CN101848811A - 用于提高近红外辐射的热输入量的氧化钨 - Google Patents

用于提高近红外辐射的热输入量的氧化钨 Download PDF

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CN101848811A
CN101848811A CN200880114766A CN200880114766A CN101848811A CN 101848811 A CN101848811 A CN 101848811A CN 200880114766 A CN200880114766 A CN 200880114766A CN 200880114766 A CN200880114766 A CN 200880114766A CN 101848811 A CN101848811 A CN 101848811A
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purposes
tungsten
nir
oxygen
formula
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CN101848811B (zh
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U·里曼
U·L·施塔德勒
M·马马克
R·克尼施卡
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BASF SE
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Abstract

本发明涉及氧化钨或钨酸盐的用途，用于在选自塑料的激光焊接、涂料的NIR固化、印刷油墨的干燥、将油墨调色剂固定在基底上、预成型塑料的加热、塑料或纸的激光标记的过程中提高近红外辐射的热输入量。

Description

用于提高近红外辐射的热输入量的氧化钨
本发明涉及氧化钨或钨酸盐提高近红外辐射的热输入量的用途。
原则上，低价氧化钨和钨青铜的IR吸收性能质是已知的。例如EP1847635公开了作为热吸收材料的Cs033WO3粒子分散体。
已发现尽管吸收相同量的能量，这些材料表现出比其它已知IR吸收剂明显较高的效力。这非常令人惊讶且至今不可解释。例如掺入涂料中的钨青铜在受到IR照射时导致了比根据其光谱吸收能力预计的高得多的温度升高。测得的温度升高比用其它已知的IR吸收剂发现的明显更高，且几乎达到用炭黑观察到的温度。或者，对于纸的激光标记，已知钨青铜或低价氧化钨比六硼化镧(一种熟知的几乎无色的IR吸收剂)的效力超过10倍。这事实上非常令人惊讶且原因未知。
许多技术方法(例如塑料的激光焊接和标记、涂料的NIR固化和干燥、印刷品的干燥、纸的激光标记、粘合剂的固化和干燥、油墨调色剂固定在基底上、加热预形成塑料等)要求通过IR辐射实现有效、快速且集中的局部热输入。IR辐射转化成热是通过将适合的IR吸收剂放在需要热的地方实现的。炭黑是公知的有效用于这种方法的IR吸收剂。但炭黑具有一大缺点，即非常深的黑色。因此，炭黑不可用于有色(黑色或灰色除外)、无色、白色或透明的体系。对于这种体系，“白色或无色的炭黑”是技术上强烈需要的。
因此，目标是研究出这种“无色和透明的炭黑”。
非常令人惊讶的是本发明的氧化钨材料非常接近此目标——尽管它带有轻微的蓝色或灰色。
但由于它将IR辐射转化成热的令人惊讶的高效率，此氧化钨材料可以以非常低的浓度应用，从而使得它本身的颜色在大多数应用中可以接受。
对于透明度同样如此：含该氧化钨的材料(塑料、涂料)仍保持高度透明。
氧化钨和钨酸盐是已知的红外屏蔽材料。出版物EP 1676890和US2007/0187653(Sumitomo Metal Mining Company)公开了一种屏蔽红外的纳米粒子分散体，其包含具有还原的氧的三氧化钨。
因此，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素；W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在涂料的NIR固化和涂料的NIR干燥过程中提高近红外辐射的热输入量。
热输入量是通过近红外辐射提供的热能，且相应于在涂料NIR固化和干燥以后达到的温度。
优选地，y为1。实例为H0.53WO3、Na0.33WO3、K0.33WO3、Cs0.33WO3、Ba0.33WO3、Rb0.33WO3。
优选使用低价氧化钨(例如WO2,7)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
钨青铜可根据EP 1676890制备，该文献指出，式MxWO3表示的钨青铜可如下制备：将偏钨酸铵与金属盐的水溶液加热至300至700℃，并将含水混合物干燥以得到固体产物。
氧化钨粉末(例如WO2.7)可由例如Osram Sylvania购得。WO2,7也可通过在等离子反应器中还原钨酸铵而制备。可将市售的WO2,7分散，然后将此分散体例如在Dynomill磨中用0.4μm锆球研磨，以得到粒度为10nm至1μm、优选10至500nm、更优选10至200nm的粒子。
施用的氧化钨或钨酸盐的量为0.01至2.0重量％。在这种量下，氧化钨的轻微蓝色就没有问题。
用于本发明方法中的NIR辐射为波长为约700nm至3000nm的短波红外辐射。NIR辐射的辐射源包括例如主发射在800至1500nm范围的市售(例如获自Adphos)常规NIR辐射发射器，二极管激光器，纤维激光器或Nd:YAG激光器。
涂料的NIR固化可用于所有类型的涂料，包括着色和未着色的涂料。取决于有机粘合剂的性质，涂料可包含溶剂和/或水或可以是无溶剂或无水的。除颜料外，它们还可包含填料和其它添加剂。任何种类的涂料都适于本发明方法中，例如粉末涂料、透明涂料、高固含量涂料、效果涂料、高光发涂料、缎光涂料、无光涂料、喷涂涂料、浸涂涂料、浇涂涂料等。相应原料和组合物是本领域技术人员已知的，且例如描述于“Lehrbuch derLacktechnologie”，Vincentz Verlag，1998中。
涂料的NIR固化是卷材涂料领域中的现有技术。由于涂料配制物本身不吸收NIR辐射，因此，干燥和/或固化期间涂料的加热速率强烈地依赖于几个因素：
·基底
·染色度
·颜料化学
这在某些涂覆过程中导致缺陷。它们是：
a)由于损失NIR辐射的低能量效率，
b)例如黑色(FW 200)相对于白色(TiO2)染色体系的不同的固化速度，
c)NIR干燥不可用于透明涂料施用，
d)尤其是白色RAL色调，例如9002、9010 & 9016，在NIR固化期间显示出低的能量效率。
在着色涂料中，尤其是在TiO2染色的体系中，重要的是加入NIR吸收剂不导致任何脱色。因此，本发明一方面是在着色涂料中的用途。
因此，需要无色以及透明的近红外线吸收剂以克服缺点a至d。现有技术的材料为有色的(Lumogen IR 765、788)，或当掺入涂料配制物中时显示浑浊(Minatec 230A-IR、Lazerflair 825、LaB6)。因此，对于所用IR吸收剂的另一要求是避免浑浊。
Minatec 230A-IR由特殊锑锡复合物(Merck)组成，Lazerflair 825是云母基的片晶类型颜料(Merck)，Lumogen IR 765和IR 788为有机四萘嵌苯-双酰亚胺(quaterrylene-bisimide，BASF)。LaB6可由Aldrich购得。
使用上述氧化钨和钨酸盐或使用炭黑在NIR固化以后达到的温度几乎相同。使用上述氧化钨和钨酸盐可达到极高温度的这种意想不到的效果不能仅用高的近红外线吸收解释。在近红外中具有较高吸收积分的材料或浓度在NIR固化循环以后显示出较低的温度提高(实施例3.1)。
实施例1(通过研磨制备WO2.7)
将240ml 0.4μm锆球加入106.5g来自Osram/Sylvania的WO2.7在450ml水中的悬浮液中。将悬浮液在Dynomill中以4500r/min研磨8小时。将得到的悬浮液过滤并干燥。粒度主要为30至100nm。
实施例1(使用等离子反应器制备氢钨青铜(H0.53WO3))
通过以10g/min操作的振动型粉末进料器将仲钨酸铵粉末((NH4)10W12H2OO42·4H2O，Osram Sylvania)裹挟在氩载气中。用在65kW的功率下操作的Tekna PL-50等离子体焰炬将流化的粉末供入等离子反应器中。在反应器的等离子体热区通常达到的温度范围为5000至10,000K。将40slpm氩、0.5slpm氢与5slpm氦[slpm＝标准升/分钟；计算slpm的标准条件定义为：Tn0℃(32°F)，Pn＝1.01巴(14.72psi)]的混合物用于保护气。通过骤冷气将反应物蒸气冷却并收集在袋式滤器中。通过粉末X射线衍射、电子显微镜和UV-vis-NIR光谱分析所得的氢钨青铜。
粒度为30至200nm。该材料在涂料或塑料等中表现出非常良好的可分散性。
实施例3.1(应用例，NIR固化)
关于在NIR固化期间的温度吸收以及最终涂料性能，在2P-PU配制物中测试不同的NIR吸收剂。
根据下表使用玻璃珠和scandex振动器将NIR吸收剂掺入研磨基料中达16小时(值以g为单位)。
  研磨基料
  Laropal A 81(可获自BASF的脲-醛树脂)在1-甲氧基-2丙基乙酸酯/二甲苯3∶1中60％ 15.7g
  EFKA 4401(聚合分散剂，可获自Ciba Inc)   0.08g
  1-甲氧基-2丙基乙酸酯(溶剂)   4.62g
  丁基乙二醇乙酸酯(溶剂)   1.16g
  NIR-A   0.19g
将研磨基料与减低配制物混合，并根据下表加入交联剂。
  减低  量，单位为g
  研磨基料  21.75
  2p PUR透明涂料＊  3.84
  MPA/BGA(95/5)  7.61
  减低  量，单位为g
  Desmodur n 3390(90％)，交联剂，来自Bayer的脂族异氰酸酯  7.50
  2p PUR透明涂料＊  量，单位为g
  Macrynal SM 510n(可获自Cytec SurfaceSpecialties的羟基官能丙烯酸树脂)  78.7
  EFKA 3030(可获自Ciba Inc.的改性聚硅氧烷，用于改善均匀性)  0.15
  二月桂酸二丁锡，在二甲苯中10％  0.1
  TINUVIN 292/TINUVIN 99-2(65/35)  2.0
  DABCO-33LV，在二甲苯中10％  0.1
  1-甲氧基-2-丙基乙酸酯  14.45
  丁基乙二醇乙酸酯  4.5
DABCO-33LV是可获自Air Products & Chemicals的三亚乙基二胺与二丙二醇的混合物，用作催化剂
TINUVIN 292是可获自Ciba Inc.的位阻胺光稳定剂(“HALS”)
TINUVIN 99-2是可获自Ciba Inc.的UV吸收剂
使用80μm的WFT(湿膜厚度)通过绕线棒施用涂料。在NIR干燥机中使用不同的灯设置(6个Adphos高燃NIR灯，输出50至100％)和1至4m/min的带速将涂料干燥。
通过测量相对于黑色的浑浊来检测NIR-A在涂料配制物中的分布。值越低，在配制物中的分布越好，并观察到更少的对目视膜性质的冲击。
  NIR吸收剂  WFT(mm)   基于固体的重量％   浑浊
  实施例1  80   1   7.1
  实施例2  80   1   8.0
  NIR吸收剂  WFT(mm)   基于固体的重量％   浑浊
  LaB6  80   1   14.3
  Minatec 230A-IR  80   1   10.4
  Lazerflair 825  80   1   15.7
直接在固化以后测量涂层表面的温度。
下表显示使用2m/min的带速、6个Adphos高燃NIR灯、输出70％、距灯100mm的结果。
上表清楚地显示H0.53WO3能以与炭黑几乎相同的程度将NIR辐射转化成热(216℃与232℃相比较)。因此，本发明氧化钨材料非常接近“无色炭黑”的目标。甚至在NIR范围(800至1500nm)具有较高吸收积分的近红外吸收剂与上述氧化钨和钨酸盐相比也表现出明显较低的温度提高(例如，浓度为0.1％的H0.53WO3与Lumogen相比较)。
这尤其在用TiO2施用中可看出(实施例3.2)。
实施例3.2(应用例，NIR固化)
所述研磨基料根据标准方法使用分散机预混合、并使用来自Lau的Disperser DAS 200另外研磨1小时而制备。使用缝式涂布机将涂料施用在预涂底漆的白色铝板上，产生约80μm的DFT。测试具有TiO2以及TiO2与NIR-A混合物的配制物。固化使用6个来自Adphos公司的6HB-NIR发射器以不同的带速进行。
特别是在卷材涂料领域中，主要的用途是在“白色”影调领域中，例如RAL 9001、9003、9010、9016。其中RAL 9010是在发射能量的有效吸收方面最关键的。为了测试加入NIR-A(实施例2)对固化速度的影响，使用45w％/w TiO2着色体系作为参比。NIR-A可以直接在研磨步骤中加入，或者对于溶剂基施用，借助基于Ciba
Figure GPA00001130971000082
4310的无树脂颜料糊加入。加入NIR-A大大缩短了固化时间(见表1)。这使得带速可以提高，从而获得涂覆线较高的生产量，或者使得灯输出降低，从而减少电费。
  w％/wTiO2   w％/w，实施例2的NIR吸收剂   用于固化的相对带速，％   Δa变化   Δb变化
  45.0   0   100   0   0
  44.95   0.05   250   -0.4   -0.8
  w％/wTiO2   w％/w，实施例2的NIR吸收剂   用于固化的相对带速，％   Δa变化   Δb变化
  44.75   0.25   350   -1.2   -2.8
  44.50   0.5   450   -1.6   -4.2
借助固化涂层对100MEK来回擦拭的稳定性确定用于固化的带速。
上表显示出固化可通过较高带速进行，且与TiO2着色体系相比，随着NIR-A1加入量的提高，仅观察到b和在CIE-Lab颜色空间内值的轻微变化。
实施例3.3(应用例，NIR固化)
使用与实施例3.2相同的配制物。使用具有基于固体的45重量％TiO2的配制物作为参比。
NIR吸收剂 基于固体的重量％   用于固化的带速[m/min] E
  无   0   0.75   0
  Minatec 230 A-IR   1   1.00   1.9
  实施例2   0.05   1.50   1.25
借助固化涂层对100MEK来回擦拭的稳定性确定用于固化的带速。
上表显示本发明NIR吸收剂(实施例2)对TiO2染色体系的脱色具有低的影响。
在另一实施方案中，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在塑料的激光标记过程中提高近红外辐射的热输入量。
优选使用低价氧化钨(例如WO2.72)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
在其它实施方案中，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在塑料的激光焊接方法中提高近红外辐射的热输入量。
优选使用低价氧化钨(例如WO2.72)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
激光辐射用于焊接过程，以生产熔融粘合的塑料。通常使用的激光波长为：808nm、850nm、940nm、980nm或1064nm。为了吸收激光辐射并将其转化成热以用于熔融过程，需要加入IR吸收剂。通常的IR吸收剂是炭黑。由于其为黑色，亮色或透明部件的焊接是不可能的。
氧化钨或钨酸盐的浓度为10至800ppm，优选100至300ppm。
可通过已知方法，例如注塑、挤出等，将氧化钨或钨酸盐直接合并到塑料部件中。
用于激光焊接方法中的塑料的实例为聚丙烯、聚乙烯醇缩丁醛、聚酰胺、聚碳酸酯、聚碳酸酯-聚对苯二甲酸乙二酯掺混物、聚碳酸酯-聚对苯二甲酸丁二酯掺混物、聚碳酸酯-丙烯腈/苯乙烯/丙烯腈-共聚物掺混物、聚碳酸酯-丙烯腈/丁二烯/苯乙烯-共聚物掺混物、聚甲基丙烯酸甲酯-丙烯腈/丁二烯/苯乙烯-共聚物掺混物(MABS)、聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚甲基丙烯酸甲酯、聚丙烯酸丁酯、聚甲基丙烯酸甲酯-聚偏氟乙烯掺混物、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、苯乙烯/丙烯腈共聚物(SAN)和聚砜及其混合物。
实施例4(应用例，塑料的激光焊接)
通过注塑机将根据实施例2的IR吸收剂以500ppm的浓度掺入聚碳酸酯板(厚度2mm)中。使用250瓦特Nd:YAG激光器将所获透明的轻微带蓝色的板与聚碳酸酯板(厚度1mm)焊接在一起。通过激光束以20毫米/秒的速度扫描表面。
产生的焊接具有优异的连接，高度透明，没有显示任何局部塑料变形，在焊接期间不产生气泡。
没有由于机械应力诱发的焊缝破裂。
用现有技术的塑料激光焊接IR吸收剂，例如Lumogen IR 765或Lumogen IR 788，在这些条件下没有发生焊接。用二极管激光器在980nm、940nm或850nm下代替激光器(1064nm)也是如此。用这些IR吸收剂仅在808nm发生焊接。
在另一实施方案中，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在粘合剂和密封剂的NIR固化和粘合剂和密封剂的NIR干燥过程中提高近红外辐射的热输入量。
优选使用低价氧化钨(例如WO2.72)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
将NIR吸收添加剂加入液体粘合剂，特别是水基粘合剂以及溶剂基粘合剂中，可通过集中吸收发射的NIR辐射改善液体粘合剂的干燥性能。
NIR辐射和用于将液体粘合剂干燥的NIR吸收添加剂可以与常规干燥法(例如热空气或IR辐射干燥)一同使用，或作为独立的干燥步骤。
将NIR吸收添加剂加入液体粘合剂中并然后在给定的恒定条件下用NIR照射，与没有NIR吸收添加剂的相同粘合剂相比，产生了更低的残余液体(水)含量。这在液体粘合剂的网纹涂覆应用中，例如在标签层压材料或带的制造中，尤其有意义。另外，在非多孔材料(例如薄膜或箔)的网状层压方法中，在层压步骤以前需要液体粘合剂完全干燥。另外，对于多孔基底，例如纸或织物，在对湿气或水敏感的基底的平坦性方面，层压之前粘合剂的完全干燥是有益的。
加入NIR吸收添加剂提供了其它优点：诱发的能量主要被吸收在粘合剂层本身中，这导致与常规干燥操作相比较低的基底温度。这提供了在温度敏感性基底(例如低熔点或可收缩的薄膜和织物)上将液体粘合剂涂料干燥的有益的可能性。
实施例5.1(应用例，粘合剂和密封剂的NIR固化)
将固体含量为69％的来自BASF Corp.的水基丙烯酸系压力敏感性粘合剂(PSA)Acronal V 212用水稀释。在来自Ciba的丙烯酸系共聚物分散剂EFKA 4585的帮助下，将实施例2的NIR吸收添加剂在速度混合机中混合。用不锈钢涂布棒将50微米粘合剂层施用至玻璃板上。在NIR发射器下通过多次之前和之后测定粘合剂的重量。
结果表明，含NIR吸收添加剂的水基粘合剂比没有添加剂的相同粘合剂更快速地干燥。
在其它实施方案中，可将NIR吸收添加剂添加至100％固体热塑性热活化粘合剂体系。通常，通过将相应的粘合剂体系涂覆或挤出在待结合的基底之一上或适合的中间载体上而产生热活化的粘合剂层。或者，可通过由含水或溶剂载体将相应粘合剂涂覆并干燥而产生热活化的粘合剂层。这样制备的粘合剂层可能摸上去是粘的，但通常不是粘的，且可转化成较小的单元，例如切开的卷或片，用于之后的活化并结合在第二基底上。热活化粘合剂也可以以自支撑的薄膜(粘合剂薄膜)、网(网粘合剂)或粉末(粉末粘合剂)的形式制造并提供。为了建立粘合，必须将这样制备的可热活化粘合剂层或自支撑粘合剂结构加热至高于其活化温度，然后与粘合基底接合。通常的粘合剂活化方法为：火焰活化、热空气活化、IR活化、借助热辊或热砑光加热板、楔或压机的活化。
由于将NIR吸收添加剂加入热活化粘合剂中，活化可便利地用NIR发射器进行。适当改性的粘合剂吸收NIR辐射；加热至高于它需要的活化温度，并可以建立粘合。随着液体粘合剂的干燥，加入NIR吸收添加剂带来了其它优点，即能量主要被粘合剂而不是基底吸收，因此温度敏感性材料也使用此粘合方法。通常的热活化粘合剂化学包括：聚烯烃、无定形α聚烯烃、改性聚烯烃(例如EVA、EAA、BAA)、聚丙烯、共聚酯、共聚酰胺、热塑性聚氨酯、聚己内酯、基于苯乙烯嵌段共聚物的热熔性粘合剂。
实施例5.2(应用例，粘合剂和密封剂的NIR固化)
将基于无定形聚α烯烃(APAO)的典型热活化热熔性粘合剂在西格马叶片捏合机中在170℃混合1小时。APAP聚合物由Evonik Industries获得，烃树脂和苯乙烯嵌段共聚物由Exxon Chemical获得，抗氧化剂由Ciba Inc.获得，松香树脂增粘剂由Eastman获得。用热熔模缝涂布机将粘合剂涂覆在硅化纸上并转移至钢板载体上。将粘合剂试样暴露在NIR辐射下，并借助激光温度计观察粘合剂表面的温度。
结果表明，不含实施例2的NIR吸收添加剂的粘合剂仅达到空白钢载体板的温度。加入不同量的NIR吸收添加剂将粘合剂表面温度分别提升至99℃、109℃和162℃。
实验-Nr： 载体板   136/08(无NIR添加剂)   137/08(0.05％NIR添加剂)   138/08(0.1％NIR添加剂)   139/08(0.5％NIR添加剂)
  NIR设置   HB6，距离100mm，功率(％)   70％   70％   70％   70％
  带速(m/min)   2   2   2   2
  粘合剂组成   Escorez 5310(烃树脂)   25   25   25   25
  Vestoplast 408(APAO)   20   20   20   20
  Irganox 1010(抗氧化剂)   1   1   1   1
实验-Nr： 载体板   136/08(无NIR添加剂)   137/08(0.05％NIR添加剂)   138/08(0.1％NIR添加剂)   139/08(0.5％NIR添加剂)
  Vector 4111(苯乙烯嵌段共聚物) 10 10 10 10
  Permalyn 6110(松香酯增粘剂) 18 18 18 18
  NIR-A   0.5   0.1   0.1
  粘合剂厚度(g/m2)   0   96   94   95   95
  照射后的温度(℃)   76   78   99   109   162
在另一实施方案中，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在纸的激光标记过程中提高近红外辐射的热输入量和效率。
优选使用低价氧化钨(例如WO2.72)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
实施例6(应用例，纸的激光标记)
使用刮条涂布机，将由45份Tioxide AH-R(锐钛矿)、54.9份丙烯酸系清漆(通过将20份来自Wacker的Vinnapas C501树脂、乙酸乙烯酯与巴豆酸的固体共聚物与80份乙酸丙酯混合而制备)和0.1份来自实施例2的材料组成的无色油墨配制物施涂到粘土涂布的纸上。
在各个功率(14至25A，20kHz，1500mms，4.2至7.6W)下用Nd:YAG激光器的激光标记得到具有高对比度的优异标记结果。
实施例7(对比例，纸的激光标记)
使用六硼化镧代替来自实施例2的材料，为了得到相同的激光标记性能，需要多达超过10倍的IR吸收剂(1.4份LaB6)。
在另一实施方案中，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在印刷油墨的干燥或将油墨调色剂固定在基底上的过程中提高近红外辐射的热输入量。
优选使用低价氧化钨(例如WO2.72)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
在另一实施方案中，本发明涉及式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在加热预成型塑料的过程中提高近红外辐射的热输入量。
优选使用低价氧化钨(例如WO2.72)和钨青铜(例如H0.53WO3、Na0.33WO3、Cs0.33WO3)。尤其优选Cs0.2-0.5WO3。
在另一实施方案中，本发明涉及掺混物提高近红外辐射的热输入量的用途，该掺混物包含如上定义的氧化钨和/或钨酸盐以及如国际公开WO2008/086931中公开的式I或II的硫代双烯金属络合物。
Figure GPA00001130971000171
Figure GPA00001130971000172
其中：
M选自Ni、Pd、Pt、Au、Ir、Fe、Zn、W、Cu、Mo、In、Mn、Co、Mg、V、Cr和Ti，
X1、X2和X3相互独立地为硫或氧，
R1、R2、R3、R4、R5和R6相互独立地为氢、NR7R8、C1-C18烷基、芳基、芳烷基、杂芳基烷基，其中R7和R8相互独立地为C1-C18烷基、芳基、芳烷基、杂芳基烷基。
C1-C18烷基的实例为丙基、异丙基、正丁基、仲丁基、叔丁基、正己基、环戊基、环己基。
芳基为苯基、萘基、蒽基或菲基。芳烷基例如为苄基。杂芳基烷基被理解为作为取代基经由低级亚烷基与选自咪唑基、吡啶基、噻吩基、呋喃基、噻唑基、吲哚基、喹啉基、吡唑基、吡嗪基、哒嗪基、嘧啶基的杂芳环连接的杂芳基。
具体实例为：
Figure GPA00001130971000181
硫代双烯金属络合物相对于氧化钨的量为5至90重量％。
在另一实施方案中，本发明涉及掺混物的用途，该掺混物包含如上定义的氧化钨和/或钨酸盐以及至少一种选自醌-二铵盐quinone-diimmoniumsalt、胺鎓盐、聚甲川(例如花菁、方酸菁squaraine、克酮酸菁croconaine)；酞菁、萘酞菁naphthalocyanine和四萘嵌苯-双酰亚胺quaterrylene-bisimide的有机IR吸收剂或者至少一种选自六硼化镧、氧化铟锡(ITO)、氧化锑锡(例如可获自Merck的Minatec 230A-IR或可获自Merck的
Figure GPA00001130971000182
颜料)的无机IR吸收剂。

Claims (22)

1.式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在涂料的NIR固化和涂料的NIR干燥过程中提高近红外辐射的热输入量。
2.根据权利要求1的用途，其中使用低价氧化钨WO2.72和选自H0.3-0.7WO3、Na0.2-0.5WO3、Cs0.2-0.5WO3的钨青铜。
3.根据权利要求1的用途，其中使用Cs0.2-0.5WO3。
4.根据权利要求1的用途，用于卷材涂料的NIR固化或NIR干燥的过程中。
5.根据权利要求1的用途，用于着色涂料的NIR固化或NIR干燥的过程中。
6.式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在塑料的激光标记过程中提高近红外辐射的热输入量。
7.根据权利要求6的用途，其中使用低价氧化钨WO2.72和选自H0.3-0.7WO3、Na0.2-0.5WO3、Cs0.2-0.5WO3的钨青铜。
8.根据权利要求6的用途，其中使用Cs0.2-0.5WO3。
9.式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在塑料的激光焊接过程中提高近红外辐射的热输入量。
10.根据权利要求9的用途，其中使用低价氧化钨WO2.72和选自H0.3-0.7WO3、Na0.2-0.5WO3、Cs0.2-0.5WO3的钨青铜。
11.根据权利要求9的用途，其中使用Cs0.2-0.5WO3。
12.式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在粘合剂和密封剂的NIR固化以及粘合剂和密封剂的NIR干燥过程中提高近红外辐射的热输入量。
13.根据权利要求12的用途，其中使用低价氧化钨WO2.72和选自H0.3-0.7WO3、Na0.2-0.5WO3、Cs0.2-0.5WO3的钨青铜。
14.根据权利要求12的用途，其中使用Cs0.2-0.5WO3。
15.式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在纸的激光标记过程中提高近红外辐射的热输入量。
16.根据权利要求15的用途，其中使用低价氧化钨WO2.72和选自H0.3-0.7WO3、Na0.2-0.5WO3、Cs0.2-0.5WO3的钨青铜。
17.根据权利要求15的用途，其中使用Cs0.2-0.5WO3。
18.式WO3-x的氧化钨的用途，其中W是钨，O是氧，x为0.1至1，和/或式MxWyOz的钨酸盐的用途，其中M为一种或多种选自NH4、H、Li、Na、K、Rb、Cs、Ca、Ba、Sr、Fe、Sn、Mo、Nb、Ta、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl的元素，W是钨，O是氧，0.001≤x/y≤1且2.0＜z/y≤3.0，用于在印刷油墨的干燥或将油墨调色剂固定在基底上的过程中提高近红外辐射的热输入量。
19.根据权利要求18的用途，其中使用低价氧化钨WO2.72和选自H0.3-0.7WO3、Na0.2-0.5WO3、Cs0.2-0.5WO3的钨青铜。
20.根据权利要求18的用途，其中使用Cs0.2-0.5WO3。
21.掺混物用于提高近红外辐射的热输入量的用途，所述掺混物包含根据权利要求1的氧化钨和/或钨酸盐以及式I或II的硫代双烯金属络合物：
Figure FPA00001130970900031
其中：
M选自Ni、Pd、Pt、Au、Ir、Fe、Zn、W、Cu、Mo、In、Mn、Co、Mg、V、Cr和Ti，
X1、X2和X3相互独立地为硫或氧；
R1、R2、R3、R4、R5和R6相互独立地为氢、NR7R8、C1-C18烷基、芳基、芳烷基、杂芳基烷基，其中R7和R8相互独立地为C1-C18烷基、芳基、芳烷基、杂芳基烷基。
22.掺混物的用途，该掺混物包含根据权利要求1的氧化钨和/或钨酸盐以及至少一种选自醌-二铵盐、胺鎓盐、聚甲川、酞菁、萘酞菁和四萘嵌苯-双酰亚胺的有机IR吸收剂或者以及至少一种选自六硼化镧、氧化铟锡(ITO)、氧化锑锡或颜料的无机IR吸收剂。
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