料的局部软化允许所希望的定点形成泡沫。
基本上所有的可以被引入到基质材料中并在加热时产生发泡气体的物质和物质组合物都是本发明的添加剂中合适的发泡剂。这些物质可以是在加热时直接分解或者发生反应，并伴随气体产生的物质。然而，这些物质还可以是通过引发而不是单独的加热开始产生气体的物质，例如通过与另一种物质反应开始产生气体，其中通过单独的加热或者通过使得pH变得接近气体产生物质，导致所述另一种物质与实际的气体产生物质发生反应，其中所述pH的变化可以通过加热引发。从发泡剂产生气体的反应机制并不限于这些实施例。
在本发明的一个实施方式中，发泡剂选自：
i)二氧化碳载体，该二氧化碳载体在分解和/或与至少一种其他物质发生反应时产生CO2气体，所述二氧化碳载体选自：
碱金属、碱土金属、铝、过渡金属和/或铵的碳酸盐、碳酸氢盐、氨基甲酸盐，优选地选自：碳酸钠、碳酸氢钠、碳酸镁、碳酸氢镁、碳酸钙、碳酸氢钙、碳酸铝、碳酸氢铝、碳酸铁、碳酸氢铁、碳酸铵、碳酸氢铵、氨基甲酸铵及其混合物；
ii)与酸载体结合的二氧化碳载体，该二氧化碳载体在分解和/或反应时产生CO2气体，其中所述二氧化碳载体选自i)中的化合物而所述酸载体选自：
含磷氧代阴离子的盐，优选为磷酸盐、缩合磷酸盐、膦酸盐、亚磷酸盐、混合的碱式磷酸盐以及氰尿酸盐；
特别优选地选自：酸式焦磷酸钠（SAPP）、一水合磷酸一钙（MCPM）、二水合磷酸二钙（DCPD）、硫酸铝钠（SAS）、磷酸铝钠（SALP）、磷酸铝镁钙、聚磷酸钙、聚磷酸镁及其混合物；
iii)在分解时至少产生N2气体的化合物，所述化合物优选选自：
偶氮化合物、酰肼、氨基脲、三唑、四唑、N-亚硝基化合物以及苯并噁嗪；
iv)在分解和/或与至少一种其他物质发生反应时产生二氧化碳和水的化合物，所述化合物优选选自：
有机羧酸及其盐，优选为柠檬酸、柠檬酸盐、富马酸以及富马酸盐；
以及
v)上述物质的组合与混合物。
基本上所有可以被引入到基质材料中并吸收激光或者IR光，使得激光或IR光的能量局部集中并在该过程中引起辐射位点加热的物质和物质组合物都是本发明的添加剂中合适的吸收剂材料。应理解，必须对吸收剂材料或者吸收剂材料的组合以及基质材料进行选择，使其对特定波长的激光或IR光和/或能量具有比单独的基质材料更高的吸收。
在本发明的一个实施方式中，吸收剂材料选自：
i)金属的磷酸盐、缩合磷酸盐、膦酸盐、亚磷酸盐以及混合的碱式磷酸盐氧代阴离子，所述金属选自第三至第六周期的第II和III主族元素，第五至第六周期的第IV主族元素，第四至第五周期的第III至VIII副族元素，以及元素周期表中的镧系元素，优选选自Cu、Sn、Ca、Mo、Fe、Co、Sn；
更优选地选自磷酸铜、磷酸锡、磷酸铁、磷酸镍、磷酸钼、磷酸钴、磷酸锰以及磷酸锑；
特别优选地选自磷酸铜、磷酸锡以及磷酸铁；
更特别优选地选自碱式磷酸铜[CHP;Cu4(OH)2(PO4)2]；
ii)金属氧化物和混合的金属氧化物；
优选选自：氧化锑（Sb2O3）、氧化锡（SnO4）、氧化钛（TiO2）、氧化锡铟（In2O3/SnO2；ITO）、氧化锡锑（ATO）；
iii)金属，优选为Al、Cr、Fe、Au或者Ag的片状颜料，该片状颜料是未涂覆的或者涂覆有一层或多层金属氧化物层，其中所述金属氧化物优选选自：二氧化钛、氧化锑（III）、氧化锌、氧化锡、二氧化锆、氧化铬、氧化镍、氧化铜、氧化钴、铁的氧化物（Fe2O3、Fe3O4），特别优选地选自单独的氧化锑（III）或者与氧化锡结合的氧化锑（III）；
iv)有机吸收剂，优选为有机NIR吸收剂，特别优选为酞菁和萘酞菁，具体为铜(II)-1,4,8,11,15,18,22,25-八丁氧基-29H,31H-酞菁或者氧钒基-2,9,16,23-四苯氧基-29H,31H-酞菁或者氧钒基-5,14,23,32-四苯基-2,3-萘酞菁或者氧钒基-2,11,20,29-四叔丁基-2,3-萘酞菁、路玛近荧光染料（lumogen）以及夸特锐烯（quaterrylene）染料。
根据本发明的另一个实施方式，对吸收剂材料进行选择，使得其吸收100至400nm的紫外（UV）波长范围的激光（例如准分子激光），或者波长范围为9000至11000nm的激光（例如CO2激光），或者吸收波长范围为700至2000nm，优选为950至1500nm的激光或者IR光。
根据本发明，用塑料或涂料、清漆或天然漆制备的基质材料含有0.01至50重量%的添加剂。在本发明的另一个实施方式中，相对于基质材料的重量计，基质材料含有1.0至30重量%或者3.0至20重量%或者5.0至10重量%的添加剂。
基质材料可以是聚合物材料（塑料）或者涂料、清漆或者天然漆。优选地，所述基质材料是热塑性聚合物。在本发明的另一个实施方式中，基质材料选自：聚乙烯醇缩丁醛（PVB）、聚丙烯（PP）、聚乙烯（PE）、聚酰胺（PA）、聚对苯二甲酸丁二酯（PBT）、聚对苯二甲酸乙二酯（PET）、聚酯、聚苯醚、聚缩醛、聚甲基丙烯酸酯、聚甲醛、聚乙烯醇缩醛、聚苯乙烯、丙烯腈-丁二烯苯乙烯（ABS）、丙烯腈-苯乙烯-丙烯酸酯（ASA）、聚碳酸酯、聚醚砜、聚醚酮、聚氯乙烯、热塑性聚氨酯和/或它们的共聚物和/或它们的混合物。
本发明还包含用于由塑料或涂料、清漆或天然漆制备的基质材料的上述添加剂，即用于使得基质材料发泡的添加剂，其可以通过激光或者IR光的照射来引发，所述添加剂至少包含如下组分：
a)至少一种吸收剂材料，该吸收剂材料嵌入或者溶解在基质材料中，吸收激光或者IR光并导致基质材料中激光或IR光照射位点的局部加热，以及
b)至少一种发泡剂，当由于激光或者IR光的照射导致被加热到超过50°C的温度时，所述发泡剂通过分解、化学转化或反应产生使得基质材料发泡的气体。
此外，本发明还包括本发明的上述类型的添加剂的用途，用于生产由塑料或涂料、清漆或天然漆制备的基质材料，所述基质材料可以通过激光或者IR光在表面形成泡沫结构，优选形成盲文（Braille script），和/或用于生产可以通过激光或者IR光的方法焊接的材料。
塑料的激光焊接是已知的，所述塑料含有用于激光或者IR光的吸收剂材料，然而这些方法的问题是，在焊接的塑料部件之间会形成或者留下裂缝或间隙，没有在塑料部件之间产生接触，从而焊接接合是不完全并且不稳定的。相反地，根据本发明的塑料部件的激光焊接，在焊接接合处熔融，由于发泡导致有益地填充了裂缝和间隙，并保证了全表面焊接接合。
相对于基质材料的重量计，优选将0.01至50重量%或者1.0至30重量%或者3.0至20重量%或者5.0至10重量%的添加剂加入到基质材料中。
在给定塑料材料的情况下，本领域的技术人员可以通过一些测试的方法，确定引入到塑料基质中用于定点发泡的添加剂的最优化组成和量。所述添加剂的组成和量取决于所使用和要发泡的塑料材料，以及视发泡条件所需的发泡结果以及所用的激光等。根据本发明的添加剂适合含有发泡剂和吸收剂，它们的重量比为20:1至1:20，优选为15:1至1:15，特别优选为10:1至1:10，更优选为5:1至1:5或者3:1至1:3。因为吸收剂材料通常是较贵的材料，优选所使用的吸收剂的量小于发泡剂。
优选地，添加剂的选择或者组成使得在低于具体的温度，特别是低于室温下，它不发生反应或者分解并形成气体。仅在升高的温度下发生气体的释放，所述升高的温度是由激光或者IR光的照射引起的。根据本发明的添加剂或者基质组分，优选在80至400°C，更优选为110至350°C，特别优选为140至300°C的温度范围内发生从发泡剂或者发泡剂组合物中的气体释放。
可以通过其他添加剂来影响添加剂中发泡剂的特性和反应性。在本发明的另一个实施方式中，添加剂可以含有例如用于防止或者延迟发泡剂的过早反应的物质，其中所述物质优选选自谷物淀粉、二氧化硅、磷酸三钙、碳酸钙、硫酸钙、硅烷、脂肪或者它们的混合物，所述谷物淀粉是例如玉米淀粉、水稻淀粉、小麦淀粉、改性面粉，所述二氧化硅是例如煅制二氧化硅、疏水性二氧化硅或者亲水性二氧化硅。所述物质的加入不但可以防止或者延迟发泡剂的过早反应，还可以对塑料基质中的反应速度发生影响。
优选可以通过所谓的母料将添加剂引入到塑料基质材料中。术语“母料”指的是以颗粒形式嵌入在塑料基质中的添加剂，其中所述添加剂的浓度高于最终应用时的浓度。它们与塑料（原料聚合物）混合用于着色或者改变特性。相比于以糊料、粉末或者液体的形式加入不同的物质，母料的优势是其保证了高加工可靠性以及非常易于操作。对于母料，通常试图尽可能地浓缩添加剂，即使用尽可能少的塑料基质材料来嵌入添加剂。将添加剂（例如还有颜料）与原料聚合物（未处理的塑料颗粒）混合用于制备母料。然后在挤出机中熔融该混合物并使其成粒。或者，还可以通过不同的称重进料机使得组分直接在挤出机中混合并熔融。由于良好的可控制性，可以对母料进行简单处理。
在母料中制备根据本发明的发泡剂的情况下，必须保证用于母料的聚合物载体材料的熔融温度不高于发泡剂的分解或者反应温度。因此，此处优选使用低熔融聚合物，例如聚乙烯，特别是LDPE或者LLDPE和EVA作为母料。
根据本发明的基质材料特别优选地是热塑性聚合物，例如，聚烯烃，如聚乙烯、聚丙烯、聚丁烯、聚甲基戊烯及其嵌段聚合物、接枝聚合物和共聚物，苯乙烯聚合物，如标准聚苯乙烯、抗冲击聚苯乙烯、苯乙烯-丙烯腈、丙烯腈-丁二烯-苯乙烯、丙烯腈-苯乙烯、丙烯酸类橡胶，含卤素乙烯基聚合物，如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯，四氟甲烷-六氟甲烷共聚物，乙烯-四氟乙烯共聚物，聚氯三氟乙烯，乙烯氯代三氟乙烯共聚物，丙烯酸聚合物，聚丙烯酸酯，聚甲基丙烯酸酯，聚缩醛，例如聚甲醛，线型缩聚物，例如聚酰胺（PA-6、PA-66、PA-610、PA-612、PA-11、PA-12等），聚碳酸酯，聚酯（例如，聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯等），聚酰亚胺，聚芳基酮，聚砜，聚氨酯，聚苯，不饱和醇和胺的聚合物或其酰基衍生物或其缩醛，如聚乙烯醇、聚乙酸乙烯酯、聚乙烯醇缩丁醛、聚苯甲酸乙烯酯，交联化的缩聚物和聚加合物，如酚基塑料、氨基塑料，环氧树脂，不饱和聚酯，聚氨酯，改性的自然存在的物质，如纤维素酯，并包括上述聚合物的共聚物或混合物。
除了塑料或者热塑性聚合物，根据本发明如下所述的任意类型的涂料、清漆或者天然漆也适合作为基质材料。
单组分涂料、清漆（1C清漆）或者天然漆包含水溶液中的分散体形式粘合剂或者溶解于溶剂中的粘合剂。在双组分涂料、清漆（2C清漆）或者天然漆的情况下，粘合剂由树脂和硬化剂组成。它们分开储存并在临加工前混合在一起。它们发生化学反应并固化（无需干燥）。许多2C涂料、清漆或者天然漆不含溶剂。粘合剂包含天然树脂和油（油漆）、植物组分（中国清漆、日本清漆）、蛋（蛋黄颜料）、阿拉伯胶（水彩）、石灰（石灰水）、胶（水胶涂料）、焦油或者沥青。
如果粘合剂不以液体形式存在，则需要可以溶解所述粘合剂的溶剂作为额外的组分。物理干燥的清漆中的溶剂通常是无色的，不得对粘合剂具有负面影响且蒸发后无残留。清漆的大多数溶剂是有机溶剂。然而，还使用了不含溶剂的体系，例如粉末涂料或者清漆颗粒在水中悬浮体。在施涂了清漆并干燥之后，成膜剂形成具有良好的化学与机械特性的粘着层（膜）。在干燥过程中，清漆固化，成膜剂变为高分子量化合物。低分子量成膜剂是例如硝化纤维素、氯乙烯-乙酸乙烯酯共聚物，高分子量成膜剂是例如不饱和聚酯树脂、环氧树脂。
根据本发明适合的涂料、清漆或者天然漆包括：油性涂料、清漆或者天然漆，硝酸纤维素涂料、清漆或者天然漆，醇酸树脂涂料、清漆或者天然漆，聚乙烯酯涂料、清漆或者天然漆，例如聚乙酸乙烯酯分散体，丙烯酸树脂类涂料、清漆或者天然漆，例如聚丙烯酸酯涂料、清漆或者天然漆以及聚甲基丙烯酸酯涂料、清漆或者天然漆，硅树脂涂料、清漆或者天然漆，环氧树脂涂料、清漆或者天然漆，以及聚氨酯涂料、清漆或者天然漆。
实施例
下面，通过实施例的方式对本发明进行更具体的说明。
实施例1
用2重量%的二磷酸二氢二钠与等摩尔部分的碳酸氢钠的混合物与1重量%的碱式硫酸铜挤出低密度的聚乙烯（LDPE）。使用购自科倍隆公司（Coperion）的ZSK 18挤出机。通过NdYAG激光束源（1064nm）的方法对所得的聚合物标记一系列字母。表面的发泡形成了可触觉到的字迹，距离表面高度为0.5mm。
实施例2
将200g的聚酰胺6（PA6）熔于布拉本德混合器中，加入2重量%（4g）的发泡剂混合物并再混合30秒，所述发泡剂混合物由单磷酸二氢一钙与等摩尔量的碳酸钙组成。然后加入基于云母的2重量%的NIR吸收剂。然后停止混合器并取出塑料。用NdYAG激光束源（1064nm）以形成文字图案的形式照射得到的聚合物材料。在该过程中得到了距离表面高度为0.5mm的可触觉到的字迹。
实施例3
用IR灯将预成形件加热到聚合物的熔点，所述预成形件由聚丙烯（PP）和0.5重量%的基于柠檬酸钠和碳酸钙的发泡剂以及另外0.1重量%的基于金属磷酸盐的吸收剂制得。在该过程中，引发发泡过程。形成发泡的表面，该发泡的表面相比于未发泡的材料具有明显改善的绝热特性。
Claims (13)
1.基质材料，该基质材料由塑料，优选地由热塑性聚合物或者涂料、清漆或者天然漆制备，其特征在于，该基质材料含有0.01至50重量%的添加剂，用于基质材料的发泡，可以通过用激光或者IR光进行照射来引发所述发泡，其中所述添加剂至少包含以下组分：
a)至少一种吸收剂材料，该吸收剂材料嵌入或者溶解在基质材料中，吸收激光或者IR光并导致基质材料中激光或IR光照射位点的局部加热，以及
b)至少一种发泡剂，当由于激光或者IR光的照射导致被加热到超过50°C的温度时，所述发泡剂通过分解、化学转化或反应产生使得基质材料发泡的气体。
2.如权利要求1所述的基质材料，其特征在于，所述发泡剂选自：
i)二氧化碳载体，该二氧化碳载体在分解和/或与至少一种其他物质发生反应时产生CO2气体，所述二氧化碳载体选自：
碱金属、碱土金属、铝、过渡金属和/或铵的碳酸盐、碳酸氢盐以及氨基甲酸盐；
优选选自：碳酸钠、碳酸氢钠、碳酸镁、碳酸氢镁、碳酸钙、碳酸氢钙、碳酸铝、碳酸氢铝、碳酸铁、碳酸氢铁、碳酸铵、碳酸氢铵、氨基甲酸铵及其混合物；
ii)与酸载体结合的二氧化碳载体，该二氧化碳载体在分解和/或反应时产生CO2气体，其中所述二氧化碳载体选自i)中的化合物而所述酸载体选自：
含磷氧代阴离子的盐，优选为磷酸盐、缩合磷酸盐、膦酸盐、亚磷酸盐、混合的碱式磷酸盐以及氰尿酸盐；
特别优选地选自：酸式焦磷酸钠（SAPP）、一水合磷酸一钙（MCPM）、二水合磷酸二钙（DCPD）、硫酸铝钠（SAS）、磷酸铝钠（SALP）、磷酸铝镁钙、聚磷酸钙、聚磷酸镁及其混合物；
iii)在分解时至少产生N2气体的化合物，所述化合物优选选自：
偶氮化合物、酰肼、氨基脲、三唑、四唑、N-亚硝基化合物以及苯并噁嗪；
iv)在分解和/或与至少一种其他物质发生反应时产生二氧化碳和水的化合物，所述化合物优选选自：
有机羧酸及其盐，优选为柠檬酸、柠檬酸盐、富马酸以及富马酸盐；
以及
v)上述物质的组合与混合物。
3.如前述任一项权利要求所述的基质材料，其特征在于，所述吸收剂材料选自：
i)金属的磷酸盐、缩合磷酸盐、膦酸盐、亚磷酸盐以及混合的碱式磷酸氧代阴离子盐，所述金属选自第三至第六周期的第II和III主族元素，第五至第六周期的第IV主族元素，第四至第五周期的第III至VIII副族元素以及元素周期表中的镧系元素，优选选自Cu、Sn、Ca、Mo、Fe、Co、Sn；
更优选地选自磷酸铜、磷酸锡、磷酸铁、磷酸镍、磷酸钼、磷酸钴、磷酸锰以及磷酸锑；
特别优选地选自磷酸铜、磷酸锡以及磷酸铁；
更特别优选地选自碱式磷酸铜[CHP;Cu4(OH)2(PO4)2]；
ii)金属氧化物和混合的金属氧化物；
优选选自：氧化锑（Sb2O3）、氧化锡（SnO4）、氧化钛（TiO2）、氧化锡铟（In2O3/SnO2；ITO）、氧化锡锑（ATO）；
iii)金属，优选为Al、Cr、Fe、Au或者Ag的片状颜料，该片状颜料是未涂覆的或者涂覆有一层或多层金属氧化物层，其中所述金属氧化物优选选自：二氧化钛、氧化锑（III）、氧化锌、氧化锡、二氧化锆、氧化铬、氧化镍、氧化铜、氧化钴、铁的氧化物（Fe2O3、Fe3O4），特别优选地选自单独的氧化锑（III）或者与氧化锡结合的氧化锑（III）；
iv)有机吸收剂，优选为有机NIR吸收剂，特别优选为酞菁和萘酞菁，具体为铜(II)-1,4,8,11,15,18,22,25-八丁氧基-29H,31H-酞菁或者氧钒基-2,9,16,23-四苯氧基-29H,31H-酞菁或者氧钒基-5,14,23,32-四苯基-2,3-萘酞菁或者氧钒基-2,11,20,29-四叔丁基-2,3-萘酞菁、路玛近荧光染料（lumogen）以及夸特锐烯（quaterrylene）染料。
4.如前述任一项权利要求所述的基质材料，其特征在于，吸收剂材料吸收100至400nm的紫外（UV）波长范围的激光，例如准分子激光，或者波长范围为9000至11000nm的激光，例如CO2激光，或者吸收波长范围为700至2000nm，优选为950至1500nm的激光或者IR光。
5.如前述任一项权利要求所述的基质材料，其特征在于，相对于基质材料的重量计，该基质材料含有1.0至30重量%或者3.0至20重量%或者5.0至10重量%的添加剂。
6.如前述任一项权利要求所述的基质材料，其特征在于，该基质材料选自：聚乙烯醇缩丁醛（PVB）、聚丙烯（PP）、聚乙烯（PE）、聚酰胺（PA）、聚对苯二甲酸丁二酯（PBT）、聚对苯二甲酸乙二酯（PET）、聚酯、聚苯醚、聚缩醛、聚甲基丙烯酸酯、聚甲醛、聚乙烯醇缩醛、聚苯乙烯、丙烯酸-丁二烯-苯乙烯（ABS）、丙烯腈-苯乙烯-丙烯酸酯（ASA）、聚碳酸酯、聚醚砜、聚醚酮、聚氯乙烯、热塑性聚氨酯和/或它们的共聚物和/或它们的混合物。
7.如前述任一项权利要求所述的基质材料，其特征在于，所述添加剂含有发泡剂和吸收剂，它们的重量比为20:1至1:20，优选为15:1至1:15，特别优选为10:1至1:10，更优选为5:1至1:5或者3:1至1:3。
8.添加剂，该添加剂用于使得由塑料或者涂料、清漆或者天然漆制得的基质材料发泡，该发泡可以通过激光或者IR光的照射来引发，其中所述添加剂至少包含以下组分：
a)至少一种吸收剂材料，该吸收剂材料嵌入或者溶解在基质材料中，吸收激光或者IR光并导致基质材料中激光或IR光照射位点的局部加热，以及
b)至少一种发泡剂，当由于激光或者IR光的照射导致被加热到超过50°C的温度时，所述发泡剂通过分解、化学转化或反应产生使得基质材料发泡的气体。
9.如权利要求8所述的添加剂，其特征在于，该添加剂含有如权利要求2所述的发泡剂。
10.如权利要求8或9中任一项所述的添加剂，其特征在于，该添加剂含有如权利要求3或4所述的吸收剂材料。
11.如权利要求8至10中任一项所述的添加剂，其特征在于，所述添加剂含有发泡剂和吸收剂，它们的重量比为20:1至1:20，优选为15:1至1:15，特别优选为10:1至1:10，更优选为5:1至1:5或者3:1至1:3。
12.如权利要求8-11中任一项所述的添加剂的用途，用于生产由塑料或涂料、清漆或天然漆制备的基质材料，所述基质材料可以通过激光或者IR光在其表面提供泡沫结构，优选盲文，和/或用于生产可以通过激光或者IR光的方法焊接的材料。
13.如权利要求12所述的用途，其特征在于，相对于基质材料的重量计，将0.01至50重量%或者1.0至30重量%或者3.0至20重量%或者5.0至10重量%的添加剂加入到基质材料中。
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| PCT/EP2011/054295 WO2011117218A1 (de) | 2010-03-26 | 2011-03-22 | Laserinduziertes kunststoffschäumen |
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| EP (1) | EP2553006B1 (zh) |
| CN (1) | CN102939330B (zh) |
| DE (1) | DE102010003366A1 (zh) |
| HK (1) | HK1181061A1 (zh) |
| PL (1) | PL2553006T3 (zh) |
| WO (1) | WO2011117218A1 (zh) |
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| CN104629064A (zh) * | 2015-01-27 | 2015-05-20 | 南京工业大学 | 一种采用激光诱导油水两相连续前端聚合快速制备双层水凝胶的方法 |
| CN105793196A (zh) * | 2013-11-11 | 2016-07-20 | 化学制造布敦海姆两合公司 | 掺杂的磷酸氢氧化铜(ii)、其制备方法及其用途 |
| CN108841031A (zh) * | 2018-05-24 | 2018-11-20 | 四川大学 | 石墨烯作为发泡剂在制备激光诱导聚合物发泡材料中的应用 |
| CN113402760A (zh) * | 2021-07-20 | 2021-09-17 | 常州大学 | 一种近红外激光诱导高分子材料局部发泡方法 |
| CN114369287A (zh) * | 2021-12-28 | 2022-04-19 | 万华化学集团股份有限公司 | 一种激光发泡助剂组合物及其制备方法和应用 |
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| TW201435830A (zh) | 2012-12-11 | 2014-09-16 | 3M Innovative Properties Co | 不顯眼之光學標籤及其方法 |
| CN103171221B (zh) * | 2013-02-25 | 2015-09-30 | 杭州西码新材料有限公司 | 基于金属氧化物可调光透过阻隔的稳定透明隔热膜 |
| CN103113723B (zh) * | 2013-02-25 | 2016-07-06 | 杭州天地数码科技股份有限公司 | 高红外阻隔率的节能透明膜的精制方法 |
| DE102013203120B3 (de) * | 2013-02-26 | 2014-05-15 | Laservision Gmbh & Co. Kg | Laserschutzmaterial und Laserschutzkomponente |
| CN108624119A (zh) | 2017-03-24 | 2018-10-09 | 卡西欧计算机株式会社 | 墨水、印刷装置、印刷方法以及造形物的制造方法 |
| DE102017106913A1 (de) * | 2017-03-30 | 2018-10-04 | Chemische Fabrik Budenheim Kg | Verfahren zur Herstellung von elektrisch leitenden Strukturen auf einem Trägermaterial |
| DE102017106911A1 (de) | 2017-03-30 | 2018-10-04 | Chemische Fabrik Budenheim Kg | Verwendung von kristallwasserfreien Fe(II)-Verbindungen als Strahlungsabsorber |
| US10934409B2 (en) | 2017-08-18 | 2021-03-02 | Owens Coming Intellectual Capital, LLC | Infrared attenuation agent blends |
| JP6835030B2 (ja) | 2018-04-27 | 2021-02-24 | カシオ計算機株式会社 | 熱膨張性シート、熱膨張性シートの製造方法及び造形物の製造方法 |
| DE102021200840A1 (de) * | 2021-01-29 | 2022-08-04 | Tesa Se | Laser-basierte Strukturierung von Trennmaterialien |
| CN117384353B (zh) * | 2023-11-28 | 2024-03-08 | 广州亚伊汽车零部件有限公司 | 一种保温隔热复合发泡材料及其制备方法 |
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| CN105793196A (zh) * | 2013-11-11 | 2016-07-20 | 化学制造布敦海姆两合公司 | 掺杂的磷酸氢氧化铜(ii)、其制备方法及其用途 |
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| CN108841031B (zh) * | 2018-05-24 | 2020-12-25 | 四川大学 | 石墨烯作为发泡剂在制备激光诱导聚合物发泡材料中的应用 |
| CN113402760A (zh) * | 2021-07-20 | 2021-09-17 | 常州大学 | 一种近红外激光诱导高分子材料局部发泡方法 |
| CN114369287A (zh) * | 2021-12-28 | 2022-04-19 | 万华化学集团股份有限公司 | 一种激光发泡助剂组合物及其制备方法和应用 |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE102010003366A1 (de) | 2011-09-29 |
| US8759409B2 (en) | 2014-06-24 |
| HK1181061A1 (zh) | 2013-11-01 |
| WO2011117218A1 (de) | 2011-09-29 |
| CN102939330B (zh) | 2015-04-15 |
| PL2553006T3 (pl) | 2015-10-30 |
| EP2553006A1 (de) | 2013-02-06 |
| EP2553006B1 (de) | 2015-07-15 |
| US20130065979A1 (en) | 2013-03-14 |
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