CN101346429B - 形成可透射激光的构件的阻燃性树脂组合物 - Google Patents

形成可透射激光的构件的阻燃性树脂组合物 Download PDF

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CN101346429B
CN101346429B CN2006800493178A CN200680049317A CN101346429B CN 101346429 B CN101346429 B CN 101346429B CN 2006800493178 A CN2006800493178 A CN 2006800493178A CN 200680049317 A CN200680049317 A CN 200680049317A CN 101346429 B CN101346429 B CN 101346429B
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resin
laser
molded resin
molded
acid
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CN101346429A (zh
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春原淳
平川阳一
花房和人
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WinTech Polymer Ltd
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WinTech Polymer Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
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    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
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    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
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    • B29C65/1629—Laser beams characterised by the way of heating the interface
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    • B29C65/1638—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding focusing the laser beam on the interface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明公开了一种可激光熔接的阻燃性树脂组合物(用于位于透射侧的构件)，其包含(A)聚酯系树脂和(B)选自次膦酸盐、二次膦酸盐和它们的聚合物(优选金属盐)中的至少一种次膦酸化合物。所述树脂组合物可以具有对于包含所述树脂组合物且厚度为2mm的模塑制品不小于15％的激光透射率。所述树脂组合物还可以含有含氟树脂、含氮阻燃剂(例如，三嗪化合物与氰尿酸和/或异氰尿酸的盐)和/或填充剂(例如玻璃纤维)等。这种树脂组合物同时实现了高水平的激光熔接性(激光透射性)和阻燃性。

Description

形成可透射激光的构件的阻燃性树脂组合物
技术领域
本发明涉及一种具有高激光透射性(或激光透射率)和优异的阻燃性的激光熔接性树脂组合物(或用于在激光熔接中的可透射激光的构件的树脂组合物)，并且涉及一种激光熔接性模塑制品(或用于激光熔接的模塑制品)，该激光熔接性模塑制品包含所述树脂组合物并且在激光熔接中用于可透射激光的构件(或透射激光的构件)。
背景技术
聚酯系树脂，例如聚对苯二甲酸丁二醇酯(PBT)系树脂具有各种优异的性能，如耐热性、耐化学性、电性能、机械性能和成形加工性(或模塑性)并且用于多种应用。应用的具体实例包括各种汽车电组件或部件(例如，各种控制单元、各种传感器和点火线圈)和安装在汽车或电器中的连接器、开关部件、继电器部件、线圈部件、变压器部件和灯部件。这些部件通常包括导电部件，并且近来具有由诸如异常过热或短路的问题所导致的增加的着火危险。因此，需要提高这些部件的阻燃性。
长期以来已经研究了PBT系树脂的阻燃性的改善。例如，日本专利申请公开230348/1993(JP-5-230348A，专利文件1)公开了一种阻燃性树脂组合物，所述组合物包含PBT系树脂，含有溴化环氧系阻燃剂、三氧化锑和/或五氧化二锑作为主要组分的阻燃助剂，和通过乳液聚合获得的聚四氟乙烯树脂。而且，日本专利申请公开256545/2000(JP-2000-256545A，专利文件2)公开了一种阻燃性聚酯树脂组合物，所述组合物包含：特殊的芳香族聚酯、溴化的环氧化合物、溴化的聚丙烯酸酯和三氧化锑。近来，出于含卤素阻燃剂如含溴阻燃剂对环境影响的关注(例如，由废物所致的缺点)，还提出使用无卤素阻燃剂。例如，日本专利申请公开70671/1993(JP-5-70671A，专利文件3)公开了一种阻燃性树脂组合物，所述组合物包含具有特定特性粘度的聚对苯二甲酸亚烷基酯、强化填充剂、蜜胺-氰尿酸加合物以及具有特殊结构的含磷阻燃剂。
另一方面，上述部件通常由多个构件(或部件)通过接合形成，或者通常将部件接合到其它部件上。为了接合这些部件或组件，使用胶粘剂、螺钉夹具、搭扣配合和各种熔接方法(例如，热板熔接、超声波熔接、振动熔接和激光熔接)。然而，在胶粘剂的使用中，用于固化胶粘剂的时间损失或者环境负荷是个问题。而且，在使用螺钉夹具的方法中，固定所需的劳力或者成本增加。在熔接方法中的热板熔接、超声波熔接和振动熔接中，可能存在由热、振动等所致的制品损害。另一方面，通过激光熔接的接合(或连接)方法没有由熔接中涉及的热或振动所致的制品损害，并且熔接方法也非常简单。因此，近来，激光熔接方法得到广泛应用，并且作为用于各种树脂组件或部件的熔接方式已经引起了关注。
然而，由于激光束的低透射性，使用激光熔接接合PBT系树脂具有熔接树脂的困难。因此，已经考虑了各种方法。例如，日本专利申请公开136601/2003(JP-2003-136601A，专利文件4)公开了一种具有适于激光熔接应用的透射率的塑性组件。该文件提到所述塑性组件包含含有聚酯的组合物，并且1mm厚的包含该组合物的模塑制品在800至1200nm波长的透射率不小于10％。日本专利申请公开26656/2001(JP-2001-26656A，专利文件5)公开了一种用于模塑制品的方法，所述方法包括：通过熔接将(A)包含(a)至少一种聚酯系共聚物的模塑制品与(B)不同于模塑制品(A)的模塑制品合成一体以得到模塑制品，所述聚酯系共聚物选自熔点为170至220℃的PBT系共聚物、熔点为200至250℃的聚对苯二甲酸乙二醇酯系共聚物和熔点为210至260℃的聚萘二甲酸乙二醇酯系共聚物。而且，专利文件5提到可以在不劣化该发明效果的范围内添加阻燃剂或阻燃助剂(如卤化物或磷化合物)。
然而，即使在常规的阻燃性聚酯系树脂组合物的激光熔接中，差的激光透射性也阻止成功的激光熔接。而且，尽管将阻燃剂和阻燃助剂在激光熔接性(激光透射性)不劣化的范围内添加到其中的树脂组合物可以进行熔接，但是这种组合物的阻燃性在实用上是不足的。因此，通过常规方法难以同时实现高水平的激光熔接性和阻燃性。[专利文件1]JP-5-230348A(权利要求1)[专利文件2]JP-2000-256545A(权利要求1)[专利文件3]JP-5-70671A(权利要求1)[专利文件4]JP-2003-136601A(权利要求2)[专利文件5]JP-2001-26656A(权利要求1和第[0027]段)
发明内容
本发明所要解决的问题
因此，本发明的一个目的是提供一种用于可透射激光的构件(或透射激光的构件)的阻燃性树脂组合物及其模塑制品(或可透射激光的构件(或透射激光的构件))，所述阻燃性树脂组合物同时实现高水平的激光熔接性(激光透射性)和阻燃性。
本发明的另一个目的是提供一种用于可透射激光的构件的阻燃性树脂组合物及其模塑制品(或可透射激光的构件或位于或设置在激光透射侧的构件)，所述阻燃性树脂组合物具有优异的激光透射性，并且在薄壁模塑制品中可以保持高的阻燃性。
本发明的另一个目的是提供一种复合模塑制品，其中通过激光熔接将具有高的阻燃性的模塑制品接合到可吸收激光的树脂模塑制品上。
本发明的另一个目的是提供一种激光熔接方法，其中以高的熔接强度将模塑制品和可吸收激光的树脂模塑制品接合在一起。解决问题的手段
本发明的发明人进行了深入研究以达到上述目的，并且最终发现聚酯系树脂和次膦酸化合物的盐的组合使用在没有激光透射性的劣化的情况下同时实现了高水平的激光熔接性和阻燃性。本发明是基于上述发现实现的。
即，本发明的激光熔接性的阻燃性树脂组合物包含(A)聚酯系树脂和(B)选自次膦酸盐、二次膦酸盐和它们的聚合物中的至少一种次膦酸化合物，并且用于形成在激光熔接中的可透射激光的构件(或者在激光熔接中位于或设置在透射侧的构件)。
聚酯系树脂(A)可以包括聚对苯二甲酸丁二醇酯系树脂(例如，聚对苯二甲酸丁二醇酯、聚对苯二甲酸丁二醇酯系共聚物等)。对于次膦酸化合物，次膦酸盐可以是由下式(1)表示的金属盐，或者二次膦酸盐可以是由下式(2)表示的金属盐。
[结构式1]式中，R1、R2、R3和R4相同或不同，并且各自表示烷基、环烷基、芳基或芳烷基，R5表示亚烷基、脂环族二价基团或芳香族二价基团；R1和R2可以结合在一起以与相邻的磷原子形成环；Mm+表示具有m价的金属，并且“m”表示2至4的整数；Mn+表示具有n价的金属，并且“n”表示2至4的整数。相对于100重量份聚酯系树脂(A)，次膦酸化合物(B)的比例可以是约10至50重量份。而且，树脂组合物还可以包含(C)含氟树脂。相对于100重量份聚酯系树脂(A)，含氟树脂(C)的比例可以是约0至1重量份(例如，约0.01至1重量份)。树脂组合物还可以包含(D)含氮阻燃剂。含氮阻燃剂(D)可以包含三嗪化合物与选自氰尿酸和异氰尿酸中的至少一种的盐。相对于100重量份聚酯系树脂(A)，含氮阻燃剂(D)的比例可以是约0.5至10重量份。
树脂组合物还可以包含(E)填充剂(例如，玻璃状填充剂)。相对于100重量份聚酯系树脂(A)，填充剂(E)的比例可以是约5至70重量份。
树脂组合物可以具有对于包含该树脂组合物且厚度为2mm的模塑制品不小于15％的激光透射率。而且，在包含树脂组合物、厚度为0.8至1mm(例如，0.8mm)的模塑制品中，树脂组合物可以具有根据UL94标准的阻燃性等级为V-0的阻燃性。
本发明还包括可透射激光的树脂模塑制品(第一树脂模塑制品)，其能够与可吸收激光的树脂模塑制品(第二树脂模塑制品)接触(特别是与可吸收激光的树脂模塑制品的表面接触)，并且可通过激光束接合到可吸收激光的树脂模塑制品上，并且包含上述树脂组合物。本发明还包括透射激光束以通过激光熔接与配对构件接合并且包含所述树脂组合物的构件。
本发明的复合模塑制品包含含有所述树脂组合物的第一树脂模塑制品以及可吸收激光并且通过激光熔接接合到第一树脂模塑制品上的第二树脂模塑制品。在复合模塑制品中，第一树脂模塑制品可以具有厚度为0.1至2mm的区域，并且第二树脂模塑制品可以接合到第一树脂模塑制品的该区域上。
而且，本发明的激光熔接方法包括：使包含树脂组合物的第一树脂模塑制品与可吸收激光的第二树脂模塑制品接触；以及在从第一树脂模塑制品向第二树脂模塑制品的方向上辐照激光束以激光熔接第一和第二树脂模塑制品。第一树脂模塑制品可以用不吸收激光的着色剂着色。第二树脂模塑制品可以包含热塑性树脂组合物，所述热塑性树脂组合物含有激光吸收剂或着色剂。此外，在激光熔接方法中，第一树脂模塑制品可以具有厚度为0.1至2mm并且激光透射率不小于15％的激光透射区，并且可以使第二树脂模塑制品的表面至少与第一树脂模塑制品的激光透射区接触，并且可以进行激光辐照以接合模塑制品。
发明效果
根据本发明，聚酯系树脂(例如，聚对苯二甲酸丁二醇酯系树脂)和特殊的次膦酸化合物的组合同时实现了高水平的激光熔接性和阻燃性，同时保持聚酯系树脂的优异性能(例如，机械性能、耐热性和耐化学性)，而不使激光透射性劣化。而且，这种组合物具有优异的激光透射性，并且即使在薄壁模塑制品中，也可以保持高的阻燃性。因此，可以通过激光熔接将具有高阻燃性的树脂模塑制品容易地接合到可吸收激光的树脂模塑制品上。此外，根据本发明的激光熔接方法，可以以高熔接强度将树脂模塑制品接合到可吸收激光的树脂模塑制品上。
附图简述
图1是说明在实施例和比较例的实施方案中的激光熔接的示意性侧视图。图2是说明在实施例和比较例的实施方案中的激光熔接的平面图。
发明详述
[用于激光熔接(或者用于可透射激光的构件)的阻燃性树脂组合物](A)聚酯系树脂作为基础树脂的聚酯系树脂包括可以由二羧酸组分和二醇组分的缩聚、羟基羧酸或内酯的缩聚、这些组分的缩聚等获得的均聚聚酯或共聚聚酯。优选的聚酯系树脂通常包括饱和的聚酯系树脂，特别是芳香族饱和的聚酯系树脂，并且特别是包括聚亚烷基芳酯(arylate)系树脂(如聚亚烷基芳酯或聚亚烷基芳酯系共聚物)，如聚对苯二甲酸丁二醇酯(PBT)系树脂(如聚对苯二甲酸丁二醇酯或聚对苯二甲酸丁二醇酯系共聚物)、聚萘二甲酸丁二醇酯(PBN)系树脂(如PBN或PBN系共聚物)、聚对苯二甲酸乙二醇酯(PET)系树脂(如PET或PET系共聚物)、聚萘二甲酸乙二醇酯(PEN)系树脂(如PEN或PEN系共聚物)。可以单独或组合使用聚酯系树脂。在聚酯系树脂中，由于高的激光熔接性，优选低结晶性或非晶芳香族聚酯系树脂。
顺便提及，二羧酸可以包括例如，脂肪族二羧酸(例如，C4-40脂肪族二羧酸，如琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二羧酸、十二烷二羧酸、十六烷二羧酸或二聚物酸，优选C4-14二羧酸)，脂环族二羧酸(例如，C8-12脂环族二羧酸，如环己烷邻二甲酸、环己烷间二甲酸、环己烷对二甲酸或降冰片烯二酸(himic acid))，除对苯二甲酸以外的芳香族二羧酸(例如，C8-16芳香族二羧酸，如邻苯二甲酸、间苯二甲酸；萘二甲酸，如2，6-萘二甲酸；和4，4’-二苯基二甲酸、4，4’-二苯氧基醚二甲酸、4，4’-二苯醚二甲酸、4，4’-二苯基甲烷二甲酸或4，4’-二苯酮二甲酸)，或者其反应衍生物[例如，能够形成酯的衍生物(或者酯形成性衍生物)，例如，低级烷基酯(例如，邻苯二甲酸或间苯二甲酸的C1-4烷基酯，如邻苯二甲酸二甲酯或间苯二甲酸二甲酯(DMI))；酰氯；以及酸酐]。另外，在必要时，可以将多羧酸(如偏苯三酸或均苯四酸)与二羧酸组合使用。
二醇可以包括例如，除1，4-丁二醇以外的脂肪族烷烃二醇(例如，C2-12烷烃二醇，如1，2-亚乙基二醇、三亚甲基二醇、丙二醇、新戊二醇、己二醇、辛二醇或癸二醇，优选C2-10烷烃二醇)、聚亚烷基二醇[例如，具有多个氧化C2-4烯单元的二醇，例如，二甘醇、二丙二醇、二丁二醇、三甘醇、三丙二醇和聚丁二醇]，脂环族二醇(例如，1，4-环己二醇、1，4-环己烷二甲醇和氢化双酚A)、芳香族二醇[例如，C6-14芳香族二醇，如对苯二酚、间苯二酚或萘二酚；双酚；双酚化合物；和亚二甲苯基二甲醇]。此外，在必要时，可以将多元醇(如甘油、三羟甲基丙烷、三羟甲基乙烷或季戊四醇)与二醇组合使用。
双酚化合物可以包括双(羟基芳基)C1-6烷烃如双(4-羟苯基)甲烷(双酚F)、1，1-双(4-羟基苯基)乙烷(双酚AD)、1，1-双(4-羟基苯基)丙烷、2，2-双(4-羟基苯基)丙烷(双酚A)，2，2-双(4-羟基-3-甲基苯基)丙烷、2，2-双(4-羟基苯基)丁烷、2，2-双(4-羟基苯基)-3-甲基丁烷、2，2-双(4-羟基苯基)己烷或2，2-双(4-羟基苯基)-4-甲基戊烷；双(羟基芳基)C4-10环烷烃如1，1-双(4-羟基苯基)环戊烷或1，1-双(4-羟基苯基)环己烷；双(4-羟基苯基)醚；4，4’-二羟基二苯基砜；4，4’-二羟基二苯硫醚；4，4’-二羟基二苯基酮；及其环氧烷加合物。环氧烷加合物可以包括双酚化合物(例如，双酚A、双酚AD和双酚F)的C2-3环氧烷加合物，例如，2，2-双-[4-(2-羟基乙氧基)苯基]丙烷、二乙氧基化双酚A(EBPA)、2，2-双-[4-(2-羟基丙氧基)苯基]丙烷和二丙氧基化双酚A。在环氧烷加合物中，相对于每一个羟基，加成的环氧烷(C2-3环氧烷如环氧乙烷或环氧丙烷)的摩尔数可以是约1至10mol，并且优选是约1至5mol。
羟基羧酸可以包括例如，羟基羧酸，如羟基苯甲酸、羟基萘甲酸、羟基苯基乙酸、乙醇酸或羟基己酸或它们的衍生物等。内酯可以包括C3-12内酯，如丙内酯、丁内酯、戊内酯或己内酯(例如ε-己内酯)等。
在上述优选的聚酯系树脂中，在聚亚烷基芳基酯系共聚物中使用的可共聚单体可以包括二醇[例如，C2-6亚烷基二醇(例如，直链或支链亚烷基二醇如1，2-亚乙基二醇、三亚甲基二醇、丙二醇或己二醇)、具有约2至4个重复氧化烯单元的聚氧化C2-4烯二醇(例如，二甘醇)，以及双酚化合物(例如，双酚化合物或其环氧烷加合物)]，二羧酸[例如，C6-12脂肪族二羧酸(例如，己二酸、庚二酸、辛二酸、壬二酸和癸二酸)，在其芳烃环的不对称位置具有两个羧基的不对称芳香族二羧酸以及1，4-环己烷二甲醇]等。在这些化合物之中，优选的化合物包括芳香族化合物，例如双酚化合物(特别是双酚A)的环氧烷加合物，以及不对称芳香族二羧酸[例如邻苯二甲酸、间苯二甲酸及其反应衍生物(例如，低级烷基酯如间苯二甲酸二甲酯(DMI))]等。
可共聚单体相对于聚酯系树脂(或单体的总量)的比例(在聚酯系树脂中的改性度)可以在不大于30mol％(约0至30mol％)，例如约0.01至30mol％的范围内选择，并且通常是约1至30mol％，优选约3至25mol％，并且更优选约5至20mol％(例如约5至15mol％)。
特别优选的聚酯系树脂包括PBT系树脂。PBT系树脂可以单独或组合使用。特别是，优选PBT和PBT系共聚物(改性的PBT)的组合。而且，为了提高阻燃性，PBT系树脂和PET系树脂(例如PET、改性的PET(PET系共聚物))可以组合使用。
PBT系树脂的熔点由于高的激光熔接性而不低于190℃(例如，约190至270℃)，优选约200至260℃，并且更优选约210至250℃。
而且，PBT系树脂的特性粘度(IV)可以从约0.5至1.3dl/g的范围内选择。为了提高模塑性能和/或机械性能，特性粘度可以优选是约0.6至1.2dl/g，并且更优选约0.65至1.1dl/g。顺便提及，PBT系树脂过分低的特性粘度可能使机械强度劣化。另一方面，PBT系树脂过分高的特性粘度可能使流动性和模塑性能劣化。
可以通过常规方法，例如酯交换和直接酯化制备聚酯系树脂。例如，通过上述常规方法，通过使对苯二甲酸或其反应衍生物和1，4-丁二醇以及在必要时的可共聚物单体共聚，可以制备PBT系树脂。
(B)次膦酸化合物次膦酸化合物可以包括例如次膦酸、二次膦酸和/或它们的聚合产物(或缩合物，例如聚次膦酸)的盐[例如，金属盐；与选自硼、铝和碱性含氮化合物中的至少一种成盐(或能成盐的)组分的盐(例如，金属盐，硼盐(如甲硼烷基化合物)、铵盐、与含氨基的含氮化合物的盐)]。次膦酸化合物可以单独或组合使用。顺便提及，次膦酸化合物可以具有链结构或环状结构。
形成盐的次膦酸、二次膦酸或它们的聚合产物可以是没有有机基团的次膦酸或没有有机基团的二次膦酸，并且在实用情况下，通常是有机次膦酸、有机二次膦酸、有机二次膦酸的聚合物(或缩合物)或其它次膦酸化合物。所述盐可以单独或以组合形式含有这些次膦酸。
在上述次膦酸化合物中，特别优选金属盐。形成盐的金属可以包括碱金属(例如钾和钠)、碱土金属(例如，镁和钙)、过渡金属(例如，铁、钴、镍和铜)、元素周期表的第12族的金属(例如锌)、元素周期表的第13族的金属(例如铝)等。所述金属盐可以含有这些金属中的一种或其至多两种。在上述金属中，优选碱土金属(例如钙)和元素周期表的第13族的金属(例如，铝)。
金属的价态不特别限于具体价态。所述价态可以是约1至4，优选约2至4，并且更优选2或3。
次膦酸的金属盐(或次膦酸金属盐)的具体实例包括由下式(1)表示的化合物。二次膦酸的金属盐(或二次膦酸金属盐)的具体实例包括由下式(2)表示的化合物。
[结构式2]
Figure S2006800493178D00091
在式中，R1、R2、R3和R4相同或不同，并且各自表示烃基，并且R5表示二价烃基。基团R1和R2可以结合在一起以与相邻的磷原子形成环。基团Mm+表示上述具有m价的金属，并且“m”表示2至4的整数。基团Mn+表示上述具有n的金属，并且“n”表示2至4的整数。由基团R1、R2、R3和R4的每一个表示的烃基可以包括烷基(例如，直链或支链C1-6烷基，如甲基、乙基、异丙基、正丁基或叔丁基)、环烷基(例如，C5-8环烷基，如环己基)、芳基(例如C6-10芳基，如苯基)、芳烷基(例如C6-10芳基-C1-4烷基，如苄基)等。在这些基团之中，优选的基团通常包括烷基(例如，优选C1-4烷基)和芳基(例如苯基)。
通过将基团R1和R2与相邻的磷原子结合而形成的环是含有磷原子作为组成环的杂原子的杂环(或杂环的环)(即，含磷原子的杂环)。所述环通常可以包括4至20元杂环，并且优选5至16元杂环。而且，含磷原子的杂环可以是双环。含磷原子的杂环可以具有取代基。
由基团R5表示的二价烃基可以包括亚烷基(alkylene)(或亚烷基(alkylidene)，例如可以具有取代基(例如C6-10芳基)的直链或支链C1-10亚烷基，如亚甲基、亚乙基、苯基亚乙基、亚丙基、三亚甲基、1，4-丁二基、或1，3-丁二基)，脂环族二价基团(例如，C5-8脂环族二价基团如亚环己基或环己烷二亚甲基)，芳香族二价基团[例如，可以具有取代基(例如C1-4烷基)的C6-10亚芳基，如亚苯基或亚甲苯基；在其芳烃环上可以具有C1-4烷基(例如甲基)的C6-10芳烃C1-4亚烷基，如亚二甲苯基；和在其芳烃环上可以具有C1-4烷基(例如甲基)的联芳基(例如，亚联苯基；直链或支链C1-4烷烃-二C6-10亚芳基，如甲烷二亚苯基；对应于二C6-10芳基醚如二苯基醚的二价基团；对应于二C6-10芳基酮如二苯酮的二价基团；以及对应于二C6-10芳基硫醚，如二苯硫醚的二价基团]等。在这些二价烃基之中，优选的二价烃基包括亚烷基(例如，特别是C1-6亚烷基)。
优选的金属盐(1)和(2)包括价态(“m”和“n”)分别为2至3的多价金属盐。次膦酸金属盐(1)的具体实例包括二烷基次膦酸钙，如二甲基次膦酸钙，甲基乙基次膦酸钙和二乙基次膦酸钙(例如，二C1-10烷基次膦酸钙)；芳基次膦酸钙，如苯基次膦酸钙或二苯基次膦酸钙(例如一或二C6-10芳基次膦酸钙)；烷基芳基次膦酸钙，如甲基苯基次膦酸钙(例如C1-4烷基-C6-10芳基-次膦酸钙)；可以具有取代基的亚烷基次膦酸的钙盐，如1-羟基-1H-正膦-1-氧化物的钙盐或2-羧基-1-羟基-1H-正膦-1-氧化物的钙盐(例如，C3-8亚烷基次膦酸钙)；对应于这些钙盐的铝盐；其它金属盐；等。
二次膦酸金属盐(2)的具体实例包括烷烃二次膦酸钙，如乙烷-1，2-双(次膦酸)钙[例如C1-10烷烃双(次膦酸)钙]；烷烃双(烷基次膦酸)钙，如乙烷-1，2-双(甲基次膦酸)钙[例如C1-10烷烃双(C1-6烷基次膦酸)钙]；对应于这些钙盐的铝盐；其它金属盐；等。
次膦酸金属盐(B)还可以包括这样的次膦酸的多价金属盐和/或这样的二次膦酸的多价金属盐的聚合物(或缩合物)。
次膦酸化合物优选包括选自次膦酸的多价金属盐、二次膦酸的多价金属盐和二次膦酸的聚合物(或缩合物)的多价金属盐中的至少一种。
在由上述式(1)或(2)表示的金属盐中，优选的次膦酸化合物具体包括二烷基次膦酸的金属盐(例如钙盐和铝盐)以及烷烃二次膦酸的金属盐(例如钙盐和铝盐)。
通过激光衍射/散射粒度分布测量装置测量的次膦酸化合物的平均粒度可以从例如约0.1至200μm的范围内选择，并且可以优选是约1至100μm，并且更优选约40至80μm。过分小的粒度有时导致激光透射性的劣化。另一方面，过分大的粒度有时导致模塑制品(例如，小型模塑制品)的模塑性能的劣化，或者有时由于分散性的劣化而导致阻燃性或机械性能的降低。
次膦酸化合物相对于100重量份聚酯系树脂(A)的比例可以从例如约5至60重量份的范围内选择。该比例优选为约10至50重量份，并且更优选约12至45重量份(例如，约15至40重量份)。在金属盐比例太低的情况下，存在的可能性是阻燃性的提高不足。在比例太高的情况下，存在的可能性是激光透射性降低，从而激光熔接性劣化。
(C)含氟树脂本发明的树脂组合物还可以含有含氟树脂。这样的含氟树脂可以包括含氟单体的均聚物或共聚物，例如含氟单体(如四氟乙烯、氯三氟乙烯、偏二氟乙烯、六氟丙烯或五氟烷基乙烯醚)的均聚物或共聚物，所述含氟单体和其它可共聚单体(例如，烯烃单体，如乙烯或丙烯；以及丙烯酸类单体，如(甲基)丙烯酸酯)的共聚物等。
含氟树脂的具体实例包括均聚物如聚四氟乙烯、聚氯三氟乙烯或聚偏二氟乙烯；以及共聚物如四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷基乙烯醚共聚物、乙烯-四氟乙烯共聚物或乙烯-氯三氟乙烯共聚物。含氟树脂可以单独或组合使用。优选的含氟树脂包括四氟乙烯的均聚物或共聚物、四氟乙烯和(甲基)丙烯酸酯的共聚物等。
含氟树脂(C)可以具有滴落抑制作用(即，抑制通过燃烧的熔融树脂的滴落的作用)。顺便提及，因为在不低于200℃的温度下经过辐照处理或热处理的含氟树脂具有差的滴落抑制作用，所以可以使用没有经过这样的处理的含氟树脂。
含氟树脂(C)相对于100重量份聚酯系树脂(A)的比例是约0至1重量份(例如约0.01至1重量份)，优选约0.05至0.7重量份，并且更优选约0.1至0.5重量份。顺便提及，当该比例太高时，可能存在由树脂组合物的粘度增加所致的模塑性能的劣化，有在其上的白点的产生所致的模塑制品外观的可能缺陷，或者由激光束的透射性的局部劣化所致的激光熔接强度的可能降低。
(D)含氮阻燃剂本发明的树脂组合物还可以含有(D)含氮阻燃剂。含氮阻燃剂可以包含含氮环状化合物，如三唑化合物或三嗪化合物(例如含氨基含氮环状化合物，如含氨基三唑化合物或含氨基三嗪化合物)、含氮环状化合物的盐等。在阻燃剂(D)中，优选三嗪化合物(例如，含氨基三嗪化合物)或其盐。
在作为含氮环状化合物的含氨基三唑化合物中，三唑化合物可以包括1，2，3-三唑(例如，1H-1，2，3-三唑；以及2H-1，2，3-三唑)、1，2，4-三唑(例如1H-1，2，4-三唑，如胍唑(guanazole)；以及4H-1，2，4-三唑，如胍嗪(guanazine)等。组成三唑环的任意原子(特别是碳原子)具有作为一个或多个取代基的一个或多个氨基。氨基的数量是例如约1至3，并且优选约1至2。
三嗪化合物可以包括各种三嗪，如含氨基的1，3，5-三嗪或含氨基的1，2，3-三嗪(例如在5-位、4，5-位或4，5，6-位具有一个或多个氨基作为一个或多个取代基的1，2，3-三嗪，以及4-氨基-苯并-1，2，3-三嗪)以及含氨基的1，2，4-三嗪(例如在3-位、5-位或3，5-位具有一个或多个氨基作为一个或多个取代基的1，2，4-三嗪)。含氨基的1，3，5-三嗪可以包括例如蜜胺[例如蜜胺、取代的蜜胺(例如C1-4烷基蜜胺，如2-甲基蜜胺和脒基蜜胺)]，蜜胺的缩合产物(蜜胺缩合物)(例如蜜白胺、蜜勒胺和氰尿酰胺)，蜜胺的共缩聚树脂(例如蜜胺-甲醛树脂、酚-蜜胺树脂、苯胍胺-蜜胺树脂和芳香族聚胺-蜜胺树脂)、氰尿酰胺类(如氰尿二酰胺或氰尿酰胺)，胍胺类[例如胍胺；C1-4烷基胍胺，如甲基胍胺；酰基胍胺如乙酰基胍胺；芳香族胍胺，如苯胍胺、苯基乙酰基胍胺或酞胍胺(phthaloguanamine)；脂环族胍胺如环己烷胍胺；脂肪族胍胺如琥珀基二胍胺(succinodiguanamine)或己二基二胍胺(adipodiguanamine)；CTU-胍胺(2，4，8，10-四氧杂螺(5.5)十一烷-3，9-双(2-乙基胍胺))；以及丙烯酰基胍胺(acryloguanamine)]等。组成三嗪环的任意原子(特别是碳原子)具有作为一个或多个取代基的一个或多个氨基。氨基的数量是例如约1至4，优选约1至3，并且更优选约2至3。
含氮环状化合物的盐可以包括上述含氮环状化合物(如含氨基的三唑化合物或含氨基的三嗪化合物)与选自具有羟基的含氮环状化合物和含氧酸(例如磷酸、硫酸、磺酸、硝酸和硼酸)中的至少一种的盐。在这些盐中，优选三嗪化合物与含羟基的含氮环状化合物(例如，具有羟基的三嗪化合物，例如氰尿酸或其衍生物(如异氰尿酸、氰尿二酰胺或氰尿酰胺))的盐，以及三嗪化合物与磷酸(例如，非缩合磷酸，如正磷酸、偏磷酸、亚磷酸，或次磷酸；以及缩合的磷酸，如连二磷酸盐、焦磷酸盐、聚磷酸盐、聚偏磷酸盐或磷酸酐的盐)的盐。
在含氮阻燃剂(D)中，特别是，优选三嗪化合物(例如含氨基的三嗪化合物)与氰尿酸和/或异氰尿酸的盐。这种盐的具体实例包括氰尿酸的蜜胺盐(例如蜜胺氰尿酸盐)、蜜勒胺盐、蜜白胺盐、氰尿酰胺盐以及对应于蜜胺盐的胍胺盐，以及对应于这些氰尿酸盐的异氰酸盐。为了提高阻燃性，稳定性并且出于经济性观点，在实际上使用蜜胺氰尿酸盐作为阻燃剂(D)。含氮阻燃剂(D)可以单独或组合使用。
含氮阻燃剂(D)相对于100重量份聚酯系树脂(A)的比例可以从0至10重量份的范围内选择，并且是例如约0.5至10重量份，优选约1至6重量份，并且更优选约2至5重量份。当含氮阻燃剂(D)的比例太高时，存在的可能性是由于激光透射性的劣化，不能获得足够的激光熔接强度。
次膦酸化合物的金属盐(B)相对于含氮阻燃剂(D)的比例(重量比)[次膦酸化合物的金属盐(B)/含氮阻燃剂(D)]是约1/1至10/1，优选约2/1至8/1，并且更优选约3/1至6/1。
(E)填充剂(或强化材料)所述树脂组合物可以含有(E)填充剂或强化材料，含有的范围在填充剂或强化材料对激光透射性没有任何不利影响的范围内。这种填充剂或强化材料(E)可以包括纤维填充剂[例如，无机纤维(例如，玻璃纤维、二氧化硅纤维、氧化铝纤维、二氧化硅·氧化铝纤维、硅酸铝纤维、氧化锆纤维、钛酸钾纤维，晶须(例如碳化硅、氧化铝、氮化硼等的晶须)以及硅灰石)以及有机纤维(例如脂肪族或芳香族聚酰胺、芳香族聚酯、含氟树脂或丙烯酸类树脂，如聚丙烯腈，由人造纤维等形成的纤维以及碳纤维)]、片状填充剂[例如滑石、云母和玻璃片]、粒状填充剂[例如玻璃珠、玻璃粉末(或粉末状玻璃)、粉碎的纤维(例如粉碎的玻璃纤维)、粘土、有机化的粘土、瓷土(高岭土)、钛酸钾、碳酸钙、氧化钛、长石矿物和石墨]。
纤维填充剂的平均直径可以是例如约1至50μm(优选约3至30μm)，并且其平均长度可以是例如约100μm至3mm(优选约300μm至1mm)。而且，片状或粒状填充剂的平均粒度可以是例如约0.1至100μm，并且优选约0.1至50μm。这些填充剂可以单独或组合使用。
在这些填充剂(E)中，优选透射激光的填充剂。这种填充剂可以根据激光束的波长选择，并且可以包括例如玻璃状填充剂或强化材料(例如，玻璃纤维、玻璃片和玻璃珠)等。特别是，优选玻璃纤维。
顺便提及，在玻璃纤维中的横截面的形状不特别限于具体形状，并且可以包括圆形、卵圆形(或椭圆形)，包括变形的椭圆形，如茧状形)、半圆形、圆弧形、多边形(如三角形或长方形(orthogon)(例如矩形和梯形))或与其类似的形状等。由于高强度以及阻燃性，在玻璃纤维中的横截面的形状优选为矩型或几乎是矩形的形状(特别是长椭圆形(oblong))。在这种玻璃纤维中，主轴(在横截面中的最大距离)相对于短轴(垂直主轴的方向上的最大距离)的比率可以是例如，约1.3至10，优选约1.5至5，并且更优选约2至4。
由于高的强度和阻燃性，玻璃纤维的横截面积可以是例如约50至500μm2，优选约100至300μm2，并且更优选约140至300μm2。
为了防止模塑制品变形，玻璃纤维的平均纤维长度优选是更短的长度。另一方面，为了提高机械性能，其平均纤维长度优选是更长的长度(例如不短于30μm)。因此，考虑到在机械性能和变形之间的平衡，平均纤维长度可以根据应用所需的性能适当地选择。平均纤维长度可以是例如约20至1500μm，优选约50至1000μm，并且更优选约70至800μm。
可以单独使用一种玻璃纤维，或者可以组合使用多种种类不同的玻璃纤维。而且，在填充剂中，玻璃纤维和其它填充剂(特别是，无机填充剂等)可以组合使用。上述其它填充剂可以单独或组合使用。
顺便提及，可以通过使用喷嘴对熔融玻璃抽丝制备玻璃纤维，所述喷嘴具有任何与上述在纤维中的横截面形状对应的衬套形状(即，从中排出熔融玻璃的衬套形状(孔形状))，例如，圆形、卵圆形、椭圆形、矩形和狭缝形)。而且，玻璃纤维可以通过下面的方法制备：从多个具有各种横截面(包括圆形)并且彼此相邻设置的喷嘴对熔融玻璃抽丝，并且将抽丝的熔融玻璃相互接合而制备单根长丝。
在必要时，可以使用常规的上浆剂或表面处理剂(或整理剂)处理填充剂(E)如玻璃纤维。上浆剂或表面处理剂可以包括例如官能化合物，如环氧系化合物、异氰酸酯系化合物、硅烷系化合物或钛酸酯系化合物。顺便提及，可以在将填充剂与其它组分(例如组分(A)、(B)、(C)和/或(D))混合之前使用上述上浆剂或表面处理剂处理填充剂，或者使用上述上浆剂或表面处理剂，通过在将填充剂与其它组分混合的过程中添加该试剂处理填充剂。上浆剂或表面处理剂相对于100重量份填充剂(例如玻璃纤维)的比例是约0至10重量份(例如约0.01至10重量份)并且优选约0.05至5重量份。
填充剂(E)相对于100重量份聚酯系树脂(A)的比例可以是从例如约0至100重量份的范围内选择的，优选约5至70重量份，并且更优选约10至65重量份(例如约15至65重量份)。根据填充剂的种类，填充剂(E)过分高的比例有时使激光透射性劣化，从而不能获得足够的熔接强度。
根据应用，本发明的树脂组合物可以含有各种添加剂，只要本发明的优点不劣化即可。可以加入到所述组合物中的添加剂可以包括例如，稳定剂(例如，抗氧化剂、紫外线吸收剂、光稳定剂和热稳定剂)，成核剂(用于结晶的成核剂)，其它阻燃剂(例如，含硫阻燃剂，含硅阻燃剂，醇系阻燃剂和含卤素阻燃剂)，阻燃助剂、润滑剂、脱模剂(或释放剂)、抗静电剂、着色剂(例如，有机或无机着色剂)、增塑剂、分散剂、其它热塑性树脂(例如，非晶或低结晶性树脂)。
在这些添加剂中，例如，为了提高激光透射性，可以使用非晶或低结晶性树脂，或者为了控制激光透射性的波动，可以使用成核剂。而且，为了提高耐热性，可以使用抗氧化剂，或为了提高脱模性和模塑性能，可以使用脱模剂。
非晶或低结晶性树脂可以包括聚碳酸酯系树脂、苯乙烯类树脂、热塑性弹性体等。这些树脂可以单独或组合使用。在这些树脂之中，为了降低树脂组合物的阻燃性的损失，优选聚碳酸酯等，并且可以将聚碳酸酯与苯乙烯类树脂和/或热塑性弹性体(特别是苯乙烯类树脂)组合使用。
成核剂可以是有机成核剂(如松香)或无机成核剂，例如，金属氧化物(例如二氧化硅、氧化铝、氧化锆、氧化钛、氧化铁和氧化锌)，金属碳酸盐(例如碳酸钙，碳酸镁和碳酸钡)，硅酸盐(例如，硅酸钙、硅酸铝和滑石)，金属碳化物(例如，碳化硅)，金属氮化物(例如，氮化硅，氮化硼和氮化钽)。这些成核剂可以单独或组合使用。成核剂可以是粒状或片状成核剂。
顺便提及，成核剂(例如，无机成核剂)的平均粒度可以是例如，约0.01至10μm，并且优选约0.02至5μm。成核剂相对于100重量份聚酯系树脂(A)的比例可以是例如，约0.001至5重量份并且优选约0.01至3重量份。
抗氧化剂可以包括常规的抗氧化剂，例如，受阻酚系抗氧化剂，受阻胺系抗氧化剂，含磷抗氧化剂和对苯二酚系抗氧化剂。所述抗氧化剂可以单独或组合使用。在抗氧化剂中，优选含磷抗氧化剂。含磷抗氧化剂具体包括一至三(支链C3-6烷基-苯基)亚磷酸酯，如三(2，4-二-叔丁基苯基)亚磷酸酯或双(2-叔丁基苯基)苯基亚磷酸酯；脂肪族多元醇的(支链C3-6烷基-芳基)亚磷酸酯，如双(2，6-二-叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯，双(2，4-二-叔丁基苯基)季戊四醇二亚磷酸酯，或者四(2，4-二-叔丁基苯基)-4，4’-二亚苯基二亚磷酸酯；磷酸三苯酯系化合物，如三(2，4-二-叔丁基苯基)磷酸酯；磷酸金属盐(例如，磷酸的碱金属盐或碱土金属盐(或其水合物)，如磷酸二氢钙或磷酸二氢钠一水合物)。在这些含磷抗氧化剂中，优选脂肪族多醇的(支链C3-6烷基-芳基)亚磷酸酯，磷酸的金属盐等。含磷抗氧化剂可以与其它抗氧化剂组合使用，所述其它抗氧化剂是例如，受阻酚系抗氧化剂[例如，脂肪族多元醇的双-至四[3-(3，5-二-支链C3-6烷基-4-羟基苯基)丙酸酯]，如甘油三[3-(3，5-二-叔丁基-4-羟基苯基)丙酸酯]或季戊四醇四[3-(3，5-二-叔丁基-4-羟基苯基)丙酸酯]]。
抗氧化剂相对于100重量份聚酯系树脂(A)的比例可以是例如，约0.005至3重量份，优选约0.01至1.5重量份(例如约0.02至1重量份)，并且更优选约0.05至0.5重量份。顺便提及，当抗氧化剂的比例太高时，抗氧化剂在树脂中的分散性可能降低或者抗氧化剂可能在模塑制品的表面上渗出。另外，存在由于渗出所致的模塑制品外观的可能缺陷。
可以使用的脱模剂可以包括例如，高级脂肪酸(例如，饱和或不饱和C10-30脂肪酸，如硬脂酸，褐煤酸或油酸)与多元醇(例如，(聚)亚烷基二醇如1，2-亚乙基二醇或聚乙二醇以及脂肪族多元醇如甘油、三羟甲基丙烷、季戊四醇或脱水山梨糖醇)的酯(包括偏酯)，蜡[例如，石蜡，微晶蜡和聚烯烃蜡(例如，聚C2-4烯烃蜡，如聚乙烯蜡或聚丙烯蜡(例如，优选低分子量聚乙烯蜡)，以及烯烃共聚物蜡，如乙烯共聚物蜡)]。酯的具体实例包括(聚)亚烷基二醇与脂肪酸的酯(例如，单酯或二酯，例如，1，2-亚乙基二醇与二硬脂酸的酯以及聚乙二醇与一月桂酸的酯)，甘油与脂肪酸的酯(例如，单酯至三酯，例如，甘油与一硬脂酸的酯以及甘油与三棕榈酸的酯)，三羟甲基丙烷与脂肪酸的酯(例如，单酯至三酯，例如，三羟甲基丙烷与一棕榈酸的酯)，季戊四醇与脂肪酸的酯(例如，单酯至四酯，例如，季戊四醇与硬脂酸的酯)，脱水山梨糖醇与脂肪酸的酯(例如，单酯至四酯，例如，脱水山梨糖醇与一硬脂酸的酯)等。脱模剂可以单独或组合使用。
脱模剂相对于100重量份聚酯系树脂(A)的比例可以是例如，约0.005至3重量份并且优选约0.01至1.5重量份。顺便提及，当脱模剂的比例太高时，脱模剂在树脂中的分散性可能降低或者脱模剂可能在模塑制品的表面上渗出。另外，存在由于渗出所致的模塑制品外观的可能缺陷。
本发明的树脂组合物具有优异的阻燃性，并且在包含树脂组合物并且具有1mm的厚度的模塑制品中，具有根据UL94标准的阻燃性等级(Underwriters Laboratories Inc的主题94)为V-0的阻燃性。另外，所述树脂组合物即使在其薄的模塑制品中也具有高的阻燃性。即使在模塑制品的厚度不大于1mm，例如，约0.6至1mm(例如，约0.8至1mm)并且优选约0.7至0.9mm(特别是0.8mm)时，树脂组合物也可以实现根据UL94标准的阻燃性等级为V-0的阻燃性。
而且，所述树脂组合物具有高的激光透射性，并且在激光熔接中用作位于透射激光束侧的构件(可透射激光的构件)。在包含树脂组合物的模塑制品中，在2mm的厚度，树脂组合物的激光透射率是例如，不小于10％(例如约10至100％)，优选不小于12％(例如约12至80％)，更优选不小于15％(例如约15至50％)，并且通常是约16至40％(例如约17至30％)。
顺便提及，对于用于激光熔接的激光束波长(例如，在上述范围内的波长的任何一个(例如940nm的波长))，树脂组合物可以具有在上述范围内的激光透射率。
因此，尽管基础树脂为聚酯系树脂(例如，PBT系树脂)，但是本发明的树脂组合物同时具有高水平的阻燃性和激光透射性。因此，所述树脂组合物可用作激光熔接用树脂组合物。特别是，所述树脂组合物可用于可透射激光的构件。而且，树脂组合物具有优异的性能，如模塑性能，机械强度，耐热性，耐化学性等。
顺便提及，树脂组合物可以含有着色剂(例如日本专利申请公开309694/2000(JP-2000-309694A)或日本专利申请公开71384/2001(JP-2001-71384A)中描述的着色剂)，只要对用于熔接的激光束的透射性没有显著劣化。所述着色剂可以包括不能吸收激光的着色剂(无机或有机着色剂)，例如黄色着色剂(例如，无机颜料，如镉黄以及有机颜料如联苯胺黄)，橙色着色剂(例如，耐晒黄)，红色颜料(例如，无机颜料如红色颜料，以及有机颜料如色淀红)，蓝色颜料(例如，无机颜料如钴蓝以及有机颜料如酞菁铜蓝)，绿色着色剂(例如无机颜料如铬绿，以及有机颜料如酞菁铜绿)，以及紫色着色剂。这种着色剂可以单独使用，或者可以组合使用多种着色剂以调节所需的色调的比例。例如，通过使用减色混合物(多种着色剂，例如，黄色着色剂和紫色着色剂的组合，以及黄色着色剂、红色着色剂和蓝色着色剂的组合)，可以将树脂着色成无彩色(灰色或黑色)。
着色剂的量不特别限于具体的量。相对于100重量份PBT系树脂，着色剂的量可以是例如，约0.001至5重量份并且优选约0.01至2重量份。
通过常规方法混合或捏合(熔融捏合)聚酯系树脂(A)和次膦酸化合物的金属盐(B)以及必要时的其它组分，可以制备本发明的树脂组合物。例如，可以通过下列方法制备所述树脂组合物：(1)包括，混合每一种组分，将所得到的混合物捏合并且使用单螺杆或双螺杆挤出机挤出成粒料，并且任选由粒料模塑为制品的方法；(2)包括一次性制备配方不同的粒料(母炼胶)，将粒料以一定比率混合(稀释)，并且模塑确定配方的制品(例如粒料)的方法；(3)包括将一种或不少于两种的组分直接供给到模塑机中的方法；等。顺便提及，例如，通过熔融捏合除易碎组分(例如，玻璃状强化材料)的组分，然后将捏合的物质与易碎组分(玻璃状强化材料)混合，或者将易碎组分通过挤出机的副进料口供给到其中，可以制备模塑制品如粒料。顺便提及，为了均匀地混合每一种组分，可以粉碎树脂组分(例如聚酯系树脂)的部分，并且可以将得到的粉碎物质与其它组分混合。
[模塑制品(树脂模塑制品)]
本发明的模塑制品(树脂模塑制品)包含上述树脂组合物，并且用于形成在激光熔接中的可透射激光的构件(或者位于或设置在激光熔接中的透射侧的构件)。所述树脂模塑制品能够与可吸收激光的树脂模塑制品(配对材料或另一个树脂模塑制品)(特别是与可吸收激光的树脂模塑制品的表面)接触，并且通过激光束可接合到配对材料上。
通过熔融捏合树脂组合物并且将捏合的物质进行常规的方法如挤塑，注塑，压塑，吹塑，真空模塑，滚塑或注气模塑，可以形成这种模塑制品。模塑制品通常通过注塑获得。注塑的条件可以根据聚酯系树脂的种类适当地选择。例如，可以在约200至300℃并且优选约250至280℃熔融捏合树脂组合物，可以在必要时将捏合的物质形成为粒料，并且可以通过使用注塑机将捏合的物质(或粒料)在约200至300℃(例如约250至280℃)的料筒温度下进行注塑。顺便提及，模塑温度可以从约40至90℃的范围内选择。为了保持激光透射性，优选模塑温度是约40至80℃(例如约45至80℃)，特别是约46至80℃。
模塑制品的形状(构造)不特别限于具体形状。因为通过由激光的熔接将模塑制品接合到配对材料(包含树脂的其它模塑制品)上，所以模塑制品通常具有至少有接触面(例如平表面)的形状，例如，片状形状。而且，本发明的模塑制品至少具有透射激光束的区域或部分(激光熔接区域)。该区域的厚度(对于激光束透射的方向的厚度)可以是例如，约0.1至3mm，优选约0.1至2mm(例如约0.2至2mm)，并且更优选约0.5至1.5mm。模塑制品可以在上述接触表面中具有这种激光熔接区域。激光透射区中的激光透射率是例如，约12至100％，优选约15至80％，并且更优选约16至50％(例如约17至40％)。
因为模塑制品具有优异的激光熔接性，所以通常可以通过激光熔接将模塑制品容易地接合到作为配对材料的树脂模塑制品上。顺便提及，在必要时，可以将激光熔接与其它熔接方法(例如，振动熔接，超声波熔接和热板熔接)组合使用。
[复合模塑制品]复合模塑制品包含含有所述树脂组合物的第一树脂模塑制品，以及树脂模塑制品(第二树脂模塑制品或粘附体)，所述的树脂模塑制品(第二树脂模塑制品或粘附体)包含可吸收激光的配对材料，并且通过激光熔接接合到第一树脂模塑制品上。顺便提及，第一树脂模塑制品至少具有如上所述可透射激光的区域(激光熔接区)。在复合模塑制品中，将第二树脂模塑制品接合到第一树脂模塑制品的这种激光透射区上。通过熔接，通常将第一树脂模塑制品和第二树脂模塑制品至少部分地合成一体。
构成第二树脂模塑制品的树脂不特别限于具体树脂，并且可以包括各种热塑性树脂，例如，烯烃树脂，乙烯基系树脂，苯乙烯类树脂，丙烯酸类树脂，聚酯系树脂，聚酰胺系树脂和聚碳酸酯系树脂。在这些树脂中，第二树脂模塑制品可以包含与构成第一树脂模塑制品(树脂组合物)的基础树脂相同种类或类型的树脂，例如聚酯系树脂，如PBT系树脂或PET系树脂(芳香族聚酯系树脂)或它们的组合物。为了进一步提高复合模塑制品的阻燃性，第二树脂模塑制品可以具有通过将阻燃剂加入其中获得的阻燃性。而且，第一和第二树脂模塑制品两者均可以包含上述阻燃性树脂组合物。顺便提及，在本发明中，因为第一树脂模塑制品具有优异的阻燃性，所以在没有将阻燃剂加入第二树脂模塑制品中的情况下，复合模塑制品可以具有在应用上足够的阻燃性。
第二树脂模塑制品可以含有激光吸收剂(或用于激光束的吸收剂)或着色剂。着色剂可以根据激光束的波长进行选择，并且可以包括无机颜料[例如，黑色颜料如炭黑(例如，乙炔黑，灯黑，热解炭黑，炉黑，槽法炭黑和克特晏(Ketjen)黑)，红色颜料(如氧化铁红)，橙色颜料(如钼酸盐橙)和白色颜料(如氧化钛)]，有机颜料(例如，黄色颜料，橙色颜料，红色颜料，蓝色颜料和绿色颜料)等。这些吸收剂或着色剂可以单独或组合使用。黑色颜料或染料，特别是炭黑通常可以用作吸收剂。炭黑的平均粒度通常可以是10至1000nm并且优选约10至100nm。相对于第二树脂模塑制品的总量，着色剂的比例是约0.1至10重量％并且优选约0.5至5重量％(例如约1至3重量％)。而且，在通过将含有激光吸收剂或着色剂(例如炭黑)的树脂片材(例如PBT系树脂片材)置于这些模塑制品之间，或者通过在这些模塑制品之间涂布(或涂覆)激光吸收剂使第一和第二模塑制品接触之后，可以通过激光束辐照将这些模塑制品接合在一起。顺便提及，含有着色剂的上述树脂片材的详情可以参考例如日本专利1829720。
可以通过将第一树脂模塑制品接合到第二树脂模塑制品上制备复合模塑制品。例如，接合可以通过下列方式进行：使第一树脂模塑制品与第二树脂模塑制品接触(特别是至少使第一树脂模塑制品的激光透射区与第二树脂模塑制品的表面接触)，在从第一树脂模塑制品(可透射激光的构件)向第二树脂模塑制品的方向上辐照激光束以熔化界面的至少一部分，并且使这些模塑制品在这些制品至少在熔化区相互接触(或熔接)的状态下冷却。在本发明中，因为可透射激光的构件，即第一树脂模塑制品包含激光透射性优异的阻燃性树脂组合物，所以第一树脂模塑制品可以通过激光熔接接合到第二树脂模塑制品上，并且可以对所得到的复合模塑制品赋予高的阻燃性。顺便提及，在必要时，通过使用透镜系统(例如，聚光镜)，可以通过将激光束聚焦在界面上，熔接在第一和第二模塑制品之间的接触表面。
激光束的种类不特别限于具体某一种。例如，可以使用波长为约600至2000nm，优选约700至1500nm，并且更优选约800至1100nm的激光束。
可用于激光熔接所述模塑制品的激光束源可以包括例如染料激光器，气体激光器(例如，受激准分子激光器，氩激光器，氪激光器和氦-氖激光器)，固态激光器(例如YAG激光器)和半导体激光器。通常将脉冲激光用作激光束。
顺便提及，在激光熔接中，激光扫描速率(或在样品上的激光辐照位置的移动速度)不特别限于具体某一个，并且可以是任意选择的。为了防止不完美的熔接并且提高熔接强度，激光扫描速率为优选约0至150mm/秒，优选约1至100mm/秒，并且更优选约2至50mm/秒。工业适用性
本发明的可激光熔接的(或激光熔接)阻燃性树脂组合物和由其形成的模塑制品(可透射激光的构件)具有优异的激光透射性和高阻燃性，并且可以用于各种应用，例如，电气或电子设备部件、办公自动化(OA)设备部件、家庭电器部件、机械设备部件、汽车部件等。特别是，模塑制品和复合模塑制品可以优选用于汽车电组件或部件(例如，各种控制单元和点火线圈部件)、电机部件、各种传感器部件、连接器部件、开关部件、继电器部件、线圈部件、变压器部件、灯部件等。实施例
下列实施例意图在于进一步详细描述本发明，并且应当决不被解释为限制本发明的范围。
实施例1至13和比较例1至6(i)粒料的制备向示于表1中的聚对苯二甲酸丁二醇酯(PBT)系树脂中，以示于表1中的比例加入示于1中的次膦酸化合物(B-1)或(B-2)，含氮阻燃剂(D-1)和/或无机填充剂(E-1)或(E-2)，并且通过V形混合器将共混物均匀地混合。通过使用螺杆直径为30mmφ的双螺杆挤出机，在从主进料口或副进料口供含氟树脂给的同时，将所得到的混合物与含氟树脂(C-1)或(C-2)在260℃的机筒温度以示于表1中的比例熔融混合，并且将熔融的混合物从模具中排出以得到线料。将得到的线料冷却，然后切割以得到粒料。顺便提及，粒料含有酚类抗氧化剂和脱模剂。
另一方面，在比较例中，根据上述方法进行不使用任何次膦酸化合物的实施例(比较例6)和使用其它阻燃剂(F-1)至(F-5)代替次膦酸化合物的实施例(比较例1至5)作为比较例。
(ii)模塑制品的制造和激光熔接使用在上述步骤(i)中获得的粒料，采用注塑机(由Toshiba公司制造)在260℃的料筒温度和80℃的模塑温度的条件下模塑出树脂模塑制品A(8cm长，1cm宽和2mm高)。而且，通过与制品A的方法相同的方法模塑出树脂模塑制品(粘附体)B，不同之处在于：使用100重量份上述粒料和3重量份作为着色剂的炭黑(由Win Tech Polymer有限公司生产，商品名“2020B”)，并且使用制品B以通过熔接接合到树脂模塑制品A上。顺便提及，树脂模塑制品B用作通过激光束加热的单元。
如在图1和图2中所示，将树脂模塑制品A(3)部分叠加在树脂模塑制品B(4)上，并且将这些制品夹住并且固定在石英玻璃板(5)和金属板(6)之间。使用由Leister Process Technologies制造的激光熔接机(″MODULAS熔接系统C型″)，在激光输出功率为40W并且扫描速率为10mm/秒的条件下，将来自光源(1)的波长为940nm的激光束(2)聚焦，并且以线宽W(2mm)会聚在树脂模塑制品A和B之间的接触表面上，并从树脂模塑制品A(3)侧辐照，以熔接模塑制品。
顺便提及，在实施例和比较例中，根据下列测量条件评价各种特性和性能。
(1)可燃性试验(UL-94)由在实施例和比较例的每一个中获得的每一种树脂组合物形成5件试样(厚度：0.8mm)。根据UL94标准(Underwriters Laboratories Inc的主题94)的方法，通过使用5件试样检查在燃烧试验中的阻燃性和滴落性能。对于阻燃性，基于在UL94中描述的标准，各种树脂组合物被分类为“V-0”，“V-1”，“V-2”，以及“非V”(不适用这些“V”等级)。
(2)激光透射率通过使用分光光度计(由JASCO公司制造，V570)，在940nm的波长测量树脂模塑制品A的激光透射率。
(3)熔接强度的测量使用拉伸试验仪(由Orientec股份有限公司制造，RTC-1325)，以5mm/分钟的速率牵拉并且剪切通过激光熔接接合在一起的树脂模塑制品A和树脂模塑制品B，并且测定熔接强度。
在实施例和比较例中，使用下列组分。
(A)PBT系树脂(A-1)聚对苯二甲酸丁二醇酯(IV＝0.8)(由Win Tech Polymer有限公司生产)(A-2)聚对苯二甲酸丁二醇酯(IV＝1.0)(由Win Tech Polymer有限公司生产)(A-3)用间苯二甲酸改性的聚对苯二甲酸丁二醇酯(由Win TechPolymer有限公司生产)(A-4)用间苯二甲酸改性的聚对苯二甲酸乙二醇酯(由Teijin Fibers有限公司生产)
(B)次膦酸化合物(B-1)通过下列方法制备的1，2-二乙基次膦酸铝将1，2-二乙基次膦酸(2106g(19.5mol))溶解在6.5升水中。在剧烈搅拌的同时，将507g(6.5mol)氢氧化铝加入该溶液中。将得到的混合物加热至85℃。将混合物在80至90℃搅拌总共65小时。然后，将混合物冷却至60℃并且经过吸滤器。将得到的剩余物在120℃的真空干燥箱中干燥直至剩余物的重量恒定。获得在不高于300℃的温度下不熔融的细粉(2140g)。产率为理论估算值的95％。通过激光衍射/散射粒度分布测量装置(由Horiba，Ltd.制造，装置名称LA920)测量获得的细粉的粒度，其平均粒度为55μm。
(B-2)1，3-乙烷-1，2-二甲基次膦酸钙将乙烷-1，2-二甲基次膦酸(325.5g(1.75mol))溶解在500ml水中。在剧烈搅拌的同时，将129.5g(1.75mol)氢氧化钙以分开的份加入该溶液中。将得到的混合物在90至95℃加热数小时，冷却并且经过吸滤器。将得到的剩余物在150℃的真空干燥箱中干燥以得到产物(335g)。该产物在不高于380℃的温度下不熔融。产率为理论估算值的85％。
(B-3)通过下列方法制备的1，2-二乙基次膦酸铝使在上述(B-1)中获得的平均粒度为55μm的细粒通过400目筛子，并且收集在筛子上的剩余物。通过与项(B-1)中相同的方法测量所获细粒的粒度，其平均粒度为72μm。
(B-4)通过下列方法制备的1，2-二乙基次膦酸铝通过使用气流粉碎机干燥粉碎根据上述(B-1)获得的平均粒度为25μm的细粒。通过与项(B-1)中相同的方法测量所获细粒的粒度，其平均粒度为4μm。
(C)含氟树脂(C-1)含氟树脂(由Mitsubishi Rayon股份有限公司生产，METABLENA3800)(C-2)含氟树脂(由Asahi Glass Fluoropolymers，Inc.生产，AFLONCD076)(D)含氮阻燃剂(D-1)蜜胺氰尿酸盐(由Ciba Specialty Chemicals K.K.生产，MC50)(E)无机填充剂(E-1)玻璃纤维(由Nitto Boseki股份有限公司生产，CSG3PA830，在横截面的形状：矩形)(E-2)玻璃纤维(由Nitto Boseki股份有限公司生产，CS3PE941，在横截面的形状：圆形)(E-3)玻璃纤维(由Nitto Boseki股份有限公司生产，CSH3PA860S，在横截面的形状：卵圆形)(F)其它阻燃剂(F-1)溴化环氧树脂(由Sakamoto Yakuhin Kogyo股份有限公司生产，SRT5000)(F-2)五溴聚丙烯酸苄酯(由Dead Sea Bromine集团生产，FR1025)(F-3)亚乙基双-四溴邻苯二甲酰亚胺(由Albemarle公司生产，SYTEXBT-93)(F-4)三氧化锑(由Nihon Seiko股份有限公司生产，PATOX-M)(F-5)缩合的磷酸酯(由Daihachi Chemical Industry股份有限公司生产)实施例和比较例的结果示于表1和2中。
[表1]
Figure S2006800493178D00271
从表中明显看出，由于高的激光透射性，使用次膦酸化合物的实施例具有高熔接强度以及阻燃性试验的优异结果。相反，在不使用次膦酸化合物而使用常规的阻燃剂的比较例中，模塑制品具有高的阻燃性，但是该制品不能通过激光熔接接合在一起(比较例1至4)。而且，在比较例中，模塑制品可以通过激光熔接接合在一起，但是该产品具有低的阻燃性(比较例5和6)。

Claims (13)

1.一种构件，所述构件透射激光束以通过激光熔接与配对构件接合，其包含一种阻燃性树脂组合物，所述阻燃性树脂组合物包含：
(A)聚酯系树脂；(B)选自二烷基次膦酸盐以及烷烃二次膦酸盐中的至少一种次膦酸化合物；和
(C)相对于100重量份所述聚酯系树脂(A)的比例为0.01至1重量份的含氟树脂，
其中所述二烷基次膦酸盐由下式(1)表示，并且所述烷烃二次膦酸盐由下式(2)表示：
[结构式1]
Figure FSB00000662857200011
其中R1、R2、R3和R4相同或不同，并且各自表示烷基；R5表示亚烷基；Mm+表示具有m价的金属，并且“m”表示2至4的整数；Mn+表示具有n价的金属，并且“n”表示2至4的整数，并且
相对于100重量份所述聚酯系树脂(A)，次膦酸化合物(B)的比例是10至50重量份。
2.根据权利要求1的构件，其中所述聚酯系树脂(A)包括聚对苯二甲酸丁二醇酯系树脂。
3.根据权利要求1的构件，其中所述树脂组合物具有对于包含所述树脂组合物且厚度为2mm的模塑制品不小于15％的激光透射率。
4.根据权利要求1的构件，其中所述含氟树脂在不低于200℃的温度下不进行辐照处理或热处理。
5.根据权利要求1的构件，其中所述树脂组合物还包含相对于100重量份所述聚酯系树脂(A)的比例为0.5至10重量份的(D)含氮阻燃剂。
6.根据权利要求5的构件，其中所述含氮阻燃剂(D)包括三嗪化合物与选自氰尿酸和异氰尿酸中的至少一种的盐。
7.根据权利要求1的构件，其中所述树脂组合物还包含相对于100重量份所述聚酯系树脂(A)的比例为5至70重量份的(E)玻璃状填充剂。
8.一种复合模塑制品，其包含：
第一树脂模塑制品，其包含权利要求1所述的构件；和
第二树脂模塑制品，其可吸收激光并且通过激光熔接接合到第一树脂模塑制品上。
9.根据权利要求8的复合模塑制品，其中第一树脂模塑制品具有厚度为0.1至2mm的区域，并且第二树脂模塑制品接合到第一树脂模塑制品的所述区域上。
10.一种用于激光熔接第一树脂模塑制品和可吸收激光的第二树脂模塑制品的方法，其中所述第一树脂模塑制品包含权利要求1所述的构件，所述方法包括：
使第一树脂模塑制品与第二树脂模塑制品接触；以及
在从第一树脂模塑制品向第二树脂模塑制品的方向上辐照激光束，
其中第一树脂模塑制品具有在2mm的厚度不小于15％的激光透射率。
11.根据权利要求10的方法，其中第一树脂模塑制品可以用不吸收激光的着色剂着色，第二树脂模塑制品包含热塑性树脂组合物，所述热塑性树脂组合物含有激光吸收剂或着色剂，使第一树脂模塑制品的表面与第二树脂模塑制品的表面相互接触，并且通过激光束辐照接合两个树脂模塑制品。
12.根据权利要求10的方法，其中第一树脂模塑制品具有厚度为0.1至2mm并且激光透射率不小于15％的激光透射区，使第二树脂模塑制品的表面至少与第一树脂模塑制品的所述激光透射区接触，并且进行所述激光辐照以接合所述模塑制品。
13.根据权利要求10的方法，其中第一树脂模塑制品包含树脂组合物，所述树脂组合物含有下列组分(A)：
(A)聚对苯二甲酸丁二醇酯系树脂。
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