CN1250625C - 适合激光焊接的着色热塑性树脂组合物、作为其着色剂的特定中性蒽醌染料及其模塑制品 - Google Patents

适合激光焊接的着色热塑性树脂组合物、作为其着色剂的特定中性蒽醌染料及其模塑制品 Download PDF

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CN1250625C
CN1250625C CNB018187757A CN01818775A CN1250625C CN 1250625 C CN1250625 C CN 1250625C CN B018187757 A CNB018187757 A CN B018187757A CN 01818775 A CN01818775 A CN 01818775A CN 1250625 C CN1250625 C CN 1250625C
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formula
dyestuff
dye
group
test piece
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CN1501958A (zh
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R·科施达
Y·哈塔斯
R·哈亚施
H·苏米
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Orient Chemical Industries Ltd
EIDP Inc
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Orient Chemical Industries Ltd
EI Du Pont de Nemours and Co
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    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
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    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B29C66/41Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43Joining a relatively small portion of the surface of said articles
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    • B29C66/733General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence
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Abstract

本发明公开适于激光(11)焊接的热塑性树脂组合物,它包括一种中性蒽醌蓝染料与其它红染料的混合物,以吸收波长短于700nm的可见光,透过波长为800nm-1200nm的激光束(11)并提高可焊接性。

Description

适合激光焊接的着色热塑性树脂组合物、 作为其着色剂的特定中性蒽醌染料及其模塑制品
                       技术领域
本发明涉及含特定蒽醌染料的热塑性树脂组合物。更具体地说,本发明涉及激光焊接性能提高的这类组合物。
                       背景技术
让2个树脂制品(分别为不透明和透明的)彼此接触,透过预设量的激光束,聚焦在它们的接头处,使接头部分熔化并连接在一起的方法(“激光焊接”)是本领域内已知的。与连接塑料制品的传统方法相比,激光焊接有几个优点。
例如,激光焊接以其操作简单、节省劳力、生产率提高、接头干净和生产成本降低而著称。该方法在各种应用中,包括在汽车工业和电气、电子工业上制造包括中空形制品在内的模塑制品中都很有用。最近,研究工作集中在热塑性树脂与一种含有机染料或颜料的着色剂的共混物领域内。通过在树脂中加入这类着色剂,就能更好地控制激光能量转化为热能。激光束透过靠近激光束光源的透明制品,被吸收系数高于上述透明制品的不透明制品大量吸收。仔细控制其中的着色剂用量,便能熔化接头部分并把两个制品连接在一起。
例如,参考日本出版(Koukoku)专利62-49850和日本出版(Koukoku)专利5(93)-42336。与激光焊接相关的其它树脂组合物在美国专利5,893,959中已有所述,该专利公开了由沿接头区的激光束焊接在一起的透明与不透明工件。2个工件都含炭黑之类的黑染料和颜料,以使它们在焊接后仍有一个基本均匀的外观。
激光焊接组合物的其它实例可见诸于美国专利5,893,959中。例如,热塑性塑料部件的颜色可以是黑的(炭黑或尼格),这种颜色在汽车工业和其它应用中普遍使用。但是,炭黑和尼格透不过主要波长在红外区(1200nm-800nm)的激光束,例如工业上广泛使用的Nd:YAG激光和二极管激光。
意外的是业已发现,两种都呈黑色的热塑性树脂组合物能用于激光焊接模塑制品,都可用于拟受激光束作用的透明与不透明部件。通过包括特定重量百分数的黑染料,可明显提高对激光束中近红外光的透射率,并兼具汽车应用中所需的耐热性和力学性能。
本发明的目的在于提供一种热塑性树脂组合物,它能使模制品呈黑色,具有优良的耐热性并对激光束,尤其对近红外区的激光束透明。本发明的另一个目的是提供选择的蒽醌蓝染料,它在模塑期间和高温应用中很少褪色。本发明的一个特点是该组合物能提供一种看上去基本均匀黑色的透明与不透明制品,它因含黑色染料而呈黑色且能大量吸收激光束,从而被激光束焊接在一起,而且具有汽车部件、电气/电子部件、机械部件和许多其它应用中所需的耐热性与力学性能的优良综合性能。参考以下对本发明的描述,能更好地理解上述目的、特点与优点。
                       发明概述
本发明涉及一种用于激光焊接的改进热塑性树脂组合物,它由热塑性树脂和一种至少包含中性蒽醌染料的黑着色剂组成,该着色剂赋予蓝色,吸收波长短于700nm的可见光并能透过波长为800nm-1200nm的激光束。除所述中性蒽醌染料之外,还可按预定重量比存在能透过红外区波长为800nm-1200nm的激光束的其它红染料,如迫位酮染料或单偶氮配合物染料。
可以达到所述目的的本发明,涉及一种适于激光焊接的热塑性树脂组合物,它包含:
1)热塑性树脂;和
2)激光透射黑着色剂,它包含式[I]或[II]的中性蒽醌染料,
其中式[I]为
Figure C0181877500051
其中,可以相同或不同的R55和R58独立地选自含1-18个碳原子的烷基;可以相同或不同的R56和R59独立地选自下列一组:烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、烷氧基羰基、羟基、羧基和卤原子;以及可以相同或不同的R57和R60独立地选自下列一组:H、烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、羧基、烷氧基羰基、羟基和卤原子,
以及其中式[II]是
Figure C0181877500061
其中,可以相同或不同的R61、R62、R63和R64独立地选自下列一组:H、烷基、链烯基、芳基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、羧基、烷氧基羰基、羟基、卤原子、式[II-a],以及P1是NR66或CO,其中R66是H烷基或芳基。
式[II-a]是:
其中P2是NH或NHCO;R65是H、烷基、芳基、烷氧基、氨基、羟基或卤原子。
使用这些组分,能使适于激光焊接的热塑性树脂组合物具有更好的可模塑性、在热塑性树脂中的溶解性、耐渗色和耐起霜性、对800nm-1200nm波长激光束的透明性和耐化学品性。另一个优点是,该组合物因使用所述式[I]或[II]的中性蒽醌染料作为所述着色剂的主要组分而具有较高的色值,从而成为黑着色剂,并具有较高的耐热性。因此,包含至少以所述中性蒽醌染料为主要组分的黑着色剂的本发明组合物,特别适合于在模塑期间要求熔化温度高于300℃的热塑性树脂。
本发明的组合物除了以蒽醌染料与红染料的混合物为组合物着色剂中所用黑染料的组分之一外,还可含其它黄染料,优选蒽醌黄染料。
适用于实践本发明的各染料的实际用量将取决于本发明组合物中与染料共混的热塑性树脂类型、所要求的颜色、所要求的色调深度和模塑制品的厚度。
                       附图简述
参考本文的附图,可更好地理解本发明。
图1示意互相接触的制品与施于其上的激光。
图2与图1同,但用的制品颜色相同。
图3示意在试片(60mm×18mm)上有缺口的试片形状与尺寸。
图4是激光焊接试验中彼此靠近的2个图3试片及试片与激光束之间相互关系的透视图。
图5示意在试片(80mm×40mm)上有缺口的试片形状与尺寸。
图6是激光焊接试验中彼此靠近的2个图5试片及试片与激光束之间相互关系的透视图。
                       发明详述
具有上述性能、用作形成本发明组合物中所含黑染料主要组分的式[I]和[II]的蒽醌染料的实例分别列于表1和2。
表1
  产品实例号 R55 R56 R57 R58 R59 R60
  I-1   CH3   CH3   H   CH3   CH3   H
  I-2   CH3   CH3   CH3   CH3   CH3   CH3
  I-3   CH3   C2H5   C2H5   CH3   C2H5   C2H5
  I-4   C2H5   C2H5   CH3   C2H5   C2H5   CH3
  I-5   C2H5   C2H5   H   C2H5   C2H5   H
  I-6   CH3   C12H25   H   CH3   C12H25   H
  I-7   CH3   OCH3   H   CH3   OCH3   H
  I-8   CH3   CH3   Cl   CH3   CH3   Cl
  I-9   CH3   CH3   C4H9   CH3   CH3   C4H9
  I-10   CH3   CH3   OH   CH3   CH3   OH
表2
  产品实例号 P1 R61 R62 R63 R64
  II-1   NH   OH   H   OH   H
  II-2   NH   Cl   H   Cl   H
  II-3   NH   H   Br   H   Br
  II-4   NH   CH3   CH3   H   H
  II-5   NCH3   H   H   H   H
  II-6   NH   NH2   H   NH2   H
  II-7   NH   H   H   H   H
  II-8   NH   OH   H   H   H
  II-9   NH   苯胺基   H   苯胺基   H
  II-10   NH   亚苄基酰胺   H   亚苄基酰胺   H
  II-11   CO   NHC4H9   H   NHC4H9   H
  II-12   CO   NH2   H   NH2   H
上述各式染料当形成黑色时具有高色值和高耐热性。
本发明组合物中的其它染料(如形成黑色的红、橙和黄染料)综述如下。
与上述蒽醌染料混合以用作包含在本发明组合物中黑着色剂的迫位酮染料是式[III]的已知产品。
式[III]:
Figure C0181877500091
与蒽醌混合以产生黑染料的迫位酮染料可单独使用也可组合使用。
用于本发明组合物的优选迫位酮染料,当考虑在树脂中的溶解性和/或分散性时,是式[IV]的那些,
式[IV]:
Figure C0181877500092
其中,可以相同或不同的P和Q独立地是能以下式[IV-a]-[IV-c]代表的结构单元。可以相同或不同的R14-R29独立地是一个选自下列一组的原子或基团:H、Cl与Br之类的卤原子、含1-18个碳原子的烷基、含1-18个碳原子的烷氧基、芳烷基、芳基;m6是1或2的数。
式[IV-a]:
Figure C0181877500093
式[IV-b]:
Figure C0181877500101
式[IV-c]:
Figure C0181877500102
属于色指数表中迫位酮类的染料是,例如,C.I.溶剂橙60、78,C.I.溶剂红135,162,178,179,C.I.紫29,C.I.颜料橙43,C.I.颜料红149。如果要提高在树脂中的溶解性与分散性,则优选溶剂型染料。
式[IV]的迫位酮染料的实例如表3所示。
表3
  产品实例号 P Q m6
  IV-1   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-a],R14=R15=R16=R17=H   1
  IV-2   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-a],R14=R15=R16=R17=Cl   1
  IV-3   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-c],R24=R25=R26=R27=R28=R29=H   1
  IV-4   式[IV-a],R14=R15=R16=R17=H  式[IV-b],R18=R19=R20=R21=R22=R23=H   1
  IV-5   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-c],R24=R25=R26=R27=R28=R29=H,R25=OC2H5   1
  IV-6   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-a],R14=R15=R17=H,R16=苯甲酰基   1
  IV-7   式[IV-b],R18=R19=R20=R22=R23=H,R21=C4H9  式[IV-a],R14=R15=H   2
  IV-8   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-c],R24=R26=R27=R28=R29=H,R25=苯基   1
  IV-9   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-a],R15=R15=R17=H,R14=Br   1
  IV-10   式[IV-b],R18=R19=R20=R21=R22=R23=H  式[IV-a],R15=R15=R17=H,R14=COOH   1
与式[I]或式[II]的蒽醌染料混合以形成包含在本发明组合物中用作着色剂中黑染料的单偶氮配合物染料能以式[V]表示。
式[V]是:
其中,可以相同或不同的R30和R31是Cl、SO2R32、SO2(-R33)(-R34)或H;其中可以相同或不同的R33和R34独立地是氢原子、线形或支化C1-C4烷基;R32是线形或支化C1-C4烷基;L3和L4独立地是O或COO;(D)+是氢离子,碱金属的阳离子、铵离子、包括脂肪族伯、仲、叔胺在内的有机胺的阳离子或季铵离子;K2是一个整数;m2是0,1或2;M2选自离子价为2-4的金属(如Zn、Sr、Cr、Al、Ti、Fe、Zr、Ni、Mn、B和Co),优选Cu之类的三价金属或Cr、Co、Ni和Al之类的三价金属。
以及B1和B2由式[V-a]或式[V-b]表示。
式[V-a]:
式[V-b]:
其中,可以相同或不同的R35和R37是Cl、SO2R32、SO2(-R33)(-R34)或H;可以相同或不同的R33和R34独立地是氢原子、线形或支化C1-C4烷基;以及可以相同或不同的R36和R38独立地是氢原子、线形或支化C1-C18烷基、羧基、羟基、C1-C18烷氧基、氨基或卤原子。
适用于上述单偶氨配合物染料中的阳离子是H+;碱金属阳离子、铵离子、包括脂肪族伯、仲、叔胺在内的有机胺的阳离子和季铵离子。
适用于形成上述单偶氮配合物染料且在染料中常用的胺,包括脂族胺、脂环族胺、烷氧基烷基胺、带链烷醇的胺、二胺、胍衍生物的胺和芳族胺。
如式[V]所示、其中B1和B2是式[V-a]的单偶氮配合物染料的实例示于表4。
式[V-c]:
Figure C0181877500132
表4
  产品实例号 R30 R31 R35 R36 M2 L3 L4 m2 K2(D)+
  V-1   H   H   H   H   Cr   COO   COO   1   H+
  V-2   Cl   Cl   SO2NH2   H   Cr   O   O   1   H+
  V-3   SO2NH2   SO2NH2   SO2NH2   H   Cr   O   O   1   H+
  V-4   Cl   Cl   SO2NH2   H   Co   O   O   1   H+
  V-5   SO2NH2   SO2NH2   H   H   Ni   O   O   1   H+
  V-6   H   H   SO2NH2   H   Cu   COO   COO   1   H+
  V-7   H   H   H   H   Cr   COO   COO   1   C4H9CH(C2H5)OC3H6N+H3
  V-8   Cl   Cl   SO2NH2   H   Cu   O   O   1   C12H25N+H2(CH2CH2O)2H
  V-9   Cl   Cl   SO2NH2   H   Cr   O   O   1   Na+
  V-10   Cl   SO2NH2   H   Cl   Co   O   O   1   H+
如式[V]所示、其中B1和B2是式[V-b]的单偶氮配合物染料的实例示于表5。
式[V-d]:
Figure C0181877500141
表5
  产品实例号 R30 R31 R35 R36 M2 L3 L4 m2 K2(D)+
  V-11   SO2NH2   SO2NH2   H   H   Co   O   O   1   H+
  V-12   H   H   SO2NH2   H   Cr   COO   COO   1   H+
  V-13   Cl   Cl   H   H   Co   O   O   1   C4H9CH(C2H5)OC3H6N+H3
  V-14   SO2NH2   SO2NH2   SO2NH2   H   Cr   O   O   1   NH4 +
  V-15   Cl   Cl   SO2NH2   H   Co   COO   COO   1   H+
  V-16   H   H   SO2NH5   H   Co   COO   COO   1   H+
通过将特定的中性蒽醌染料与上述单偶氮配合物红染料或黄染料组合,我们能获得一种耐热性优良的黑着色剂。
上述单偶氮配合物染料能具有优良的耐热性。
与式[I]或式[II]的蒽醌染料混合以形成用作本发明着色剂中黑染料的蒽吡啶酮染料能用式[VI]表示,
式[VI]:
其中,可以相同或不同的R67-R71独立地选自下列一组:H、烷基、芳基、链烯基、烷氧基、氨基、羟基、卤原子、酰基、酰氧基、酰胺、酰基-N-烷基酰胺、羧基、烷氧基羰基、环己酰胺、磺酰基、式[VI-a];以及R67-R74中至少一个是磺酰基;其中P3是C-R72或N;R72是H、烷基、芳基、烷氧基、苯甲酰基或苄基;其中(G)3+代表铵离子或一个衍生自有机胺化合物或一种碱性染料的阳离子;其中s是1或2,m5是一个1-4的整数以及K5是比值m5/s;
式[VI-a]:
Figure C0181877500161
进一步,P4是O或NH,以及可以相同或不同的R73-R75独立地选自下列一组:H、烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、羟基、卤原子、酰基、酰氧基、酰胺基、酰基-N-烷基酰胺、羧基、烷氧基羰基或磺酰基。
适用于生产染料中上述蒽吡啶酮染料的胺,包括脂族胺、脂环族胺、烷氧基烷基胺、带链烷醇的胺、二胺、胍衍生物的胺及芳族胺。
式[VI]的蒽吡啶酮染料的实例示于表6中。
表6
  产品实例号 R67,R68,R69,R70,R71 P3 K5(G)∑+
  VI-1   R68=R69=R71=H,R67=CH3,R7=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=R75=H   CH   H3N+(CH2)6NH2
  VI-2   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=R75=H   CH   (CH3)3N+C12H25
  VI-3   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R 74=R75=H   CH   C2H5OC3H6N+H3
  VI-4   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=CH3,R75=H   CH   C4H9N+H3
  VI-5   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=CH3,R75=H   CH   N-三甲基-N-苄基铵
  VI-6   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=R74=SO3 -,R75=H   CH   2(CH3)4N+
  VI-7   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=C4H9,R75=H   CH   C12H25N+H2(CH2CH2O)2H
  VI-8   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=Cl,R75=H   CH   N-三甲基-N-苄基铵
  VI-9   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=CH3,R75=H   N   C2H5OC3H6N+H3
  VI-10   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=C8H17,R75=H   N   C12H25N+H3
  VI-11   R68=R69=R71=H,R67=H,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=R75=CH3   C-C4H9   二(对甲基苯基)胍铵
  VI-12   R67=R69=R71=H,R68=式[VI-a]-1R70=式[VI-a]-2,式[VI-a]-1:P4=O,R73=SO3 -,R74=C13H27,R75=H式[VI-a]-2:P4=NH,R73=SO3 -,R74=R75=CH3   C-苯甲酰基   (CH3)3N+C12H25
  VI-13   R67=R69=R71=H,R68=式[VI-a]-1R70=式[VI-a]-2,式[VI-a]-1:P4=O,R73=SO3 -,R74=CH3,R75=H式[VI-a]-2:P4=NH,R73=SO3 -,R74=R75=CH3   C-苯甲酰基   N-三甲基-N-苄基铵
  VI-14   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=O,R73=SO3 -,R74=R75=H   C-苯甲酰基   (C4H9)4N+
  VI-15   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=R75=H   CH   N-三甲基-N-苄基铵
  VI-16   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R73=SO3 -,R74=CH3,R75=H   CH   H3N+(CH2)6NH2
  VI-17   R68=R69=R71=H,R67=CH3,R70=式[VI-a],式[VI-a]:P4=NH,R74=SO3 -,R74=C8H17,R75=H   N   二苯基胍铵
吸收波长短于500nm、具有诸如黄、橙和红色且可以与中性蒽醌混合以产生黑色的蒽醌染料以下列色指数描述。
红染料
C.I.溶剂红52、57、111、114、136、137、138、139、143、144、145、146、147、148、149、150、151、、152、155、156、168、169、170、171、、172、177、181、190、191、194、199、200、201。
橙染料
C.I.溶剂橙35、55、64、65、66、68、69、71、77、86、87、163。
黄染料
C.I.溶剂黄100、109、117、125、156、158、163或C.I.瓮黄1、2、3。
适合于形成黑染料的组合物综述如下:
实施例1-黑染料
式[I-2]的中性蒽醌染料:式[IV-3]的迫位酮红染料:下式[a]的蒽醌黄染料的重量比为5∶3∶2。
式[a]:
Figure C0181877500181
实施例2-黑染料
式[I-3]的中性蒽醌染料:式[IV-3]的迫位酮红染料:式[a]的蒽醌黄染料的重量比为5∶4∶1。
实施例3-黑染料
式[II-9]的中性蒽醌染料:式[IV-2]的迫位酮红染料:式[a]的蒽醌黄染料的重量比为6∶3∶1。
实施例4-黑染料
式[II-3]的中性蒽醌染料:式[IV-3]的迫位酮红染料:下式[b]的蒽醌黄染料的重量比为3∶2∶1。
式[b]:
Figure C0181877500191
实施例5-黑染料
式[I-4]的中性蒽醌染料:式[V-2]的单偶氮配合物染料:式[a]的蒽醌黄染料的重量比为6∶2∶1。
实施例6-黑染料
式[I-5]的中性蒽醌染料:式[V-3]的单偶氮配合物染料:式[b]的蒽醌黄染料的重量比为5∶2∶1。
实施例7-黑染料
式[II-4]的中性蒽醌染料:式[V-2]的单偶氮配合物染料:式[a]的蒽醌黄染料的重量比为5∶3∶2。
实施例8-黑染料
式[I-1]的中性蒽醌染料:式[VI-5]的蒽吡啶酮染料:式[a]的蒽醌黄染料的重量比为5∶4∶1。
实施例9-黑染料
式[I-2]的中性蒽醌染料:式[VI-2]的蒽吡啶酮染料:式[V-16]的单偶氮配合物染料的重量比为5∶3∶1。
实施例10-黑染料
式[II-4]的中性蒽醌染料:式[V-2]的单偶氮配合物染料:式[b]的蒽醌黄染料的重量比为6∶3∶1。
用作模塑树脂以进行激光焊接的树脂可以是任何树脂,只要它们是热塑性树脂即可。从耐热性和透明性角度看,优选聚酰胺树脂和聚酯树脂,但也可用包括聚碳酸酯树脂在内的其它热塑性树脂,不论单独使用或彼此组合使用,或与上述优选树脂组合使用均可。
适用于本发明的聚酰胺树脂的几个实例包括二羧酸与二胺的缩聚产物,氨基酸的缩聚产物和环内酰胺的开环聚合产物。适用于本申请的二羧酸的实例包括己二酸、壬二酸、癸二酸、十二烷双酸、间苯二甲酸和对苯二甲酸。适用的二胺的实例包括丁二胺、己二胺、辛二胺、十一烷二胺、十二烷二胺、2-甲基戊二胺、2-甲基辛二胺、三甲基己二胺、二(对-氨基环己基)甲烷、间-二甲苯二胺和对-二甲苯二胺。作为氨基酸的实例,可用11-氨基十二烷酸。适用的环内酰胺包括己内酰胺和月桂内酰胺。缩聚产物和开环聚合产物的具体实例包括脂族聚酰胺如尼龙6、尼龙66、尼龙46、尼龙610、尼龙612、尼龙11、尼龙12,半芳族聚酰胺如聚间二甲苯己内酰胺(尼龙MXD-6)、聚对苯二甲酸己二酰胺(尼龙6T)、聚间苯二甲酸己二酰胺(尼龙6I)和聚对苯二甲酸壬烷二酰胺(尼龙9T)以及这些聚合物的共聚物与混合物。适用的共聚物包括尼龙6/66、尼龙66/6I、尼龙6I/6T和尼龙66/6T。
在本发明实践中,宜与着色剂共混的一大类普通聚酯模塑组合物是本领域内已知的。它们包括通常是二羧酸和二元醇的缩聚产物。二羧酸可选自下列一组:己二酸、壬二酸、癸二酸、十二烷双酸、对苯二甲酸、间苯二甲酸、萘二羧酸和二苯基二羧酸,以及二元醇可选自下列一组:乙二醇、丙二醇、丁二醇、己二醇、新戊二醇、环己二醇和双酚A。优选的聚酯包括聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丙二酯(PGT)、聚对苯二甲酸丁二酯(PBT)、聚2,6-萘二羧酸乙二酯(PEN)、聚对苯二甲酸环己烷二甲酯(PCT)和它们的共聚物和混合物。作为共聚物的实例,可以在缩聚产物中加入一些二羧酸或一些二元醇。聚酯聚合物可以与少量具有3个以上官能团的1,3,5-苯三酸、偏苯三酸、1,2,4,5-均苯四酸、甘油和季戊四醇之类的组分共聚。
还可存在包括聚碳酸酯在内的其它聚合物,只要不明显改变本发明组合物的基本特性即可。
可用于本发明组合物中的黑着色剂,优选包含中性蒽醌染料与至少其它红染料按预定重量比的混合物,所述中性蒽醌染料赋予蓝色、吸收短于700nm波长可见光并透过红外区波长为800nm-1200nm的激光束,所述红染料透过红外区波长为800nm-1200nm的激光束,如迫位酮染料或单偶氮配合物染料。
当组合物至少包含聚酰胺6为聚酰胺树脂组合物的主要组分时,含中性蒽醌染料的黑着色剂的用量为0.01-1重量%。上述染料混合物的用量可取决于要求不同激光焊接性的应用。
本发明的组合物可含一种无机填料或增强剂,包括,例如,纤维增强剂如玻璃纤维和碳纤维、玻璃珠、玻璃箔、滑石粉、高岭土、硅灰石、二氧化硅、碳酸钙、钛酸钾和云母。其中优选玻璃纤维。适用于本发明的玻璃纤维是一般用作热塑性树脂与热固性树脂增强剂的那些。
选自用于树脂组合物不同应用的一种或多种任选化合物都可包含在本发明的组合物中。
一般而言,添加剂化合物可包括阻燃剂、冲击改性剂、粘度改性剂、耐热改性剂、润滑剂、抗氧剂和UV-和其它稳定剂。本发明聚酰胺树脂组合物中这类添加剂化合物的含量以它们不会损害其特性为度。
在本发明中,提供适合于激光焊接的热塑性树脂组合物,用来制备对激光束透明的制品,以便与对激光束不透明的制品激光焊接在一起。这类不透明制品及其组合物在例如DE-A-4432081中已有所述。
参考本文的附图,图1是一种传统焊接装置的示意图。激光束1穿过第一制品2到达含激光束吸收组合物的第二制品3,已吸收激光能量的制品3的表面4被熔化并与第一制品2的表面压在一起而将它们焊接在一起。如图2所示,2个热塑性部件5和6必须具有不同的透射系数和吸收系数,而在2个颜色相同的制品表面8难以焊接。在图2中,激光束1施加在部件5的表面7。
在本文图3和5中,示意了一块实施例激光焊接试验中所用的下试片10。所注尺寸在试片10上产生一个缺口。上试片9具有相同的结构与尺寸。在图4和6中,示意了上试片9与下试片10的连接,以及为形成焊接,激光11的移动(在箭头方向上)。
实施例
本发明用下列实施例和对比实施例加以说明。
实施例A
用一台烘干设备,将未增强尼龙6ZYTEL颗粒(购自杜邦公司,商品名ZYTEL7301)在120℃烘8小时以上,并按下述配方称重。
尼龙6                             ……400g
下式[I-2]的蒽醌蓝染料             ……0.40g
下式[IV-3]的迫位酮红染料          ……0.24g
下式[a]的蒽醌黄染料               ……0.16g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
对于这个和含有该特定尼龙级的所有其它试验,用一台注塑机(Kawaguchi Tekko公司产品,商品名:K50-C),以250℃的料筒温度和60℃的模具温度,以常规方法注塑成型前述所得混合物,得到一种均匀的黑色试片(48×86×3(mm)),试片具有优良外观和表面光泽,无颜色不均匀性。在注塑成型机中保持15min后所得试片未褪色。
实施例B
尼龙6(同实施例A)                  ……400g
下式[I-4]的蒽醌蓝染料             ……0.36g
下式[IV-3]的迫位酮红染料          ……0.28g
下式[b]的蒽醌黄染料               ……0.16g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例A所述制备与试验试片,结果报告在下表7中。在注塑成型机中保持15min后所得试片未褪色。
对比实施例C
尼龙6(同实施例A)                  ……400g
下式[c]的蒽醌紫染料               ……0.68g
下式[d]的醌型pthalone黄染料       ……0.12g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例A所述制备与试验试片,结果报告在下表7中。在注塑成型机中保持15min后所得试片褪色且不均匀。
式[c]:
Figure C0181877500221
式[d]:
Figure C0181877500231
对比实施例D
尼龙6(同实施例A)                   ……400g
下式[e]的蒽醌绿染料                ……0.48g
下式[f]的蒽醌红染料                ……0.32g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例A所述制备与试验试片,结果报告在下表7中。在注塑成型机中保持15min后所得试片褪色且不均匀。
式[e]:
Figure C0181877500232
式[f]:
对比实施例E
尼龙6(同实施例A)                   ……400g
下式[e]的蒽醌绿染料                ……0.48g
下式[g]的双偶氮红染料              ……0.32g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例A所述制备与试验试片,结果报告在下表7中。在注塑成型机中保持15min后所得试片褪色且不均匀。
式[g]:
Figure C0181877500241
对比实施例F
尼龙6(同实施例A)                   ……400g
下式[h]的蒽醌蓝染料                ……0.53g
下式[IV-3]的迫位酮红染料           ……0.18g
下式[a]的蒽醌黄染料                ……0.09g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例A所述制备与试验试片,结果报告在下表7中。在注塑成型机中保持15min后得到的试片褪色且不均匀。
式[h]:
Figure C0181877500242
表7
  实施例A   实施例B   对比实施例C   对比实施例D   对比实施例E   对比实施例F
  透射率   TA   0.96   0.97   0.90   0.95   0.95   0.95
  TB   1.00   1.02   0.85   0.86   0.94   0.97
  OD   2.42   2.42   2.45   2.42   2.42   2.39
  耐热性ΔE   0.46   0.38   1.73   1.55   1.62   1.86
  耐湿性ΔE   0.75   0.68   1.08   1.56   2.73   1.14
  TG/DTA放热峰(℃)吸热峰(℃) 363.3/无 359.1/无 320.9/179.5 369.7/154.6 367.2/196.2 327.4/102.4
该试验表明,在实施例A和B中,耐热性与耐湿性未降低。尤其是,在TG/DTA分析中,实施例A和B无吸热峰。这说明象实施例A和B这样的组合物即使在注塑机中保持一段时间(例如15min)后,由模塑成型得到的试片性能仍未降低。另一方面,在尼龙6的熔点以下出现吸热峰的对比实施例C、D、E和F,则在以同样方法模塑后很可能要褪色。注塑成型机越大,则在注塑机内热保留性能就越重要。
实施例G
用一台真空干燥设备将未增强聚酯(由对苯二甲酸与乙二醇制备,当以其在重量比为1∶1的苯酚/二氯代苯混合溶剂中1%的溶液在25℃测定时,特性粘数为0.85)在120℃烘8小时以上,并按以下配方称重。
聚酯                                 ……400g
下式[II-9]的蒽醌蓝染料               ……0.40g
下式[IV-3]的迫位酮红染料             ……0.24g
下式[a]的蒽醌黄染料                  ……0.16g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
对于这个和含有该特定级聚酯的所有其它试验,用一台注塑机(Kawaguchi Tekko公司产品,商品名:K50-C),以290℃的料筒温度和60℃的模具温度,以常规方法注塑成型前述所得混合物,得到一种均匀的黑色试片(48×86×3(mm)),试片具有优良外观和表面光泽,无颜色不均匀性。在注塑成型机中保持15min后,所得试片未褪色。
实施例H
聚酯(同实施例G)                     ……400g
下式[I-2]的蒽醌蓝染料               ……0.40g
下式[IV-3]的迫位酮红染料            ……0.24g
下式[a]的蒽醌黄染料                 ……0.16g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例G所述制备与试验试片,结果报告在下表8中。在注塑成型机中保持15min后,所得试片未褪色。
实施例I
聚酯(同实施例G)                     ……400g
下式[I-4]的蒽醌蓝染料               ……0.36g
下式[IV-3]的迫位酮红染料            ……0.28g
下式[b]的蒽醌黄染料                 ……0.16g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例G所述制备与试验试片,结果报告在下表8中。在注塑成型机中保持15min后,所得试片未褪色。
对比实施例J
聚酯(同实施例G)                     ……400g
下式[c]的蒽醌紫染料                 ……0.68g
下式[d]的Quinlpthalone黄染料        ……0.12g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例G所述制备与试验试片,结果报告在下表8中。在注塑成型机中保持15min后,所得试片褪色且不均匀。
对比实施例K
聚酯(同实施例G)                     ……400g
下式[e]的蒽醌绿染料                 ……0.48g
下式[f]的蒽醌红染料                 ……0.32g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例G所述制备与试验试片,结果报告在下表8中。在注塑成型机中保持15min后,所得试片褪色且不均匀。
对比实施例L
聚酯(同实施例G)                     ……400g
下式[e]的蒽醌绿染料                 ……0.48g
下式[g]的双偶氮红染料               ……0.32g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例G所述制备与试验试片,结果报告在下表8中。在注塑成型机中保持15min后,所得试片褪色且不均匀。
对比实施例M
聚酯(同实施例G)                     ……400g
下式[h]的蒽醌蓝染料                 ……0.53g
下式[IV-3]的迫位酮红染料            ……0.18g
下式[a]的蒽醌黄染料                 ……0.09g
将以上各式产物在一个不锈钢转鼓内搅拌并混合1小时。
如以上实施例G所述制备与试验试片,结果报告在下表8中。在注塑成型机中保持15min后所得试片褪色且不均匀。
表8
实施例G 实施例H 实施例I   对比实施例J   对比实施例K   对比实施例L   对比实施例M
  透射率   TA   0.88   0.93   0.93   0.92   0.93   0.92   0.93
  TB   0.85   0.93   0.93   0.89   0.93   0.89   0.96
  OD   1.78   1.81   1.80   1.86   1.78   1.85   1.78
  耐湿性ΔE   3.15   3.56   3.30   5.02   4.64   4.48   4.55
  升华试验ΔE   5.32   9.72   7.07   19.33   12.36   11.97   17.42
  TG/DTA放热峰(℃)/吸热峰(℃) 532.8/无 363.3/无 359.1/无 320.9/179.5 369.7/154.6 367.2/196.2 327.4/102.4
该试验表明,在实施例G,H和I中,耐湿性未降低。尤其是,与对比实施例J,K,L和M相比,实施例G,H和I表现为低升华。因此,即使将由实施例G,H或I着色的热塑性树脂组合物,放在如汽车或电子工业中较高温度的空间内,其着色剂也不会迁移到其它部件。而且在注塑机中的热保留性方面,出现了与尼龙6相同的结果。
试验方法
(1)透射性
用Hitachi生产的带60球式分光计、波长从远紫外到近红外的U-3410分光光度计,以波长分别为940nm(半导体激光)和1064nm(YAG激光)的激光束,测定试片在400nm-1200nm范围内的透射率(T)。确定940nm的透射率:1064nm的透射率之比(TA)和940nm的透射率:天然树脂的透射率之比(TB),并在实施例之间进行比较。
(2)外观和表面光泽
评价试片外观的方法是,用Macbeth生产的反射密度计TR-927测定试片的反射密度(OD)。试片的OD值越高,说明有更好的表面光洁度且富有光泽。
(3)耐热性
用比色计(Juki生产,商品名:JP7000)测定每块试片放置并保持在160℃烘箱内15天“前”、“后”的褪色量ΔE。
(4)耐湿性
用比色计(Juki生产,商品名:JP7000)测定每块试片放置并保持在80℃(湿度95%)调温箱内7天“前”、“后”的褪色ΔE量。
(5)TG(热重分析仪)/DTA(差热分析仪)
用TG/DTA分析仪(Seiko Instrument生产,商品名:SII EXSTAR6000)在加热炉内测定每种试验着色剂粉末的TG和DTA,加热炉内输入200ml/min的空气,从30-55℃起,以10℃/min的速率升温,当达到550℃时,保持28min。
(6)升华试验
用比色计(Juki生产,商品名:JP7000)测定粘贴在各试片上的白色条带放置并保持在140℃烘箱内3小时“前”、“后”的ΔE量,以确定染料升华量。
粘贴在试片上的白带的ΔE越高,表明其升华越严重。
实施例N和对比实施例O和P
将玻璃纤维增强尼龙6(Zytel73G30L,购自杜邦公司)与染料按表9所示之量进行干混。将该共混料模塑成两类试片:一类用来测力学性能,另一类用来激光焊接。测力学性能用的试片在Toshiba IS170FIII注塑机上按IS03167模塑成型,料筒温度定在260℃,模具温度定在80℃。激光焊接用试片的尺寸如图3所示,在Sumitomo Juki75T注塑机上模塑成型,料筒温度定在250℃,模具温度定在80℃。
拉伸强度和伸长率按ISO527测定,缺口冲击强度按ISO179测定。
用2块上述试片结合图4的描述进行激光焊接。用实施例N和对比实施例0作为上试片以及对比实施例P作为下试片。用功率为50W、直径为3mm和不同速度的二极管激光(波长940nm,Rofin-Sinar LaserGmbH制造)进行辐照。焊接试片的拉伸强度在Autograph(ShimazuSeisakusho制造)上以5mm/min的速率将两试片拉开进行测试,并记录最大载荷。
表9
  实施例N   对比实施例O   对比实施例P
  73G30L           kg式[I-2]蓝染料式[IV-3]红染料式[a]黄染料式[e]绿染料式[g]红染料炭黑   4.99253.75g2.25g1.50g   4.99254.50g3.00g   4.9910g
  拉伸强度         MPa伸长率           %缺口冲击强度     KJ/m2   1743.912.8   1814.213.3   1853.412.2
  激光焊接,50W2.5m/min         Kgf5m/min           Kgf10m/min          Kgf 195196115 189177110 ---
实施例Q和对比实施例R与S
将玻璃纤维增强尼龙66(Zytel70G33HSlL,购自杜邦公司)与染料按表10所示之量进行干混。将共混料模塑成两类试片:一类用来测力学性能,另一类用来激光焊接。测力学性能用的试片在Toshiba IS170FIII注塑机上按IS03167模塑成型,料筒温度定在280℃,模具温度定在80℃。激光焊接用试片的尺寸如图3所示,在Sumitomo Juki75T注塑机上模塑成型,料筒温度定在270℃,模具温度定在80℃。
拉伸强度和伸长率按ISO 527测定,缺口冲击强度按ISO 179测定。
用2块上述试片结合图4的描述进行激光焊接。用实施例Q和对比实施例R作为上试片以及对比实施例S作为下试片。用功率为80W、直径为3mm和不同速度的二极管激光(波长940nm,Rofin-Sinar LaserGmbH制造)进行辐照。焊接试片的拉伸强度在Autograph(ShimazuSeisakusho制造)上以5mm/min的速率将两试片拉开进行测试,并记录最大载荷。
表10
  实施例Q   对比实施例R   对比实施例S
  70G33HSlL        kg式[I-4]蓝染料式[IV-3]红染料式[a]黄染料式[e]绿染料式[g]红染料炭黑   4.99253.75g2.25g1.50g   4.99254.50g3.00g   4.9910g
  拉伸强度         MPa伸长率%缺口冲击强度     KJ/m2   1993.412.3   2073.813.5   2073.211.9
  激光焊接,80W2.5m/min         Kgf5m/min           Kgf10m/min          Kgf 97195194 75185187 ---
实施例T-实施例V,对比实施例W-AA
将未增强尼龙6(Zytel→7301,购自杜邦公司)与染料按表11所示之量进行干混。将共混料在K50-C注塑机(Kawaguchi Steel K.K.制造)上模塑成激光焊接用试片,尺寸如图5所示,料筒温度定在250℃,模具温度定在60℃。
用2块如上所述的试片结合图6的描述进行激光焊接。用实施例T-V和对比实施例W-Z作为上试片以及对比实施例AA作为下试片。用功率为50W、直径为3mm、速度为1m/min的二极管激光(波长940nm,Rofin-Sinar Laser GmbH制造)进行辐照。焊接试片的拉伸强度在Autograph(Shimazu Seisakusho制造)上以50mm/min的速率将两试片拉开进行测试,并记录最大载荷。
表11
  实施例T   实施例U   实施例V   对比实施例W   对比实施例X   对比实施例Y   对比实施例Z   对比实施例AA
 尼龙6式[I-4]蓝染料式[IV-3]红染料式[a]黄染料式[II-9]蓝染料式[I-2]蓝染料式[c]紫染料式[d]黄染料式[e]绿染料式[f]红染料式[g]红染料式[h]蓝染料NUBIAN配合物黑G04   400g0.40g0.24g0.16g   400g0.24g0.16g0.40g   400g0.24g0.16g0.40g   400g0.68g0.12g   400g0.48g0.32g   400g0.48g0.32g   400g0.18g0.09g0.53g   400g0.80g
 940nm的透射率(2mm厚)激光焊接强度(Kgf) 170 151 292 194 195 171 188 -
NUBIAN配合物黑G04(产品名;Orient Chemical Industries公司产品):一种碳与尼格的混合物。
实施例AB和对比实施例AC-AE
将玻璃纤维增强聚酯(由对苯二甲酸与乙二醇制备,当以其在重量比为1∶1的苯酚/二氯代苯混合溶剂中1%的溶液在25℃测定时,特性粘数为0.85,并含聚酯树脂组合物总重量30重量%的NipponElectric Glass公司生产的短切玻璃纤维187H,如实施例G所述烘干)与染料按表12所示之量进行干混。将共混料模塑成两类试片:一类用来测力学性能,另一类用来激光焊接。测力学性能用的试片在Toshiba IS 170FIII注塑机上按ISO3167模塑成型,料筒温度定在290℃,模具温度定在60℃。激光焊接用的试片尺寸如图3所示,在Sumitomo Juki 75T注塑机上模塑成型,料筒温度定在280℃,模具温度定在60℃。
拉伸强度和伸长率按ISO 527测定,缺口冲击强度按ISO 179测定。
用2块上述试片结合图4的描述进行激光焊接。用实施例AB和对比实施例AC-AD作为上试片以及对比实施例AE作为下试片。用功率为50W、直径为3mm和常规速度的二极管激光(波长940nm,Rofin-SinarLaser GmbH制造)进行辐照。焊接试片的拉伸强度在Autograph(Shimazu Seisakusho制造)上以5mm/min的速率将两试片拉开进行测试,并记录最大载荷。
表12
  实施例AB   对比实施例AC   对比实施例AD   对比实施例AE
  73G 30L          kg式[I-2]蓝染料式[IV-3]红染料式[a]黄染料式[c]紫染料式[d]黄染料式[e]绿染料式[g]红染料炭黑   4.99253.75g2.25g1.50g 6.375g1.125g   4.99254.50g3.00g   4.9910g
  拉伸强度         MPa伸长率%缺口冲击强度     KJ/m2   1354.313.0   1334.314.0   1354.013.0   1502.710.5
  激光焊接,50W5m/min           Kgf 150 144 145 -

Claims (7)

1.一种适用于激光焊接的热塑性树脂组合物,它包含
1)聚酰胺或聚酯;
2)一种包含式[I]中性蒽醌染料的激光透射黑着色剂其中,式[I]是
其中,相同或不同的R55和R58独立地选自含1-18个碳原子的烷基;相同或不同的R56和R59独立地选自下列一组:烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、烷氧基羰基、羟基、羧基和卤原子;以及相同或不同的R57和R60独立地选自下列一组:H、烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、羧基、烷氧基羰基、羟基和卤原子。
2.权利要求1的组合物,它还包含一种与所述中性蒽醌染料混合以形成所述黑着色剂的第二染料。
3.权利要求2的组合物,其中所述第二染料选自下列一组:迫位酮染料、单偶氮配合物染料和蒽醌染料。
4.权利要求1的组合物,它还包含增强剂。
5.一种由权利要求1的组合物形成的透明制品。
6.一种通过激光焊接不透明制品与权利要求5的透明制品所形成的制品。
7.一种宜与聚酰胺或聚酯混合并适合于激光焊接的黑着色剂,它包含一种式[I]中性蒽醌染料与至少一种其它红染料的混合物,所述中性蒽醌染料赋予蓝色,吸收波长短于700nm的可见光,透过红外区中波长为800nm-1200nm的激光束,所述其它红染料透过红外区中波长为800nm-1200nm的激光束;
式[I]是
Figure C018187750003C1
其中,相同或不同的R55和R58独立地选自含1-18个碳原子的烷基;相同或不同的R56和R59独立地选自下列一组:烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、烷氧基羰基、羟基、羧基和卤原子;以及相同或不同的R57和R60独立地选自下列一组:H、烷基、芳基、链烯基、烷氧基、氨基、N-烷基酰胺、N-芳基酰胺、酰基、酰胺、羧基、烷氧基羰基、羟基和卤原子。
CNB018187757A 2000-11-13 2001-11-13 适合激光焊接的着色热塑性树脂组合物、作为其着色剂的特定中性蒽醌染料及其模塑制品 Expired - Lifetime CN1250625C (zh)

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