CN102850730B - 激光透射性树脂成形品及其复合成形品 - Google Patents
激光透射性树脂成形品及其复合成形品 Download PDFInfo
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- CN102850730B CN102850730B CN201210040854.3A CN201210040854A CN102850730B CN 102850730 B CN102850730 B CN 102850730B CN 201210040854 A CN201210040854 A CN 201210040854A CN 102850730 B CN102850730 B CN 102850730B
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- resin
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- molding
- brominated
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Classifications
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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
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- 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
- B29C65/16—Laser beams
- B29C65/1629—Laser beams characterised by the way of heating the interface
- B29C65/1635—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
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- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/112—Single lapped joints
- B29C66/1122—Single lap to lap joints, i.e. overlap joints
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- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/43—Joining a relatively small portion of the surface of said articles
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- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General 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
- B29C66/71—General 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 composition of the plastics material of the parts to be joined
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- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/81—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps
- B29C66/812—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
- B29C66/8126—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps characterised by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
- B29C66/81266—Optical properties, e.g. transparency, reflectivity
- B29C66/81267—Transparent to electromagnetic radiation, e.g. to visible light
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- 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
- B29C65/16—Laser beams
- B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
- B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
- B29C65/1616—Near infrared radiation [NIR], e.g. by YAG lasers
-
- 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
- B29C65/16—Laser beams
- B29C65/1629—Laser beams characterised by the way of heating the interface
- B29C65/1654—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined
- B29C65/1658—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined scanning once, e.g. contour laser welding
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- 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
- B29C65/16—Laser beams
- B29C65/1677—Laser beams making use of an absorber or impact modifier
-
- 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
- B29C65/82—Testing the joint
- B29C65/8207—Testing the joint by mechanical methods
-
- 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
- B29C65/82—Testing the joint
- B29C65/8207—Testing the joint by mechanical methods
- B29C65/8215—Tensile tests
-
- 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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General 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
- B29C66/73—General 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
- B29C66/733—General 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
- B29C66/7332—General 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 at least one of the parts to be joined being coloured
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
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Abstract
本发明提供了以聚酯系树脂为基础且可兼有高水平的激光熔接性(激光透射性)和阻燃性的激光透射性树脂成形品。所述激光透射性树脂成形品由树脂组合物形成,所述树脂组合物包含聚酯系树脂(A)(PB T系树脂等)和选自溴化(甲基)丙烯酸系树脂、溴化苯乙烯系树脂、溴化聚碳酸酯系树脂和溴化环氧树脂中的至少一种溴系化合物(B)以及平均粒径2~10μm的锑氧化物(C)。这种成形品具有优异的激光透射性和阻燃性,厚度1mm的激光透射率为20%以上,厚度0.8mm的基于UL 94标准的阻燃性评价可以是V-0。所述树脂组合物可以进一步含有填充剂、含氟树脂、聚碳酸酯系树脂、磷系化合物和/或晶核剂等。
Description
本申请是申请日为2008年5月27日、申请号为2008800186427、发明名称为“激光透射性树脂成形品及其复合成形品”的专利申请的分案申请。
技术领域
本发明涉及激光透射性高且阻燃性优异的、由激光熔接用(激光熔接的透射侧部件用)树脂组合物形成的可用作对激光的透射侧部件的激光熔接用成形品(激光透射侧成形品)以及使用该成形品的复合成形品。
背景技术
聚酯系树脂例如聚对苯二甲酸丁二酯(PBT)系树脂由于具有优异的耐热性、耐化学品性、电特性、机械特性和成形加工性等各种特性,可用于许多用途。作为具体的用途,可以列举出各种汽车用电装部件(各种控制单元、各种传感器、点火线圈等)、汽车和电气制品中搭载的连接器类、开关部件、继电器部件、线圈部件、变压器部件、灯部件等。这些部件大多具有导电部,在这些部件中,近年来,由于异常过热、短路等故障的影响引起起火的危险性增加,正在寻求改善阻燃性。
以往就改善PBT系树脂等聚酯系树脂的阻燃性进行了研究。例如,日本特开2000-256545号公报(专利文献1)中公开了含有特定比例的特定芳香族聚酯、溴化环氧化合物、溴化聚丙烯酸酯和三氧化锑的阻燃性聚酯树脂组合物。该文献中记载,关于三氧化锑,优选使用纯度98%以上、粒径0.1~5μm的那些,纯度99%以上、粒径0.5~3μm的那些是特别优选的。像这样通过溴化合物与锑化合物的组合来表现阻燃性的方法是已知的。其中,日本特开昭61-66746号公报(专利文献2)中记载,在聚对苯二甲酸丁二酯中使用作为阻燃剂的芳香族溴化合物(二苯醚的溴5~10取代化合物、乙二醇二苯醚等芳香环氢的溴5~10取代化合物等低分子量溴化合物、芳香族聚碳酸酯、环氧化合物的单体和它们的聚合物的溴化物、聚苯乙烯低聚物的溴化物、溴化氰脲酸酯化合物等)和作为阻燃助剂的平均粒径1μm以上(优选2μm以上,尤其5~7μm)的三氧化锑,可以改良阻燃性聚对苯二甲酸丁二酯组合物的熔融热稳定性。
另外,在这些文献中关于阻燃性聚酯树脂组合物的激光透射性和激光熔接均没有任何记载。
另一方面,上述的部件(成形品)大多通过多个部件(或零件)的接合等来制作或者在形成部件之后与其他部件接合。而且,各零件或部件的接合利用粘合剂、螺钉固定、卡扣接合(snap-fit)、各种熔接方法(热板熔接、超声波熔接、振动熔接、激光熔接等)等。然而,使用粘合剂时,存在粘合剂至固化为止的工序耗时和对环境产生负荷的问题。另外,对于螺钉固定来说,连结的工时和成本增加。在熔接方法当中,热板熔接、超声波熔接、振动熔接由于热、振动等有可能损伤制品。与此相反,用激光熔接的接合方法没有因为伴随熔接的热或振动而损坏制品,且熔接工序也非常简易。因此,最近激光熔接法的应用更加广泛,作为各种树脂部件的熔接方法受到注目。
然而,以PBT系树脂为代表的聚酯系树脂由于激光的透射性低,具有难以熔接的问题,对此提出了各种方案。例如,日本特开2003-136601号公报(专利文献3)公开了一种塑料部件,它是具有适用于激光熔接的应用领域的透射性的塑料部件,前述塑料部件包括含有聚酯的组合物,在800~1200nm的波长下,用由前述组合物制作的成形品测定的每1mm厚度的透射率为10%以上。该文献中记载,为了改善阻燃性,可以添加阻燃剂和阻燃助剂。另外,日本特开2001-26656号公报(专利文献4)中公开了一种制造成形体的方法,包括通过对成形品(A)和其他的成形品(B)进行熔接加工而使之一体化,所述成形品(A)由选自熔点为170~220℃的PBT系共聚物、熔点为200~250℃的聚对苯二甲酸乙二酯系共聚物和熔点为210~260℃的聚萘二甲酸乙二酯系共聚物中的至少一种聚酯系共聚物(a)构成。该文献中记载,在不损害发明效果的范围内,可以添加卤化物、磷化合物等阻燃剂、阻燃助剂等。然而,这些文献中记载的阻燃性聚酯系树脂组合物中,缺乏对激光的透射性,难以充分地进行激光熔接。
此外,日本特表2006-509893号公报(专利文献5)中公开了一种聚酯树脂组合物,其是阻燃性的可激光熔接的聚酯树脂组合物,包含(A)10~90重量%的热塑性聚酯、(B)1~35重量%的含磷阻燃剂、(C)1~25重量%的酚聚合物和(D)1~25重量%的热塑性丙烯酸聚合物。在该文献的树脂组合物虽然可以兼有激光透射性和聚酯树脂组合物所要求的实用上充分的阻燃性,但由于以酚聚合物为必需成分,因此存在的问题是,成形品变色为茶褐色,此外,使热挠曲温度降低,损害了聚酯树脂组合物所要求的实用上充分的色调和热特性。
照此,在现有技术中,可以兼有激光熔接性和高的阻燃性,进一步兼有高水平的这些特性和聚酯树脂组合物所要求的其他特性则是困难的。
专利文献1:日本特开2000-256545号公报(权利要求书、段落号[0028])
专利文献2:日本特开昭61-66746号公报(权利要求书,第2页右下栏18行~第3页左上栏9行,第3页左上栏17~19行)
专利文献3:日本特开2003-136601号公报(权利要求书、段落号[0018])
专利文献4:日本特开2001-26656号公报(权利要求书、段落号[0027])
专利文献5:日本特表2006-509893号公报(权利要求书)
发明内容
发明要解决的问题
因此,本发明的目的在于,提供激光透射性树脂成形品以及使用该成形品的复合成形品,其虽然以聚酯系树脂(尤其聚对苯二甲酸丁二酯等聚芳香族酸亚烷基酯(polyalkylenearylate)系树脂)为基础,但可以兼有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在于,提供可以兼有高水平的激光熔接性和阻燃性,且具有优异的色调和热稳定性的激光透射性树脂成形品以及使用该成形品的复合成形品。
本发明的又一个目的在于,提供具有优异的激光透射性,同时成形很薄时也能维持高的阻燃性的激光透射性树脂成形品以及使用该成形品的复合成形品。
本发明的再一个目的在于,提供通过激光熔接将具有高的阻燃性的成形品与可吸收激光的树脂成形品接合而成的复合成形品。
用于解决问题的方案
本发明人等为了实现前述课题进行了深入研究,结果发现,用将特定的溴系化合物(或溴系阻燃剂)与具有特定粒径的锑氧化物组合而成的聚酯系树脂组合物形成激光透射性部件时,虽然以聚酯系树脂(尤其聚对苯二甲酸丁二酯等聚芳香族酸亚烷基酯系树脂)为基础,但不损害激光透射性,可以兼有高水平的激光熔接性与阻燃性,从而完成了本发明。
即,本发明的激光透射性树脂成形品(或激光透射侧成形品)是能够与可吸收激光的激光吸收性树脂成形品接触,使激光透射而与前述激光吸收性树脂成形品接合的激光透射性树脂成形品,其中该激光透射性树脂成形品由树脂组合物(有时称之为激光熔接中的透射侧部件用树脂组合物、激光熔接用(透射侧部件用)阻燃性树脂组合物等)形成,该树脂组合物包含聚酯系树脂(A)和选自溴化(甲基)丙烯酸系树脂、溴化苯乙烯系树脂、溴化聚碳酸酯系树脂和溴化环氧树脂中的至少一种溴系化合物(B)(或溴系阻燃剂(B))以及具有较大粒径(平均粒径约2~10μm)的锑氧化物(C)。
这种成形品具有优异的激光透射性,例如在厚度1mm(或厚度1mm的成形品)时,激光透射率可以为20%以上。
在前述成形品(或树脂组合物)中,前述聚酯系树脂(A)可以是聚芳香族酸亚烷基酯系树脂(聚芳香族酸C2-4亚烷基酯系树脂等,尤其聚对苯二甲酸丁二酯系树脂)。
前述锑氧化物(C)尤其可以是选自三氧化锑、五氧化锑和锑酸钠(sodium antimonate)中的至少一种。
在前述成形品(或树脂组合物)中,相对于100重量份聚酯系树脂(A),溴系化合物(B)的比例可以是约10~50重量份,相对于100重量份聚酯系树脂(A),锑氧化物(C)的比例可以是约5~30重量份。
前述成形品(或树脂组合物)可以进一步含有聚碳酸酯系树脂(D)和磷系化合物(E)。前述成形品(或树脂组合物)可以进一步含有结晶促进剂(F)。前述成形品(或树脂组合物)可以进一步含有填充材料。另外,前述成形品(或树脂组合物)可以进一步含有含氟树脂。
本发明的成形品(或树脂组合物)具有优异的阻燃性,在厚度0.8mm时(或厚度0.8mm的成形品),基于UL 94标准的阻燃性评价通常可以是V-0。
本发明还包含通过激光熔接将前述激光透射性树脂成形品与可吸收激光的激光吸收性树脂成形品接合而成的复合成形品。这种复合成形品可以是:激光透射性树脂成形品至少具有使激光透射的、厚度为0.1~1.0mm的部位的树脂成形品,并在该部位与激光吸收性树脂成形品接合的复合成形品。前述复合成形品例如可以通过对激光透射性树脂成形品与激光吸收性树脂成形品的接触面,从前述激光透射性树脂成形品侧向着激光吸收性树脂成形品的方向照射激光来制造。
发明效果
在本发明的激光透射性树脂成形品中,由于将聚酯系树脂(聚对苯二甲酸丁二酯系树脂等)、特定的溴系化合物(溴系阻燃剂)和特定粒径的锑氧化物组合,因此虽然以聚酯系树脂(尤其聚对苯二甲酸丁二酯系树脂等聚芳香族酸亚烷基酯系树脂)为基础,但可以兼有高水平的激光熔接性(激光透射性)和阻燃性。因此,虽然保持聚酯系树脂的优异性质(机械特性、耐热性、耐化学品性等),却不损害激光透射性,可以兼有高水平的激光熔接性与阻燃性。另外,本发明的激光透射性树脂成形品由于可以基本上不含有酚聚合物等,因此,兼有高水平的激光熔接性与阻燃性,且具有优异的色调和热稳定性。进一步,本发明的激光透射性树脂成形品具有优异的激光透射性,且即使成形很薄,也能维持高的阻燃性。因此,可以获得通过将具有高的阻燃性的成形品(尤其薄成形品)与可吸收激光的树脂成形品通过激光熔接而被接合而成的复合成形品。
附图说明
图1是用于说明实施例和比较例中的激光熔接的示意侧面图。
图2是用于说明实施例和比较例中的激光熔接的示意俯视图。
具体实施方式
本发明的激光透射性树脂成形品(或激光透射侧成形品)是能够与可吸收激光的激光吸收性树脂成形品接触,使激光透射而与前述激光吸收性树脂成形品接合的激光透射性树脂成形品,并用特定的聚酯系树脂组合物形成。而且,本发明中还包含这种激光熔接用的特定聚酯系树脂组合物(激光熔接中的透射侧部件用树脂组合物、激光熔接用(透射侧部件用)阻燃性树脂组合物)。
前述树脂组合物(有时称之为激光熔接用树脂组合物、激光熔接用阻燃性树脂组合物、聚酯系树脂组合物、透射侧部件用树脂组合物、树脂组合物等)包含聚酯系树脂(A)、特定的溴系化合物(B)和特定的锑氧化物(C)。
(聚酯系树脂(A))
作为基础树脂的聚酯系树脂是通过二羧酸成分与二醇成分的缩聚、羟基羧酸或内酯的缩聚或者这些成分的缩聚等而获得的均聚酯或共聚酯。
作为二羧酸成分,例如可以列举出脂肪族二羧酸(例如己二酸、庚二酸、辛二酸、壬二酸、癸二酸、二聚酸等C4-40二羧酸,优选C4-14二羧酸),脂环式二羧酸(例如六氢对苯二甲酸等C8-12二羧酸),芳香族二羧酸(例如对苯二甲酸、邻苯二甲酸、间苯二甲酸;2,6-萘二羧酸等萘二羧酸;4,4’-二苯基二羧酸、4,4’-二苯基醚二羧酸、4,4’-二苯基甲烷二羧酸、4,4’-二苯基酮二羧酸等C8-16二羧酸)或它们的反应性衍生物[例如,低级烷基酯(对苯二甲酸二甲酯、邻苯二甲酸二甲酯、间苯二甲酸二甲酯(DMI)等对苯二甲酸、邻苯二甲酸或间苯二甲酸的C1-4烷基酯等)、酰氯、酸酐等可形成酯的衍生物]等。此外,根据需要,除了二羧酸成分以外,可以并用偏苯三酸、均苯四酸等多元羧酸成分等。
作为二醇成分,例如可以列举出脂肪族二醇(例如乙二醇、三亚甲基二醇、丙二醇、1,4-丁二醇、新戊二醇、己二醇、辛二醇、癸二醇等C2-12烷烃二醇,优选C2-10烷烃二醇),聚亚烷基二醇[具有多个氧化C2-4亚烷基单元的二醇,例如二乙二醇~四乙二醇、二丙二醇~四丙二醇、聚四亚甲基二醇等],脂环族二醇(例如,1,4-环己烷二醇、1,4-环己烷二甲醇、氢化双酚A等),芳香族二醇[例如,氢醌、间苯二酚、萘二醇等C6-14芳香族二醇;联苯酚;双酚类;苯二甲醇等]等。
作为双酚类,可以列举出双(4-羟苯基)甲烷(双酚F)、1,1-双(4-羟苯基)乙烷(双酚AD)、1,1-双(4-羟苯基)丙烷、2,2-双(4-羟苯基)丙烷(双酚A)、2,2-双(4-羟基-3-甲基苯基)丙烷、2,2-双(4-羟苯基)丁烷、2,2-双(4-羟苯基)己烷等双(羟基芳基)C1-6烷烃;1,1-双(4-羟苯基)环己烷等双(羟基芳基)C4-10环烷烃;双(4-羟苯基)醚;4,4’-二羟基二苯基砜;4,4’-二羟基二苯基硫醚;4,4’-二羟基二苯基酮以及它们的环氧烷烃加成物。作为环氧烷烃加成物,可以列举出双酚类的C2-3环氧烷烃加成物,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、二丙氧基化双酚A等。在环氧烷烃加成物中,环氧烷烃(环氧乙烷、环氧丙烷等C2-3环氧烷烃)的加成摩尔数相对于各羟基为约1~10摩尔,优选为约1~5摩尔。
此外,根据需要,除了二醇成分以外,可以并用甘油、三羟甲基丙烷、三羟甲基乙烷、季戊四醇等多元醇成分。
羟基羧酸包含例如羟基安息香酸、羟基萘甲酸、羟基苯乙酸、羟基乙酸、羟基己酸等羟基羧酸或它们的衍生物等。内酯包含丙内酯、丁内酯、戊内酯、己内酯(例如,ε-己内酯等)等C3-12内酯等。
聚酯系树脂可以单独或将两种以上组合使用。聚酯系树脂当中,从激光熔接性考虑,低结晶性或非晶性芳香族聚酯系树脂是优选的。
优选的聚酯系树脂包含饱和聚酯系树脂,尤其芳香族饱和聚酯系树脂,通常大多使用聚对苯二甲酸丁二酯(PBT)系树脂(PBT(均聚物)或PBT系共聚物等)、聚萘二甲酸丁二酯(PBN)系树脂(PBN(均聚物)或PBN系共聚物等)、聚对苯二甲酸乙二酯(PET)系树脂(PET(均聚物)或PET系共聚物)、聚萘二甲酸乙二酯(PEN)系树脂(PEN(均聚物)或PEN系共聚物等)等聚芳香族酸亚烷基酯系树脂(例如聚芳香族酸C2-6亚烷基酯系树脂,优选聚芳香族酸C2-4亚烷基酯系树脂,更优选聚对苯二甲酸C2-4亚烷基酯)。
这种聚芳香族酸亚烷基酯系树脂包含例如聚芳香族酸亚烷基酯(均聚物)、聚芳香族酸亚烷基酯系共聚物等。
作为聚芳香族酸亚烷基酯系共聚物(尤其聚对苯二甲酸亚烷基酯系共聚物)中使用的共聚性单体,可以列举出二醇类[与聚芳香族酸亚烷基酯系聚合物中的亚烷基单元(例如亚乙基、1,4-亚丁基等)不同的亚烷基单元对应的C2-6亚烷基二醇(例如,乙二醇、三亚甲基二醇、1,2-丙二醇、己二醇等直链或支链亚烷基二醇等),具有重复数约2~4的氧化亚烷基单元的聚C2-4亚烷基二醇(二乙二醇等),双酚类(双酚类或其环氧烷烃加成物等)等],二羧酸类[例如,C6-12脂肪族二羧酸(己二酸、庚二酸、辛二酸、壬二酸、癸二酸等),羧基在芳烃环的非对称位置上取代的非对称芳香族二羧酸,1,4-环己烷二甲醇等],羟基羧酸(前面例示的化合物等),内酯(己内酯等前面例示的化合物)等。在这些化合物当中,芳香族化合物,例如双酚类(尤其双酚A)的环氧烷烃加成物以及非对称芳香族二羧酸[邻苯二甲酸、间苯二甲酸及其反应性衍生物(间苯二甲酸二甲酯(DMI)等的低级烷基酯)等]等是优选的。
相对于聚酯系树脂(尤其聚芳香族酸亚烷基酯系树脂)(或单体的总量),共聚性单体的比例(改性量)例如为30mol%以下(例如0~30mol%),例如可以从约0.01~30mol%的范围内选择,通常可以为约1~30mol%,优选为约3~25mol%,更优选为约5~20mol%(例如5~15mol%)。
尤其优选的聚酯系树脂是PBT系树脂(PBT、改性PBT(PBT系共聚物)。PBT系树脂可以单独使用或将两种以上组合使用。另外,从改善阻燃性、机械物性的观点考虑,PBT系树脂可以与其他聚芳香族酸亚烷基酯系树脂(例如PET(均聚物)、改性PET(PET系共聚物)等PET系树脂等)并用。
从激光熔接性的观点考虑,PBT系树脂的熔点例如为约190℃以上(例如约190~270℃),优选为约200~260℃,更优选为约210~250℃。
另外,PBT系树脂的特性粘度(IV)可以选自例如约0.5~1.3dL/g的范围,从成形性和/或机械特性的观点来看,优选为约0.6~1.2dL/g,进一步优选为约0.65~1.1dL/g。特性粘度过低时,机械强度有可能降低,特性粘度过高时,流动性甚至成形性有可能降低。另外,特性粘度(IV)例如可以在邻氯酚中在温度35℃的条件下测定。
聚酯系树脂可以使用市售品,也可以用常用的方法例如酯交换、直接酯化法等来制备。例如,PBT系树脂可以通过用上述常用的方法让对苯二甲酸或其反应性衍生物与1,4-丁二醇和根据需要的可共聚的单体进行共聚来制备。
(溴系化合物(B))
本发明中,作为与锑氧化物(C)组合的阻燃剂,使用特定的溴系阻燃剂,即,使用选自含溴(甲基)丙烯酸系树脂(或溴化(甲基)丙烯酸系树脂,例如溴化聚(甲基)丙烯酸苄酯系树脂(例如聚(甲基)丙烯酸五溴苄酯等溴化聚(甲基)丙烯酸苄酯)、聚(甲基)丙烯酸五氯苄酯等(甲基)丙烯酸卤化苄基酯的均聚物或共聚物等)等的溴化聚(甲基)丙烯酸酯),含溴苯乙烯系树脂[或溴化苯乙烯系树脂,例如,溴化苯乙烯等苯乙烯系树脂的溴化物(或对苯乙烯系树脂进行溴化处理的溴化物),溴化苯乙烯系单体的均聚物或共聚物等;例如聚溴化苯乙烯等],含溴聚碳酸酯系树脂(或溴化聚碳酸酯系树脂,例如,溴化双酚A型聚碳酸酯树脂等溴化双酚型聚碳酸酯树脂),以及含溴环氧系树脂[或溴化环氧系树脂,例如溴化双酚型环氧树脂(溴化双酚A型环氧树脂等)等溴化环氧树脂;溴化双酚型苯氧树脂(溴化双酚A型苯氧树脂等)等溴化苯氧树脂等]中的至少一种溴系化合物(B)。
通过将这种特定的溴系化合物与后述的具有特定粒径的锑氧化物组合,可以为前述树脂组合物(或激光透射性树脂成形品)同时赋予高的阻燃性和激光透射性。
在溴系化合物中,相对于溴系化合物总体,溴原子的比例(重量比例)通常可以从30重量%以上(例如约35~90重量%)的范围内选择,优选为40重量%以上(例如约45~90重量%),进一步优选为50重量%以上(例如约55~85重量%)。
以下详细描述溴系化合物。
含溴(甲基)丙烯酸系树脂包含溴化聚(甲基)丙烯酸酯(或含溴聚(甲基)丙烯酸酯或聚溴化(甲基)丙烯酸酯),尤其溴化聚(甲基)丙烯酸苄酯系树脂等。溴化聚丙烯酸酯系树脂可以是例如用下述式表示的化合物。
[化学式1]
(式中,m表示2以上的整数,R表示烃基,X表示氢原子或卤素原子,至少一个X是溴原子。)
代表性溴化聚(甲基)丙烯酸酯系树脂包含溴化聚(甲基)丙烯酸苄酯系树脂[例如,以(甲基)丙烯酸溴化苄酯(例如(甲基)丙烯酸五溴苄酯,(甲基)丙烯酸四溴苄酯,(甲基)丙烯酸三溴苄酯)为聚合成分的树脂,例如(甲基)丙烯酸溴化苄酯的均聚物或共聚物,(甲基)丙烯酸溴化苄酯与共聚性单体的共聚物等]等。
在溴化聚(甲基)丙烯酸苄酯系树脂中,作为共聚性单体,可以列举出乙烯基单体(尤其没被溴化的乙烯基系单体),例如(甲基)丙烯酸;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸苄酯之类的(甲基)丙烯酸酯类;苯乙烯等苯乙烯系单体;(甲基)丙烯腈等氰化乙烯基系单体;富马酸、马来酸等不饱和羧酸或其酸酐;醋酸乙烯酯等羧酸乙烯基酯类等。另外,作为共聚性单体,还可以使用交联性乙烯基单体,例如聚(甲基)丙烯酸酯(例如二甲苯二(甲基)丙烯酸酯、四溴二甲苯二(甲基)丙烯酸酯等),二烯系单体(例如丁二烯、异戊二烯等),二乙烯基苯等。这些共聚性单体可以单独使用或将两种以上组合使用。
另外,在(甲基)丙烯酸溴化苄酯与共聚性单体的共聚物中,相对于全部构成单体,(甲基)丙烯酸溴化苄酯的比例可以为50mol%以上(例如约55~99.5mol%),优选为60mol%以上(例如约65~99mol%),进一步优选为70mol%以上(例如约75~98mol%)。
含溴(甲基)丙烯酸系树脂(尤其溴化聚(甲基)丙烯酸苄酯系树脂)的数均分子量例如为约1000~300000,优选为约3000~200000,进一步优选为约5000~150000。
另外,含溴苯乙烯系树脂(或溴化苯乙烯系树脂)例如可以是用下述式表示的树脂。
[化学式2]
(式中,j表示2以上的整数,m表示1~4的整数。)
代表性含溴苯乙烯系树脂(或溴化苯乙烯系树脂)包含以溴化苯乙烯系单体(例如二溴苯乙烯、三溴苯乙烯等溴化苯乙烯)为聚合成分的树脂,例如溴化苯乙烯系单体的均聚物或共聚物(溴化聚苯乙烯等),溴化苯乙烯系单体与共聚性单体的共聚物等。共聚性单体包含以上例示的共聚性单体等。共聚性单体可以单独或将两种以上组合使用。
另外,在溴化苯乙烯系单体与共聚性单体的共聚物中,相对于全部构成单体,溴化苯乙烯系单体的比例可以为50mol%以上(例如约55~99.5mol%),优选为60mol%以上(例如约65~99mol%),更优选为70mol%以上(例如约75~98mol%)。
含溴苯乙烯系树脂的数均分子量例如可以为约1000~300000,优选为约3000~200000,更优选为约5000~150000。
含溴聚碳酸酯系树脂(溴化聚碳酸酯系树脂、聚溴化碳酸酯系树脂)例如可以是用下述式表示的树脂。
[化学式3]
(式中,R和R’分别表示氢原子或烃基,X表示烃基、羰基、醚基、-S-或-SO2-,k和m分别表示1~4的整数,n表示2以上的整数。)
在上述式的R和R’中,作为烃基,例如可以列举出碳数1~10的烷基(甲基、乙基、丙基、异丙基等)等烷基。另外,在X中,作为烃基,可以列举出二价的C1-10烃基(亚甲基、亚乙基、2-亚丙基等C1-4烃基)等。
代表性含溴聚碳酸酯系树脂包含以含溴双酚类(或溴化双酚类,例如四溴双酚A等溴化双(羟苯基)C1-10烷烃等)为聚合(基础)成分(或二醇成分)的聚碳酸酯系树脂,例如溴化双酚A型聚碳酸酯树脂(例如四溴双酚A碳酸酯聚合物或低聚物)等溴化双酚型聚碳酸酯树脂等。另外,含溴聚碳酸酯系树脂的二醇成分可以单独或将两种以上组合,也可以包含没被溴化的二醇成分(例如双酚A等的双(羟苯基)C1-10烷烃)。
含溴聚碳酸酯系树脂的数均分子量例如可以为约1000~40000,优选为约2000~30000。
含溴环氧树脂(溴化环氧树脂)例如可以是用下述式表示的树脂。
[化学式4]
[式中,X表示溴原子,i和j表示1~4的整数,n表示0以上的整数,T1和T2可以相同或不同,表示缩水甘油基或-CH2CH(OH)CH2OPh(式中,Ph表示可以具有取代基的卤化苯基)。]
代表性含溴环氧树脂(溴化环氧树脂)包含以含溴双酚类(或溴化双酚类,例如四溴双酚A等溴化双(羟苯基)C1-10烷烃等)为聚合成分(或二醇成分)的环氧树脂,例如溴化双酚A型环氧树脂等溴化双酚型环氧树脂(例如四溴双酚A与表氯醇的反应产物)。另外,溴化环氧树脂的二醇成分可以单独使用或将两种以上组合,也可以包含没被溴化的二醇成分(例如双酚A等双(羟苯基)C1-10烷烃)。另外,含溴环氧树脂的末端与前述式的T2的情况同样地可以进行封端处理。尤其,以四溴双酚A为聚合(基础)成分的环氧树脂(或含有四溴双酚A和二缩水甘油醚的环氧树脂)在配合量过多时,成形品中的黑斑状的异物增加、损害机械特性和/或电特性、在激光熔接时产生异常过热、有可能损害熔接性,因此优选进行封端处理。
含溴环氧树脂的数均分子量例如可以为约1000~40000,优选为约2000~30000,进一步优选为约3000~20000。
在这些含溴树脂中,从具有优异的激光熔接的稳定性的观点来看,尤其优选使用选自溴化聚(甲基)丙烯酸酯系树脂(尤其溴化聚丙烯酸苄酯系树脂等溴化聚丙烯酸酯系树脂)和溴化苯乙烯系树脂(溴化聚苯乙烯等)中的至少一种。
在前述树脂组合物(或激光透射性树脂成形品)中,相对于100重量份聚酯系树脂(A),溴系化合物(B)的比例例如为约5~70重量份,优选为约8~60重量份,进一步优选为约10~50重量份(例如15~40重量份)。在以上述比例使用溴系化合物(B)时,容易有效地表现高的阻燃性和维持聚酯系树脂固有的优异特性(机械特性、电特性、成形加工性)。
(锑氧化物(C))
作为锑氧化物,可以列举出例如氧化锑[三氧化锑(或三氧化二锑,Sb2O3等),五氧化锑(或五氧化二锑,xNa2O·Sb2O5·yH2O(x=0~1,y=0~4)等)等]、锑酸盐[锑酸金属盐(例如锑酸钠等碱金属盐,锑酸镁等碱土金属盐等)、锑酸铵等]等。
在这些锑氧化物当中,氧化锑(尤其三氧化锑、五氧化锑)、锑酸钠(sodium antimonate)是优选的。锑氧化物可以单独使用或者将两种以上组合使用。
另外,根据需要,锑氧化物可以用环氧化合物、硅烷化合物、异氰酸酯化合物和/或钛酸酯化合物等表面处理剂进行表面处理。
本发明中,作为锑氧化物,使用具有特定粒径的锑氧化物。锑氧化物的平均粒径可以从2μm以上的范围内选择,例如为约2~10μm,优选为约2.5~9μm(例如3~8μm)。另外,平均粒径例如可以通过激光衍射/散射式粒度分布测定装置等作为中值粒径来获得。另外,使用常用的溴系阻燃剂和锑氧化物时,树脂组合物或激光透射性树脂成形品的激光透射性降低,不能进行激光熔接。然而,本发明中,通过将这种特定粒径的锑氧化物与特定的前述溴系化合物并用,可以为聚酯系树脂(尤其PBT等芳香族聚酯系树脂)赋予高水平的高阻燃性与激光透射性。另外,如果锑氧化物的粒径过大,施加机械应力时,容易形成破坏的起点,产生脆性,此外还降低阻燃性。另外,如果锑氧化物的粒径过小,有可能的是,损害激光透射性,使聚酯系树脂(A)本身分解,或者促进聚酯系树脂(A)与含卤素树脂系阻燃剂(B)的反应,损害成形稳定性。
在本发明的树脂组合物中,相对于100重量份聚酯系树脂(A),锑氧化物(C)的比例例如可以为约3~40重量份,优选为约5~30重量份,更优选为约10~50重量份。另外,在配合量过少时,不能表现充分的阻燃性;而在配合量过多时,有可能损害聚酯系树脂固有的机械特性、成形加工特性,或者由于激光的散射和遮蔽效果而降低激光透射性。
另外,在前述树脂组合物(或激光透射性树脂成形品)中,溴系化合物(B)与锑氧化物(C)的比例即前者/后者(重量比)=约95/5~30/70,优选为约90/10~40/60,进一步优选为约80/20~50/50。
(聚碳酸酯系树脂(D))
本发明的树脂组合物可以包含聚碳酸酯系树脂。
聚碳酸酯系树脂通常是通过二羟基化合物与光气或碳酸二苯酯等碳酸酯的反应所获得的树脂。二羟基化合物可以是脂环族化合物等,但优选为芳香族化合物(尤其双酚化合物)。
作为双酚化合物,可以列举出前述聚酯系树脂项中所示的双酚类[例如,双酚A等双(羟基芳基)C1-6烷烃;双(羟基芳基)C4-10环烷烃;4,4’-二羟基二苯醚;4,4’-二羟基二苯基砜;4,4’-二羟基二苯基硫醚;4,4’-二羟基二苯基酮等]。优选的聚碳酸酯系树脂包含双酚A型聚碳酸酯。
另外,聚碳酸酯系树脂容易与聚酯系树脂(尤其聚对苯二甲酸丁二酯系树脂)相容,具有高的改善激光透射性的效果。另外,在使用聚碳酸酯系树脂时,可以有效地改善成形体的翘曲。相对于100重量份聚酯系树脂(A),聚碳酸酯系树脂的优选配合量例如可以为约5~100重量份,优选为约10~70重量份,更优选为约10~50重量份。聚碳酸酯系树脂的配合量过多时,有可能聚酯系树脂(例如PBT系树脂)失去结晶性,且耐化学品性、耐热性降低。
(磷系化合物(E))
为了稳定结晶性、激光透射性,前述树脂组合物(或激光透射性树脂成形品)中可以进一步添加磷系化合物(或含磷化合物)。磷系化合物的优选实例可以列举出亚磷酸酯类{例如三(2,4-二叔丁基苯基)亚磷酸酯、双(2-叔丁基苯基)苯基亚磷酸酯等单~三(支链C3-6烷基-苯基)亚磷酸酯;双(2,6-二叔丁基苯基)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、四(2,4-二叔丁基苯基)-4,4’-双亚苯基二亚磷酸酯等脂肪族多元醇的(支链C3-6烷基-芳基)亚磷酸酯等},亚膦酸酯类(四(2,4-二叔丁基苯基)-4,4’-双亚苯基二亚膦酸酯等)等,磷酸酯类[例如,三(2,4-二叔丁基苯基)磷酸酯等三苯基磷酸酯系化合物],磷酸盐(例如磷酸二氢钙、磷酸二氢钠一水合物等磷酸碱金属盐或碱土金属盐(或其水合物)等磷酸金属盐)。在这些磷系化合物当中,脂肪族多元醇的(支链C3-6烷基-芳基)亚磷酸酯、磷酸金属盐等是优选的。
相对于100重量份聚酯系树脂(A),磷系化合物的配合量例如为0.01~3重量份,优选为0.03~2重量份,进一步优选为0.05~1.0重量份。配合量少时,不能有助于结晶性、激光透射性的稳定,而在配合量过多时,有可能发生渗出、成形品的绝缘性降低,在周围有金属的情况下,有可能发生金属腐蚀、电路短路的不良影响。
(结晶促进剂(F))
同样为了稳定结晶性、激光透射性,前述树脂组合物(或激光透射性成形品)中可以在不损害激光透射性范围内添加结晶促进剂。作为结晶促进剂,例如可以是松香等有机成核剂,但可以适宜地使用无机成核剂,例如金属氧化物(硅石、氧化铝、氧化锆、氧化钛、氧化铁、氧化锌等)、金属碳酸盐(碳酸钙、碳酸镁、碳酸钡等)、硅酸盐(硅酸钙、硅酸铝、滑石等)、金属碳化物(碳化硅等)、金属氮化物(氮化硅、氮化硼、氮化钽等)等。这些结晶促进剂可以单独或将两种以上组合使用。结晶促进剂可以是粉粒状或板状。
另外,结晶促进剂(无机成核剂等)的平均粒径例如为约0.01~10μm,优选为约0.02~5μm。另外,平均粒径例如通过激光衍射/散射式的粒度分布测定装置作为中值粒径来获得。相对于100重量份聚酯系树脂,结晶促进剂的比例例如为0.001~10重量份,优选为0.01~7重量份。
前述树脂组合物(或激光透射性成形品)还可以包含填充材料(或补强材料),只要在不对激光的透射性施加不良影响的范围内。
这种填充材料(或填充剂)包含纤维状填充材料[例如无机质纤维(例如玻璃纤维、硅石纤维、氧化铝纤维、硅石-氧化铝纤维、硅酸铝纤维、氧化锆纤维、钛酸钾纤维、晶须(碳化硅、氧化铝、氮化硼等晶须)、硅灰石等)、有机质纤维(例如脂肪族或芳香族聚酰胺、芳香族聚酯、氟树脂、聚丙烯腈等丙烯酸树脂、人造丝等形成的纤维、碳纤维等)等]、板状填充材料[例如滑石、云母、玻璃薄片等]、粉粒状填充材料[例如玻璃珠粒、玻璃粉、研磨纤维(例如研磨玻璃纤维等)、粘土、有机化粘土、高岭土、钛酸钾、碳酸钙、氧化钛、长石系矿物、石墨等]等。
纤维状填充材料的平均粒径(平均纤维直径)例如可以为约1~50μm(优选为3~30μm),平均长度(平均纤维长度)例如可以为约100μm~3mm(优选为300μm~1mm)。另外,板状或粉粒状填充材料的平均粒径例如可以为约0.1~100μm,优选为约0.1~50μm。这些填充材料可以单独使用或将两种以上组合使用。
在这些填充材料当中,可透射激光的填充材料是优选的。这种填充材料可以根据激光的波长来选择,尤其,玻璃质填充材料或补强材料(玻璃纤维、玻璃薄片、玻璃珠粒等)是优选的。
另外,对玻璃纤维的截面形状没有特定限制,可以列举出圆形、椭圆形(或长圆形,还包括眉毛形等变形椭圆)、半圆、扇形(圆弧)、多角形(三角形、方形(矩形、梯形等)等)或它们的类似形状等。
根据需要,填充材料或补强剂可以通过常用的集束剂或表面处理剂来处理。作为集束剂或表面处理剂,例如可以列举出环氧系化合物、异氰酸酯系化合物、硅烷系化合物、钛酸酯系化合物等官能性化合物等。另外,填充材料在与其他成分(成分(A)、(B)和(C)等)混合之前可以预先用上述集束剂或表面处理剂来进行处理,也可以在将填充材料与其他成分混合的同时通过添加集束剂或表面处理剂来进行处理。相对于100重量份填充材料(玻璃纤维等),集束剂或表面处理剂的比例例如为约0~10重量份(例如0.01~10重量份),优选为约0.05~5重量份。
相对于100重量份聚酯系树脂,填充材料的比例例如可以在约0~200重量份的范围内选择,优选为约5~150重量份,进一步优选为约10~100重量份(例如15~65重量份)。填充材料的比例过多时,根据填充材料的种类,有可能损害激光透射性且不能获得充分的熔接强度。
本发明的树脂组合物可以进一步含有含氟树脂。这种含氟树脂包括含氟单体的均聚物或共聚物,例如含氟单体(四氟乙烯、氯三氟乙烯、偏二氟乙烯、六氟丙烯、全氟烷基乙烯基醚等)的均聚物或共聚物、前述含氟单体与其他共聚性单体(乙烯、丙烯等烯烃系单体、(甲基)丙烯酸酯等丙烯酸系单体等)的共聚物等。
作为这种含氟树脂,具体地可以例举聚四氟乙烯、聚氯三氟乙烯、聚偏二氟乙烯等均聚物;四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟烷基乙烯基醚共聚物、乙烯-四氟乙烯共聚物、乙烯-氯三氟乙烯共聚物等共聚物。含氟树脂可以单独或将两种以上组合使用。作为优选的含氟树脂,可以列举出四氟乙烯的均聚物或共聚物、四氟乙烯与(甲基)丙烯酸酯的共聚物等。
含氟树脂可以具有防滴效果(即,防止随着燃烧而熔融的树脂滴下的效果)。另外,进行放射线处理或200℃以上的热处理的含氟树脂由于防滴效果低劣,因此可以使用不进行这种处理的含氟树脂。
相对于100重量份聚酯系树脂(A),含氟树脂的比例为约0~3重量份(例如0.01~3重量份),优选为约0.05~2重量份,更优选为约0.1~1.5重量份。其中,前述比例过多时,有可能的是,树脂组合物的粘度升高,成形性降低,在成形品中产生白色斑点,损害外观,局部的激光透射率降低,激光熔接强度降低。
视需要而定,在不损害本发明的效果的范围内,根据用途等,在前述树脂组合物(或激光透射性树脂成形品)中可以添加各种添加剂,例如稳定剂(抗氧化剂、紫外线吸收剂、光稳定剂、热稳定剂等)、其他阻燃剂(例如含硫阻燃剂、含硅阻燃剂、醇系阻燃剂、氮系阻燃剂、磷系阻燃剂等)、阻燃助剂、润滑剂、脱模剂、抗静电剂、着色剂(有机或无机染料和颜料等)、增塑剂、分散剂、其他热塑性树脂(例如非晶性或低结晶性树脂等)等。尤其,在最近,还提出了基于除了溴系阻燃剂等卤素系阻燃剂以外的非卤素系阻燃剂的阻燃化,例如可以并用日本特开平5-70671号公报、日本特开平8-73720号公报等中所示的磷系阻燃剂。
作为前述抗氧化剂,可以列举出常用的抗氧化剂,例如位阻酚系抗氧化剂、位阻胺系抗氧化剂、氢醌系抗氧化剂等。抗氧化剂可以单独或将两种以上组合使用。在抗氧化剂当中,位阻酚系抗氧化剂是优选的,例如,作为抗氧化剂,位阻酚系抗氧化剂[例如甘油三[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、季戊四醇四[3-(3,5-二叔丁基-4-羟苯基)丙酸酯]等脂肪族多元醇的二~四[3-(3,5-二-支链C3-6烷基-4-羟苯基)丙酸酯]等可以单独或与其他抗氧化剂并用。
相对于100重量份聚酯系树脂(A),抗氧化剂的比例例如为约0.005~3重量份,优选为约0.01~1.5重量份(例如0.02~1重量份),进一步优选为约0.05~0.5重量份。另外,抗氧化剂比例过多时,有可能在树脂中的分散性降低,抗氧化剂在成形品表面渗出,而且成形品的外观随着渗出有可能变差。
作为脱模剂,例如可以使用高级脂肪酸(例如硬脂酸、褐煤酸、油酸等C10-30饱和或不饱和脂肪酸等)与多元醇(例如乙二醇、聚乙二醇等(聚)亚烷基二醇、甘油、三羟甲基丙烷、季戊四醇、脱水山梨醇等脂肪族多元醇等)的酯(也包含偏酯),蜡[例如石蜡、微晶蜡、聚烯烃系蜡(聚乙烯蜡、聚丙烯蜡等聚C2-4烯烃系蜡(优选低分子量聚乙烯蜡等)、乙烯共聚物蜡等烯烃共聚物蜡等)等]等。作为前述酯的具体例子,可以列举出(聚)亚烷基二醇脂肪酸酯(单酯或二酯,例如乙二醇二硬脂酸酯、聚乙二醇单月桂酸酯等)、甘油脂肪酸酯(单酯~三酯,例如甘油单硬脂酸酯、甘油三棕榈酸酯等)、三羟甲基丙烷脂肪酸酯(单酯~三酯,例如三羟甲基丙烷单棕榈酸酯等)、季戊四醇脂肪酸酯(单酯~四酯,季戊四醇硬脂酸酯等)、脱水山梨醇脂肪酸酯(单酯~四酯,例如脱水山梨醇单硬脂酸酯等)等。脱模剂可以单独或将两种以上组合使用。
相对于100重量份聚酯系树脂(A),脱模剂的比例例如为约0.005~3重量份,优选为约0.01~1.5重量份。其中,在脱模剂的比例过多时,有可能在树脂中的分散性降低,脱模剂在成形品表面渗出,而且成形品的外观随着渗出有可能变差。
另外,在不显著损害对用于熔接的激光的透射性的范围内,前述树脂组合物还可以含有着色剂(例如日本特开2000-309694号公报、日本特开2001-71384号公报中记载的着色剂等)。作为着色剂,可以列举出对激光为非吸收性的着色剂(无机或有机染料和颜料),例如黄色染料和颜料(镉黄等无机颜料、联苯胺黄等有机颜料)、橙色染料和颜料(汉撒黄等)、红色颜料(红色无机颜料等无机颜料、色淀红等有机颜料)、蓝色颜料(钴蓝等无机颜料、酞菁蓝等有机颜料)、绿色染料和颜料(铬绿等无机颜料、酞菁绿等有机颜料)、紫色染料和颜料等。这种着色剂可以单独使用,也可以将多种着色剂组合使用以调整为所需的色调。例如,利用减色混合(多种染料和颜料如黄色染料和颜料与紫色染料和颜料的组合、黄色染料和颜料与红色染料和颜料以及蓝色染料和颜料的组合等),可以将前述树脂组合物着色成无彩色(灰色、黑色)。
对这种着色剂的用量没有特定限制,相对于100重量份聚酯系树脂(A),例如可以为约0.001~5重量份,优选为约0.005~3重量份,进一步优选为约0.01~2重量份。
前述树脂组合物(或激光透射性树脂成形品)具有优异的阻燃性,用树脂组合物形成的成形品在厚度0.8mm时,基于UL94标准(Underwriters Laboratories的Subject 94)的阻燃性评价通常为V-0。而且,前述树脂组合物(或激光透射性树脂成形品)即使成形很薄也具有高的阻燃性,即使前述成形品的厚度为约0.8mm以下,例如为约0.3~0.8mm,优选为约0.4~0.75mm,基于UL94标准的阻燃性评价也能达到V-0。
前述树脂组合物可以是粉粒体混合物或熔融混合物(粒料等)。这种树脂组合物可以通过用常用的方法将聚酯系树脂(A)、溴系化合物(B)和锑氧化物(C)(和此外根据需要的其他成分)混合或混炼(熔融混炼)来制备。尤其,前述树脂组合物由于具有优异的成形性,因此可以有效地作为各成分[聚酯系树脂(A)、溴系化合物(B)和锑氧化物(C)(和根据需要的其他成分)]的熔融混合物(熔融混炼物)获得。熔融混合物可以通过用常用的方法将各成分熔融混炼来制备。例如,前述树脂组合物可以通过下述方法制备:(1)将各成分混合,用挤出机(单螺杆或双螺杆挤出机)混炼、挤出,制备粒料,根据需要进一步进行成形的方法;(2)暂且制备组成不同的粒料(母料),混合(稀释)规定量的所述粒料用于成形,获得规定组成的成形品(粒料等)的方法;(3)将各成分的一种或两种以上直接加入成形机的方法等。另外,粒料等成形品可以在将除了脆性成分(玻璃系补强材料等)以外的成分熔融混合之后再混合脆性成分(玻璃系补强材料)来制备,并且可以从挤出机的侧给料口给料。另外,为了均匀地配合各成分,可以将树脂成分(聚酯系树脂等)的一部分微粉化,然后将所得粉体与其他成分混合。另外,本发明的树脂组合物可以以混合物(例如粉粒体或熔融混合物)的形态原样用于制造成形体。
前述树脂组合物(或激光透射性树脂成形品)尽管由聚酯系树脂形成,但对激光具有高的光线透射性,适合于激光熔接。例如对于厚度1.0mm的成形品,前述树脂组合物(或激光透射性树脂成形品)的激光透射率例如为约20%以上(例如约20~100%),优选为约25%以上(例如25~80%),进一步优选为约30%以上(例如30~50%),通常为约20~40%(例如20~30%)。另外,前述树脂组合物(或激光透射性树脂成形品)对于用于激光熔接的激光波长(例如后述激光波长范围内的任何一种波长(例如波长940nm))可以具有上述范围的激光透射率。
这样,本发明的树脂组合物的基础树脂虽然是聚酯系树脂(PBT系树脂等),但具有高水平的阻燃性和激光透射性,因此可以用作激光熔接用树脂组合物,可用于形成如前所述的激光熔接中的透射侧部件。另外,树脂组合物还具有优异的成形性、机械强度、耐热性、耐化学品性等性质。
因此,本发明的树脂组合物可适宜地用作激光熔接用的树脂组合物,具体地说,激光熔接中的透射侧部件用树脂组合物(有时称之为激光透射性树脂成形品用树脂组合物、用于形成激光透射性树脂成形品的树脂组合物、激光熔接中的透射侧部件用的树脂组合物等)。另外,前述激光透射性树脂成形品(有时称之为激光透射性成形品、激光透射侧树脂成形品、激光透射侧成形品、激光透射性树脂部件、激光透射性部件等)如前所述是能够与可吸收激光的激光吸收性树脂成形品接触,使激光透射,与前述树脂成形品接合的成形品,并且是用前述树脂组合物形成的成形品。
[成形品]
本发明的激光透射性树脂成形品由前述树脂组合物(即,激光熔接中的透射侧部件用树脂组合物)形成,可用于形成激光熔接的透射侧部件。
这种成形品(激光透射性树脂成形品)如上所述将前述树脂组合物(或各成分)熔融混炼,用挤出成形、注塑成形、压缩成形、吹塑成形、真空成形、旋转成形、气体喷射成形等常用方法来成形,但通常通过注塑成形来成形。成形品尤其可以是通过注塑成形而成形的成形品(注塑成形品)。注塑成形的条件可以根据聚酯系树脂的种类而适当地选择,例如在约200~300℃、优选在约250~280℃下将树脂组合物熔融混炼,根据需要制备粒料,通过注塑成形机在机筒温度约200~300℃(例如250~280℃)的条件下注塑成形。另外,模具温度可以在约40~100℃(例如40~90℃)的范围内选择,从维持激光透射性的观点来看,模具温度可以为约40~95℃(例如45~90℃),优选为约40~80℃(例如45~80℃),尤其优选为约50~85℃(例如46~80℃)。
对成形品的形状没有特定限制,为了通过激光熔接与配合材料(其他树脂成形品)接合而使用,通常是至少具有接触面(平面等)的形状(例如板状)。另外,本发明的成形品至少具有使激光透射的部位(激光熔接的部位,激光熔接部位),这种部位的厚度(激光透射的方向的厚度)例如为约0.1~1.5mm,优选为约0.2~1.0mm,进一步优选为约0.5~0.8mm。成形品例如在前述接触面区域中可以具有这种激光熔接部位。
本发明还包含用前述激光透射性成形品形成的复合成形品(或复合成形体或复合成形部件或复合成形树脂部件)。这种复合成形品是通过激光熔接将由前述树脂组合物形成的前述激光透射性树脂成形品(或第一成形品)与配合材料的激光吸收性树脂成形品(有时称为激光吸收侧树脂成形品、激光吸收侧成形品、激光吸收侧树脂部件、激光吸收侧部件、第二成形品、被粘物等)接合而成的成形品,两成形品相互一体化。另外,第一树脂成形品如前所述至少具有激光透射的部位(激光熔接部位),在复合成形品中,这种激光透射部位(或激光熔接部位)与第二树脂成形品接合。第一树脂成形品和第二树脂成形品通常通过接合至少部分地一体化。
对构成前述第二树脂成形品的树脂没有特定限制,可以列举出各种热塑性树脂,例如烯烃系树脂、乙烯基系树脂、苯乙烯系树脂、丙烯酸系树脂、聚酯系树脂、聚酰胺系树脂、聚碳酸酯系树脂等。在这些树脂当中,可以用与构成前述第一树脂成形品(前述树脂组合物)的基础树脂相同种类或同一系统的树脂,例如PB T系树脂、PET系树脂等聚酯系树脂(芳香族聚酯系树脂)或其组合物形成第二树脂成形品。为了进一步提高复合成形品的阻燃性,第二树脂成形品可以用阻燃剂等阻燃。另外,第一树脂成形品和第二树脂成形品二者可以用前述阻燃性树脂组合物形成。另外,本发明中,第一树脂成形品由于具有优异的阻燃性,即使不利用阻燃剂等对第二树脂成形品进行阻燃处理,也可以为复合成形品提供实用上充分的阻燃性。
第二树脂成形品可以含有对激光的吸收剂或着色剂。前述着色剂可根据激光的波长来选择,可以列举出无机颜料[炭黑(例如乙炔黑、灯黑、热炭黑(Thermal Black)、炉法炭黑(furnace black)、槽法炭黑(Channel Black)、科琴炭黑(Ketjenblack)等)等黑色颜料、氧化铁红等红色颜料、钼橙等橙色颜料、氧化钛等白色颜料等]、有机颜料(黄色颜料、橙色颜料、红色颜料、蓝色颜料、绿色颜料等)等。这些吸收剂可以单独或将两种以上组合使用。作为吸收剂,通常可以使用黑色颜料或染料,尤其炭黑。炭黑的平均粒径通常可以为约10~1000nm,优选为约10~100nm。相对于全部第二树脂成形品,着色剂的比例为约0.1~10重量%,优选为约0.5~5重量%(例如1~3重量%)。另外,在第一和第二树脂成形品之间,可以夹持含有炭黑等激光吸收剂或着色剂的树脂片(PBT系树脂片等),或者涂布激光吸收剂,将两成形体密合,然后通过激光照射进行接合。另外,关于前述含有着色剂的树脂片的细节,例如可以参照日本特许第1829720号公报等。
这种复合成形品可以通过将第一树脂成形品与第二树脂成形品接合来制备。即,复合成形品可以通过将激光照射于激光透射性树脂成形品与激光吸收性树脂成形品的接触面(或界面)上来制备。具体地说,通过使第一成形品与第二成形品接触(尤其,至少使激光透射部位或接合部进行面接触),照射激光,以至少部分地熔融第一成形品与第二成形品的界面,并在使接合面密合(熔合)的状态下冷却来进行接合。在这种复合成形品中,如果使用本发明的成形品,通过熔合可以获得高的接合强度,可以与通过照射激光没有熔合的非熔合部件保持同等的高熔合强度。
激光的照射通常从第一树脂成形品侧(透射部件侧)朝向第二成形品的方向进行。而且,通过这种激光照射,使含有吸收剂或着色剂的第二成形体的界面发热,从而使第一成形品与第二成形品熔合。另外,根据需要,利用透镜体系,将激光聚集在第一成形品与第二成形品的界面上,将接触界面熔合。本发明中,由于透射侧部件,即第一树脂成形品是由前述激光透射性优异的前述树脂组合物形成的,因此可以与第二树脂成形品进行有效地激光熔接,可以赋予复合成形品以高的阻燃性。
对激光的种类没有特定限制,例如可以使用波长为约600~2000nm,优选为约700~1500nm,进一步优选为约800~1200nm(例如800~1100nm)的激光。
作为可用于成形品的激光熔接的激光源,例如可以利用色素激光、气体激光(准分子激光、氩激光、氪激光、氦-氖激光等)、固体激光(YAG激光等)、半导体激光等。作为激光,通常利用脉冲激光。
另外,对激光熔接的激光扫描速度(激光照射位置在样品上移动的速度)没有特定限制,可以任意地选择。为了防止熔接不良和提高熔接强度,前述激光扫描速度例如优选为约0~150mm/秒,更优选为约1~100mm/秒,进一步优选为约2~50mm/秒。
前述成形品由于具有优异的激光熔接性,因此通常可以容易地通过激光熔接与配合材料的树脂成形品接合。另外,根据需要,可以将激光熔接与其他熔接法(例如振动熔接法、超声波熔接法、热板熔接法等)组合。
产业上的可利用性
本发明的激光熔接用阻燃性树脂组合物及其成形品(透射侧部件)具有优异的激光透射性和高的阻燃性,因此可以适用于各种用途,例如电气和电子部件、办公室自动化(OA)设备部件、家用电器部件、机械结构部件、汽车结构部件等。成形品和复合成形品尤其适宜用于汽车电装部件(各种控制单元、点火线圈部件等)、发动机部件、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
以下根据实施例来更详细地说明本发明,然而,本发明不限于这些实施例。
另外,在实施例和比较例中使用以下成分。
聚酯系树脂(A):
(A1)聚对苯二甲酸丁二酯(特性粘度=0.69dL/g,胜技高分子株式会社制造)
(A2)改性聚对苯二甲酸丁二酯(在对苯二甲酸与1,4-丁二醇的反应中,代替一部分对苯二甲酸(12.5mol%),使用12.5mol%间苯二甲酸二甲酯(DMI)作为共聚成分所制备的改性聚对苯二甲酸丁二酯,特性粘度=0.76dL/g)
(A3)聚对苯二甲酸丁二酯-聚己内酯弹性体(聚对苯二甲酸丁二酯与聚己内酯的共聚物,TEIJIN FIBERS LIMITED制造,Q4110)。
溴系化合物(B):
(B1):溴化聚丙烯酸酯(聚(丙烯酸五溴苄酯),デッドシ一ブロミングル一プ公司制造,FR 1025)
(B2):溴化聚苯乙烯(ァルベマ一ル(株)制造,PyroChek68PB)
(B3):溴化聚碳酸酯(溴化双酚A型聚碳酸酯,帝人化成(株)制造,Fire Guard FG-7500)
(B4):溴化环氧树脂(溴化双酚A型环氧树脂,阪本药品工业(株)制造,SRT5000)
(B5):亚乙基双(四溴邻苯二甲酰亚胺)(SAYTEX BT-93,ァルベマ一ル(株)制造)。
锑氧化物(C):
(C1)五氧化锑(平均粒径3.8μm,日产化学工业(株)制造,サンェポックNA-1030)
(C2)三氧化锑(平均粒径6.3μm,日本精矿(株)制造,PATOX-L)
(C3)三氧化锑(平均粒径1.2μm,日本精矿(株)制造,PATOX-M)
另外,锑氧化物的粒径使用激光衍射/散射式粒度分布测定装置((株)堀场制作所制造,LA-920),以蒸馏水作为分散介质来测定,所得中值粒径作为粒径。
聚碳酸酯树脂(D):
(D1)聚碳酸酯树脂(三菱ェンジニァリングプラスチックス(株)制造,ュ一ピロンS-3000)。
磷系化合物(E):
(E1)磷酸二氢钠(米山化学工业(株)制造,磷酸二氢钠)
(E2)四(2,4-二叔丁基苯基)-4,4’-双亚苯基二亚膦酸酯(クラリァントジャパン(株)制造,Sandostab P-EPQ)
结晶促进剂(F):
(F1)氮化硼(水岛合金铁(株),氮化硼FS-1)
(F2)滑石(林化成(株)制造,TALCAN PAWDER PL-NN)
填充材料(G):
(G1)玻璃纤维(直径13μm,日本电气硝子(株)制造,ECS 03T-187)
(G2)玻璃纤维(直径10μm,日本电气硝子(株)制造,ECS 03T-187H)
(G3)玻璃薄片(日本板硝子(株)制造,REFG-108)。
含氟树脂(H):
(H1)聚四氟乙烯(旭硝子(株)制造,Aflon PTFE C D076)
(H2)聚四氟乙烯-丙烯酸芯-壳聚合物(Mitsubishi RayonCo.,Ltd.制造,METABLEN A-3800)
(实施例1~19和比较例1~12)
(1)粒料的制备
按表1~3所示的比例将各成分[溴系化合物(B)、锑氧化物(C)和/或聚碳酸酯系树脂(D)、磷系化合物(E)、晶核剂(F)]与表1~3所示的聚酯系树脂(A)配合,用V型掺混机均匀地混合。使用30mmφ的双螺杆挤出机将所得混合物与表1所示比例的填充材料(G)、含氟树脂(H)在260℃的筒温度下熔融混合,将从模头喷出的线材冷却后切断,获得粒料。另外,该粒料含有0.3重量份酚系抗氧化剂(チバ(株)制造,“Irganox 1010”)与0.5重量份脱模剂(クラリァント(株)制造,“Wax E”)。
(2)成形品的制作和激光熔接
使用上述(1)获得的粒料,通过注塑成形机((株)东芝制造),在机筒温度260℃和模具温度80℃的条件下成形树脂成形品A(长8cm×宽1cm×厚1.0mm)。另外,作为用于与树脂成形品A熔接的树脂成形品(被粘物)B,除了使用100重量份前述粒料和3重量份黑色着色用炭黑(胜技高分子株式会社制造,商品名“2020B”)以外,与树脂成形品A同样地制作着色的树脂成形品B。另外,树脂成形品B起着基于激光的发热体的作用。
(3)熔接性的判定(强度的测定)
如图1和图2所示,在树脂成形品A(3)与树脂成形品B(4)以一部分重叠的方式接触的状态下,用石英玻璃板(5)和金属板(6)夹持固定,用ラィスタ一公司制造的激光熔接机(MODULAS C类型),用波长940nm的激光,从光源(1)将激光(2)以线宽W(2mm)聚光到树脂成形品A与树脂成形品B的接触面上,从树脂成形品A(3)侧,在10~50W的激光输出范围内、在5W步长和扫描速度10mm/秒的条件下照射激光,进行熔接实验。对于熔接实验后的成形品,使用拉伸试验机(ORIENTEC CO.,LTD.制造,RT C-1325),以5mm/分钟将激光熔接的树脂成形品A与树脂成形品B拉伸剪切,剪切强度超过300N则判断为“熔接”。另外,在与熔接面垂直方向上切断,用立体显微镜观察熔接面的碳化和发泡状态,判定有无过度熔接。从以上结果判断熔接,无碳化和发泡状态则评为“3”,发泡状态被见到、但熔接也被确认则评为“2”,碳化显著、激光透射不充分则评为“1”,2以上判断为激光熔接性良好。
结果在表1~3中示出。另外,在表1~3中,阻燃性和激光光线透射率如下所述测定和评价。
(A)阻燃性(燃烧性试验(UL-94))
按照Underwriters Laboratories的Subject 94(UL94)的方法,使用实施例和比较例的树脂组合物制作的5个试验片(厚度:0.8mm)测试阻燃性和树脂燃烧时的滴下特性。阻燃性按照UL 94中记载的评价方法分类为V-0、V-1、V-2以及不对应于这些V等级的等级(表示为notV)。
(B)激光光线透射率
使用分光光度计(日本分光(株)制造,V570,带有积分球)测定波长940nm下的树脂成形品A的光线透射率。
从表1和表2可以看出,在使用特定的溴系化合物和特定的锑氧化物的实施例中,由于激光的透射性高,因此获得了高熔接强度,熔接判定为3或2。另外,阻燃性的结果也是优异的。与此相反,在使用除此以外的含卤素化合物和锑氧化物的比较例中,即使阻燃性高,也不能熔接,或者即使能够通过激光熔接接合,阻燃性也是非常低的。
Claims (9)
1.一种激光透射性树脂成形品,所述激光透射性树脂成形品能够与可吸收激光的激光吸收性树脂成形品接触,使激光透射而与所述激光吸收性树脂成形品接合,其中该激光透射性树脂成形品由树脂组合物形成,该树脂组合物包含聚酯系树脂(A)和为溴化(甲基)丙烯酸系树脂的溴系化合物(B)以及具有2~10μm平均粒径的锑氧化物(C)。
2.根据权利要求1所述的激光透射性树脂成形品,其在厚度1mm时的激光透射率为20%以上。
3.根据权利要求1或2所述的激光透射性树脂成形品,其中所述锑氧化物(C)是选自三氧化锑、五氧化锑和锑酸钠中的至少一种。
4.根据权利要求1或2所述的激光透射性树脂成形品,其中,相对于100重量份聚酯系树脂(A),溴系化合物(B)的比例是10~50重量份,锑氧化物(C)的比例是5~30重量份。
5.根据权利要求1或2所述的激光透射性树脂成形品,其进一步含有聚碳酸酯系树脂(D)和磷系化合物(E)。
6.根据权利要求1或2所述的激光透射性树脂成形品,其进一步含有结晶促进剂(F)。
7.根据权利要求1或2所述的激光透射性树脂成形品,其在厚度0.8mm时,基于UL94标准的阻燃性评价为V-0。
8.一种复合成形品,其通过激光熔接将权利要求1~7的任一项所述的激光透射性树脂成形品与可吸收激光的激光吸收性树脂成形品接合而形成。
9.根据权利要求8所述的复合成形品,其中,所述激光透射性树脂成形品是至少具有使激光透射的、厚度为0.1~1.0mm的部位的树脂成形品,并在该部位与激光吸收性树脂成形品接合。
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CN101875783B (zh) * | 2010-07-14 | 2012-09-26 | 深圳市科聚新材料有限公司 | 一种增强聚己二酰丁二胺材料及其制备方法 |
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CN103415565A (zh) * | 2011-03-08 | 2013-11-27 | 巴斯夫欧洲公司 | 含有羧酸盐的激光透明聚酯 |
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US10836113B2 (en) | 2015-01-22 | 2020-11-17 | Mitsubishi Engineering-Plastics Corporation | Laser welding member, and molded article |
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