CN100584882C - 透射激光的着色聚烯烃树脂组合物以及激光焊接的方法 - Google Patents
透射激光的着色聚烯烃树脂组合物以及激光焊接的方法 Download PDFInfo
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- CN100584882C CN100584882C CN200480004230A CN200480004230A CN100584882C CN 100584882 C CN100584882 C CN 100584882C CN 200480004230 A CN200480004230 A CN 200480004230A CN 200480004230 A CN200480004230 A CN 200480004230A CN 100584882 C CN100584882 C CN 100584882C
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- polyolefin resin
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Classifications
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Abstract
含有蒽醌盐形式的染料的透射激光的着色聚烯烃树脂组合物；以及激光焊接的方法，其中，通过照射激光，将所述树脂组合物的激光透射材料和激光吸收材料的接触部位进行焊接，使得激光穿过所述激光透射材料并且被激光吸收材料吸收，所述激光透射材料与激光吸收材料相互接触：(见右式)A，B：-NH-或-O-；R1-R3：氢，氨基，羟基，卤素；R4-R13：氢，烷基，硝基，磺基；Kin+：有机铵离子；m：1或2；n：1或2；所述磺基是-SO3或-SO3M，-SO3的数量是m，M代表氢或碱金属。
Description
技术领域
本发明涉及一种包含蒽醌盐形成的染料的透射激光的着色聚烯烃树脂组合物，以及使用所述透射激光的着色聚烯烃树脂组合物的激光焊接方法。
背景技术
合成树脂材料的激光焊接例如可以如下所述进行。如图1所示，加入激光透射材料的一个部分与另一个加入激光吸收材料的部分相互接触。当从激光透射材料面向激光吸收材料辐射激光时，已经透过激光透射材料的激光被激光吸收材料吸收并产生热量。通过该热量，激光吸收材料在已吸收激光部位的周围被熔化，并且激光透射材料也被熔化，两部分的树脂熔合在一起，冷却后，获得足够的焊接强度，激光透射材料和激光吸收材料牢固地结合在一起。激光焊接的特点包括：具有不必使产生激光的部分与将要焊接的部分相接触下进行焊接的能力；因为加热是局部的，对于周围部位的热影响最小；避免了机械震动；能够焊接细微部分和结构；高的再现性；可保持高气密性；高焊接强度；不明显的焊接部位；不产生灰尘等。
传统地，树脂部件通过用夹具(螺栓、螺钉、夹子等)夹紧、使用粘合剂粘合、振动焊接、超声焊接等连接在一起。激光焊接可达到节约劳动力、提高生产率、降低生产成本等功效，因为通过简单操作即可获得相当于或高于采用传统方法所获得的强度水平，实现牢固的焊接，并且振动和热影响最小。由于这些特点，激光焊接适于连接功能元件、电子元件等，因为它们需要避免振动或热的影响，例如，汽车工业、电/电子工业以及其它领域，并且适用于连接复杂形状的树脂部件。
作为一种涉及激光焊接的技术，日本专利公报HEI-11-170371描述了一种激光焊接方法，包括如下过程：辐射激光，使之聚集于一个区域，在该区域上，一个包含激光吸收热塑性合成树脂的不透明部件和一个包含激光透射的热塑性合成树脂的无色透明部件相互接触。然而，在这种情况下，当从无色透明部件侧看，焊接部分与非焊接部分在颜色和光滑度上都是不同的，产生外观差的问题。
此外，WO02/36329描述了聚烯烃树脂的激光焊接，使用蒽醌染料和perinone染料作为着色剂。然而，如果使用普通的中性染料来着色聚烯烃树脂，染料未必牢固，因为聚烯烃树脂与染料的结合性小，并且还因为使用的中性染料在树脂中具有非常高的溶解性，造成渗色现象，在与其它聚烯烃树脂接触时染料可迁移到别的地方。这不但在使用激光焊接时，而且在着色聚烯烃树脂的一般状况下，都是严重的问题。
考虑到在先技术中的前述问题，研制出本发明，本发明目的是提供一种激光透射的着色聚烯烃树脂组合物，它对于激光波长范围(波长从800nm至1200nm，如808，820，840，940和1064nm)是高度透过的，它在树脂部件激光焊接前的热处理过程中，着色的聚烯烃树脂部件不会发生颜色消退，它使得激光焊接基本上不发生染料的升华，并且它拥有足够的抗渗色性质；以及提供一种使用同样的透射激光的着色聚烯烃树脂组合物的激光焊接的方法。
发明内容
本发明的透射激光的着色聚烯烃组合物包含一种蒽醌盐形成的染料(即一种由阴离子组分构成的盐形成的染料，其可从蒽醌酸性染料和有机氨组分获得)，由下面通式(1)表示：
在通式(1)中，
A和B各自独立地代表-NH-或-O-
R1至R3各自独立地代表氢、氨基、羟基或卤素，
R4至R13各自独立地代表氢、烷基、硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M可以相同或不同，只要SO3M的数量是2或更大。
在聚烯烃树脂中由于与染料微弱结合而一般不易固着，上述由通式(1)表示的蒽醌盐形成的染料稳定固着在聚烯烃树脂中，并且与树脂相容。因此，通过用这种蒽醌盐形式的染料着色，可能获得一种透射激光的聚烯烃树脂部件，它是热稳定的，对环境不敏感，并且它拥有极好的激光透射能力。
前述的蒽醌盐形式的染料的一大特点是蒽醌结构中存在两个以下结构。
同样重要的是，应该调节蒽醌盐形式的染料中磺基的数量。
本发明的透射激光的着色聚烯烃树脂组合物能很好透射半导体激光器产生的约800nm至YAG激光器产生的约1100nm波长范围的射线，即激光，该组合物呈现如高耐热牢度和耐光牢度，具有好的抗迁移性、耐化学性等，并呈现明亮的颜色。着色的树脂部件与所述透射激光的着色聚烯烃树脂组合物可以进行激光焊接，而不会使树脂部件在激光焊接前的加热处理中发生颜色消退，基本上没有染料升华。本发明使用母料着色的透射激光的着色聚烯烃树脂组合物着色更均匀，不呈现因着色剂引起的光散射，并呈现良好的激光透射能力。
同时，本发明的激光焊接的方法包括：通过辐射激光，焊接包含任何前述透射激光的着色聚烯烃树脂的激光透射材料与激光吸收材料的接触部位，使得激光透射材料透过激光，并且激光被激光吸收材料吸收，所述激光透射材料与激光吸收材料相互接触。
根据本发明的激光焊接方法，激光透射材料与激光吸收材料的接触部位可通过辐照激光被焊接，使得激光透射材料透过激光，并且激光被激光吸收材料吸收，所述激光透射材料和激光吸收材料相互接触。这种激光焊接的方法中，激光透射材料可以进行激光焊接而不会在激光焊接前的热处理过程中使树脂部件褪色，基本上没有染料升华。
附图简要说明
图1是激光焊接试验的侧视图。
图2是激光焊接试验的斜视图。
实施本发明的方式
本发明的透射激光的着色聚烯烃树脂组合物包含至少一种由上面式(1)表示的蒽醌盐形式的染料。由于所述蒽醌盐形式的染料具有大的分子量并且与聚烯烃树脂特别是聚丙烯树脂能高度结合，它对本发明的透射激光的着色聚烯烃树脂组合物的耐热性和抗升华性品质是有效的。
在本发明中使用的聚烯烃并非用于限制。
作为聚烯烃树脂的例子，有α-烯烃如乙烯、丙烯、丁烯-1、3-甲基丁烯-1、4-甲基戊烯-1和辛烯-1的均聚物或其共聚物，或这些与其它可共聚的不饱和单体的共聚物(作为共聚物，述及有嵌段共聚物、无规共聚物和接枝共聚物)。
更具体地，述及的聚乙烯树脂如高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯、乙烯-乙酸乙烯酯共聚物和乙烯-丙烯酸乙酯共聚物；聚丙烯树脂如丙烯均聚物、丙烯-乙烯嵌段共聚物或无规共聚物以及丙烯-乙烯-丁烯-1共聚物；聚丁烯-1，聚-4-甲基戊烯-1等。
这些聚烯烃树脂可以单独使用，或两种或更多种组合使用。作为本发明中聚烯烃的其它例子，有聚烯烃弹性体，如聚丙烯树脂弹性体，各种包含上述树脂作为主要组分的热塑性弹性体(包括各种橡胶)，包含合成蜡或天然蜡的聚烯烃，等等。
在本发明中，优选使用其中的聚丙烯树脂和/或聚乙烯树脂。特别优选聚丙烯树脂。所述聚丙烯树脂不受限制，可在一个宽分子量范围内被使用。
作为聚烯烃树脂，可使用一种用不饱和羧酸或其衍生物进行酸改性的聚烯烃，将包含发泡剂的发泡聚丙烯加入到该树脂中而不影响所需的效果，等等。
作为如前所述的丙烯共聚物，优选包含75重量％或更高的丙烯，特别是包含90重量％或更高的丙烯的那些，因为它们保留了聚丙烯树脂所特有的结晶度、硬度、耐化学性等。
作为前述可共聚的单体的具体例子，有一种或两种或更多种类的具有2或4至12个碳原子的α-烯烃，如乙烯、1-丁烯、异丁烯、戊烯-1、3-甲基-丁烯、己烯-1、4-甲基-戊烯-1、3，4-二甲基-丁烯-1、庚烯-1、3-甲基-己烯-1、辛烯-1和癸烯-1；
环烯如环戊烯、降冰片烷和1，4，5，8-二亚甲基-1，2，3，4，4a，8，8a-6-八氢萘；
二烯如5-亚甲基-2-降冰片烷、5-亚乙基-2-降冰片烷、1，4-己二烯、甲基-1，4-己二烯和7-甲基-1，6-辛二烯；
乙烯基单体如氯乙烯、偏二氯乙烯、丙烯腈、乙酸乙烯酯、丙烯酸、甲基丙烯酸、丙烯酸丁酯、甲基丙烯酸甲酯和顺丁烯二酸酐；等等。
本发明中的蒽醌盐形式的染料可通过来自蒽醌酸性染料的阴离子和有机铵离子(如来自伯胺、仲胺、叔胺、胍或松香胺等的阳离子)的成盐反应来获得。该成盐反应可采用一种通常已知的离子反应。例如，一种具有两个磺基的酸染料组分分散在水中，以1.5至2.3mol/mol染料的比例，将有机胺组分溶解在盐酸水溶液中；将该溶液逐滴加入到所述的分散液中，搅拌数小时，进行反应。过滤反应混合物，用水洗涤滤出的滤饼并干燥，获得本发明的蒽醌盐形式的染料。
对上述通式(1)，其表示本发明的蒽醌盐形式的染料，A、B和R1至R13分别代表以下的基团或原子。
A和B各自独立地代表-NH-或-O-。
R1至R3各自独立地代表氢、氨基、羟基或卤素(如Cl，Br)。
R4至R13各自独立地代表氢、烷基(如有1至8个碳原子的烷基，如甲基、乙基、丙基、异丙基、正丁基、叔丁基、正戊基、异戊基、己基、庚基和辛基)、硝基或磺基。
Kin+代表有机铵离子；m代表1或2，n代表1或2。
对于本发明的透射激光的着色聚烯烃树脂组合物，较好是上面通式(1)中，R4至R8中至少一个是磺基，并且，R9至R13中至少一个是磺基。
在本发明中，作为对应于蒽醌盐形式的染料的阴离子组分的蒽醌酸染料的具体的例子有以下例子。然而，本发明并不限于这些例子。
化合物例子(1)-1
化合物例子(1)-2
化合物例子(1)-3
化合物例子(1)-4
化合物例子(1)-5
在前面的通式(1)中，Kin+是一种有机铵离子，构成本发明中蒽醌盐形式的染料的有机铵组分，可以由以下通式(2)或(3)表示。
在上面通式(2)中，R14至R17各自独立地代表，
氢，
烷基(如具有1至12个碳原子的烷基，可以是支链的，如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、己基、庚基、辛基、壬基、癸基、十一烷基和十二烷基)，
环烷基(如具有3至8个碳原子的环烷基团，如环丙基、环戊基、环己基和环庚基，或二氢重氮乙胺(dihydroaziethylamine)残基)，
烷氧基烷基(如具有2至20个碳原子的烷氧基烷基，如[甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基或辛氧基等]-[甲基、乙基、丙基、丁基、戊基或辛基等]等，即乙氧基甲基、甲氧基乙基等)，
烷醇基(如-CH2OH、-C2H4OH、-C3H6OH等)，
有或没有取代基[如氨基、低级(1至4个碳原子)烷基、卤素如Cl和Br]的芳基(如苯基、低级-烷基-取代的苯基、卤代苯基、萘基、氨基萘基)，
有或没有取代基[如氨基、有1至4个碳原子的烷基、卤素如Cl和Br]的芳烷基(如苄基、α-甲基苄基、α，α-二甲基苄基、α-丁基苄基、苯乙基)、萘烷基[如萘甲基、萘乙基等])，或
由下面通式(C)表示的基团。
上面通式(3)中，R18至R21各自独立地代表氢，或有或没有取代基[如氨基、低级(1至4个碳原子)烷基、卤素如Cl和Br]的芳基(如苯基、低级烷基-取代的苯基、卤代苯基、萘基、氨基萘基)。
由上面通式(2)和(3)表示的有机铵组分可获自下面列举的有机胺，然而，这些并不构成对本发明的限制。
具体地有：
脂族胺，如己胺、戊胺、辛胺、2-乙基己基胺、二-(2-乙基己基)胺和十二烷基胺；
脂环族胺，如环己胺、二-环己胺和二氢重氮乙胺；
烷氧基烷胺，如3-丙氧基丙胺、二-(3-乙氧基丙)胺、3-丁氧基丙胺、辛氧基丙胺和3-(2-乙基己氧基)丙胺；
萘胺，如α-萘胺、β-萘胺、1，2-萘二胺、1，5-萘二胺和1，8-萘二胺；
萘烷基胺如1-萘基甲胺；
含烷醇基的胺，如N-环己乙醇胺、N-十二烷基乙醇胺和N-十二烷基亚氨基-二-乙醇；
以及胍(衍生物)如1，3-二苯基胍，1-o-甲苯基胍和二-o-甲苯基胍。
对于上面由通式(2)表示的有机铵组分中，特别优选的基团列在表1中。
表1
由通式(3)表示的有机铵组分中，特别优选的基团列在表2中。
表2
特别地，在挤出机、注射成型机等机器中，如表2中所示的芳族胍在加热条件下不挥发。因此，对于前面由通式(1)表示的蒽醌盐形式的染料，含有这种芳族胍作为有机铵组分的那些染料不会分解，即使经过例如在成型过程中的热熔处理也不会分解，并且显示成型的产品中优良的可分散性。结果，获得的成型产品的激光透射性优良。
本发明中使用的蒽醌盐形式的染料具有一种颜色，如蓝色、紫色或绿色。作为用于本发明的透射激光的着色聚烯烃树脂组合物的着色剂，可使用具有各种颜色的蒽醌盐形式的染料，可单独使用，或两种或多种所述盐形式的染料组合使用。同样，作为用于本发明的透射激光的着色聚烯烃树脂组合物的着色剂，可使用一种或两种或多种颜料或染料，它们具有仅在蒽醌盐形式的染料的可见光吸收带以外的吸收带，或具有除可见光吸收带还具有可见光以外的吸收带，与上述蒽醌盐形式的染料一起，可以在激光波长带(波长为800nm至1200nm)透射光。通过混合为其它着色剂的具有一种颜色如黄色或红色的染料或色料，提供如上所述的良好的激光透射，可以产生不同的颜色。例如，通过在前述蒽醌盐形式的染料中的紫色染料和另一种黄色着色剂，可以产生黑的颜色。所述透射激光的着色聚烯烃树脂组合物中，黑色树脂组合物是工业上重要的。
作为能够给予树脂颜色的其它着色剂的例子，有偶氮盐形式的染料和/或恩吡啶酮(anthrapyridone)染料，呈现彩色的颜色，如黄色、橙色和红色，并且可透射激光。
在本发明的透射激光的着色聚烯烃树脂组合物中，可与通式(1)的蒽醌盐形式的染料一同使用的偶氮盐形式染料的阴离子组分所对应的酸性染料的具体的例子如下。红色酸性染料，如C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266；黄色酸性染料，如C.I.酸性黄4，9，17，18，19，23，36，41，42，49，105，199，200和219。然而，本发明不限于这些例子。
在本发明的透射激光的着色聚烯烃树脂组合物中，可与通式(1)的蒽醌盐形式的染料一同使用的蒽吡啶酮盐形式染料的阴离子组分所对应的酸性染料的具体的例子有：红色酸性染料，如C.I.酸性红80，81，82和143。然而，本发明不限于这些例子。
在本发明的透射激光的着色聚烯烃树脂组合物中，着色剂的用量可以在如相对于聚烯烃树脂的0.01至10重量％范围。优选量为0.1至5重量％，更优选为0.1至1重量％。
本发明的透射激光的着色聚烯烃树脂组合物的母料(高浓度成型产品)可通过如下方法获得：在滚混机或超级混合器中，混合将作为母料原料的聚烯烃树脂粉末或颗粒，和包含至少一种上面通式(1)的蒽醌盐形式的染料的着色剂，然后，通过在挤出机、分批捏炼机、辊捏合机等中热熔化，进行造粒或粗粒化。也可以通过如下方法获得母料，将前述着色剂加入到作为母料原料的聚烯烃树脂中，同时保持在合成后的溶液中，然后除去溶剂。
通过将获得的着色颗粒或粗粒化的着色剂(在本发明中，这种着色剂形式是指作为母料)与聚烯烃树脂混合，并通过常规方法成型，可以获得一种具有优良的激光透射品质的更均一的激光透射树脂部件。特别是，当使用蒽醌盐形式的染料和多种着色剂组合的黑色混合着色剂时，该影响是显著的。
同样地，母料可包含例如相对于聚烯烃树脂的1至30重量％的前述的着色剂。该含量比较好是5至15重量％。
T着色树脂/T非着色树脂，即波长为940nm的激光在本发明的透射激光的着色聚烯烃树脂组合物中的透射比T着色树脂与波长为940nm的激光在相同组成但无着色剂的非着色树脂中的透射比T非着色树脂的比值，该比值较好是0.8至1.2。
本发明的透射激光的着色聚烯烃树脂组合物可包含适量的各种增强材料，根据它们的应用和预期用途而定。对这些增强材料没有特别的限制，只要对合成树脂的常规增强有用。例如，可使用玻璃纤维、碳纤维、其它无机纤维和有机纤维(芳族聚酰胺、聚苯硫醚、尼龙、聚酯、液晶聚合物等)等，对要求透明度的树脂，优选玻璃纤维来增强。玻璃纤维的纤维长度较好2至15mm，纤维直径较好1至20μm。对玻璃纤维的形式没有限制，可以是任何形式，如粗纱纤维或捻合纤维。所述玻璃纤维可以单独使用或两种或更多种结合使用。较好地，相对于100重量％的聚烯烃，玻璃纤维含量为5至120重量％。如果该含量小于5重量％，不能获得足够的玻璃纤维增强效果；如果含量超过120重量％，成型加工性很可能下降。玻璃纤维的含量较好为10至60重量％，最好为20至50重量％。
本发明的透射激光的着色聚烯烃树脂组合物可包含适量的各种填料，根据它们的应用和预期用途而定。例如可以使用片状填料，如云母、绢云母和玻璃片；硅酸盐如滑石、高岭土、粘土、硅灰石、膨润土、石棉、水合硅酸铝；金属氧化物如氧化铝、氧化硅、氧化镁、氧化锆和氧化钛；碳酸盐如碳酸钙，碳酸镁和自云石；硫酸盐如硫酸钙和硫酸钡，以及颗粒填料，如玻璃珠、陶瓷珠、氮化硼和碳化硅。作为本发明的优选的填料例子有滑石。尽管填料的有用粒径范围很广，从细微的0.03μm至约100μm，优选0.03至10μm粒径的那些填料用于本发明的透射激光的着色聚烯烃树脂组合物以及激光焊接方法。填料含量优选为：相对于100重量％的聚烯烃树脂，5至50重量％的填料。如果含量低于5重量％，不能获得足够的填充效果；如果含量超过50重量％，激光透射明显下降。该含量优选为10至50重量％，特别是10至40重量％。
本发明的透射激光的着色聚烯烃树脂组合物中也可配入各种需要的添加剂，所述添加剂包括如助色剂、分散剂、稳定剂、增塑剂、质量改进剂、紫外吸收剂或光稳定剂、抗氧化剂、抗静电剂、润滑剂、脱模剂、促结晶剂、晶核化剂和阻燃剂。
本发明的透射激光的着色聚烯烃树脂组合物可采用任选的混合方法来混合原料而获得。通常优选将这些混合成分最大程度地均质化。更具体地，例如，所有原料在机械混合器如掺混机、捏合机、班伯里密炼机、开炼机或挤出机中混合和均质化，产生着色的聚烯烃树脂组合物。或者，一些原料在机械混合器中混合后，加入剩余的成分，接着进一步混合和均质化，产生树脂组合物。另外，首先在加热的挤出机中，在熔化状态下，将预先干混合的原料捏合和均质化，然后挤成针状物，再将针状物切成所需的长度，生产出颗粒状的着色树脂组合物(着色颗粒)。
本发明的透射激光的着色聚烯烃树脂组合物的成型可以通过普通应用的各种程序进行。例如，本发明的透射激光的着色聚烯烃树脂组合物可以在加工机器如挤出机、注射模塑机或辊炼机中，使用着色的颗粒成型，也可通过在适当的混合器中混合聚烯烃树脂颗粒或粉末、经研磨的着色剂、以及必要的各种添加剂，并使用加工机器进行成型。可以采用任何常用的成型方法，如注塑、挤塑、压塑、发泡成型、吹塑、真空成型、注射吹塑、旋转成型、压延成型和溶液流延。通过这样成型，可获得各种形状的激光透射材料。
本发明的激光焊接方法包括：通过辐照激光，将包含前述透射激光的着色的热塑性树脂组合物的激光透射材料与激光吸收材料的接触部位焊接，使得激光透射材料透过激光，并且激光被激光吸收材料吸收，所述激光透射材料和激光吸收材料相互接触。
作为能够在本发明的激光焊接方法中进行激光焊接的树脂组合的例子，有：聚丙烯树脂组合、聚乙烯树脂组合、聚丙烯树脂和聚乙烯树脂的组合、聚丙烯树脂和热塑性弹性体(特别是烯烃热塑性弹性体)的组合、聚丙烯树脂和热塑性树脂(如聚酰胺和聚碳酸酯)的组合。
通常，激光焊接的优点包括：由于可进行三维焊接，因此增加了将要焊接的激光透射材料和激光吸收材料的成型树脂产品的模具形状的自由程度；由于不同于振动焊接，在焊接表面上不存在毛刺，因此改进了外观；以及由于不产生振动和磨耗粉尘，因此适用于电子组件。相反地，其缺点包括：需要事先投资设备，如激光焊接机器；并且由于在进行焊接的都由树脂制成的激光透射材料和激光吸收材料的成型过程中发生下陷，可能在焊接部件之间形成间隙。尤其是间隙的问题在进行激光焊接时是最被关注的；在许多情况下，基于将要焊接的部件的形状，个别地制作用于固定的夹紧装置如夹钳。已知，如果产生0.02mm的间隙，与没有间隙的状态相比，焊接强度降低一半，如果间隙为0.05mm或更多，则焊接失败。
可用的激光焊接机器包括：扫描型，其中激光器移动；掩蔽型，其中要进行焊接的部件移动；以及激光同时从多个方向辐照到要进行焊接的部件上的机型。扫描在汽车工业中是引人注意的，以5m/min的扫描速度作为生产操作时间的标准。
因为激光焊接依赖于激光的光能转化为热能，焊接作业相当大地受到激光焊接条件的影响。通常，由照射的激光在吸收部件表面产生的热量可以通过下面的等式计算：吸收部件表面的热量(J/mm2)＝激光输出(W)/[扫描速度(mm/sec)×激光的光点直径(mm)]
为提高生产率，必须提高扫描速度；为了达到该目的，需要一种高输出型的激光焊接机器。
此外，为了提高焊接强度，在激光吸收部件表面进行一定程度的加热是必要的。所述加热必须结合各种条件来确定，所述条件如提高输出设定、降低扫描速度以及减小光点直径。因为由激光供给太强的表面加热影响焊接部位的外观，在极端的状况下可引起激光吸收部件冒烟，激光焊接条件的设定很重要，并且将要焊接的激光透射树脂材料的激光透射比是极为重要的。鉴于前述的条件，在本发明的激光焊接方法中，优选将进行焊接的激光透射材料和激光吸收材料的接触部位在满足公式(A)的状态下进行焊接。这样，能获得具有焊接强度的焊接产品。
Q＝P/(S·φ)＞0.4....(A)
其中
Q：激光吸收材料表面上的热量(J/mm2)
P：激光透射材料透过的激光输出量(W)
S：激光扫描速度(mm/sec)
φ：激光的光点直径(mm)
优选地，激光吸收材料含有一种加入了例如炭黑和/或其它激光吸收剂的激光吸收的着色树脂组合物，所述炭黑和/或其它激光吸收剂作为吸收激光的黑色着色剂。
作为可被用作前述黑色着色剂和激光吸收剂的物质，述及的有炭黑、苯基尼格、苯胺黑等等。作为其它激光吸收剂的例子，可以论及的是酞菁、萘酞菁、perilene、quaterylene、金属配合物、方形酸衍生物、亚胺正离子型染料(immoniumdye)、聚甲炔等；
它们中的两种或多种可以进行混合，获得一种黑色激光吸收剂。此外，也可以使用前述的激光透射着色剂和激光吸收剂的组合。一种优选的吸收激光的黑色着色剂是炭黑和尼格的组合。
作为具有好的激光吸收性能的炭黑，其初级粒径在15至100nm(优选15至50nm)，BET比表面积在30至500m2/g(优选100至300m2/g)的那些炭黑。
在这种激光吸收的着色树脂组合物中，着色剂的用量可以是例如：相对于聚烯烃树脂的0.01至10重量％，优选为0.05至5重量％。激光吸收材料可以和激光透射材料相同的方式制备，但是激光吸收材料的含量是不同的。
作为本发明的透射激光的着色聚烯烃组合物以及激光焊接方法的主要应用的例子，有汽车部件。更具体的有，例如：在内部的仪表板以及在发动机室的共振器(消音器)。通常，使用粘合剂难以连接聚烯烃树脂部件；为将它们连接起来，进行特殊的加工如表面处理是必要的。当采用激光焊接时，不需要预处理、熔合树脂等；在强度和再循环方面激光焊接可称得上超过粘合剂。
实施例
由下面实施例更详细米色本发明，但是，这些实施例不构成限制。
参见表3，由制备实施例1至8制备的着色剂被用在各自的比较例中。所有这些着色剂是单盐形成的染料或者是两种或多种盐形成的染料的混合染料。上面化合物例子所示的阴离子组分对应于各制备实施例的酸性染料，在表1或表2中所示的有机铵组分对应于各制备实施例的有机胺。通过各酸性染料和各有机胺的成盐反应，获得制备实施例4至8和比较制备实施例1至8中的每一C.I.酸性红266(单偶氮酸性染料)、C.I.酸性黄49(单偶氮酸性染料)、C.I.酸性红143(蒽吡啶酮酸性染料)、C.I.酸性红97(双偶氮酸性染料)、C.I.酸性红144(双偶氮酸性染料)、C.I.酸性黄42(单偶氮酸性染料)、C.I.酸性紫43(蒽醌酸性染料)、C.I.酸性蓝41(蒽醌酸性染料)、C.I.酸性蓝62(蒽醌酸性染料)和C.I.酸性蓝260(蒽醌酸性染料)以及每一有机胺的盐形成的染料。
制备实施例1至3以及比较制备例1至4的每一着色剂包括单盐形成的染料，而制备实施例4至8以及比较制备例5至8的着色剂是使用简单的机械混合器，按照在含量比值栏所示的各重量含量比例混合多种盐形成的染料制备的黑色着色剂。
例如，制备实施例1的着色剂按照下面所述制备。首先，将10克由化合物例(1)-1表示的蒽醌酸性染料分散在500ml水中。另外，将5mg盐酸和7g有机胺S-4溶解在150ml水中。室温下，将该溶液逐滴加入到所述蒽醌酸性染料的分散液中，在40至45℃搅拌1小时进行反应。接着，将温度升高到60至70℃，使反应产物颗粒化，将反应混合物调节到pH6.5至7.5，搅拌1小时。过滤反应混合物，用水洗涤滤出的滤饼，产生12.0g(产率75％)的蒽醌盐形成的染料。
表3
实施例1
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例1的着色剂....0.80g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的蓝色试件。
实施例2
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例2的着色剂....0.80g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均均着色的绿色试件。
实施例3
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例3的着色剂....0.80g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的紫色试件。
实施例4
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例4的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例5
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例5的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例6
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例6的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例7
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例7的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例8
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)制备实施例8的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例9
聚丙烯树脂(未增强)....900g(由Japan Polychem制造，产品编号：BC05B)制备实施例8的着色剂....100g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。使用单轴挤出机(由Enpura Sangyo制造，产品编号：E30SV)，在220℃筒温，将获得的混合物在熔融状态下混合。接着，该混合物在水箱中冷却，然后使用造粒机切粒，并进行干燥，生产出黑色母料。
纤维增强的聚丙烯树脂....384g(由Japan Polychem制造，产品编号：HG30U)黑色母料....12g
将上述成分被置于不锈钢滚混机中，搅拌混合20分钟。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例10
低密度聚乙烯树脂....400g(由Japan Polychem制造，产品编号：LC604)制备实施例8的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在180℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例11
高密度聚乙烯树脂....400g(由Japan Polychem制造，产品编号：HJ290)制备实施例8的着色剂....1.20g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在210℃筒温和40℃模具温度，获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
实施例12
聚烯烃交联热塑性弹性体....400g(由Advanced Elastomer Systems Japan制造，产品编号：Santoprene 8211-65)
制备实施例1的着色剂....0.40g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在200℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的蓝色试件。
实施例13
聚丙烯树脂(未增强)....790g(由Japan Polychem制造，产品编号：BC05B)
制备实施例8的着色剂....10g
滑石....200g
将上述成分在高速混合器中搅拌混合20分钟。使用单轴挤出机(由EnpuraSangyo制造，产品编号：E30SV)，在220℃筒温，将获得的混合物在熔融状态下混合。接着，该混合物在水箱中冷却，然后使用造粒机切粒，并进行干燥，得到黑色颗粒。
接着，采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在200℃筒温和40℃模具温度，将它们进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
比较例1
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例1的着色剂....0.80g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得紫色试件。
比较例2
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例2的着色剂....0.80g
将上述成分被置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得蓝色试件。
比较例3
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例3的着色剂....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得蓝色试件。
比较例4
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例4的着色剂....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得蓝色试件。
比较例5
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例5的着色剂....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得黑色试件。
比较例6
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例6的着色剂....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得黑色试件。
比较例7
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例7的着色剂....1.20g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得黑色试件。
比较制备例8
纤维增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
比较制备例8的着色剂....1.20g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得黑色试件。
物理性质评价
采用下面所述方法，评价在实施例1至8和比较例1至8获得的透射激光的着色聚烯烃树脂组合物以及同样成型的未着色聚烯烃树脂(PP)试件的物理性质。结果列在下面的表4和5中。
(1)透射比测定
每种试件加入到分光光度计(由JASCO Corporation制造，产品编号：V-570型)中，确定它们在λ＝400至1200nm波长范围的透射比。表4和5显示了各试件对940nm波长的半导体激光的透射比。
(2)抗升华试验和评价
将一种施用有白色PET(聚对苯二甲酸乙二醇酯树脂)膜的试件置于烘箱中，在160℃保持3小时。然后，从试件上除下PET膜并放置在无色透明OHP(字幕投影仪)片上进行观察。如果染料没有迁移到PET膜，可以判定染料具有抗升华品质。
(3)耐热性试验和评价
在上述实施例1至8和比较例1至8的注射成型中，将各成分的混合物进行常规制粒，然后混合物的剩余部分在220℃筒体中保留15秒；然后进行注射成型，制得试件。
如果与通过常规制粒获得的试件的颜色相比，在筒体中保留15分钟后获得的试件颜色的变色/褪色没有加剧，可判断它是耐热性的。
(4)抗渗色试验和评价
上述实施例1至8和比较例1至8获得的每种试件以及用氧化钛着色的白色试件在厚度方向叠置，在叠置方向上施加200g(1.96N)/cm2的压力，使它们在80℃保持100小时。接着，检测着色剂转移到白色试件的程度。如果着色剂没有转移到白色试件，判断试件具有抗渗色品质。
(5)用于激光焊接试验的激光吸收试件的制备以及激光焊接试验
如下制备加入聚烯烃的激光吸收试件(激光吸收材料)。
纤维-增强的聚丙烯树脂....400g(由Japan Polychem制造，产品编号：HG30U)
炭黑....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在220℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色激光吸收试件。
低密度聚乙烯树脂....400g(由Japan Polychem制造，产品编号：LC604)
炭黑....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在180℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
高密度聚乙烯树脂....400g(由Japan Polychem制造，产品编号：HJ290)
炭黑....0.80g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在210℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
聚烯烃交联的热塑性弹性材料....400g(由Advanced Elastomer SystemsJapan制造，产品编号：Santoprene 8211-65)
炭黑....0.40g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在200℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
含滑石的聚烯烃树脂....400g
炭黑....2.00g
将上述成分置于不锈钢滚混机中，搅拌混合1小时。采用常规方法，使用注射模塑机(由Toyo Machinery&Metal Co.，Ltd.制造，产品编号：Si-50)，在200℃筒温和40℃模具温度，将获得的混合物进行注射成型；获得具有良好外观和表面光泽的均匀着色的黑色试件。
如图1(侧视图)和图2(斜视图)所示，实施例1至11和比较例1至8的每种试件10与激光吸收试件12[都为60mm长×18mm宽×3mm厚(对于20mm长度，为1.5mm厚)]，以20mm长×18mm宽×1.5mm厚的部分相互接触层叠。
使用30W输出功率的二极管激光器[波长：940nm，连续操作](由Fine DeviceCompany制造)，从试件10上方用激光束14(光点直径)辐照对叠层叠部分(见图)，同时在横向上以可变的扫描速度进行扫描(方向垂直于图1平面)。在相同材料的试件之间进行焊接。
如果试件10透过激光，并且激光被激光吸收试件12吸收，激光吸收试件12将产生热量，通过该热量，激光吸收试件12的吸收激光部位的周围发生熔化，并且试件10也发生熔化，两个试件的树脂熔合在一起，通过冷却，两个试件连接在一起。在图2中，16表示焊接部分。
(6)拉伸强度试验
使用抗拉强度试验器(AG-50kNE，由Shimadzu Corporation制造)，按照JIS K7113-1995，以10mm/min牵拉速度，对前面(5)获得的经焊接的产品进行拉伸强度试验，同时在试件10面和激光吸收试件12面在纵向进行(在图1中为左-右方向)，以确定其拉伸焊接强度。
在表4和5中，实施例1至8描述了针对聚丙烯的结果，实施例9针对低密度聚乙烯(LDPE)，实施例10针对高密度聚乙烯(HDPE)，以及实施例11针对热塑性弹性体。
表4
表5
在抗升华试验中，比较例的着色聚烯烃树脂组合物都被判定为不合格。在抗渗色试验中，比较例3和5的着色聚烯烃树脂组合物也被判定为不合格。
Claims (29)
1.透射激光的着色聚烯烃树脂组合物，包含下面的式(1)表示的蒽醌盐形式染料和红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料；所述聚烯烃树脂组合物包含相对于所述聚烯烃树脂的5至50重量％滑石，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M是相同或不同，只要SO3M的数量是2或更大。
2.权利要求1所述的透射激光的着色聚烯烃树脂组合物，其特征在于，除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
3.权利要求1或2所述的透射激光的着色聚烯烃树脂组合物，其特征在于，所述组合物包含相对于所述聚烯烃树脂的10至40重量％滑石。
4.权利要求1或2所述的透射激光的着色聚烯烃树脂组合物，其特征在于，所述的聚烯烃树脂是聚丙烯树脂。
5.激光焊接的方法，包括：通过辐照激光，焊接激光透射材料和激光吸收材料的接触部位，使得激光透过激光透射材料并被激光吸收材料吸收，并且所述激光透射材料与激光吸收材料相互接触；所述激光透射材料包含一种透射激光的着色聚烯烃树脂组合物，该组合物包含由下面通式(1)表示的蒽醌盐形式的染料和红色偶氮盐形式的染料以及相对于聚烯烃树脂的5至50重量％的滑石，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，以及
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M是相同或不同，只要SO3M的数量是2或更大；
上述红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料。
6.权利要求5所述的激光焊接方法，其特征在于，除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
7.权利要求5或6所述的激光焊接方法，其特征在于，所述聚烯烃树脂是聚丙烯树脂，所述激光吸收材料包含一种加入炭黑和/或其它激光吸收着色剂的吸收激光的着色树脂组合物。
8.权利要求5或6所述的激光焊接方法，其特征在于，激光透射材料和激光吸收材料的接触部位在满足公式(A)的状态下进行焊接：
Q＝P/(S·φ)＞0.4....(A)
其中
Q：以J/mm2计的激光吸收材料表面上的热量
P：以W计的激光透射材料透过的激光输出量
S：以mm/sec计的激光扫描速度
φ：以mm为单位的激光的光点直径。
9.透射激光的着色聚烯烃树脂组合物，包含由下面式(1)表示的蒽醌盐形式的染料和红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，所述的聚烯烃树脂是聚烯烃弹性体，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M相同或不同，只要SO3M的数量是2或更大。
10.权利要求9所述的透射激光的着色聚烯烃树脂组合物，其特征在于除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
11.激光焊接的方法，包括：通过辐照激光，焊接激光透射材料和激光吸收材料的接触部位，使得激光透射材料透过激光，并且激光被激光吸收材料吸收，并且所述激光透射材料与激光吸收材料相互接触；所述激光透射材料包含一种透射激光的着色聚烯烃树脂组合物，该组合物包含由下面通式(1)表示的蒽醌盐形式染料和红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，所述聚烯烃树脂是聚烯烃弹性体，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M相同或不同，只要SO3M的数量是2或更大。
12.权利要求11所述的激光焊接方法，其特征在于，除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
13.权利要求11或12所述的激光焊接方法，其特征在于，所述的聚烯烃弹性体是聚丙烯弹性体，所述的激光吸收材料包含一种加入炭黑和/或其它激光吸收着色剂的吸收激光的着色树脂组合物。
14.权利要求11或12所述的激光焊接方法，其特征在于，激光吸收材料包含一种加入炭黑和/或其它激光吸收着色剂的吸收激光的着色树脂组合物。
15.权利要求11或12所述的激光焊接方法，其特征在于，激光透射材料和激光吸收材料的接触部位在满足公式(A)的状态下进行焊接：
Q＝P/(S·φ)＞0.4....(A)
其中
Q：以J/mm2计的激光吸收材料表面上的热量
P：以W计的激光透射材料透过的激光输出量
S：以mm/sec计的激光扫描速度
φ：以mm为单位的激光的光点直径。
16.激光焊接的方法，包括：通过辐照激光，焊接激光透射材料和激光吸收材料的接触部位，使得激光透过激光透射材料并被激光吸收材料吸收，并且所述激光透射材料与激光吸收材料相互接触；所述激光透射材料包含一种透射激光的着色聚丙烯树脂组合物，该组合物包含一种由下面通式(1)表示的蒽醌盐形式的染料和红色偶氮盐形式的染料以及相对于所述聚丙烯烯烃树脂的5至120重量％的增强玻璃纤维，所述红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M相同或不同，只要SO3M的数量是2或更大。
17.权利要求16所述的激光焊接方法，其特征在于，除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
18.权利要求16或17所述的激光焊接方法，其特征在于，激光吸收材料包含一种加入炭黑和/或其它激光吸收着色剂的吸收激光的着色树脂组合物。
19.权利要求16或17所述的激光焊接方法，其特征在于，所述的激光吸收材料包含一种加入炭黑的吸收激光的着色树脂组合物，所述炭黑的初级粒径为15至50nm。
20.权利要求16或17所述的激光焊接方法，其特征在于，激光透射材料和激光吸收材料的接触部位在满足公式(A)的状态下进行焊接：
Q＝P/(S·φ)＞0.4....(A)
其中
Q：以J/mm2计的激光吸收材料表面上的热量
P：以W计的激光透射材料透过的激光输出量
S：以mm/sec计的激光扫描速度
φ：以mm为单位的激光的光点直径。
21.激光焊接的方法，包括：通过辐照激光，在满足下面公式(A)的状态下焊接激光透射材料和激光吸收材料的接触部位，使得激光透射材料透过激光，并且激光被激光吸收材料吸收，并且所述激光透射材料与激光吸收材料相互接触；所述激光透射材料包含一种聚烯烃树脂组合物，该组合物包含由下面通式(1)表示的蒽醌盐形式的染料和红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，所述激光吸收材料包含加入炭黑和/或其它激光吸收着色剂的吸收激光的着色树脂组合物，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M相同或不同，只要SO3M的数量是2或更大；
Q＝P/(S·φ)＞0.4....(A)
其中
Q：以J/mm2计的激光吸收材料表面上的热量
P：以W计的透过激光透射材料的激光输出量
S：以mm/sec计的激光扫描速度
φ：以mm为单位的激光的光点直径。
22.权利要求21所述的激光焊接方法，其特征在于，除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
23.权利要求22所述的激光焊接方法，其特征在于，所述炭黑的初级粒径为15至100nm。
24.权利要求23所述的激光焊接方法，其特征在于，所述炭黑的BET比表面积为30至500m2/g。
25.透射激光的着色聚烯烃树脂组合物，包含下面的式(1)表示的蒽醌盐形式染料和红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，所述聚烯烃树脂组合物包含相对于所述聚烯烃树脂的10至60重量％增强玻璃纤维，所述的聚烯烃树脂是聚丙烯树脂，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M是相同或不同，只要SO3M的数量是2或更大。
26.权利要求25所述的透射激光的着色聚烯烃树脂组合物，其特征在于除所述的蒽醌盐形式染料和红色偶氮盐形式的染料以外，该组合物还含有黄色着色剂。
27.下面的式(1)表示的蒽醌盐形式染料作为聚烯烃树脂组合物中的透射激光的着色剂的应用，所述聚烯烃树脂组合物还进一步包含红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料；所述的聚烯烃树脂组合物包含相对于所述聚烯烃树脂的5至50重量％滑石，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M是相同或不同，只要SO3M的数量是2或更大。
28.下面的式(1)表示的蒽醌盐形式染料作为聚烯烃树脂组合物中的透射激光的着色剂的应用，所述聚烯烃树脂组合物还进一步包含红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，所述的聚烯烃树脂是聚烯烃弹性体，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M是相同或不同，只要SO3M的数量是2或更大。
29.下面的式(1)表示的蒽醌盐形式染料作为着色聚烯烃树脂组合物中的透射激光的着色剂的应用，所述聚烯烃树脂组合物还进一步包含红色偶氮盐形式的染料，该红色偶氮盐形式的染料的阴离子组分所对应的酸性染料为选自C.I.酸性红1，3，4，5，7，8，9，10，12，13，14，17，18，23，24，26，27，30，33，34，35，37，40，41，54，60，66，70，73，74，88，97，102，112，115，135，137，138，141，143，144，148，150，151，176，231和266的红色酸性染料，所述聚烯烃树脂组合物包含相对于所述聚烯烃树脂的10至60重量％增强玻璃纤维，所述的聚烯烃树脂是聚丙烯树脂，
在通式(1)中，
A和B各自独立地代表-NH-或-O-，
R1至R3各自独立地代表氢，氨基，羟基或卤素，
R4至R13各自独立地代表氢，烷基，硝基或磺基，
Kin+代表有机铵离子，
m代表1或2，
n代表1或2；
所述磺基是-SO3或SO3M，-SO3的数量是m，M代表氢或碱金属，并且各M是相同或不同，只要SO3M的数量是2或更大。
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| JP6353686B2 (ja) * | 2014-04-10 | 2018-07-04 | 三菱重工業株式会社 | 再突入機の製造方法 |
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| DE19960104A1 (de) | 1999-12-14 | 2001-06-21 | Bayer Ag | Laserdurchstrahlschweißbare thermoplastische Formmassen |
| JP5072150B2 (ja) * | 2000-06-20 | 2012-11-14 | オリヱント化学工業株式会社 | ポリオレフィン系樹脂着色用組成物及びポリオレフィン系着色樹脂組成物 |
| DE10054859A1 (de) | 2000-11-06 | 2002-05-08 | Basf Ag | Verfahren zum Verbinden von Formteilen |
| DK1353990T3 (da) * | 2000-11-13 | 2006-09-04 | Du Pont | Farvede, termoplastiske harpikssammensætninger til lasersvejsning, specifikke neutrale anthraquinonfarvestoffer som farvemidler derfor og stöbte produkter deraf |
| CA2423779A1 (en) * | 2000-11-13 | 2002-07-25 | E.I. Du Pont De Nemours And Company | Fabricated resin products for laser welding and including transmitting and absorbing black colorants, and colored resin compositions therefor |
| US20030065074A1 (en) * | 2000-11-13 | 2003-04-03 | Reiko Koshida | Colored thermoplastic resin compositions for laser welding anthraquinone colorants therefor and molded product therefrom |
| JP4073202B2 (ja) * | 2000-11-13 | 2008-04-09 | オリヱント化学工業株式会社 | レーザー光透過性着色樹脂組成物用着色剤及びその関連技術 |
-
2004
- 2004-02-12 KR KR1020057014178A patent/KR100842200B1/ko active IP Right Grant
- 2004-02-12 WO PCT/JP2004/001459 patent/WO2004072175A1/ja active IP Right Grant
- 2004-02-12 CN CN200480004230A patent/CN100584882C/zh not_active Expired - Lifetime
- 2004-02-12 US US10/544,317 patent/US7732512B2/en not_active Expired - Lifetime
- 2004-02-12 DE DE602004007624T patent/DE602004007624T2/de not_active Expired - Lifetime
- 2004-02-12 EP EP07010812A patent/EP1860148B1/en not_active Expired - Lifetime
- 2004-02-12 EP EP04710498A patent/EP1593709B1/en not_active Expired - Lifetime
- 2004-02-12 JP JP2005504975A patent/JP4639148B2/ja not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2004072175A1 (ja) | 2006-06-01 |
| JP4639148B2 (ja) | 2011-02-23 |
| EP1593709B1 (en) | 2007-07-18 |
| KR20050107405A (ko) | 2005-11-11 |
| EP1860148B1 (en) | 2012-05-02 |
| US7732512B2 (en) | 2010-06-08 |
| EP1860148A1 (en) | 2007-11-28 |
| DE602004007624D1 (de) | 2007-08-30 |
| DE602004007624T2 (de) | 2008-04-10 |
| WO2004072175A1 (ja) | 2004-08-26 |
| US20060142451A1 (en) | 2006-06-29 |
| EP1593709A4 (en) | 2006-03-08 |
| KR100842200B1 (ko) | 2008-06-30 |
| CN1751091A (zh) | 2006-03-22 |
| EP1593709A1 (en) | 2005-11-09 |
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