CN101868495A - 可激光焊接的热塑性组合物及其制备方法和制品 - Google Patents
可激光焊接的热塑性组合物及其制备方法和制品 Download PDFInfo
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- CN101868495A CN101868495A CN200880116735A CN200880116735A CN101868495A CN 101868495 A CN101868495 A CN 101868495A CN 200880116735 A CN200880116735 A CN 200880116735A CN 200880116735 A CN200880116735 A CN 200880116735A CN 101868495 A CN101868495 A CN 101868495A
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Images
Classifications
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Abstract
本申请公开了一种可激光焊接的组合物,其包含:按可激光焊接的组合物的总重量计,大于0至99.95重量%的热塑性聚合物组分;0.00001至5重量%的近红外光吸收性物质;0.0至0.02重量%的炭黑;以及0.05至20重量%的白色颜料。
Description
背景技术
本发明涉及可激光焊接的热塑性组合物及其制备方法和制品。
通过透射焊接对两种聚合物制品进行近红外(NIR)激光焊接要求其中一种聚合物制品对于激光是至少部分透射的,而另一种聚合物制品吸收相当数量的激光。吸收性聚合物在暴露区受热温度升高,导致吸收性聚合物与透射性聚合物二者的熔融,从而产生界面处的焊接。
热塑性聚合物通常对于近红外光(在本申请中,辐射波长为800至1400纳米)是透明的。为了在给定的激光辐照下提高吸收以及产生更多的热量,在聚合物中添加近红外光吸收添加剂。所述添加剂包括通常也至少低程度地吸收可见光(在本申请中,波长350至800纳米)的颜料和染料。这对于获得浅颜色(包括白色)的聚合物基底是不利的,因为即使低水平的近红外光吸收颜料也能引起可视觉上察觉和不期望的颜色变化。
白色和浅色的聚合物通常通过共混颗粒状的无机颜料与聚合物来形成。这导致混有这些物质的聚合物共混物呈现高度的不透明性和光亮的外观。然而,这样的颜料通常对红外光和可见光均具有高反射率;也就是说,它们在表面上散射光线而没有吸收光线。
对已有的聚合物制剂进行改进以改善近红外激光的吸收或透射,这增加了可近红外激光焊接的材料的可选择度。然而,仍然需要发展在激光焊接工艺中使用的不透明且浅色的激光吸收聚合物组合物(包括白色的组合物)。
发明内容
上述在获得不透明且浅色或白色的可激光焊接的热塑性材料中的挑战通过本申请公开的几种实施方式得到了克服。
在一种实施方案中,可激光焊接的组合物包含:按可激光焊接的组合物的总重量计,大于0至99.95重量%的热塑性聚合物组分;0.00001至5重量%的近红外光吸收性物质;0.0至0.02重量%的炭黑;以及0.05至20重量%的白色颜料。
在另一种实施方案中,制备可激光焊接的组合物的方法包括:熔融共混如本申请所公开的各组分以形成可激光焊接的组合物。
本申请公开了包含所述可激光焊接的组合物的制品。
一种制备制品的方法包括成形、挤出、流延或模塑如本申请所公开的可激光焊接的组合物的熔体。
一种激光焊接制品包含:对于近红外辐射波长至少是部分透射的第一可激光焊接的热塑性组件,以及包含权利要求1的组合物的第二可激光焊接的组件,其中所述第一可激光焊接的热塑性组件的表面的至少一部分与所述第二可激光焊接的组件的表面的至少一部分激光焊接。
在另一种实施方案中,一种激光焊接热塑性组件的方法包括:使对于近红外辐射波长为部分透射的第一热塑性组件的表面的至少一部分与第二可激光焊接的组件的表面的至少一部分接触,所述第二可激光焊接的组件包含如本申请所公开的可激光焊接的组合物;用近红外激光穿过所述第一热塑性组件照射至所述第二可激光焊接的组件,照射强度能有效地使所述第一热塑性组件与所述第二可激光焊接的组件焊接。
通过参考下面的附图和具体说明,将会更容易理解上述和其它特征及优点。
附图说明
附图是通过穿过近红外透射性组件的辐照将近红外透射性组件与近红外吸收性组件进行激光焊接的示意图。
具体实施方式
本发明人出乎意料地发现,具有优异的焊接强度的不透明且白色或浅色的可激光焊接的组合物可通过使用特定的白色颜料获得。该发现是基于这样的可激光焊接的组合物,其包含热塑性聚合物组分,白色颜料,以及吸收波长800至1400纳米的辐射的近红外(NIR)吸收性物质。所述可激光焊接的组合物可具有明亮的外观,同时具有与由不含白色颜料的聚合物组合物形成的那些制品相当并常常有很大提高的焊接强度。这些性能特征是用户所高度看重的。
在本申请中,化合物采用标准命名法描述。除非上下文另外清楚地指出,单数形式的“一(a)”、“一种(an)”和“该(the)”包括复数指示物。所有参考文献通过参考并入本文。术语“其组合”是指存在一种或多种所指出的组分,任选地存在一种或多种未指出的组分。除了在操作例或另有说明的以外,在本说明书和权利要求中提到各组分的量、反应条件等的所有数值或表达式应该理解为在所有情况下用用语“约”来修饰。在本专利申请中公开了各种数值范围。由于这些范围是连续的,因此它们包括介于最小值和最大值之间的每一数值。除非另有说明,本申请中规定的各种数值范围是近似值。本文中对于相同性能或用量所公开的全部范围包括所公开的端点且是可独立组合的。
可在申请中使用的热塑性聚合物组分是为本领域技术人员所知的,其可包括但不限于:烯烃聚合物,包括聚乙烯及其共聚物和三元共聚物,聚丁烯及其共聚物和三元共聚物,聚丙烯及其共聚物和三元共聚物;α-烯烃聚合物,包括乙烯和至少一种α-烯烃的线型或基本上线型的互聚物以及无规立构的聚(α-烯烃);橡胶状嵌段共聚物;聚酰胺;聚酰亚胺;聚酯诸如聚(芳酯)(poly(arylates))、聚(对苯二甲酸乙二醇酯)和聚(对苯二甲酸丁二醇酯);乙烯基聚合物(诸如聚氯乙烯)和聚乙烯酯(诸如聚醋酸乙烯酯);丙烯酸类均聚物、共聚物和三元共聚物;环氧聚合物;聚碳酸酯、聚酯-聚碳酸酯;聚苯乙烯;聚(亚芳基醚),包括聚苯醚;聚氨酯;苯氧基树脂;聚砜;聚醚;缩醛树脂;聚氧化乙烯;以及它们的组合。更具体地,所述聚合物选自下组:聚乙烯、乙烯共聚物、聚丙烯、丙烯共聚物、聚酯、聚碳酸酯、聚酯-聚碳酸酯、聚酰胺、聚(亚芳基醚),以及它们的组合。
烯烃聚合物(诸如聚乙烯、聚丙烯和聚丁烯)是一大类聚合物,其通常称为烯键式不饱和单体的聚合物,以及前述聚合物与高级烯烃诸如具有4至10个碳原子的α-烯烃或者醋酸乙烯酯等的共聚物和三元共聚物。烯烃即乙烯常常与乙烯基单体(诸如丙烯酸酯类或羧酸化合物的乙烯基酯类化合物)共聚。具体的丙烯酸酯类单体包括丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸甲氧基乙酯、丙烯酸甲氧基乙酯,等等。羧酸的乙烯基酯类包括醋酸乙烯酯、丁酸乙烯酯,等等。此类的常用聚合物包括例如乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸正丁酯共聚物以及乙烯-丙烯酸甲酯共聚物。
在一种具体的实施方案中,所述热塑性聚合物组分包含选自下组的聚合物:烯烃聚合物、聚酰胺、聚酰亚胺、聚苯乙烯、聚亚芳基醚、聚氨酯、苯氧基树脂、聚砜、聚醚、缩醛树脂、聚酯、乙烯基聚合物、丙烯酸类聚合物、环氧聚合物、聚碳酸酯、聚酯-聚碳酸酯、苯乙烯-丙烯腈共聚物以及它们的组合。更具体地,所述热塑性聚合物组分包含选自下组的聚合物:聚碳酸酯、聚酯、聚酰胺以及它们的组合。还更具体地,所述热塑性聚合物组分包含聚碳酸酯与聚酯的组合。
合适的聚酯包括式(1)的重复单元:
其中T是源自C8-12芳族二羧酸或C5-7脂环族二羧酸或其化学等价物的残基,D是源自C6-12芳族二醇或C2-12脂肪族二醇或其化学等价物的残基。
可用于制备聚酯单元的芳族二羧酸的实例包括间苯二甲酸,对苯二甲酸,1,4-萘二羧酸,1,5-萘二羧酸,2,6-萘二羧酸,和包括至少一种前述二羧酸的组合。示例性的脂环族二羧酸包括降冰片烯二羧酸,1,4-环己烷二羧酸,等。任何前述二羧酸的化学等价物包括二烷基酯,例如,二甲基酯,二芳基酯,酐,盐,酰氯,酰溴,等。
具体的二羧酸是对苯二甲酸,间苯二甲酸,萘二羧酸,1,4-环己烷二羧酸(顺式或反式),或包括至少一种前述二羧酸的组合。具体的二羧酸包括间苯二甲酸和对苯二甲酸的组合,其中间苯二甲酸与对苯二甲酸的重量比为91∶9至2∶98。
合适的C6-12芳族二醇包括但不限于间苯二酚,氢醌,和焦儿茶酚,以及二醇如1,5-萘二醇,2,6-萘二醇,1,4-萘二醇,4,4’-二羟基联苯,双(4-羟基苯基)醚,双(4-羟基苯基)砜,等,和包括至少一种前述芳族二醇的组合。
示例性的C2-12脂肪族二醇包括但不限于直链,支化的,或脂环族烷烃二醇如乙二醇,丙二醇,即,1,2-和1,3-丙二醇,2,2-二甲基-1,3-丙烷二醇,2-乙基-2-甲基-1,3-丙烷二醇,1,4-丁烷二醇,1,4-丁-2-烯二醇,1,3-和1,5-戊烷二醇,一缩二丙二醇,2-甲基-1,5-戊烷二醇,1,6-己烷二醇,二甲醇十氢化萘,二甲醇双环辛烷,1,4-环己烷二甲醇,包括它的顺式-和反式-异构体,三甘醇,1,10-癸烷二醇;和包括至少一种前述二醇的混合物。任何前述二醇的化学等价物包括酯,如二烷基酯,二芳基酯,等。具体的脂肪族二醇是环己烷二甲醇,乙二醇,或包括环己烷二甲醇和乙二醇的组合。
在一种实施方案中,T源自环己烷二羧酸,对苯二甲酸,间苯二甲酸,任何前述物质的化学等价物,或包括至少一种前述物质的组合,和D源自1,4-环己烷二甲醇,C2-4二醇,前述化合物的化学等价物,或包括至少一种前述物质的组合。
在式(1)的范围内的具体类型的聚酯是聚(苯二甲酸亚环烷基酯)如聚(对苯二甲酸环己烷二甲醇酯)(PCT),其具有式(2)的重复单元:
其中,根据式(8),T源自对苯二甲酸,D源自1,4-环己烷二甲醇。
另一在式(1)的范围内的具体类型的聚酯是聚(环烷烃二酸亚环烷基酯),其中T和D各自含有环烷基基团。在一种实施方案中,T源自环己烷二羧酸,D是源自以下物质的二价基团:1,6-己烷二醇,二甲醇十氢化萘,二甲醇双环辛烷,1,4-环己烷二甲醇和它的顺式-和反式-异构体,1,10-癸烷二醇,等。特别有利的聚(环烷烃二酸亚环烷基酯)是聚(环己烷-1,4-二亚甲基环己烷-1,4-二羧酸酯),也称为聚(1,4-环己烷-二甲醇-1,4-环己烷二羧酸酯)(PCCD),其具有式(3)的重复单元:
其中T源自1,4-环己烷二羧酸,D源自1,4-环己烷二甲醇。
其它具体的聚酯是源自芳族二羧酸与以下混合物的共聚酯:线型脂肪族二醇尤其是乙二醇,丁二醇,聚(乙二醇)或聚(丁二醇),与脂环族二醇如1,4-己烷二醇,二甲醇十氢化萘,二甲醇双环辛烷,1,4-环己烷二甲醇和它的顺式-和反式异构体,1,10-癸烷二醇,等的混合物。包括线型脂肪族或脂环族酯单元的酯单元可以在聚合物链中作为单独的单元存在,或者作为相同类型的单元的嵌段存在。在一种实施方案中,这种类型的聚酯是聚(对苯二甲酸1,4-环己烷二亚甲基酯)-共聚-聚(对苯二甲酸乙二醇酯),称为PCTG(此时大于50mol%的酯基团源自对苯二甲酸1,4-环己烷二亚甲基酯),或者PETG(此时小于50mol%的酯基团源自对苯二甲酸1,4-环己烷二亚甲基酯)。在一种具体的实施方案中,聚(对苯二甲酸1,4-环己烷二亚甲基酯)-共聚-聚(对苯二甲酸乙二醇酯)包括至多25mol%的源自C2-4二醇的残基。
聚酯可通过以下方法获得:如上所述的界面聚合反应或熔融加工缩合(melt-process condensation),溶液相缩合,或酯交换聚合,其中,例如,可以使用酸催化剂将二烷基酯如对苯二甲酸二甲酯与乙二醇进行酯交换反应,产生聚(对苯二甲酸乙二醇酯)。可使用支化的聚酯,在该聚酯中添加了支化剂如,具有三个或更多个羟基的醇(glycol)或者三官能或更高官能的羧酸。此外,根据组合物的最终用途,有时期望在聚酯上具有各种浓度的酸和羟基端基。
聚酯在25℃的氯仿中测定的特性粘度可为0.3至2分升每克,具体地0.45至1.2分升每克。通过凝胶渗透色谱测定,聚酯的重均分子量(Mw)可为10,000至200,000道尔顿,具体地20,000至100,000道尔顿。
合适的聚碳酸酯包括式(1)的碳酸酯重复结构单元:
其中R1基团总数的至少60%含有芳族有机基团,余下的为脂族、脂环族或芳族基团。在一种实施方案中,每个R1为C6-30芳族基团,即含有至少一个芳族部分。R1可源自式HO-R1-OH的二羟基化合物,具体是式(5)的二羟基化合物:
HO-A1-Y1-A2-OH (5)
其中A1和A2各自为单环二价的芳基,Y1是单键或具有一或多个分隔A1和A2的原子的桥接基团。在示例性的实施方案中,一个原子分隔A1和A2。具体地,R1各自可源自式(6)的二羟基芳族化合物:
其中Ra和Rb各自表示卤素或C1-12烷基,并且可为相同或不同;p和q各自独立地为0至4的整数。也在式(6)中,Xa表示连接两个羟基取代的芳族基团的桥接基团,其中桥接基团和每个C6亚芳基的羟基取代基在所述C6亚芳基上彼此处于邻位、间位或对位(优选对位)。在一种实施方案中,所述桥接基团Xa是单键,-O-,-S-,-S(O)-,-S(O)2-,-C(O)-,或C1-18有机基团。所述C1-18有机桥接基团可为环状的或非环的,芳族或非芳族,并且还可包括杂原子如卤素、氧、氮、硫、硅或磷。可设置该C1-18有机桥接基团,使得所述连接到其上的C6亚芳基各自连接到所述C1-18有机桥接基团的同一烷叉碳原子或不同的碳原子。在一种实施方案中,p和q各自为1,Ra和Rb各自为C1-3烷基,具体地为甲基,其在每个亚芳基上处于羟基的间位。
在一种实施方案中,Xa是取代的或未取代的C3-18环烷叉,式-C(Rc)(Rd)-的C1-25烷叉(其中Rc和Rd各自独立地为氢、C1-12烷基、C1-12环烷基、C7-12芳烷基、C1-12杂烷基或环状C7-12杂芳烷基),或式-C(=Re)-的基团(其中Re是二价C1-12烃基)。这种类型的示例性的基团包括亚甲基,环己基亚甲基,乙叉,新戊叉,和异丙叉,以及2-[2.2.1]-双环庚叉,环己叉,环戊叉,环十二烷叉,和金刚烷叉。
其它有用的式HO-R1-OH的芳族二羟基化合物包括式(7)的化合物:
其中每个Rh独立地为卤素原子,C1-10烃基例如C1-10烷基和C1-10卤代烷基,C6-10芳基或者C6-10卤代芳基;及n为0~4。所述卤素通常为溴。
具体的芳族二羟基化合物的一些说明性实例包括下面的化合物:4,4′-二羟基联苯、1,6-二羟基萘、2,6-二羟基萘、二(4-羟基苯基)甲烷、二(4-羟基苯基)二苯基甲烷、二(4-羟基苯基)-1-萘基甲烷、1,2-二(4-羟基苯基)乙烷、1,1-二(4-羟基苯基)-1-苯基乙烷、2-(4-羟基苯基)-2-(3-羟基苯基)丙烷、二(4-羟基苯基)苯基甲烷、2,2-二(4-羟基-3-溴苯基)丙烷、1,1-二(羟基苯基)环戊烷、1,1-二(4-羟基苯基)环己烷、1,1-二(4-羟基苯基)异丁烯、1,1-二(4-羟基苯基)环十二烷、反式-2,3-二(4-羟基苯基)-2-丁烯、2,2-二(4-羟基苯基)金刚烷、α,α′-二(4-羟基苯基)甲苯、二(4-羟基苯基)乙腈、2,2-二(3-甲基-4-羟基苯基)丙烷、2,2-二(3-乙基-4-羟基苯基)丙烷、2,2-二(3-正丙基-4-羟基苯基)丙烷、2,2-二(3-异丙基-4-羟基苯基)丙烷、2,2-二(3-仲丁基-4-羟基苯基)丙烷、2,2-二(3-叔丁基-4-羟基苯基)丙烷、2,2-二(3-环己基-4-羟基苯基)丙烷、2,2-二(3-烯丙基-4-羟基苯基)丙烷、2,2-二(3-甲氧基-4-羟基苯基)丙烷、2,2-二(4-羟基苯基)六氟丙烷、1,1-二氯-2,2-二(4-羟基苯基)乙烯、1,1-二溴-2,2-二(4-羟基苯基)乙烯、1,1-二氯-2,2-二(5-苯氧基-4-羟基苯基)乙烯、4,4′-二羟基二苯甲酮、3,3-二(4-羟基苯基)-2-丁酮、1,6-二(4-羟基苯基)-1,6-己二酮、乙二醇二(4-羟基苯基)醚、二(4-羟基苯基)醚、二(4-羟基苯基)硫醚、二(4-羟基苯基)亚砜、二(4-羟基苯基)砜、9,9-二(4-羟基苯基)芴、2,7-二羟基芘、6,6′-二羟基-3,3,3′,3′-四甲基螺(双)茚满(″螺双茚满双酚″)、3,3-二(4-羟基苯基)苯酞、2,6-二羟基二苯并-p-二氧芑、2,6-二羟基噻蒽、2,7-二羟基酚黄素(phenoxathin)、2,7-二羟基-9,10-二甲基吩嗪、3,6-二羟基二苯并呋喃、3,6-二羟基硫芴、2,7-二羟基咔唑、间苯二酚、取代的间苯二酚化合物(例如5-甲基间苯二酚、5-乙基间苯二酚、5-丙基间苯二酚、5-丁基间苯二酚、5-叔丁基间苯二酚、5-苯基间苯二酚、5-枯基间苯二酚、2,4,5,6-四氟间苯二酚、2,4,5,6-四溴间苯二酚等);邻苯二酚;对苯二酚;取代的对苯二酚(例如2-甲基对苯二酚、2-乙基对苯二酚、2-丙基对苯二酚、2-丁基对苯二酚、2-叔丁基对苯二酚、2-苯基对苯二酚、2-枯基对苯二酚、2,3,5,6-四甲基对苯二酚、2,3,5,6-四叔丁基对苯二酚、2,3,5,6-四氟对苯二酚、2,3,5,6-四溴对苯二酚等),以及包含至少一种前述二羟基化合物的组合。
式(6)的双酚化合物的具体实例包括:1,1-二(4-羟基苯基)甲烷、1,1-二(4-羟基苯基)乙烷、2,2-二(4-羟基苯基)丙烷(下称“双酚A”或“BPA”)、2,2-二(4-羟基苯基)丁烷、2,2-二(4-羟基苯基)辛烷、1,1-二(4-羟基苯基)丙烷、1,1-二(4-羟基苯基)正丁烷、2,2-二(4-羟基-1-甲基苯基)丙烷、1,1-二(4-羟基-叔丁基苯基)丙烷、3,3-二(4-羟基苯基)苯并吡咯酮、2-苯基-3,3-二(4-羟基苯基)苯并吡咯酮(PPPBP),及1,1-二(4-羟基-3-甲基苯基)环己烷(DMBPC)。也可以使用包含至少一种前述二羟基化合物的组合。在一种具体的实施方案中,聚碳酸酯为来源于双酚A的线型均聚物,其中式(6)中,A1和A2各自为对亚苯基,Y1为异丙叉。
其它示例性的聚碳酸酯包括聚硅氧烷-聚碳酸酯共聚物,其包括式(4)的碳酸酯单元和式(6)和/或(7)的聚硅氧烷单元,
其中R2各自独立地为相同或不同的C1-13一价有机基团,Ar各自独立地为相同或不同的C6-36亚芳基,其中键直接连接至芳族基团上,R3各自独立地为相同或不同的二价C1-30有机基团,和E是平均值为2至1,000的整数。
具体地R2可为C1-C13烷基,C1-C13烷氧基,C2-C13烯基,C2-C13烯氧基,C3-C6环烷基,C3-C6环烷氧基,C6-C14芳基,C6-C10芳氧基,C7-C13芳烷基,C7-C13芳烷氧基,C7-C13烷芳基,或C7-C13烷芳氧基。前述基团可用氟、氯、溴或碘或其组合完全或部分卤化。在一种实施方案中,当期望透明的聚硅氧烷-聚碳酸酯时,R是未被卤素取代的。可将前述R基团的组合用于相同的共聚物中。
式(6)中的Ar基团可源自C6-C30二羟基亚芳基化合物,例如上面式(6)或(7)的二羟基亚芳基。示例性的二羟基亚芳基化合物是1,1-双(4-羟基苯基)甲烷,1,1-双(4-羟基苯基)乙烷,2,2-双(4-羟基苯基)丙烷,2,2-双(4-羟基苯基)丁烷,2,2-双(4-羟基苯基)辛烷,1,1-双(4-羟基苯基)丙烷,1,1-双(4-羟基苯基)正丁烷,2,2-双(4-羟基-1-甲基苯基)丙烷,1,1-双(4-羟基苯基)环己烷,双(4-羟基苯基)硫醚,和1,1-双(4-羟基-叔丁基苯基)丙烷。
式(7)中的R3基团可为C1-C13亚烷基,C3-C6亚环烷基,或C6-C14亚芳基。在一种实施方案中,每个R3为式(8)的基团:
其中R6是C2-C8亚烷基,每个M为相同或不同的卤素,氰基,硝基,C1-C8烷基硫基,C1-C8烷基,C1-C8烷氧基,C2-C8烯基,C2-C8烯氧基,C3-C8环烷基,C3-C8环烷氧基,C6-C10芳基,C6-C10芳氧基,C7-C12芳烷基,C7-C12芳烷氧基,C7-C12烷芳基,或C7-C12烷芳氧基,和n各自独立地为0,1,2,3,或4。
式(6)和(7)中的E值可根据热塑性组合物中每种组分的类型和相对量、组合物的期望性质等类似考虑而宽泛地变化。通常,E的平均值为2至1,000,具体地约2至500,更具体地约5至100。在一种实施方案中,E的平均值为10至75,在又一实施方案中,E的平均值为40至60。当E为较低值时,例如,小于40,可期望地使用较大量的聚碳酸酯-聚硅氧烷共聚物。相反,当E具有较高值时,例如,大于40,可能需要使用较少量的所述共聚物。
在具体的实施方案中,聚硅氧烷单元具有式(7),其中R2各自独立地为相同或不同的C1-3一价有机基团,R3各自为相同或不同的二价C1-10有机基团,和E为2至500的整数。在具体的实施方案中,R2各自为相同或不同的C1-3烷基或C1-3卤代烷基,R3各自具有式(8),其中R6为相同的C1-5亚烷基,各M为相同的并且为溴或氯,C1-3烷基,C1-3烷氧基,苯基,氯苯基,或甲苯基,和E为平均值为4至100的整数。在又一实施方案中,R2各自为甲基,R3各自具有式(8),其中R6为三亚甲基,M为甲氧基,n为1。该聚碳酸酯-硅氧烷共聚物由Sabic Innovative Plastics通过商业途径出售。
聚碳酸酯可通过本领域已知的方法如界面聚合反应和熔体聚合制备。聚碳酸酯的重均分子量可为10,000至200,000道尔顿,具体地20,000至100,000道尔顿,通过凝胶渗透色谱(GPC)测定,使用交联的苯乙烯-二乙烯基苯柱,并校准至聚碳酸酯参照物。GPC样品以约1mg/ml的浓度制备,并且以约1.5ml/min的流速洗脱。
所述热塑性聚合物组合物还可包含聚酯-聚碳酸酯共聚物。所述聚酯-聚碳酸酯共聚物包括共聚物总重量的15至95wt.%的芳化酯单元和5至85wt.%的碳酸酯单元。
芳化酯单元具有式(9):
其中R4各自独立地为卤素或C1-4烷基,和p为0至3。该芳化酯单元可源自对苯二甲酸和间苯二甲酸或其化学等价物的混合物与以下化合物的反应:例如,5-甲基间苯二酚、5-乙基间苯二酚、5-丙基间苯二酚、5-丁基间苯二酚、5-叔丁基间苯二酚、2,4,5-三氟间苯二酚、2,4,6-三氟间苯二酚、4,5,6-三氟间苯二酚、2,4,5-三溴间苯二酚、2,4,6-三溴间苯二酚、4,5,6-三溴间苯二酚、儿茶酚、氢醌、2-甲基氢醌、2-乙基氢醌、2-丙基氢醌、2-丁基氢醌、2-叔丁基氢醌、2,3,5-三甲基氢醌、2,3,5-三叔丁基氢醌、2,3,5-三氟氢醌、2,3,5-三溴氢醌,或包括至少一种前述化合物的组合。
聚酯-聚碳酸酯共聚物中的芳族碳酸酯单元具有如上所述的式(4)。具体地,该碳酸酯单元源自式(6)的二羟基化合物,具体地式(6)的化合物,其中Xa为式-C(Rc)(Rd)-的C1-25烷叉,其中Rc和Rd各自独立地为氢,C1-12烷基,C1-12环烷基,C7-12芳烷基,C1-12杂烷基,或者环状C7-12杂芳烷基,或式-C(=Re)-的基团,其中Re为二价C1-12烃基,甚至更具体地为双酚-A。
在具体的实施方案中,聚酯-聚碳酸酯共聚物是聚(间苯二甲酸-对苯二甲酸-间苯二酚酯)-共聚-(双酚-A碳酸酯)共聚物,其包含式(10)的重复结构:
聚酯-聚碳酸酯共聚物包括源自与链终止剂(也称为封端剂)反应的端基,该链终止剂限制分子量的生长速度,也控制聚碳酸酯的分子量。所述链终止剂是式(11)的单酚类化合物
其中R5各自独立地为卤素,C1-22烷基,C1-22烷氧基,C1-22烷氧基羰基,C6-10芳基,C6-10芳氧基,C6-10芳氧基羰基,C6-10芳基羰基,C7-22烷芳基,C7-22芳烷基,C6-302-苯并三唑,或三嗪,和q为0至5。本申请所用的C6-16苯并三唑包括未取代的和取代的苯并三唑,其中苯并三唑取代有至多三个卤素,氰基,C1-8烷基,C1-8烷氧基,C6-10芳基,或C6-10芳氧基。
示例性的式(11)的单酚类链终止剂包括苯酚,对枯基-苯酚,对叔丁基苯酚,羟基联苯,氢醌的单醚如对甲氧基苯酚,烷基-取代的苯酚(包括具有含8至9个碳原子的支化的链烷基取代基的那些苯酚),单酚类UV吸收剂如4-取代的-2-羟基二苯甲酮,水杨酸芳基酯,二酚的单酯如间苯二酚单苯甲酸酯,2-(2-羟基芳基)苯并三唑,2-(2-羟基芳基)-1,3,5-三嗪,等。具体的单酚类链终止剂包括苯酚,对枯基苯酚,和间苯二酚单苯甲酸酯。
其它示例性的链终止剂包括,例如单羧酸卤化物,单卤甲酸酯,等。这些链终止剂可具有式(11),其中存在-C(O)X或-OC(O)Cl基团代替酚羟基,X为卤素,尤其是溴或氯。可具体地提及单羧酸氯化物和单氯甲酸酯。示例性的单羧酸氯化物包括单环单羧酸氯化物如苯甲酰氯,C1-22烷基-取代的苯甲酰氯,4-甲基苯甲酰氯,卤素-取代的苯甲酰氯,溴苯甲酰氯,肉桂酰氯,4-桥亚甲基四氢化邻苯二甲酰胺苯甲酰氯,及其组合;多环的单羧酸氯化物如偏苯三酸酐氯化物,及萘甲酰氯;以及单环和多环单羧酸氯化物的组合。具有至多22个碳原子的脂族单羧酸的氯化物是合适的。官能化的脂族单羧酸氯化物如丙烯酰氯和甲基丙烯酰氯也是合适的。单氯甲酸酯包括单环的单氯甲酸酯如氯甲酸苯酯,烷基取代的氯甲酸苯酯,氯甲酸对枯基苯酯,甲苯氯甲酸酯,及其组合。也可使用不同的链终止剂的组合,例如两种不同的单酚类链终止剂的组合,或者单酚类链终止剂和单氯甲酸酯链终止剂的组合。
选择聚酯-聚碳酸酯共聚物的制造中所用的链终止剂的类型和量,从而提供这样的共聚物,该共聚物的Mw为1,500至100,000道尔顿,具体地1,700至50,000道尔顿,和更具体地2,000至40,000道尔顿。分子量测定使用凝胶渗透色谱利用交联的苯乙烯-二乙烯基苯进行,并且校准至双酚-A聚碳酸酯参照物。将样品制成1毫克每毫升的浓度,并且以1.0毫升每分钟的速度洗脱。
所述可激光焊接的组合物的热塑性聚合物组分可任选地包含抗冲改性剂。示例性的抗冲改性剂是天然橡胶、低密度聚乙烯、高密度聚乙烯、聚丙烯、聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-乙烯-丙烯-二烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、苯乙烯-丙烯腈共聚物、乙烯-丙烯共聚物、乙烯-丙烯-二烯三元共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-甲基丙烯酸缩水甘油酯共聚物,聚(对苯二甲酸乙二醇酯)-聚(四氢呋喃)二醇嵌段共聚物、聚对苯二甲酸乙二醇酯/间苯二甲酸乙二醇酯-聚(四氢呋喃)二醇嵌段共聚物、硅橡胶,或者包含至少一种前述改性剂的组合。具体的抗冲改性剂组分是甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)与苯乙烯-丙烯腈共聚物(SAN)的组合。
抗冲改性剂的存在量可以是0至40wt.%(重量%),按组合物的总重量计。在具体的实施方案中,抗冲改性剂的存在量为总组合物的1至30wt.%具体3至20wt.%。
在一种实施方案中,所述热塑性聚合物组分在可激光焊接的组合物中的存在量为大于0至99.5wt.%,更具体为30至99wt.%,甚至更具体为80至98wt.%,按可激光焊接的组合物的总重量计。所述含量可变化,从而获得组合物所期望的可焊接性及其它性质。
在一种具体的实施方案中,所述热塑性聚合物组分包含聚碳酸酯,而在另一种实施方案中,所述热塑性聚合物组分包含聚碳酸酯和抗冲改性剂。例如,所述热塑性聚合物组分可包含50至100wt.%的聚碳酸酯和0至50wt.%的抗冲改性剂,具体为80至100wt.%的聚碳酸酯和0至20wt.%的抗冲改性剂,其中前述含量各自基于热塑性聚合物组分的总重量。任选地,在热塑性聚合物组分中只存在聚碳酸酯,或者只存在聚碳酸酯和抗冲改性剂。
在另一种实施方案中,所述热塑性聚合物组分包含聚碳酸酯与聚酯的组合,更具体地聚碳酸酯、聚酯和抗冲改性剂的组合。所述聚碳酸酯可包含源自双酚A、聚(对苯二甲酸丁二醇酯)和核壳聚合物类型的抗冲改性剂(具体为MBS,或者MBS与SAN的组合)的单元。在这些实施方案中,所述热塑性聚合物组分包含10至90wt.%,具体为40至60wt.%的所述聚碳酸酯,10至90wt.%,具体为40至60wt.%重量%的所述聚酯,以及0至40wt.%,具体为1至20wt.%的抗冲改性剂,各自按热塑性聚合物组分的总重量计。在一种实施方案中,所述热塑性聚合物组分包含40至60重量%的所述聚碳酸酯,40至60重量%的所述聚酯,以及1至20重量%的所述抗冲改性剂,并且其中所述聚碳酸酯包含源自双酚A的单元,所述聚酯是聚(对苯二甲酸丁二醇酯),以及所述抗冲改性剂是核壳聚合物。
所述可激光焊接的聚合物组合物还包含白色颜料,例如,二氧化钛(TiO2)、硫化锌(ZnS)、氧化锡、氧化铝(AlO3)、氧化锌(ZnO)、硫酸钙、硫酸钡(BaSO4)、碳酸钙(例如,白垩)、碳酸镁、硅酸钠、硅酸铝、二氧化硅(SiO2,即硅石)、云母、粘土、滑石,前述物质的掺杂金属的形式,以及包含至少一种前述物质的组合。更具体地,白色无机颜料选自金红石或锐钛型二氧化钛、硫化锌,以及它们的涂敷形式诸如硅烷化的二氧化钛。也可使用不同种类的白色颜料的组合。所述白色颜料的平均粒度为0.01至10微米,具体为0.05至1微米,更具体为0.1至0.6微米。
在一种实施方案中,所述白色颜料是粒径为0.01至10微米的二氧化钛。在又一种实施方案中,所述白色颜料是平均粒径为0.1至0.6微米的二氧化钛。
在另一种实施方案中,所述白色颜料是平均粒径为0.01至10微米的硫化锌。在另一种实施方案中,所述白色颜料是平均粒径为0.1至0.6微米的硫化锌。
在一种实施方案中,除了二氧化钛、硫化锌或它们的组合之外,所述可激光焊接的组合物不含其它白色颜料。在另一种实施方案中,所述可激光焊接的组合物不含硫酸钡、云母、滑石或炭黑。
所述白色颜料在可激光焊接的组合物中的存在量为0.05至20wt.%,更具体为0.1至15wt.%,甚至更具体为0.5至10wt.%,按可激光焊接的组合物的总重量计。
所述可激光焊接的组合物还包含近红外光吸收性物质(吸收辐射波长800至1400纳米的物质),所述近红外光吸收性物质并不高度吸收可见光(辐射波长350纳米至800纳米)。具体而言,所述近红外光吸收性物质可选自:有机染料(包括多环有机化合物诸如苝类化合物),纳米尺寸的化合物,金属络合物(包括金属氧化物、混合金属氧化物、复合氧化物、金属硫化物、金属硼化物、金属磷酸盐、金属碳酸盐、金属硫酸盐、金属氮化物、六硼化镧、氧化铯钨、氧化铟锡、氧化锑锡、氧化铟锌),以及它们的组合。在一种实施方案中,所述近红外光吸收性物质的平均粒度为1至200纳米。
取决于所使用的具体的NIR吸收性物质,所述NIR吸收性物质在可激光焊接的组合物中的存在量可以占组合物的0.00001至5wt.%。合适的含量提供有效的近红外吸收,并且本领域普通技术人员无需大量实验就可容易地确定。例如,六硼化镧和氧化铯钨在所述组合物中的存在量为0.00001至1wt.%,还更具体为0.00005至0.1wt.%,最具体为0.0001至0.01wt.%,按可激光焊接的组合物的总重量计。在一种实施方案中,所述NIR吸收性物质可方便地预分散在一小部分的热塑性聚合物中,然后可将这预分散的成分加至组合物中。例如,所述NIR吸收性物质可与聚碳酸酯预混,以提供含0.01至5%的NIR吸收性物质的组分,然后将该组分加至剩余的成分中。作为选择,所述NIR吸收性物质可进行配混或挤出,然后将该配混/挤出的成分加至组合物中。作为选择,所述NIR吸收性物质可在没有配混或挤出NIR吸收性物质的情况下加至组合物中。
可激光焊接的组合物可以包括通常添加到这种类型的组合物中的各种其它添加剂,条件是选择所述的添加剂,从而不显著有害地影响该组合物的期望性质。也可使用添加剂的混合物。
合适的添加剂包括抗氧化剂、热稳定剂、光稳定剂、紫外线吸收剂、猝灭剂(quencher)、增塑剂、润滑剂、脱模剂、防静电剂、填料、阻燃剂、防滴剂、辐射稳定剂、脱模剂,或它们的组合。当存在时,除了阻燃剂和填料之外,每种前述添加剂的用量通常,对于热塑性共混物,为共混物总重量的例如0.001至15wt.%,具体地共混物总重量的0.01至5wt.%,阻燃剂更通常的用量为组合物的总重量的1至10wt.%,填料例如玻璃纤维的存在量为组合物的总重量的大于0至50wt.%,具体地组合物的总重量的15至30wt.%。
在一种实施方案中,所述可激光焊接的组合物包含0.1至5wt.%的热稳定性、抗氧化剂和猝灭剂,各自基于可激光焊接的组合物的总重量。在另一种实施方案中,不存在填料。
示例性的抗氧化剂包括:例如,有机亚磷酸酯诸如亚磷酸三(壬基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯等;烷基化的一元酚或多元酚;多元酚与二烯的烷基化的反应产物,诸如四[亚甲基(3,5-二叔丁基-4-羟基氢化肉桂酸酯)]甲烷等;对甲酚或二环戊二烯的丁基化反应产物;烷基化氢醌;羟基化硫代二苯醚;烷叉-双酚;苄基化合物;β-(3,5-二叔丁基-4-羟基苯基)丙酸与一元醇或多元醇的酯;β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或多元醇的酯;硫代烷基或硫代芳基化合物的酯,例如二硬脂基硫代丙酸酯、二月桂基硫代丙酸酯、双十三烷基硫代二丙酸酯、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、季戊四醇基-四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯等;β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺等,或包含至少一种前述抗氧化剂的组合。抗氧化剂的用量基于所述组合物的总重量可以是0.0001~1重量%。
示例的热稳定添加剂包括:例如,有机亚磷酸酯如亚磷酸三苯酯、亚磷酸三(2,6-二甲基苯基)酯、亚磷酸三(混合的单-和二-壬基苯基)酯等;膦酸酯如苯基膦酸二甲酯(dimethylbenzene phosphonate)等;磷酸酯如磷酸三甲酯等,或者含有至少一种前述热稳定剂的组合。热稳定剂的用量基于所述组合物的总重量可以是0.0001~1重量%。
示例性的光稳定剂和/或紫外线(UV)吸收添加剂包括:例如,苯并三唑类如2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)苯并三唑和2-羟基-4-正辛氧基二苯甲酮等,或者含有至少一种前述光稳定剂的组合。光稳定剂的用量基于所述组合物的总重量可以为0.0001~1重量%。
示例性的吸收UV的添加剂包括:例如,羟基二苯甲酮类、羟基苯并三唑类、羟基苯并三嗪类、氰基丙烯酸酯类、草酰二苯胺类、苯并噁嗪酮类、2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(CYASORB5411)、2-羟基-4-正辛氧基二苯甲酮(CYASORB531)、2-[4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛氧基)-苯酚(CYASORB1164)、2,2’-(1,4-亚苯基)双(4H-3,1-苯并噁嗪-4-酮)(CYASORBUV-3638)、1,3-双[(2-氰基-3,3-二苯基丙烯酰基)氧基]-2,2-双[[(2-氰基-3,3-二苯基丙烯酰基)氧基]甲基]丙烷(UVINUL3030)、2,2’-(1,4-亚苯基)双(4H-3,1-苯并噁嗪-4-酮)、1,3-双[(2-氰基-3,3-二苯基丙烯酰基)氧基]-2,2-双[[(2-氰基-3,3-二苯基丙烯酰基)氧基]甲基]丙烷;纳米尺寸的无机材料如粒度各自小于100纳米的氧化钛、氧化铈和氧化锌;等等;或者含有至少一种前述紫外光吸收剂的组合。紫外光吸收剂的用量基于所述组合物的总重量可以为0.0001~1重量%。
也可以使用增塑剂、润滑剂和/或脱模剂添加剂。这些类型的材料存在显著的重叠,其中包括例如邻苯二甲酸酯,例如二辛基-4,5-环氧-六氢邻苯二甲酸酯;三(辛氧基羰基乙基)异氰脲酸酯;三硬脂精;二-或多官能芳族磷酸酯,例如间苯二酚四苯基二磷酸酯、氢醌的双(二苯基)磷酸酯和双酚A的双(二苯基)磷酸酯;聚-α-烯烃;环氧化豆油;有机硅,其中包括硅油;酯,例如脂肪酸酯,诸如烷基硬脂酯,例如硬脂酸甲酯;硬脂酸硬脂酯、四硬脂酸季戊四醇酯等;硬脂酸甲酯与亲水和疏水非离子型表面活性剂(包括聚乙二醇聚合物、聚丙二醇聚合物及其共聚物)的混合物,例如在合适溶剂内的硬脂酸甲酯和聚乙二醇-聚丙二醇共聚物;蜡,例如蜂蜡、褐煤蜡、石蜡等。这些物质的用量基于所述组合物的总重量可以为0.001~1重量%、具体为0.01~0.75重量%、更具体为0.1~0.5重量%。
也可以使用无机阻燃剂,例如,C2-16烷基磺酸盐如全氟丁烷磺酸钾(Rimar盐)、全氟辛烷磺酸钾、全氟己烷磺酸四乙基铵、及二苯砜磺酸钾等;通过例如碱金属或碱土金属反应形成的盐(如锂、钠、钾、镁、钙和钡盐)以及无机酸复盐,例如含氧阴离子如碳酸的碱金属和碱土金属盐如Na2CO3、K2CO3、MgCO3、CaCO3和BaCO3,或者氟阴离子络合物如Li3AlF6、BaSiF6、KBF4、K3AlF6、KAlF4、K2SiF6和/或Na3AlF6等。当存在时,无机阻燃剂盐可以0.1~5重量%的量存在,基于组合物的总重量。
可使用的有机阻燃剂包括各种含磷的化合物具体为芳族含磷的化合物以及含溴或含氯的有机物。可使用含磷-氮键的有机化合物,也可使用化合物诸如膦酸酯(盐)、亚膦酸酯(盐)、亚磷酸酯(盐)、氧化膦和磷酸酯,例如磷酸三乙酯、磷酸三苯酯、磷酸三(二氯丙)酯、磷酸三(2-氯乙)酯、磷酸三(二溴丙)酯、磷酸三(溴氯丙)酯,等等。含溴的有机物包含直接与有机部分例如芳族或脂环族的环相连的溴原子,例如源于下面物质的化合物:溴化的双酚A、四溴邻苯二甲酸酐等,以及五溴环己烷、五溴氯环己烷、六溴环己烷、1,2-二溴-4-(1,2-二溴乙基)-环己烷、四溴环辛烷、六溴环辛烷、六溴环十二烷、氯化石蜡,以及类似的含溴或氯的脂族或脂环族化合物。
合适的猝灭剂包括无机酸诸如磷酸一氢锌或者有机酸诸如磷酸。
所述可激光焊接的组合物可通过本领域中通用的方法制备。例如,一种制备可激光焊接的组合物的方法包括熔融共混所述热塑性聚合物组分、白色颜料、NIR吸收性物质以形成可激光焊接的组合物。更具体地,首先将粉末状的热塑性聚合物组分、白色颜料、NIR吸收性物质及其它任选的添加剂(包括稳定剂包,例如抗氧化剂、γ射线稳定剂、热稳定剂、紫外光稳定剂等)在HENSCHEL-Mixer高速混合机中共混。其他低剪切方法诸如手工混合也可以完成该共混。然后,通过进料斗将共混物加入挤出机的进料喉。作为选择,一种或多种成分可以通过侧充填机于进料口和/或下游直接加入挤出机来混入组合物中。作为选择,任何期望的添加剂也可以配混成母料(具体是白色颜料),然后在该工艺的任何时刻与剩余的聚合物成分合并。挤出机一般在高于使组合物流动所需温度的温度进行操作。将挤出物立即在水浴中骤冷并造粒。这种粒料可以用于随后的模塑、成形或成型。在具体的实施方案中,一种制备可激光焊接的组合物的方法包括使上述组合物中的任一种熔融以形成可激光焊接的组合物。
本申请还提供了包含所述组合物的成形、成型或模塑制品。在一种实施方案中,制品通过挤出、流延、吹塑或注塑所述可激光焊接的组合物的熔体来形成。制品可呈膜或片材。在具体的实施方案中,提供了包含上述组合物中的任一种的各种成形、成型或模塑制品。
在另一种具体的实施方案中,可激光焊接的组合物及由其形成的制品包含:按可激光焊接的组合物的总重量计,75至99.5重量%的所述热塑性聚合物组分,其中所述热塑性聚合物组分包含聚碳酸酯、聚酯或者它们的组合;0.0001至1重量%的所述近红外光吸收性物质;以及0.5至5重量%的所述白色颜料,其中所述白色颜料选自颗粒状的二氧化钛、硫化锌以及它们的组合,其中所述可激光焊接的组合物不含其它白色颜料。
在另一种具体的实施方案中,可激光焊接的组合物及由其形成的制品包含:按可激光焊接的组合物的总重量计,75至99.5重量%的所述热塑性聚合物组分,其中所述热塑性聚合物组分包含含有源自双酚A的单元的聚碳酸酯,聚(对苯二甲酸丁二醇酯),以及甲基丙烯酸酯-苯乙烯-丁二烯抗冲改性剂;0.0001至0.5重量%的所述近红外光吸收性物质,其中所述近红外光吸收性物质包括六硼化镧、氧化铯钨或者它们的组合;以及0.5至5重量%的所述白色颜料,其中所述白色颜料选自颗粒状的二氧化钛、硫化锌以及它们的组合,其中所述可激光焊接的组合物不含其它白色颜料。
还公开了激光焊接制品,其包含第一热塑性组件,所述第一热塑性组件对于近红外辐射波长是透射的;以及第二可激光焊接的组件,所述第二可激光焊接的组件包含本申请所公开的可激光焊接的组合物,其中所述第一热塑性组件的表面的至少一部分与所述第二可激光焊接的组件的表面的至少一部分激光焊接。所述激光焊接制品在所述第一热塑性组件与所述第二可激光焊接的组件之间的拉伸剪切强度可为10N/mm2至50N/mm2,根据以5毫米/分钟的速度进行的拉伸剪切试验测定。在一种实施方案中,所述激光焊接制品在所述第一热塑性组件与所述第二可激光焊接的组件之间的拉伸剪切强度大于15N/mm2,根据本申请所述的拉伸剪切试验测定。在一种实施方案中,所述激光焊接制品在所述第一热塑性组件与所述第二可激光焊接的组件之间的拉伸剪切强度大于20N/mm2,根据本申请所述的拉伸剪切试验测定。
在一种具体的实施方案中,公开了一种激光焊接制品,其中所述第二可激光焊接的组件包含:75至99重量%的所述热塑性聚合物组分,其中所述热塑性聚合物组分包含含有源自双酚A的单元的聚碳酸酯,聚(对苯二甲酸丁二醇酯),以及甲基丙烯酸酯-苯乙烯-丁二烯抗冲改性剂;0.0001至1重量%的所述近红外光吸收性物质,其中所述近红外光吸收性物质为六硼化镧、氧化铯钨或者它们的组合;以及0.5至5重量%的所述白色颜料,其中所述白色颜料是二氧化钛颜料,并且其中所述第二可激光焊接的组件不包含其它白色颜料;以及在所述第一热塑性组件与所述第二可激光焊接的组件之间的拉伸剪切强度大于15N/mm2,根据以5毫米/分钟的速度进行的拉伸剪切试验测定。
本申请还公开了一种激光焊接热塑性组件的方法,其包括:使对于近红外辐射波长至少部分透射的第一可激光焊接的热塑性组件的表面的至少一部分与第二可激光焊接的组件的表面的至少一部分接触,所述第二可激光焊接的组件包含权利要求1的可激光焊接的组合物;用近红外激光穿过所述第一热塑性组件照射至所述第二可激光焊接的塑料组件,照射强度能有效地使所述第一热塑性组件与所述第二可激光焊接的组件焊接。
在附图中示例说明了用于制品10的上述方法。第一热塑性组件12包含本领域中已知的任意热塑性聚合物组分,只要它对近红外光是至少部分透射的。使激光照射14定向穿过第一热塑性组件12至第二可激光焊接的组件16,此处激光照射14被吸收,导致两层的界面18处产生热量。热量在这两层之间产生局部的熔融池20,导致第一热塑性组件12与第二可激光焊接的组件16的焊接。通常沿着搭接的点照射的直线路径进行激光照射12,从而产生焊缝22。
通过以下非限制性实施例进一步说明本发明。
实施例
原料
表A中所示的原料用于下面的实施例中。
表A
名称 | 描述/商品名 | 来源 |
PBT-1 | 聚(对苯二甲酸1,4-丁二醇酯),特性粘度(IV)=1.2cm3/g,在60∶40苯酚/四氯乙烷中测量 | Sabic InnovativePlastics |
PC-1 | 双酚A聚碳酸酯,MVR=20.9(300℃/1.2kg) | Sabic InnovativePlastics |
PBT-2 | 聚(对苯二甲酸1,4-丁二醇酯),特性粘度(IV)=0.66cm3/g,在60∶40苯酚/四氯乙烷中测量 | Sabic InnovativePlastics |
PC-2 | 双酚A聚碳酸酯,MVR=5.9(300℃/1.2kg) | General Electric |
MBS | 甲基丙烯酸甲酯-丁二烯-苯乙烯聚合物 | Rohm&Haas |
ABS树脂 | 51.8%丁二烯,36.9%苯乙烯,11.3%丙烯腈;MFI=13.5(220℃,10kg) | Sabic InnovativePlastics |
Poly-SAN-2 | 34%丙烯腈,66%苯乙烯;MVR=4.5(230℃,1.2kg) | Sabic InnovativePlastics |
PE | 聚乙烯,低密度 | Sabic InnovativePlastics |
AO 1010 | IRGANOXTM 1010 | Ciba Geigy |
UVA 5411 | TINUVINTM 329 | Ciba SpecialityChemicals |
H3PO3 | 亚磷酸 | Quaron |
名称 | 描述/商品名 | 来源 |
PELTP | SEENOXTM 412 | Clariant |
UVA 327 | TINUVINTM 327 | Ciba SpecialityChemicals |
HALS 770 | TINUVINTM 770 | Ciba SpecialityChemicals |
硅油预混料87/13 | TAG63/硅油87/13 | SPECHIM SA |
EBS蜡 | UNIWAXTM 1760EBS | Uniqema |
PEPG | PLURIOLPETM 8800 | BASF |
氧化镁 | REMAGTM AC | Spaeter C.GmbH |
二季戊四醇/季戊四醇的棕榈酸酯/硬脂酸酯 | LOXIOLTM EP8578 | Cognis |
亚磷酸三(二-叔丁基苯基)酯 | IRGAFOSTM 168 | Ciba SpecialityChemicals |
烷基磺酸钠 | ATMERTM 191 | Croda |
TiO2 | KRONOSTM 2450KRONOSTM 3000KRONOSTM 3025UV-TITANTM P580 | KronosKronosKronosKeyser&Mackay |
PC-LaB6 | KHCS-06TM颜料分散体 | Alconix Europe |
GmbH | ||
PC-CTO | YMCS-06TM颜料分散体 | Alconix EuropeGmbH |
LaserflairTM 825 | IriodinTM LS 825 | Merck&Co. |
颜料棕24 | Sicotan黄K2001FG | BASF |
颜料红101 | BayferroxTM 140MPL | Lanxess |
颜料蓝29 | ULTRAMARINETM蓝51 | Holliday |
名称 | 描述/商品名 | 来源 |
溶剂红135 | MacrolexTM红EG | Lanxess |
溶剂黄163 | ORACETTM黄GHS | Ciba SpecialityChemicals |
技术和工序
近红外(NIR)透射和反射数据在Hitachi U-3410或Perkin-Elmer Lambda950分光光度计在1064nm进行采集。所测部件的厚度在下表中给出。
为了焊接,如图所示将高光泽表面60mm×60mm×1.6mm试样16与相应的高光泽表面部件12放置在一起。对于表A、B和C中所示的部件,其是LEXANEXL1414T-NA8A005T,而对于表D中的组合物其是LEXAN103R-111。然后用光束直径为2mm的二极管激光(960nm)对搭接的区域进行照射。功率和扫描速度示于表中。
将激光焊接的试样锯成条,例如宽15mm或20mm的条,然后焊接品的拉伸强度通过下面方法测定:夹紧试样,利用拉伸试验机(Lloyd draw bench:LR30K)在焊接区域以5毫米/分钟的速率施加力。焊接强度计算为断裂时最大载荷除以焊接面积,所述焊接面积计算为焊接宽度(激光光束宽度)乘以焊接的长度(例如15mm或20mm)。
NIR吸收性物质(六硼化镧(LaB6)和氧化铯钨(CTO))各自以在聚碳酸酯中的单一分散体提供,载量为分散体的0.25wt%。所述LaB6和CTO的初级粒子大小(通过X-ray测定)为20纳米。这些颗粒在PC中形成松散的至多120纳米的附聚物。
PC/PBT样品通过在Werner&Pfleiderer 25mm双螺杆挤出机上熔融挤出制备,采用标称熔体温度250至275℃,25英寸(635mm)的水银真空度和450rpm。挤出物造粒,在100℃干燥3小时。
ABS样品通过在Werner&Pfleiderer 25mm双螺杆挤出机上熔融挤出制备,采用标称熔体温度220至260℃,25英寸(635mm)的水银真空度和450rpm。挤出物造粒,在90℃干燥3小时。
PC样品通过在Werner&Pfleiderer 25mm双螺杆挤出机上熔融挤出制备,采用标称熔体温度290至320℃,25英寸(635mm)的水银真空度和450rpm。挤出物造粒,在120℃干燥3小时。
试样16由干燥的粒料制备,对于PC/PBT在标称温度250至290℃注塑;对于ABS样品250至290℃;对于PC样品290至320℃,以形成用于大多数的下面试验的试样。
此外,待与试样16焊接的尺寸6mm×6mm×2.5mm的试样12(图1)由Lexan EXL1414T-NA8A005T和Lexan 103R-111制备,根据数据表制备。
结果
组合物根据表1、2、3和4配制。所有的含量是以重量%计,基于组合物的总重量。
表1
成分 | CEx1 | CEx2 | Ex1 | Ex2 | Ex3 | Ex4 | Ex5 | CEx3 | Ex6 |
PBT-1 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 |
PC-1 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 |
PBT-2 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 |
MBS | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
PE | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
AO 1010 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
UVA 5411 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
H3PO3 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
PELTP | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
TiO2 a | - | 0.5 | 1.2 | 1.8 | 2.5 | 5.0 | - | 2.5 | |
PC-LaB6 | - | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | - | - |
PC-2 | 40.0 | 39.5 | 38.9 | 38.3 | 37.7 | 37.0 | 34.5 | 39.5 | 37.0 |
LS 825 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.5 | 0.5 |
透射,在1064nmb | 69.3 | 58.0 | 15.5 | 8.0 | 4.7 | 3.1 | 1.4 | 47.2 | 17.0 |
反射,在1064nmb | 22.0 | 15.9 | 41.1 | 47.8 | 54.0 | 68.4 | 71.2 | 2.4 | 56.8 |
焊接速率(毫米/分钟) | 15 | 15 | 15 | 15 | 15 | 15 | 20 | 20 | |
激光功率(W) | 130 | 130 | 130 | 130 | 115 | 125 | 80 | 80 | |
焊接强度(N/mm2) | n.w. | 25.3 | 26.6 | 27.6 | 28.8 | 31.5 | 32.5 | 18.9 | 25.3 |
aKRONOS 2450(d50m=0.31微米);b1.0mm厚部件,利用HitachiU-3410测量;c不可焊接。
讨论
实施例1-6证明了本发明的组合物的有益效果。当试样16选自不含NIR吸收性添加剂的CEx 1时,激光焊接失败。CEx2与实施例1-5相比以及CEx3与实施例6相比表明,颜料(诸如TiO2)的添加增加了在NIR的光学散射的量。然而,基于实施例1-6的激光焊接制品具有优异的拉伸强度,这说明其具有比不含白色颜料的对照样品更强的焊接。
表2
组分 | Ex7 | Ex8 | Ex9 | Ex10 | Ex11 | Ex12 |
PBT-1 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 | 30.6 |
PC-1 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 | 10.7 |
PBT-2 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 | 9.23 |
MBS | 7 | 7 | 7 | 7 | 7 | 7 |
PE | 2 | 2 | 2 | 2 | 2 | 2 |
AO 1010 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
UVA5411 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
H3PO3 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
PELTP | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
TiO2 | 2.5a | 2.5b | 2.5c | 2.5d | - | - |
ZnS | - | - | - | - | 2.5 | - |
BaSO4 | 2.5 | |||||
PC LaB6 | 0.5 | 0.5 | 0.5 | |||
PC CTO | 1.0 | 1.0 | 1.0 | |||
PC-2 | 38.88 | 38.28 | 37.68 | 36.98 | 34.48 | 39.48 |
透射,在1064nm(e) | 19.5 | 3.9 | 5.2 | 1.4 | 17.8 | 37.6 |
反射,在1064nm(e) | 35.0 | 58.2 | 49.3 | 52.0 | 41.5 | 10.8 |
焊接速率(毫米/分钟) | 25 | 15 | 25 | 15 | 15 | 25 |
激光功率(W) | 130 | 115 | 100 | 90 | 70 | 120 |
组分 | Ex7 | Ex8 | Ex9 | Ex10 | Ex11 | Ex12 |
焊接强度(N/mm2) | 26.9 | 29.8 | 26.4 | 25.1 | 22.2 | 20.2 |
aUV-titan P580(d50m=0.03微米);bKRONOS 3000(d50m=0.58微米);cKRONOS 3025(d50m=4.35微米);dKRONOS 2450e1.0mm厚的部件,利用Hitachi U-3410测量。
讨论
通过表1中的实施例4与表2中的实施例7-9相比,显然的是,二氧化钛的粒度影响焊接品的拉伸强度。实施例10-12的比较也显示所用的白色颜料的类型影响焊接品的拉伸强度。
表3
组分 | CEx4 | Ex13 | Ex14 |
Poly-SAN-2 | 31.47 | 31.36 | 31.27 |
颜料蓝29 | 0.015 | 0.015 | 0.015 |
颜料棕24 | 0.010 | 0.010 | 0.010 |
颜料红101 | 0.008 | 0.008 | 0.008 |
TiO2 a | 7.85 | 7.85 | 7.85 |
PC LaB6 | 0 | 0.44 | 0.87 |
亚磷酸三(二-叔丁基苯基)酯 | 0.44 | 0.44 | 0.44 |
UVA 327 | 0.22 | 0.22 | 0.22 |
HALS 770 | 0.22 | 0.22 | 0.22 |
烷基磺酸钠 | 0.44 | 0.44 | 0.43 |
硅油预混物87/13 | 0.61 | 0.61 | 0.61 |
EBS蜡 | 1.74 | 1.75 | 1.73 |
PEPG | 0.87 | 0.87 | 0.87 |
MgO | 0.09 | 0.09 | 0.09 |
ABS树脂360 | 27.99 | 27.87 | 27.74 |
组分 | CEx4 | Ex13 | Ex14 |
Poly-SAN 2548 | 27.99 | 27.87 | 27.74 |
透射,在1064nmb | 5.9 | 0.0 | 0.0 |
反射,在1064nmb | 92.4 | 81.7 | 66.8 |
焊接速率(毫米/分钟) | 20 | 20 | 20 |
激光功率(W) | 80 | 80 | 80 |
焊接强度(N/mm2) | n.w.c | 17.7 | 19.1 |
aKRONOS 2450(d50m=0.31微米);b1.0mm厚的部件,利用HitachiU-3410测量;c不可焊接。
讨论
表3中的结果显示本发明组合物的有益效果在不同的热塑性组合物中得到保持(比较CEx 4与实施例13-14)。
表4
组分 | CEx5 | Ex15 | Ex16 | Ex17 | Ex18 |
PC-2 | 98.4 | 97.8 | 95.9 | 96.7 | 96.7 |
UVA 5411 | 0.15 | 0.15 | 0.15 | 0.15 | 0.15 |
IRGAFOSTM 168 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
LOXIOLTM EP8578 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
TiO2 a | 1.2 | 2.5 | 1.0 | 1.0 | |
PC CTO | 1 | 1 | 1 | ||
PC LaB6 | 1 | 1 | |||
溶剂红135 | 0.5 | 0.5 | |||
溶剂黄163 | 0.2 | 0.5 | |||
炭黑 | 0.003 | ||||
透射,在1064nm(b) | 31.6 | 1.9 | 0.3 | 0.6 | 0.5 |
组分 | CEx5 | Ex15 | Ex16 | Ex17 | Ex18 |
反射,在1064nmb | 8.0 | 45.1 | 55.9 | 32.4 | 31.6 |
焊接速率(毫米/分钟) | 20 | 20 | 20 | 20 | 20 |
激光功率(W) | 80 | 80 | 80 | 80 | 80 |
焊接强度(N/mm2) | 19.8 | 27.6 | 31.4 | 25.8 | 26.3 |
aKRONOSTM 2450;b利用Perkin-Elmer Lambda 950在1.6mm试板上测量
讨论
通过比较CEx 5与实施例15-16,证明了在不同热塑性组合物中本发明组合物的有益效果。基于实施例15-16的激光焊接制品显示添加TiO2增大了在NIR的光学散射的量,但是提高了焊接品的拉伸剪切强度。
虽然出于说明的目的阐述了典型的实施方案,但是前面的说明不应该被认为是对本发明保护范围的限制。相应地,在不脱离本发明的精神和范围的条件下,本领域技术人员可想到各种修改、调整和替换。
Claims (25)
1.一种可激光焊接的组合物,其包含:按可激光焊接的组合物的总重量计,
大于0至99.95重量%的热塑性聚合物组分;
0.00001至5重量%的近红外光吸收性物质;
0.0至0.02重量%的炭黑;以及
0.05至20重量%的白色颜料。
2.权利要求1的可激光焊接的组合物,其中所述热塑性聚合物组分包含选自下组的聚合物:烯烃聚合物、聚酰胺、聚酰亚胺、聚苯乙烯、聚亚芳基醚、聚氨酯、苯氧基树脂、聚砜、聚醚、缩醛树脂、聚酯、乙烯基聚合物、丙烯酸类聚合物、环氧聚合物、聚碳酸酯、聚酯-聚碳酸酯、苯乙烯-丙烯腈共聚物,以及它们的组合。
3.权利要求1的可激光焊接的组合物,其中所述热塑性聚合物组分包含选自下组的聚合物:聚碳酸酯、聚酯、聚酰胺,以及它们的组合。
4.权利要求1-2中任一项的可激光焊接的组合物,其中所述热塑性聚合物选自下组:聚(对苯二甲酸丁二醇酯)、聚(对苯二甲酸乙二醇酯),以及它们的组合。
5.权利要求1-3中任一项的可激光焊接的组合物,其中所述热塑性聚合物组分包含聚碳酸酯与聚酯的组合。
6.权利要求1-4中任一项的可激光焊接的组合物,其中所述热塑性聚合物组分包含10至90重量%的聚碳酸酯,10至90重量%的聚酯,,0至40重量%的抗冲改性剂,各自按热塑性聚合物组分的总重量计。
7.权利要求1-6中任一项的可激光焊接的组合物,其中所述热塑性聚合物组分还包含抗冲改性剂,其中所述抗冲改性剂为天然橡胶、低密度聚乙烯、高密度聚乙烯、聚丙烯、聚苯乙烯、聚丁二烯、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-乙烯-丙烯-二烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、苯乙烯-丙烯腈共聚物、乙烯-丙烯共聚物共聚物、乙烯-丙烯-二烯三元共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-甲基丙烯酸缩水甘油酯共聚物、聚对苯二甲酸乙二醇酯-聚(四氢呋喃)二醇嵌段共聚物、聚对苯二甲酸乙二醇酯/间苯二甲酸乙二醇酯-聚(四氢呋喃)二醇嵌段共聚物、硅橡胶、或者包含至少一种前述抗冲改性剂的组合。
8.权利要求1-7中任一项的可激光焊接的组合物,其中所述热塑性聚合物组分包含:40至60重量%的聚碳酸酯,40至60重量%的聚酯,以及1至20重量%的抗冲改性剂,并且其中所述聚碳酸酯包含源自双酚A的单元,所述聚酯为聚(对苯二甲酸丁二醇酯),以及所述抗冲改性剂为核壳聚合物。
9.权利要求1-8中任一项的可激光焊接的组合物,其中所述近红外光吸收性物质选自下组:多环有机化合物、苝类化合物、金属氧化物、混合金属氧化物、金属络合物、金属硫化物、金属硼化物、金属磷酸盐、金属碳酸盐、金属硫酸盐、金属氮化物、六硼化镧、氧化铯钨、氧化铟锡、氧化锑锡、氧化铟锌,以及它们的组合。
10.权利要求1-9中任一项的可激光焊接的组合物,其中所述近红外光吸收性物质选自下组:六硼化镧、氧化铯钨,以及它们的组合。
11.权利要求1-10中任一项的可激光焊接的组合物,其中所述近红外光吸收性物质的平均粒度为1至200纳米。
12.权利要求1-11中任一项的可激光焊接的组合物,其包含0.1至15重量%的白色颜料,按可激光焊接的组合物的总重量计。
13.权利要求1-12中任一项的可激光焊接的组合物,其中所述白色颜料的平均粒度为0.01至10微米。
14.权利要求1-13中任一项的可激光焊接的组合物,其中所述白色颜料选自下组:颗粒状二氧化钛颜料、颗粒状硫化锌颜料,以及它们的组合。
15.权利要求14的可激光焊接的组合物,其中所述组合物基本上不合除了二氧化钛、氧化锌或者它们的组合之外的其它白色颜料。
16.权利要求1-15中任一项的可激光焊接的组合物,其中所述组合物不包含硫酸钡、云母、滑石或炭黑。
17.权利要求1-16中任一项的可激光焊接的组合物,其包含:按可激光焊接的组合物的总重量计,
75至99.5重量%的所述热塑性聚合物组分,其中该热塑性聚合物组分包含聚碳酸酯、聚酯或者它们的组合;
0.0001至1重量%的所述近红外光吸收性物质;以及
0.5至5重量%的所述白色颜料,其中所述白色颜料选自颗粒状的二氧化钛、硫化锌以及它们的组合,其中所述的可激光焊接的组合物不含其它白色颜料。
18.权利要求1的可激光焊接的组合物,其包含:按可激光焊接的组合物的总重量计,
75至99.5重量%的所述热塑性聚合物组分,其中该热塑性聚合物组分包含含有源自双酚A的单元的聚碳酸酯,聚(对苯二甲酸丁二醇酯),以及甲基丙烯酸酯-苯乙烯-丁二烯抗冲改性剂;
0.0001至0.5重量%的所述近红外光吸收性物质,其中该近红外光吸收性物质包括六硼化镧、氧化铯钨或者它们的组合;以及
0.5至5重量%的所述白色颜料,其中该白色颜料选自颗粒状的二氧化钛,硫化锌以及它们的组合,其中所述可激光焊接的组合物不合其它白色颜料。
19.一种制备可激光焊接的组合物的方法,其包括熔融共混权利要求1-18中任一项权利要求的各组分以形成可激光焊接的组合物。
20.包含权利要求1-19中任一项的可激光焊接的组合物的制品。
21.一种制备制品的方法,其包括成形、挤出、流延或模塑权利要求1-19中任一项的可激光焊接的组合物的熔体。
22.一种激光焊接制品,其包括:
第一可激光焊接的热塑性组件,其对于近红外辐射波长至少是部分透射的,以及
第二可激光焊接的组件,其包含权利要求1-19中任一项的组合物,
其中所述第一可激光焊接的热塑性组件的表面的至少一部分与所述第二可激光焊接的组件的表面的至少一部分激光焊接。
23.权利要求20的激光焊接制品,其中根据以5毫米/分钟的速度进行的拉伸剪切试验测定,在所述第一热塑性组件与所述第二可激光焊接的组件之间的拉伸剪切强度为10N/mm2至50N/mm2。
24.权利要求22的激光焊接制品,其中所述第二可激光焊接的组件包含:
75至99重量%的所述热塑性聚合物组分,其中所述热塑性聚合物组分包含含有源自双酚A的单元的聚碳酸酯,聚(对苯二甲酸丁二醇酯),以及甲基丙烯酸酯-苯乙烯-丁二烯抗冲改性剂;
0.0001至1重量%的所述近红外光吸收性物质,其中所述近红外光吸收性物质为六硼化镧、氧化铯钨或者它们的组合;和
0.5至5重量%的所述白色颜料,其中所述白色颜料为二氧化钛颜料,并且其中所述第二可激光焊接的组件不含其它白色颜料;以及
其中根据以5毫米/分钟的速度进行的拉伸剪切试验测定,在所述第一热塑性组件与所述第二可激光焊接的组件之间的拉伸剪切强度大于15N/mm2。
25.一种激光焊接热塑性组件的方法,其包括:
使对于近红外辐射波长透射的第一可激光焊接的热塑性组件的表面的至少一部分与第二可激光焊接的热塑性组件的表面的至少一部分接触,所述第二可激光焊接的热塑性组件包含权利要求1-19中任一项的可激光焊接的组合物;
用近红外激光穿过所述第一热塑性组件照射至所述第二可激光焊接的热塑性组件,照射强度能有效地使所述第一可激光焊接的热塑性组件与所述第二可激光焊接的热塑性组件焊接。
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Publication number | Publication date |
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CN101868495B (zh) | 2013-06-12 |
WO2009066232A1 (en) | 2009-05-28 |
IN2010DE02191A (zh) | 2011-02-04 |
EP2212375A1 (en) | 2010-08-04 |
JP2011503338A (ja) | 2011-01-27 |
US20090130451A1 (en) | 2009-05-21 |
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