CN1863870A - 激光熔敷用树脂组合物和成形品 - Google Patents

激光熔敷用树脂组合物和成形品 Download PDF

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Publication number
CN1863870A
CN1863870A CNA2004800292589A CN200480029258A CN1863870A CN 1863870 A CN1863870 A CN 1863870A CN A2004800292589 A CNA2004800292589 A CN A2004800292589A CN 200480029258 A CN200480029258 A CN 200480029258A CN 1863870 A CN1863870 A CN 1863870A
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CN
China
Prior art keywords
molding
resin
resin combination
laser
acid
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Granted
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CNA2004800292589A
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CN100376630C (zh
Inventor
坂田耕一
高山胜智
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Poly Plastics Co., Ltd.
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WinTech Polymer Ltd
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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
    • 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
    • B29C65/1635—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
    • 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
    • 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
    • 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
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    • 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
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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
    • 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
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    • B29C66/242—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours
    • B29C66/2424—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours being a closed polygonal chain
    • B29C66/24243—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours being a closed polygonal chain forming a quadrilateral
    • B29C66/24244—Particular design of joint configurations particular design of the joint lines, e.g. of the weld lines said joint lines being closed or non-straight said joint lines being closed, i.e. forming closed contours being a closed polygonal chain forming a quadrilateral forming a rectangle
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/53—Joining single elements to tubular articles, hollow articles or bars
    • B29C66/534—Joining single elements to open ends of tubular or hollow articles or to the ends of bars
    • B29C66/5346—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat
    • B29C66/53461—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat joining substantially flat covers and/or substantially flat bottoms to open ends of container bodies
    • 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
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/65—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles with a relative motion between the article and the welding tool
    • B29C66/652—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles with a relative motion between the article and the welding tool moving the welding tool around the fixed article
    • 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
    • B29C66/7334—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 glossy or matt, reflective or refractive
    • B29C66/73343—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 glossy or matt, reflective or refractive at least one of the parts to be joined being matt or refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/7392—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 material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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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    • 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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    • 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
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明提供一种以聚对苯二甲酸丁二酯(PBT)为基质，能够均匀熔敷，而且具有高的熔敷强度的激光熔敷用PBT类树脂组合物、以及其成形品。激光熔敷用树脂组合物相对于聚对苯二甲酸丁二酯类树脂(均聚酯或者共聚酯)(A)100重量份，含有聚苯乙烯类热塑性弹性体或聚酯类热塑性弹性体等弹性体(B)1－50重量份、聚碳酸酯类树脂(C)5－100重量份、增塑剂(芳香族多元羧酸酯、丙烯酸类增塑剂等)(D)1－10重量份和玻璃纤维等填充剂或者补强剂(E)0－100重量份。如果由该树脂组合物调制成形品，则由上述成形品部位的不同产生的光线透过率的变化幅度小。因此，可以与对应材均匀地进行激光熔敷。

Description

激光熔敷用树脂组合物和成形品
技术领域
本发明涉及激光熔敷性高、成形加工性优异的聚对苯二甲酸丁二酯类树脂组合物、以及使用它的成形品。
背景技术
聚对苯二甲酸丁二酯(PBT)类树脂由于其耐热性、耐化学性、电特性、机械特性、以及成形加工性等各种特性优异，可用于多种用途。作为具体的用途，可以举例为各种汽车用电气安装部件(各种控制单元、各种传感器、点火线圈等)、连接器类、开关部件、继电器部件、线圈部件等。作为这些部件有时需要气密性，为了简单地制作这些部件，可利用粘合剂、加热板熔敷、超声波熔敷等接合方法。但是，在这些接合方法中，存在几个问题。例如如果使用粘合剂，则存在的问题是到粘合剂固化为止的工序时间的损失和对环境造成的负担。另外，就加热板熔敷和超声波熔敷而言，产品有可能因热或振动等遭到损坏。
另一方面，利用激光熔敷的接合方法中，产品不会因随着熔敷产生的热和振动遭到损坏，熔敷工序也非常简单。但是，当通过激光熔敷接合PBT类树脂时，由于激光的透过性低，会发生碳化等，因此被指出实际上不可能完成熔敷。在特开2001-26656号公报(专利文献1)中，公开了通过用熔敷加工使由具有特定范围熔点的聚酯类共聚物形成的成形品和其它的成形品一体化而制造成形体的方法。在该文献中，记载了均聚芳酸亚烷基酯树脂(聚对苯二甲酸丁二酯、聚对苯二甲酸乙二酯、聚萘二甲酸乙二酯)的激光熔敷强度较小。
在特开平10-245481号公报(专利文献2)中，公开了在由热塑性聚碳酸酯树脂和聚对苯二甲酸乙二酯等热塑性聚酯树脂构成的组合物中，按照1-10重量％的比例，混合在交联丙烯酸酯类弹性体的存在下使以甲基丙烯酸酯为主成分的单体进行接枝聚合得到的甲基丙烯酸酯类树脂(接枝树脂)而得到的热塑性树脂组合物。在该文献中，记载了在上述树脂组合物中，按照1.5/1～4/1(重量比)的比例使用双酚A型聚碳酸酯树脂和聚对苯二甲酸乙二酯树脂的例子。另外，作为上述组合物的热熔敷法，还记载了加热板熔敷法、振动熔敷法或者超声波熔敷法。但是，在该组合物中，要想提高熔敷强度，必须使用上述接枝树脂，同时如果使用该接枝树脂，则机械强度和耐热性容易下降。
另外，有时用以PBT类树脂为基质的成形品，相对于激光的透过率根据部位的不同而进行变化。因此，如果把这样的成形品与对应材(树脂成形品)进行激光熔敷，则有时使成形品和作为对应材的成形品不能在接触界面均匀而且牢固地熔敷。
专利文献1：特开2001-26656号公报(权利要求的范围)
专利文献2：特开平10-245481号公报(权利要求的范围)
发明内容
因此，本发明的目的在于提供以PBT类树脂为基质，同时均匀熔敷性高，可以均匀熔敷的激光熔敷用PBT类树脂组合物及其成形品。
本发明的另一目的在于提供激光熔敷性优异，而且能够获得高的熔敷强度的激光熔敷用PBT类树脂组合物、以及其成形品。
本发明人等为了实现上述课题而进行了专心研究，结果发现如果组合PBT类树脂、聚碳酸酯类树脂、弹性体和增塑剂进行注射模塑成形，则可以不依赖于成形品的部位，相对于激光的透过率高，而且均匀，使PBT类树脂组合物的成形品和对应材(树脂成形品)能在界面均匀而且牢固地进行激光熔敷，从而完成了本发明。
即，本发明的激光熔敷用树脂组合物(或者激光熔敷性树脂组合物)包含聚对苯二甲酸丁二酯类树脂(A)、弹性体(B)、聚碳酸酯类树脂(C)和增塑剂(D)。作为基质树脂的聚对苯二甲酸丁二酯类树脂(A)也可以是聚对苯二甲酸丁二酯、或者用30摩尔％以下的共聚性单体改性的聚对苯二甲酸丁二酯类共聚物。弹性体的折射率在温度25℃下也可以为约1.52-1.59，增塑剂的折射率在温度25℃下也可以为约1.45-1.60。激光熔敷性树脂组合物还可以另外含有填充剂或者补强剂(E)。填充剂或者补强剂(E)没有特别的限制，例如，也可以是玻璃质填充剂或者补强剂(玻璃纤维、玻璃片、玻璃珠等)等。树脂组合物各成分的比例也可以是例如相对于聚对苯二甲酸丁二酯类树脂(A)100重量份，弹性体(B)为约1-50重量份，聚碳酸酯类树脂(C)为约5-100重量份，增塑剂(D)为约1-10重量份，填充剂或者补强剂(E)为约0-100重量份。另外，为了使光透过性稳定，也可以向树脂组合物中加入成核剂(F)。
由本发明的树脂组合物形成的成形品由于光线透过性(相对于激光的光线透过性)高，而且由成形品部位的不同产生的透过率的差小，所以适合于宽范围的激光熔敷。例如，在由注射模塑成形形成的纵80mm×横80mm×厚2mm的成形品中，照射800-1200mm波长的光线时，根据上述成形品部位的不同产生的光线透过率的变化幅度(光线透过率的最大值和最小值的差)为10％以下。
由本发明的树脂组合物形成的成形品与对应材的激光熔敷性优异。因此，本发明不仅包括由上述树脂组合物形成的成形品，而且还包括该成形品和对应材的树脂成形品通过激光熔敷进行接合形成的复合成形品。该复合成形品由上述树脂组合物形成，而且可以通过使位于激光透过侧的成形品和位于激光受光侧的对应材的树脂成形品接触，通过照射激光使上述成形品和上述树脂成形品进行接合来制造。
就本发明来说，由于将PBT类树脂、弹性体、聚碳酸酯类树脂和增塑剂组合使用，所以可以虽然以PBT类树脂为基质，但是透过率在整个成形品中都均匀，均匀熔敷性高，可以通过激光熔敷与对应材均匀熔敷。另外，激光熔敷性优异，可以获得高的熔敷强度。因此，可以获得以PBT类树脂为基质，激光熔敷性优异的组合物和成形品、和以高的熔敷强度进行接合的复合成形品。
附图说明
图1是用于说明实施例中的激光熔敷的示意图。
具体实施方式
[树脂组合物]
(A)聚对苯二甲酸丁二酯类树脂
作为基质树脂即聚对苯二甲酸丁二酯(PBT)类树脂，可列举以对苯二甲酸丁二酯为主成分(例如，约50-100重量％，优选约60-100重量％，更优选约75-100重量％)的均聚酯或者共聚酯(聚对苯二甲酸丁二酯、聚对苯二甲酸丁二酯共聚酯)等。
作为共聚酯(对苯二甲酸丁二酯类共聚物或者改性PBT树脂)中的可以共聚的单体(以下有时仅称为共聚性单体)，可列举除了对苯二甲酸之外的二羧酸、除了1，4-丁二醇之外的二元醇、含氧酸、内酯等。共聚性单体可以使用一种或者二种以上组合使用。
作为二羧酸，可以举例为例如脂肪族二羧酸(例如，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、二聚酸等C4-40二羧酸，优选C4-14二羧酸)、脂环式二羧酸(例如，六氢邻苯二甲酸、六氢间苯二甲酸、六氢对苯二甲酸、降冰片烯二酸等C8-12二羧酸)、除对苯二甲酸以外的芳香族二羧酸(例如，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’-二苯氧基醚二羧酸、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)、或者它们的反应性衍生物(例如，低级烷基酯(邻苯二甲酸二甲酯、间苯二甲酸二甲酯(DMI)等邻苯二甲酸或者间苯二甲酸的C1-4烷基酯等)、酰氯、酸酐等可以形成酯的衍生物)等。另外，也可以根据需要混合使用苯偏三酸、苯均四酸等多元羧酸等。
作为二元醇，可以举例为例如除1，4-丁二醇以外的脂肪族亚烷基二醇(例如，乙二醇、丙撑二醇、丙二醇、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)、聚氧亚烷基二醇[具有多个氧C2-4亚烷基单元的二醇，例如二甘醇、二丙二醇、二丁二醇、三甘醇、三丙二醇、聚丁二醇等]、脂肪族二醇(例如，1，4-环己二醇、1，4-环己二甲醇、氢化双酚A等)、芳香族二醇[例如，对苯二酚、间苯二酚、萘二醇等C6-14芳香族二醇；联酚；双酚类；亚二甲苯基二醇等]等。另外，也可以根据需要混合使用丙三醇、三羟甲基丙烷、三羟甲基乙烷、季戊四醇等多元醇。
作为上述双酚类，可列举双(4-羟基苯基)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、2，2-双(4-羟基苯基)-4-甲基戊烷等双(羟基芳基)C1-6烷烃；1，1-双(4-羟基苯基)环戊烷、1，1-双(4-羟基苯基)环己烷等双(羟基芳基)C4-10环烷烃；4，4’-二羟基二苯基醚；4，4’-二羟基二苯基砜；4，4’-二羟基二苯基硫化物；4，4’-二羟基二苯基酮、以及这些的烯化氧加成物。作为烯化氧加成物，可以举例为双酚类(例如，双酚A、双酚AD、双酚F等)的C2-3烯化氧加成物，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。在烯化氧加成物中，烯化氧(环氧乙烷、环氧丙烷等C2-3烯化氧)的加成摩尔数相对于各羟基为约1-10摩尔，优选约1-5摩尔。
作为含氧酸，包括例如含氧安息香酸、含氧萘甲酸、羟基苯乙酸、乙醇酸、含氧己酸等羟酸或者这些的衍生物等。作为内酯，包括丙内酯、丁内酯、戊内酯、己内酯(例如，ε-己内酯等)等C3-12内酯等。
作为优选的共聚性单体，可以举例为二元醇类[C2-6亚烷基二醇(乙二醇、丙撑二醇、丙二醇、己二醇等直链状或者支链状亚烷基二醇等)、具有重复单元数为约2-4的含氧亚烷基单元的聚含氧C2-4亚烷基二醇(二甘醇等)、双酚类(双酚类或者其烯化氧加成物等)等]、二羧酸类[C6 -12脂肪族二羧酸(己二酸、庚二酸、辛二酸、壬二酸、癸二酸等)、羧基在芳环的非对称位置上进行取代的非对称芳香族二羧酸、1，4-环己二甲醇等]等。这些化合物中，优选芳香族化合物如双酚类(特别是双酚A)的烯化氧加成物、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)等低级烷基酯)等]等。
作为PBT类树脂，优选均聚酯(聚对苯二甲酸丁二酯)和/或共聚酯(共聚物)，共聚性单体的比例(改性量)为30摩尔％以下(0-30摩尔％)。在共聚物中，共聚性单体的比例例如可以选自约0.01-30摩尔％的范围，通常为约1-30摩尔％，优选约3-25摩尔％，更优选约5-20摩尔％(例如5-15摩尔％)。
PBT类树脂可以通过用惯用的方法例如酯交换、直接酯化法等使对苯二甲酸或者其反应性衍生物和1，4-丁二醇和根据需要而加的可以共聚的单体进行共聚来制备。
(B)弹性体
作为弹性体，可以使用各种热塑性弹性体。弹性体的折射率例如在温度25℃下也可以为约1.52-1.59，优选为约1.53-1.58。弹性体的折射率如果过小或者过大，则透过光的散射有时变得显著，有时造成熔敷能量下降。
弹性体通常由硬链段(或者硬质性部分)和软链段(或者软质性部分)构成。弹性体(热塑性弹性体)也可以是聚苯乙烯类弹性体、聚酯类弹性体、聚酰胺类弹性体、聚氨酯类弹性体、聚烯烃类弹性体、聚氯乙烯类弹性体、含氟热塑性弹性体等。这些弹性体可以单独使用或者二种以上组合使用。
作为聚苯乙烯类弹性体，可列举由苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯基单体的均聚或者共聚物构成的硬链段和由选自α-C2-12烯烃(乙烯、丙烯、丁烯等)、二烯(丁二烯、异戊二烯等)等的单体的均聚或者共聚物构成的软链段的嵌段共聚物或者其加氢嵌段共聚物。
作为聚酯类弹性体，可列举由聚芳酸亚烷基酯(聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯等聚芳酸C2-4亚烷基酯、用共聚成分(间苯二甲酸等上述列举的共聚性单体)1-30摩尔％(例如，约3-25摩尔％)改性或者共聚改性聚芳酸C2-4亚烷基酯)构成的硬链段和由聚己内酯、具有含氧C2-6亚烷基单元的脂肪族聚醚(聚C2-6亚烷基二醇等)或脂肪族聚酯构成的软链段的嵌段共聚物。
聚酰胺类弹性体通常是由聚酰胺构成的硬链段和由聚C2-6亚烷基二醇等脂肪族聚醚构成的软链段的嵌段共聚物。作为聚氨酯类弹性体，可列举由短链二元醇的聚氨酯构成的硬链段和由脂肪族聚醚或脂肪族聚酯构成的软链段的嵌段共聚物，例如，聚酯尿烷弹性体、聚醚尿烷弹性体等。
作为聚烯烃类弹性体，可列举由聚苯乙烯或者聚丙烯构成的硬链段和由乙烯-丙烯橡胶或乙烯-丙烯-二烯橡胶构成的软链段的共聚物、结晶性硬链段和非结晶性软链段的共聚物[例如，由结晶性间规1，2-聚丁二烯构成的硬链段和由无定形1，2-聚丁二烯构成的软链段的共聚物(间规1，2-聚丁二烯类弹性体)、由结晶性反1，4-聚异戊二烯构成的硬链段和由非结晶性1，4-聚异戊二烯构成的软链段的共聚物(反1，4-聚异戊二烯类弹性体)]等。
作为聚烯烃类弹性体，还包括具有弹性体性能的乙烯类共聚物，例如，乙烯、与选自脂肪酸乙烯酯类(醋酸乙烯酯、丙酸乙烯酯等)、丙烯酸酯类(丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等丙烯酸C1-10烷基酯等)、苯乙烯类单体(苯乙烯、α-甲基苯乙烯、乙烯基甲苯等)的至少一种共聚性单体以及根据需要的(甲基)丙烯酸等的共聚物。作为这种烯烃类弹性体，可列举例如乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸C1-8烷基酯共聚物(乙烯-丙烯酸酯共聚物(EEA)、乙烯-丙烯酸丁酯共聚物等)、乙烯-丙烯酸C1-8烷基酯-(甲基)丙烯酸共聚物、乙烯-苯乙烯共聚物等。
热塑性弹性体的嵌段结构没有特别的限制，也可以是三嵌段结构、多嵌段结构、星形嵌段结构等。
作为优选的热塑性弹性体，包括聚苯乙烯类弹性体、聚酯类弹性体。作为代表的聚苯乙烯类弹性体，可列举苯乙烯-二烯-苯乙烯嵌段共聚物[苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)等]、加氢嵌段共聚物[苯乙烯-乙烯·丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯·丙烯-苯乙烯嵌段共聚物(SEPS)、无规苯乙烯-丁二烯共聚物的加氢聚合物]、引入官能基(环氧基、羧基、酸酐等)的改性共聚物[将二烯的不饱和键环氧化的环氧化苯乙烯-二烯共聚物(环氧化苯乙烯-二烯-苯乙烯嵌段共聚物或者其加氢聚合物等)等]。
作为代表的聚酯类弹性体，包括聚酯-聚酯型热塑性弹性体[例如，由聚芳酸C2-4亚烷基酯(尤其是具有聚对苯二甲酸丁二酯单元的均聚物、或者使共聚成分(乙二醇、间苯二甲酸等)按照约5-20摩尔％的比例进行共聚形成的共聚物)等芳香族类结晶性聚酯构成的硬链段和由脂肪族聚酯(聚己二酸乙二酯、聚己二酸丁二酯等C2-6亚烷基二醇和C6-12烷烃二羧酸的聚酯等)构成的软链段的嵌段共聚物]、聚酯-聚醚型热塑性弹性体[例如，由上述芳香族类结晶性聚酯构成的硬链段和聚四甲撑醚乙二醇等聚含氧C2-4亚烷基二醇等聚醚构成的软链段的嵌段共聚物]、液晶性热塑性弹性体[例如，由液晶分子构成的硬链段和由上述脂肪族聚酯构成的软链段的嵌段共聚物]等。
热塑性弹性体中，硬链段(或者硬质成分)和软链段(或者软质成分)的重量比例通常是前者/后者＝约10/90-90/10，优选约20/80-80/20，更优选约30/70-70/30(例如40/60-60/40)。
弹性体的使用量相对于PBT类树脂(A)100重量份为约1-50重量份(例如1-40重量份)，优选约2-40重量份(例如2-30重量份)，更优选约5-35重量份(例如5-30重量份)。
(C)聚碳酸酯(PC)类树脂
聚碳酸酯类树脂可以根据二羟基化合物和光气或者碳酸二苯酯等碳酸酯的反应得到。二羟基化合物也可以是脂环族化合物等，但是优选芳香族化合物(特别是双酚化合物)。
作为双酚化合物，可列举在上述PBT类树脂项中列举的双酚类(例如，双(羟基芳基)C1-6烷烃；双(羟基芳基)C4-10环烷烃；4，4’-二羟基二苯基醚；4，4’-二羟基二苯基砜；4，4’-二羟基二苯基硫化物；4，4’-二羟基二苯基酮等)。作为优选的聚碳酸酯类树脂，包括以双酚F、双酚AD、双酚A、1，1-双(羟基苯基)C5-6环烷烃为基质的聚碳酸酯，尤其是双酚A型聚碳酸酯。
聚碳酸酯类树脂(C)的使用量可以相对于PBT类树脂(A)100重量份选自约5-100重量份(例如10-100重量份)的范围，通常为约10-80重量份(例如10-60重量份)，优选约10-60重量份(例如20-40重量份)。
增塑剂(D)
作为增塑剂，可列举例如各种增塑剂，例如酯类增塑剂(芳香族多元羧酸酯、脂肪族多元羧酸酯、聚酯、蔗糖脂肪酸酯等)、磷酸酯类增塑剂(磷酸三丁酯、磷酸三-2-乙基己酯、磷酸三苯酯、磷酸三甲苯酯等)、丙烯酸类聚合物等。这些增塑剂可以单独使用或者二种以上组合使用。这些增塑剂之中，优选沸点高的增塑剂(例如，沸点约250-400℃，优选约270-400℃，更优选约300-400℃的增塑剂)。
芳香族多元羧酸酯只要是具有多个酯基(烷氧基羧基、环烷基氧基羰基、芳烷基氧基羰基等)的芳香族化合物就可以，例如，可以用式φ-(COOR)n(式中，φ表示苯、萘环等C6-12芳环，R表示烷基、环烷基或者芳烷基，n表示2以上的整数，各基团COOR的R可以相同也可以不同)表示。这些芳香族多元羧酸酯可以一种或者二种以上并用。
作为芳香族多元羧酸酯成分的多元羧酸，可列举例如芳香族二羧酸(邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二羧酸、这些的酸酐等)、芳香族三羧酸(偏苯三酸或者其酸酐等)、芳香族四羧酸(均苯四甲酸或者其酸酐)等。
芳香族多元羧酸酯类增塑剂中，系数n通常为约2-6，优选为约2-4(尤其约3-4)。n为3以上的多元羧酸酯由于耐热性高，所以有利。
作为构成烷基酯的烷基，可列举例如丁基、叔丁基、戊基、己基、辛基、2-乙基己基、异壬基、癸基、异癸基、三异癸基等直链状或者支链状C1-20烷基等。优选的烷基是直链状或者支链状C3-16烷基，特别是直链状或者支链状C4-14烷基。作为构成环烷基酯的环烷基，可列举环己基等C5-10环烷基，作为构成芳烷基酯的芳烷基，可列举苄基等C6-12芳基-C1-4烷基。
作为代表的芳香族多元羧酸酯，可列举偏苯三酸三C4-20烷基酯(偏苯三酸三丁酯、偏苯三酸三辛酯、偏苯三酸三(2-乙基己基)酯、偏苯三酸三异癸基酯等)、偏苯三酸三C5-10环烷基酯(偏苯三酸三环己酯等)、偏苯三酸三芳烷基酯(偏苯三酸三苄酯等)、偏苯三酸二烷基一芳烷基酯(偏苯三酸二(2-乙基己基)一苄酯)、均苯四甲酸四C4-20烷基酯(均苯四甲酸四丁酯、均苯四甲酸四辛酯、均苯四甲酸四2-乙基己基酯、均苯四甲酸四异癸基酯等)、均苯四甲酸四芳烷基酯(均苯四甲酸四苄酯等)、均苯四甲酸二烷基二芳烷基酯(均苯四甲酸四二(2-乙基己基)二苄酯)等。另外，羧酸酯也可以是具有不同的酯基(烷氧基羧基、环烷基氧基羰基、芳烷基氧基羰基等)的混合酯。
作为脂环族多元羧酸酯类增塑剂，可列举与前述芳香族多元羧酸酯相对应的脂环族多元羧酸酯，例如，脂环族三羧酸(甲基环己烷三羧酸或者其酸酐等)的酯(直链状或者支链状C1-20烷基酯(特别是直链状或者支链状C4-14烷基酯)、C5-10环烷基酯、芳烷基酯(特别是苄酯))等。
聚酯类增塑剂包括由二羧酸成分[脂肪族二羧酸(己二酸、癸二酸等C6-12烷烃二羧酸)、芳香族二羧酸(邻苯二甲酸、萘二羧酸等非对称性芳香族二羧酸)]和二元醇成分(丁二醇、新戊二醇、六甲撑二醇等C2-10烷烃二醇等)反应生成的聚酯(包括低聚酯)。这些聚酯类增塑剂可以单独使用或者二种以上组合使用。聚酯类增塑剂的重均分子量通常也可以为约500-10000(特别是800-8000)。
作为磷酸酯类增塑剂，可列举磷酸三烷基酯(磷酸三丁酯、磷酸三-2-乙基己酯等磷酸C4-14烷基酯)、磷酸三芳基酯(磷酸三苯酯、磷酸三甲苯酯等磷酸三C6-12芳基酯等)等。
丙烯酸类聚合物的增塑剂(以下有时仅称为丙烯酸类增塑剂)至少是(甲基)丙烯酸类单体的均聚或者共聚物，例如，也可以是(甲基)丙烯酸类单体和共聚性单体的共聚物((甲基)丙烯酸类单体和苯乙烯类单体的共聚物)。该增塑剂也可以是低聚物(例如，重均分子量为约500-8000(优选800-5000)的低聚物)。另外，丙烯酸类增塑剂有时称为流动性改善剂。
作为(甲基)丙烯酸类单体，可列举(甲基)丙烯酸、(甲基)丙烯酸酯[例如(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2-乙基己酯等(甲基)丙烯酸C1-18烷基酯，(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟乙酯等(甲基)丙烯酸羟烷基酯，(甲基)丙烯酸缩水甘油酯等]、(甲基)丙烯酰胺、(甲基)丙烯腈等。这些(甲基)丙烯酸类单体可以单独或者二种以上组合使用。
作为苯乙烯类单体，可列举例如苯乙烯、乙烯基甲苯、α-甲基苯乙烯、氯苯乙烯、乙烯基萘等。这些苯乙烯类单体可以单独或者二种以上组合使用。在这些苯乙烯类单体之中，优选苯乙烯、乙烯基甲苯、α-甲基苯乙烯，特别优选苯乙烯。
(甲基)丙烯酸类单体和苯乙烯类单体的重量比例例如可以选自前者/后者＝约10/90-90/10的范围，也可以是约20/80-80/20，优选约30/70-70/30。
另外，根据需要，也可以使共聚性单体共聚。作为共聚性单体，可列举例如聚合性多元羧酸(富马酸、马来酸等)、乙烯基酯类单体(例如醋酸乙烯酯、丙酸乙烯酯等)等。这些共聚性单体可以单独或者二种以上组合使用。
增塑剂的折射率只要不损害激光的透过性就没有特别的限制，例如为约1.45-1.6，优选约1.48-1.58。
作为增塑剂，往往使用非挥发性增塑剂，例如芳香族多元羧酸酯类增塑剂和丙烯酸类增塑剂。
增塑剂(D)的使用量可以相对于PBT类树脂(A)100重量份选自约1-20重量份(例如1-15重量份)的范围，通常为约1-10重量份，优选约1-8重量份(例如1-6重量份)。
填充剂或者补强剂(E)
树脂组合物也可以含有填充剂或者补强剂(E)。作为这样的填充剂或者补强剂(E)，包括纤维状补强材料[例如，无机质纤维(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、须晶纤维(碳化硅、氧化铝、氮化硼等须晶纤维等)等)、有机质纤维(例如，由脂肪族或者芳香族聚酰胺、芳香族聚酯、含氟树脂、聚丙烯腈等丙烯酸树脂、人造丝等形成的纤维等)等]、板状补强材料(例如，滑石、云母、玻璃片等)、粉粒状补强材料[例如，玻璃珠、玻璃粉、研磨纤维(milled fiber)(例如研磨玻璃纤维等)、硅灰石(wollastonite)等]。硅灰石也可以是板状、柱状、纤维状等形式。纤维状补强材料的平均直径可以是例如约1-50μm(优选3-30μm)，平均长度可以是例如约100μm-3mm(优选500μm-1mm)。另外，板状或者粉粒状补强材料的平均直径可以是例如约0.1-100μm，优选约0.1-50μm。这些补强材料可以单独或者二种以上组合使用。
在这些填充剂或者补强剂(E)之中，优选可以使激光透过的补强材料。这样的补强材料可以根据激光的波长进行选择。作为这样的补强材料，可以列举例如玻璃类或者玻璃质填充剂或者补强材料(玻璃纤维、玻璃片、玻璃珠等)等，特别优选玻璃纤维，例如具有高强度和刚性的玻璃纤维(切短纤维等)等。
填充剂或者补强剂(E)的比例可以相对于PBT类树脂100重量份选自约0-100重量份(例如0-80重量份)的范围，通常为约10-100重量份(例如10-80重量份)，优选约20-80重量份，更优选约30-80重量份(例如50-70重量份)。
成核剂(F)
作为成核剂(F)，通常使用无机成核剂(例如，二氧化硅、氧化铝、氧化锆、氧化钛等金属氧化物；碳酸钙、碳酸钡等金属碳酸盐；滑石等板状无机物或者硅酸盐；炭化硅等金属碳化物；氮化硅、氮化硼、氮化钽等金属氮化物等)，但是也可以使用有机成核剂。成核剂(例如，无机成核剂)的平均粒径是可以是例如约0.01-10μm，优选约0.01-5μm(例如，0.01-2μm)，更优选约0.01-1μm。
成核剂(F)相对于聚对苯二甲酸丁二酯类树脂(A)100重量份的比例为约0.001-5重量份(例如0.01-5重量份)，优选约0.01-3重量份(例如0.01-2重量份)，更优选约0.01-1重量份(例如0.01-0.5重量份)。
也可以向树脂组合物中加入各种添加剂，例如稳定剂(抗氧化剂、紫外线吸收剂、热稳定剂等)、阻燃剂、滑剂、脱模剂、抗静电剂、无机填充剂、染料等着色剂、分散剂、抗静电剂、填充剂等。另外，己知在PBT类树脂和聚碳酸酯类树脂之间产生酯交换反应，而有利的是使用普通的稳定剂(例如，磷化物类抗氧化剂等磷类稳定剂)可防止这种反应。此外，为了改善耐水解性、耐热冲击性等，也可以加入双酚A型环氧化合物、酚醛清漆型环氧化合物等环氧化合物。另外，相对于激光的反射成分(例如，几乎反射波长800-1200nm区域的入射光的成分(例如，氧化钛等))只要是不损害激光熔敷性的范围就可以使用，但是通常往往不加入这种反射成分。另外，如果需要，也可以与其它的树脂[苯乙烯类树脂(例如，聚苯乙烯树脂、丙烯腈-苯乙烯共聚物等)、丙烯酸类树脂(聚甲基丙烯酸甲酯等)、聚对苯二甲酸乙二酯类树脂(具有对苯二甲酸乙二酯单元的共聚物等)、聚酰胺树脂、聚苯醚类树脂等热塑性树脂、热固化性树脂等]组合使用。
本发明的PBT类树脂组合物也可以是粉粒状混合物或熔融混合物(颗粒等)。本发明的树脂组合物可以制造成形性高、机械强度和耐热性高的成形体或者成形品。特别是，用本发明的树脂组合物形成的成形品虽然由PBT类树脂组合物形成，但是光线透过性(特别是相对于激光的光线透过性)高，适合激光熔敷。例如，在以边浇口方式通过由宽2mm的铸口的注射模塑成形(例如，在实施例中记载的条件下的注射模塑成形)形成的成形品[长80mm×宽80mm×厚2mm]中，800-1200nm波长的光线透过率在厚度方向为约20％以上(例如，20-70％)，优选约25％以上(例如，25-60％)，更优选约30％以上(例如，30-50％)。而且，由本发明的树脂组合物形成的成形品光透过性根据成形品的部位(场所)产生的变化小，激光均匀透过。例如，在将本发明的树脂组合物进行注射模塑成形形成的上述成形品[长80mm×宽80mm×厚2mm]中，当沿厚度方向照射800-1200nm波长的光线(激光)时，由成形品部位的不同产生的光线透过率的变化幅度为约10％以下(0-10％)，优选约7％以下(0-7％)，更优选约5％以下(0-5％)，特别优选约3％以下(0-3％)，也可以是约2-6％。因此，可以宽范围地均匀而且牢固地进行激光熔敷，可以提高熔敷界面部分的气密性。另外，由于由激光产生的熔敷性高，所以可用于制造利用激光进行熔敷的成形体。
[成形体]
成形体可以用常用的方法制造由PBT类树脂(A)、弹性体(B)、聚碳酸酯类树脂(C)、增塑剂(D)、根据需要的填充剂或者补强材料(E)和/或成核剂(F)等构成的树脂组合物，所述常用的方法是例如(1)将各成分混合，用单轴或者双轴挤压机进行混合并挤压而调制成粒状，然后成形的方法，(2)先调制组成不同的颗粒(母料)，将该规定量颗粒混合(稀释)并用于成形，从而获得规定组成的成形品的方法，(3)直接向成形机中加入各成分中的1种或者2种以上的方法等。另外，颗粒也可以例如通过将除脆性成分(玻璃类补强材料等)之外的成分熔融混合后，再混合脆性成分(玻璃类补强材料)的方法调制。
成形体也可以通过将上述PBT类树脂组合物熔融混炼后，用挤压成形、注射模塑成形、模压成形、吹塑成形、真空成形、旋压成形、气体注射成形法等常用的方法成形，但是通常用注射模塑成形法进行成形。注射模塑成形的条件可以适当选择，例如，可以在约250-280℃下将PBT类树脂组合物熔融混炼，根据需要调制颗粒，利用注射模塑成形机，在气缸温度约250-280℃的条件下进行注射模塑成形。另外，模温度可以为60℃以下(例如，约40-60℃)，但是为了获得均匀的激光光线透过率的成形体，优选模温度为约65-90℃(例如，70-90℃)。
成形品的形状没有特别限制，但是由于通过激光熔敷将成形品与对应材(其它的树脂成形品)接合而使用，所以通常是至少具有接触面(平面等)的形状(例如板状)。另外，本发明的成形体由于相对于激光的透过性高，所以激光透过部位的成形品的厚度(激光透过方向的厚度)可以选择较宽的范围，也可以是例如约0.1-5mm，优选约0.1-4mm，更优选约0.1-3mm(例如0.5-3mm)。
作为激光光源，没有特别限制，例如，可以使用色素激光器、气体激光器(激元激光器、氩气激光器、氪激光器、氦氖激光器等)、固体激光器(YAG激光器等)、半导体激光器等。作为激光，通常使用脉冲激光。
上述成形品由于激光熔敷性优异，所以通常优选通过激光熔敷使其与对应材的树脂成形品进行熔敷，但是如果需要，也可以用其它的热熔敷法，例如振动熔敷法、超声波熔敷法、加热板熔敷法等使其与其它的树脂成形品熔敷。
本发明还公开了进行激光熔敷的复合成形品。该复合成形品是将由上述PBT类树脂组合物形成的成形品(第1成形品)和对应材的树脂成形品(第2成形品，被附体)通过激光熔敷进行接合一体化而成的。例如，可以通过使第1成形品和第2成形品接触(特别是至少使接合部分进行面接触)后，照射激光，使第1成形品和第2成形品的界面至少局部熔化而使接合面粘合，之后通过冷却将二种成形品进行接合、一体化，成为一个成形体。在这样的复合成形体中，如果使用本发明的成形体，则可通过熔敷获得高的接合强度，从而可以保持与用激光照射时不发生熔敷的非熔敷部件相同的高熔敷强度。因此，即使进行激光熔敷实际上也不会使接合强度下降，可以获得牢固接合的复合成形体。
作为构成上述对应材的树脂成形品的树脂，没有特别限制，可列举各种热塑性树脂，例如烯烃类树脂、乙烯基类树脂、苯乙烯类树脂、丙烯酸类树脂、聚酯类树脂、聚酰胺类树脂、聚碳酸酯类树脂等。在这些树脂之中，也可以由与构成上述PBT类树脂组合物的树脂相同种类或者相同类别的树脂(PBT类树脂、PET类树脂等聚酯类树脂(芳香族聚酯类树脂)，聚碳酸酯类树脂等)或者其组合物构成对应材。例如，也可以分别由本发明的PBT类树脂组合物形成第1成形体和第2成形体。
上述PBT类树脂组合物(或者第1成形体)只要不损害激光透过性(例如，相对于波长800-1200nm激光的透过性)，就可以包括着色剂(例如，特开2000-309694号公报和特开2001-71384号公报中记载的着色剂等)。作为着色剂，可列举相对于激光为非吸收性的着色剂(无机或者有机染颜料)，例如黄色染颜料(钙黄等无机颜料，联苯胺黄等有机颜料)、橙色染颜料(汉撒黄等)、红色颜料(红色颜料等无机颜料，色淀红等有机颜料)、蓝色颜料(钴蓝等无机颜料，铜酞花青蓝等有机颜料)、绿色颜料(铬绿等无机颜料，铜酞花青绿等有机颜料)、紫色染颜料等。这种着色剂可以单独使用，也可以多个着色剂组合使用而调整为所希望的色调。例如，可以利用减色混合(多种染颜料，例如黄色染颜料和紫色染颜料的组合，黄色染颜料和红色染颜料和蓝色染颜料的组合等)将树脂着色为没有色彩(灰色或黑色)。也可以通过使用这种着色剂不能目视识别第1成形体和第2成形体。第1成形体中着色剂的总使用量没有特别的限制，例如，可以相对于树脂100重量份为约0.01-10重量份(例如0.01-7重量份)，优选约0.01-5重量份。
被附体(或者对应材)也可以含有相对于激光的吸收剂或者着色剂。上述着色剂可以根据激光的波长进行选择，可列举无机颜料[碳黑(例如乙炔碳黑、灯黑、热裂法碳黑、炉黑、槽法碳黑、科琴黑等)等黑色颜料，红色氧化铁等红色颜料，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、紫色颜料等)等。这些吸收剂可以单独或者二种以上组合使用。作为吸收剂，通常可以使用黑色颜料或者染料，特别是碳黑。碳黑的平均粒径通常为约10-1000nm，优选约10-100nm。着色剂的比例相对于被附体整体为约0.1-10重量％，优选约0.5-5重量％(例如0.5-3重量％)。
激光照射通常从第1成形体向第2成形体的方向进行，通过在包括吸收剂或者着色剂的第2成形体的界面上放热，使第1成形体和第2成形体进行熔敷。即，可以通过使位于激光透过侧的第1成形体(由本发明的树脂组合物形成的成形品)和位于激光受光侧的第2成形体(对应材的树脂成形品)接触，通过照射激光使上述第1成形体和上述第2成形体进行接合，获得复合成形品。而且，也可以根据需要使用透镜系，在第1成形品和第2成形品的界面上使激光聚光，从而在接触界面进行熔敷。
本发明优选的方式如下：
(1)聚对苯二甲酸丁二酯类树脂(A)选自具有对苯二甲酸丁二酯单元的均聚酯和共聚酯的至少一种的上述激光熔敷性组合物。
聚对苯二甲酸丁二酯类树脂(A)选自聚对苯二甲酸丁二酯和共聚酯的至少一种，并且共聚酯的共聚性单体选自双酚类及其烯化氧加成物、非对称芳香族二羧酸、以及可以形成这些酯的衍生物的至少一种的上述树脂组合物。
聚对苯二甲酸丁二酯类树脂(A)选自聚对苯二甲酸丁二酯和共聚酯的至少一种，并且共聚酯的共聚性单体是选自邻苯二甲酸、间苯二甲酸、双酚A的烯化氧加成物、以及它们的反应性衍生物中至少一种的前述树脂组合物。
聚对苯二甲酸丁二酯类树脂(A)选自聚对苯二甲酸丁二酯和用1-20摩尔％共聚性单体改性的聚对苯二甲酸丁二酯类共聚物的至少一种的上述树脂组合物。
(2)弹性体(B)选自聚苯乙烯类弹性体和聚酯类弹性体的至少一种的上述树脂组合物。
(3)增塑剂(D)的折射率为1.45-1.60的上述树脂组合物。
(4)相对于聚对苯二甲酸丁二酯类树脂(A)100重量份，含有1-40重量份弹性体(B)、5-80重量份聚碳酸酯类树脂(C)、1-10重量份增塑剂(D)和0-100重量份填充剂或者补强剂(E)的上述树脂组合物。
(5)在由注射模塑成形形成的纵80mm×横80mm×厚2mm(边浇口铸口宽2mm)的成形品中，800-1200nm波长的光线透过率为20％以上，照射800-1200nm波长的光线时，由上述成形品部位的不同产生的光线透过率的变化幅度为7％以下的上述树脂组合物。
(6)由上述树脂组合物形成的注射模塑成形品(或者激光熔敷性注射模塑成形品)。
工业上的可利用性
得到的复合成形品由于具有高的熔敷强度，激光照射对PBT类树脂产生的损坏也少，所以可以适用于各种用途，例如电气·电子部件、办公自动化(OA)机器部件、家电机器部件、机械结构部件、汽车结构部件等。特别适合用于汽车电气安装部件(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
下面，根据实施例更加详细地说明本发明，但是本发明并不限于这些
实施例。
实施例1-10和比较例1-2
在实施例和比较例中，使用以下的PBT类树脂(A)、弹性体(B)、聚碳酸酯类树脂(C)、增塑剂(D)、填充剂或者补强剂(E)、成核剂(F)和着色剂。
PBT类树脂(A)
(A-1)间苯二甲酸二甲酯(DMI)改性PBT树脂
在对苯二甲酸和1，4-丁二醇的反应中，使用12.5摩尔％的DMI作为共聚成分来代替对苯二甲酸的一部分(12.5摩尔％)，从而调制改性聚对苯二甲酸丁二酯。
弹性体(B)
(B-1)含有环氧基的聚苯乙烯类热塑性弹性体ESBS[Daicel化学工业(株)制“EPOFRIEND AT504”]
(B-2)聚酯类热塑性弹性体[东洋纺(株)制“GP200”]
(B-3)聚苯乙烯类热塑性弹性体[Kuraray(株)制“Septon 4055”]
聚碳酸酯类树脂(C)
(C-1)聚碳酸酯树脂(帝人化成(株)制“PANLITE L-1225”)
增塑剂(D)
(D-1)芳香族多元羧酸酯[旭电化工业(株)制ADR CIZER-UL-100]
(D-2)丙烯酸类增塑剂[东亚合成(株)制ARUFON UP-1020]
(D-3)苯乙烯-丙烯酸类流动改性剂[东亚合成(株)制ARUFONXFM-910]
填充剂或者补强剂(E)
(E-1)玻璃纤维[日东洋纺织(株)制“CS3J-948S”，平均纤维直径φ11μm，平均纤维长400μm]
成核剂(F)
(F-1)氮化硼[川奇制铁(株)制FS-1]
(F-2)滑石[日本Talc(株)制Talc 3A]
着色剂
紫色染颜料[Clariant Japan制SANDOPLAST VIOLET RSB]
黄色染颜料[Clariant Japan制SANDOPLAST YELLOW 2G]
按照表1中所示的比例(重量比)，将各成分用两轴挤压机(日本制钢所制，30mmφ)在260℃进行混炼，从而制作颗粒。将得到的颗粒用注射模塑成形机((株)东芝制)，在气缸温度260℃和模温度80℃的条件下进行注射模塑成形，使试验片A(纵80mm×横80mm×厚2mm，边浇口，铸口宽2mm)成形。
另外，作为相对于上述试验片A的被熔敷体B，使用上述颗粒100重量份和黑色着色用炭黑(Win Tech Polymer(株)制，商品名“2020C”)5重量份进行注射模塑成形，制作壁厚2mm的箱形试验体B。该箱形试验体B是长80mm、宽40mm和高20mm的长方体状，上端面开口。另外，在下端面上，用激光熔敷进行密封，然后使用钻床形成用于施加内压的孔(φ10mm)。另外，试验体B作为基于激光的发热体发挥作用。
如图1中所示，在箱形试验体B(4)的开口端部分使试验片A(3)重叠而使其接触，使用激光熔敷机(Leister社制)，由激光振荡器的头部(1)开始调整激光(2)的焦点，在试验片A和箱形试验体B的接触面上按照线宽1.5mm使其聚光。然后，从试验片A(3)侧，在扫描速度10mm/秒的条件下照射波长940nm的激光进行熔敷，从而制作箱形试验体B的开口部分被试验片A(3)密封的盒状复合体。
(1)气密性(均匀熔敷性)
对于由激光熔敷获得的试验片A和试验体B的盒状复合体，在水中施加30秒内压0.02MPa，根据接合部分有无产生气泡来评价气密性。
(2)光线透过率
对于试验片A的各部位，使用分光光度计(日本分光(株)制“V570)”测量波长940nm下的光线透过率(％)，从而计算出光线透过率的最大值和最小值的差(变化幅度，％)。
实施例和比较例的结果示于表1中。
[表1]
表1
                                    实施例   比较例
  1   2   3   4   5   6   7   8   9   10   1   2
  (A)PBT类树脂(A-1)DMI改性PBT树脂   100   100   100   100   100   100   100   100   100   100   100   100
  (B)弹性体
  (B-1)ESBS   20   30   20   20
  (B-2)聚酯类   20   10   20   10   10   10   10
  (B-3)聚苯乙烯类   10
  (C)PC类树脂(C-1)L-1225   25   25   25   25   25   25   25   25   25   25   25   25
  (D)增塑剂
  (D-1)UL100   4   4   4   4   2   4   4   4
  (D-2)UP1020   4
  (D-3)XFM910   4
  增塑剂的折射率   1.48   1.48   1.48   1.48   1.46   1.58   1.48   1.48   1.48   1.48
  (E)填充剂或者补强剂(E-1)玻璃纤维   65   65   60   68   65   65   60   60   60   60   65   60
  着色剂
  紫色染颜料   0.05
  黄色染颜料   0.01
  (F)成核剂
  (F-1)氮化硼   0.02   0.02
  (F-2)滑石   0.2
  光线透过率的最大值(％)   31   32   34   27   32   31   27   21   21   20   42   45
  光线透过率的最小值(％)   25   28   30   24   28   27   24   20   20   19   28   30
  光线透过率(％)的变化幅度   6   4   4   3   4   4   3   1   1   1   14   15
  气密性   ○   ○   ○   ○   ○   ○   ○   ○   ○   ○   ×   ×
就实施例来说，试验片A对激光的光线透过率均匀，同时可以均匀熔敷，气密性高。与此相反，就比较例来说，光线透过率根据部位变化较大，气密性低。

Claims (13)

1.一种激光熔敷用树脂组合物，包含聚对苯二甲酸丁二酯类树脂(A)、弹性体(B)、聚碳酸酯类树脂(C)和增塑剂(D)。
2.如权利要求1所述的树脂组合物，其中，聚对苯二甲酸丁二酯类树脂(A)是聚对苯二甲酸丁二酯、或者用30摩尔％以下的共聚性单体改性的聚对苯二甲酸丁二酯类共聚物。
3.如权利要求1所述的树脂组合物，其中，弹性体(B)的折射率在温度25℃为1.52-1.59。
4.如权利要求1所述的树脂组合物，其中，增塑剂(D)是选自芳香族多元羧酸酯和丙烯酸类聚合物中的至少一种。
5.如权利要求1所述的树脂组合物，其中，增塑剂(D)的折射率在温度25℃为1.45-1.60。
6.如权利要求1所述的树脂组合物，其中，相对于聚对苯二甲酸丁二酯类树脂(A)100重量份，含有弹性体(B)1-50重量份、聚碳酸酯类树脂(C)5-100重量份和增塑剂(D)1-10重量份。
7.如权利要求1所述的树脂组合物，其中，还含有填充剂或者补强剂(E)。
8.如权利要求7所述的树脂组合物，其中，填充剂或者补强剂(E)是玻璃质。
9.如权利要求1所述的树脂组合物，其中，还含有成核剂(F)。
10.如权利要求1所述的树脂组合物，其中，在由注射模塑成形形成的纵80mm×横80mm×厚2mm的成形品中，照射800-1200nm波长的光线时，基于上述成形品部位的不同而产生的光线透过率的变化幅度为10％以下。
11.一种成形品，由权利要求1所述的树脂组合物形成。
12.一种复合成形品，由权利要求1所述的树脂组合物形成的成形品和对应材的树脂成形品通过激光熔敷进行接合而形成。
13.一种复合成形品的制造方法，使由权利要求1所述的树脂组合物形成并且位于激光透过侧的成形品与位于激光受光侧的对应材的树脂成形品接触，通过照射激光使上述成形品与上述树脂成形品接合。
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