CN111971165B - 覆层用组合物及金属/树脂接合部件的制造方法 - Google Patents

覆层用组合物及金属/树脂接合部件的制造方法 Download PDF

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CN111971165B
CN111971165B CN201980024859.7A CN201980024859A CN111971165B CN 111971165 B CN111971165 B CN 111971165B CN 201980024859 A CN201980024859 A CN 201980024859A CN 111971165 B CN111971165 B CN 111971165B
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metal
base material
composition
metal base
resin member
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CN111971165A (zh
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细谷守
岩井武
藤本隆史
前田知宏
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Huichuang Co ltd
Tokyo Ohka Kogyo Co Ltd
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Huichuang Co ltd
Tokyo Ohka Kogyo Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/34Laser welding for purposes other than joining
    • B23K26/342Build-up welding
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29C66/73General 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
    • B29C66/739General 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
    • B29C66/7392General 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
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Abstract

本发明提供一种在接合金属基材与树脂部件时,使用含有金属粉末、粘合剂与有机溶剂的覆层用组合物。并且使用具有以下工序的金属/树脂接合部件的制造方法:在金属基材的至少一部分涂布该覆层用组合物的工序;对金属基材中的该覆层用组合物的涂布部照射激光的工序;在金属基材中的激光照射部上配置树脂部件的工序;加热激光照射部与树脂部件的界面从而将金属基材与树脂部件接合的工序。

Description

覆层用组合物及金属/树脂接合部件的制造方法
技术领域
本发明涉及覆层用组合物及金属/树脂接合部件的制造方法。本申请基于2018年4月13日在日本申请的日本特愿2018-077976号主张优先权,将其内容援引于此。
背景技术
近年来,从环境负荷的方面来看,在汽车中自然要求削减二氧化碳(CO2)排放量。
对此,生产了抑制作为燃料的汽油的消耗的混合动力车或电动汽车。此外,为了实现燃料消耗率的改善,车身的轻量化备受瞩目,正在推进对车身应用更轻量且坚固的新材料的研究。
作为所述新材料,可以例举将不同种类的材料彼此接合而得的材料。
在将不同种类的材料彼此接合时,通常使用粘接剂。但是,粘接剂的使用对环境的负荷较大,粘接剂本身会发生历时劣化,且在接合强度方面也成为问题。
作为解决上述问题的技术,提出有以不使用粘接剂的方式将不同种类的材料彼此接合的方法。
例如,在专利文献1中,公开有以下接合方法:使金属粉末附着于金属基材的一个面,照射激光从而形成与该金属基材合金化而得的重叠微细粒子结构,将树脂部件按压于该重叠微细粒子结构,对其界面照射激光来加热,由此将金属基材与树脂部件接合。
现有技术文献
专利文献
专利文献1:日本专利第5953559号公报
发明内容
发明要解决的技术问题
但是,在专利文献1记载的接合方法中,由于在金属基材上涂布粉末状的金属,因此在金属基材配置在倾斜面的情况下,难以稳定地接合金属基材与树脂部件。此外,在进行接合的地点为进行振动等不适合粉末的使用的环境下,以往还存在金属基材与树脂部件的接合较为困难的问题。
本发明是鉴于上述情况而完成的,其目的在于提供一种不使用粘接剂而进一步提高了金属基材与树脂部件的接合强度的金属/树脂接合部件的制造方法,以及能够稳定地接合金属基材与树脂部件的覆层用组合物。
用于解决上述技术问题的方案
为了解决上述技术问题,本发明采用了以下的构成。
即,本发明的第1方案是一种覆层用组合物,其特征在于,含有金属粉末、粘合剂与有机溶剂。
本发明的第2方案是一种金属/树脂接合部件的制造方法,该金属/树脂接合部件由金属基材与树脂部件接合而得,该金属/树脂接合部件的制造方法的特征在于,具有:在所述金属基材的至少一部分涂布本发明的第1方案的覆层用组合物的工序;对所述金属基材中所述覆层用组合物的涂布部照射激光的工序;在所述金属基材中的激光照射部上配置所述树脂部件的工序;加热所述激光照射部与所述树脂部件的界面从而将所述金属基材与所述树脂部件接合的工序。
发明效果
根据本发明的金属/树脂接合部件的制造方法,能够不使用粘接剂地制造金属基材与树脂部件的接合强度更加提高的金属/树脂接合部件。
此外,根据本发明的覆层用组合物,能够稳定地接合金属基材与树脂部件。
附图说明
图1是示出使用实施例4的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
图2是示出使用比较例4的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
图3是示出使用比较例9的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
图4是示出使用比较例11的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
具体实施方式
(覆层用组合物)
本实施方式的覆层用组合物含有金属粉末、粘合剂与有机溶剂。
本发明中的“覆层用组合物”是指在作为母材的金属基材面进行熔融凝固而形成焊缝(合金的突起物)的材料。
<金属粉末>
作为构成本实施方式中的金属粉末的金属,例如可以例举铝、镍、铬、铁、铜、钛、硅、钴基合金(Stellite)、钒或将它们中的多种合金化而得的物质等。
金属粉末可以单独使用1种,也可以将2种以上组合使用。通过将2种以上的金属组合,容易在焊缝表面形成多孔质结构,例如容易提高金属基材与树脂部件的接合强度。
金属粉末优选包含钛,例如可以优选地例举包含钛与铝的金属粉末。
金属粉末的平均粒径例如为10μm以上100μm以下左右。
本发明中的“粉末的平均粒径”是指通过公知的粒度分布测量装置所测量的粉末的体积平均粒径的值。
金属粉末的含量相对于覆层用组合物的总量(100质量%)优选为25~70质量%,更优选为30~65质量%,进一步优选为40~60质量%,特别优选为50~60质量%。
若金属粉末的含量在所述优选范围的下限值以上,则例如容易进一步提高金属基材与树脂部件的接合强度,另一方面,若为所述优选范围的上限值以下,则作为组合物而言容易处理。
<粘合剂>
本实施方式中的粘合剂在覆层用组合物中作为金属粉末的分散剂发挥作用,此外,也作为粘度调整剂发挥作用。
所述粘合剂能够使用有机化合物,也能够使用无机化合物。
作为所述粘合剂中的有机化合物,例如可以例举纤维素化合物、聚丙烯酸及其它丙烯酸化合物、聚乙烯醇缩醛、聚乙烯醇、环氧化合物等。
作为纤维素化合物,具体可以例举羟丙基纤维素、羟乙基纤维素。
作为所述粘合剂中的无机化合物,例如可以例举粘土矿物。作为粘土矿物,具体可以例举膨润土、蒙皂石(smectite)、蒙脱石(montmorillonite)。
粘合剂可以单独使用1种,也可以将2种以上组合使用。
粘合剂优选有机化合物,其中,从容易调整组合物的粘度来看,更优选包含纤维素化合物。作为纤维素化合物,优选羟丙基纤维素。
在羟丙基纤维素中,例如从容易提高金属基材与树脂部件的接合强度来看,优选质均分子量(Mw)为100000~800000的羟丙基纤维素,更优选Mw为110000~700000的羟丙基纤维素,进一步优选Mw为120000~650000的羟丙基纤维素。
此外,从与金属的粘接性较强且与金属粉的分散性良好来看,粘合剂优选为包含聚乙烯醇缩醛的粘合剂,其中特别优选为包含聚乙烯醇缩丁醛的粘合剂。在聚乙烯醇缩丁醛中,例如,从容易提高金属基材与树脂部件的接合强度来看,优选Mw为10000~80000的聚乙烯醇缩丁醛,更优选Mw为30000~80000的聚乙烯醇缩丁醛,进一步优选Mw为50000~70000的聚乙烯醇缩丁醛。
粘合剂的含量优选为相对于覆层用组合物的总量(100质量%)为0.000001~10质量%,更优选为0.00001~5质量%。
在使用羟丙基纤维素作为粘合剂的情况下,羟丙基纤维素的含量优选为相对于覆层用组合物的总量(100质量%)为0.00001~5质量%,进一步优选为0.0001~2质量%,特别优选为0.001~2质量%。
在使用聚乙烯醇缩丁醛作为粘合剂的情况下,聚乙烯醇缩丁醛的含量相对于覆层用组合物的总量(100质量%)优选为0.1~10质量%,进一步优选为0.2~7质量%,特别优选为0.5~5质量%。
若粘合剂的含量为所述优选范围的下限值以上,则例如容易进一步提高金属基材与树脂部件的接合强度,且该组合物对金属基材的涂布性进一步提高。另一方面,若为所述优选范围的上限值以下,则作为组合物而言容易处理。
<有机溶剂>
本实施方式中的有机溶剂例如可以例举成为上述的金属粉末及粘合剂的分散剂的有机溶剂。
作为上述有机溶剂,具体可以例举:甲醇、乙醇、正丙醇、异丙醇、正戊醇、仲戊醇、叔戊醇、异戊醇、2-甲基-1-丙醇、2-乙基丁醇、新戊醇、正丁醇、仲丁醇、叔丁醇、正己醇、2-庚醇、3-庚醇、2-甲基-1-丁醇、2-甲基-2-丁醇、4-甲基-2-戊醇、1-丁氧基-2-丙醇、丙二醇单丙基醚、5-甲基-1-己醇、6-甲基-2-庚醇、1-辛醇、2-辛醇、3-辛醇、4-辛醇、2-乙基-1-己醇、2-(2-丁氧基乙氧基)乙醇等链状结构的醇;环戊烷甲醇、1-环戊基乙醇、环己醇、环己烷甲醇、环己烷乙醇、1,2,3,6-四氢苄醇、外-降冰片醇、2-甲基环己醇、环庚醇、3,5-二甲基环己醇、苄醇、萜品醇等具有环状结构的醇;γ-丁内酯等内酯类;丙酮、甲基乙基酮、环己酮、甲基正戊基酮、甲基异戊基酮、2-庚酮等酮类;乙二醇、二乙二醇、丙二醇、二丙二醇、甘油等多元醇;乙二醇单乙酸酯、二乙二醇单乙酸酯、丙二醇单乙酸酯、或二丙二醇单乙酸酯等具有酯键的化合物、所述多元醇类或所述具有酯键的化合物的单甲醚、单乙醚、单丙醚、单丁醚等单烷基醚或单苯基醚等具有醚键的化合物等多元醇类的衍生物[这些之中,优选为丙二醇单甲醚乙酸酯(PGMEA)、丙二醇单甲醚(PGME)];二氧六环这样的环式醚类、乳酸甲酯、乳酸乙酯(EL)、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等酯类;苯甲醚、乙基苄基醚、甲基甲苯基醚、二苯醚、二苄醚、苯乙醚、丁基苯基醚、乙苯、二乙苯、戊苯、异丙苯、甲苯、二甲苯、异丙基甲苯、均三甲苯等芳香族类有机溶剂;二甲亚砜(DMSO)等。
有机溶剂可以单独使用1种,也可以将2种以上组合使用。
有机溶剂优选包含醇。作为醇,优选为所述链状结构的醇、多元醇,具体可以例举乙醇、甘油。
此外,有机溶剂优选包含多元醇类的衍生物。作为多元醇类的衍生物,具体可以例举PGMEA、PGME。
有机溶剂的含量相对于覆层用组合物的总量(100质量%)优选为25~70质量%,更优选为30~60质量%,进一步优选为35~50质量%。
<其它成分>
本实施方式的覆层用组合物还可以进一步含有上述的金属粉末、粘合剂及有机溶剂以外的其它成分。
作为其它成分,例如可以例举碳粉末、表面活性剂等。
本实施方式的覆层用组合物优选进一步含有碳粉末。通过同时具有碳粉末,容易在作为母材的金属基材面进行熔融凝固而形成焊缝。
碳粉末的平均粒径例如为10nm以上100μm以下左右。
碳粉末的含量相对于覆层用组合物的总量(100质量%)优选为0.1~15质量%,更优选为0.5~10质量%,进一步优选为1~8质量%。
若碳粉末的含量为所述优选范围的下限值以上,则例如容易进一步提高金属基材与树脂部件的接合强度,另一方面,若为所述优选范围的上限值以下,则组合物的流动性变得更加良好。
在本实施方式的覆层用组合物中,所述碳粉末与所述金属粉末的混合比率(质量比)优选为金属粉末/碳粉末=3~30,更优选为4~20,进一步优选为5~15。
若两者的混合比率(质量比)为所述优选范围的下限值以上,则例如容易进一步提高金属基材与树脂部件的接合强度,另一方面,若为所述优选范围的上限值以下,则组合物的流动性变得更加良好。
覆层用组合物的制造方法:
本实施方式的覆层用组合物例如能够通过具有以下工序的制造方法制造:制备粘合剂与有机溶剂的混合液的工序、以及将所述混合液与金属粉末混合的工序。
在粘合剂与有机溶剂的混合液中,粘合剂浓度相对于该混合液(100质量%)优选为0.00001~10质量%,更优选为0.0001~5质量%,进一步优选为0.001~1质量%。
若粘合剂浓度为所述优选范围的下限值以上,则该组合物对金属基材的涂布性进一步提高,另一方面,若为所述优选范围的上限值以下,则容易将组合物调整为适当的粘度。
所述混合液与所述金属粉末的混合比率(质量比)例如为混合液/金属粉末=3/7~5/5左右。
在将所述混合液与金属粉末混合时,也可以掺混预先混合了金属粉末与碳粉末的混合粉末。
在上述实施方式的覆层用组合物中,优选使所述金属粉末分散在所述粘合剂与所述有机溶剂的混合液中。
实施方式的覆层用组合物的形态例如可以例举糊料、浆料、悬浮液等形态,优选为糊料。
这里所说的“糊料”是指具有流动性且具有高粘性的状态,粘度在1000cps(1Pa·s)以上20万cps(200Pa·s)以下的范围内的物质。糊料的粘度表示使用E型粘度计在25℃下测量的值。
(金属/树脂接合部件的制造方法)
第1实施方式的制造方法是制造金属基材与树脂部件接合而得的金属/树脂接合部件的方法,具有:在所述金属基材的至少一部分涂布上述的覆层用组合物的工序(以下称为“工序(i)”);对所述金属基材中的所述覆层用组合物的涂布部照射激光的工序(以下称为“工序(ii)”);在所述金属基材中的激光照射部上配置所述树脂部件的工序(以下称为“工序(iii)”);加热所述激光照射部与所述树脂部件的界面,从而将所述金属基材与所述树脂部件接合的工序(以下称为“工序(iv)”)。
在本实施方式中,作为母材的金属基材例如可以例举铝合金、铝压铸、不锈钢、SPCC(冷轧钢板)等。
在本实施方式中,作为树脂部件,例如可以例举聚酰胺(尼龙6、尼龙6,6等)、聚碳酸酯、聚丙烯、聚苯硫醚等。
[工序(i)]
在工序(i)中,在金属基材的至少一部分涂布上述的覆层用组合物。
覆层用组合物的涂布方法没有特别限定,例如可以例举利用丝网涂布、点胶机、喷涂等的方法。
涂布在金属基材的覆层用组合物的涂布膜的厚度根据该组合物的掺混成分等适当设定即可,例如为50~200μm左右。
[工序(ii)]
在工序(ii)中,对金属基材中的所述覆层用组合物的涂布部照射激光。
作为照射所述涂布部的激光,只要是能够加热金属粉末的激光即可,例如可以例举半导体激光、纤维激光、Nd:YAG激光、二氧化碳气体激光等。
对所述涂布部照射激光,使金属粉末熔融。该熔融状态的金属与金属基材合金化,在金属基材面形成焊缝(合金的突起物,所谓的堆焊部位)。此外,通过激光照射进行加热将粘合剂等烧失。
从金属基材与树脂部件的接合强度的方面来看,该焊缝的大小(相对于金属基材面的高度)优选为1μm以上200μm以下。此外,该焊缝具有重叠微细粒子结构。
在本发明中,“重叠微细粒子结构”是指对于微细凹凸形状面进一步重叠地重合有微细凹凸形状的结构的微细结构。通过在金属基材面形成具有重叠微细粒子结构的焊缝,从而发挥锚固效果。
另外,在该重叠微细粒子结构中形成由共晶、固溶体或金属互化物中的任一种构成的合金层的情况也包括在内。
[工序(iii)]
在工序(iii)中,在所述金属基材中的激光照射部上配置所述树脂部件。
作为在激光照射部上配置树脂部件的方法,例如可以例举将作为树脂部件的材料的树脂组合物涂布在激光照射部上而成膜的方法、或将该树脂组合物的成形体配置在激光照射部上的方法。
此外,在激光照射部上配置树脂部件时,优选将所述树脂部件与所述金属基材抵接,并且进行按压。
将所述树脂部件按压于所述金属基材时的按压程度通常在0.1~3MPa的压力范围内选择最佳的条件即可。由此,能够充分提高两者的接合强度。
[工序(iv)]
在工序(iv)中,加热所述激光照射部与所述树脂部件的界面,通过将所述金属基材与所述树脂部件接合从而得到金属/树脂接合部件。
加热界面的方法没有特别限定,例如可以例举利用加热器进行加热、利用激光照射进行加热。
形成于金属基材面的具有重叠微细粒子结构的焊缝对于所述激光的波长不具有透过性。因此,在利用激光照射进行加热的情况下,照射到焊缝面的该激光被转化为热。转化而得的热传递至被抵接并按压的树脂部件面,使树脂部件熔融。熔融的树脂部件渗透至所述重叠微细粒子结构的内部,其结果为,金属基材与树脂部件牢固地接合。
此外,在利用激光照射进行加热的情况下,通常是从树脂部件侧照射激光的方法。但是,在激光不透过树脂部件且另一方的金属基材吸收该激光的情况下,与通常情况相反,从金属基材侧照射激光,由此能够利用金属的传热加热金属基材与树脂部件的界面。
在上述第1实施方式的制造方法中,使用在含有金属粉末的同时还含有粘合剂的覆层用组合物在金属基材面形成具有重叠微细粒子结构的焊缝。因此,根据第1实施方式的制造方法,能够不使用粘接剂地制造金属基材与树脂部件的接合强度更加提高的金属/树脂接合部件。
关于通过第1实施方式的制造方法制造的金属/树脂接合部件的接合强度例如为35~50MPa。
此外,由于采用的覆层用组合物通过在含有金属粉末的同时还含有粘合剂及有机溶剂而体现出适度的粘性,因此即使在金属基材配置于倾斜面的情况下也能够将该组合物可靠地涂布在预定接合部位。
此外,与金属粉末相比,采用的覆层用组合物能够以更少的使用量、且以更均匀的状态将金属涂布在预定接合部位。因此,尤其提高了激光照射时的覆层用组合物的利用效率。
此外,与金属粉末相比,采用的覆层用组合物即使在金属基材为宽幅尺寸时也能够均匀地进行涂布。因此,该组合物对于宽幅尺寸的部件彼此的接合是有用的。
在采用的覆层用组合物中,由于在含有金属粉末的同时还含有粘合剂,因此具有适度的疏密分布,容易形成凹凸较大的焊缝。因此,能够更加提高接合强度,并且能够稳定地将金属基材与树脂部件接合。
<其它实施方式>
本发明的覆层用组合物及金属/树脂接合部件的制造方法并不限定于上述实施方式,例如,在第1实施方式的制造方法中,优选使用1种以上的与构成所述金属基材的金属相同的金属与除此以外的金属的混合金属粉末作为用于覆层用组合物的金属粉末。通过应用含有上述混合金属粉末的覆层用组合物,可提高金属粉末与金属基材的相溶性。因此,变得容易在金属基材面形成具有适度的疏密分布的焊缝。由此,能够更牢固且稳定地将金属基材与树脂部件接合。
根据上述实施方式的制造方法,能够不使用粘接剂地将金属基材与树脂部件更牢固地接合。因此,应用了本发明的制造方法作为用于制造实现车身轻量化的新材料的方法是有用的。
实施例
以下,通过实施例对本发明进行进一步详细的说明,但本发明不受这些例子限定。
<覆层用组合物的制备>
(实施例1~24、比较例1~11)
将表1~表6所示的各成分混合,制备各例的覆层用组合物。各例的覆层用组合物的形态也一并记载。
【表1】
Figure BDA0002716181060000101
【表2】
Figure BDA0002716181060000102
【表3】
Figure BDA0002716181060000111
【表4】
Figure BDA0002716181060000112
【表5】
Figure BDA0002716181060000113
【表6】
Figure BDA0002716181060000121
表1~表6中,各缩写分别具有以下的意思。[]内的数值为组合物中的含量(相对于组合物的总量(100质量%)的比例(质量%))。
(M)-1:铝粉末,体积平均粒径40μm
(M)-2:钛粉末,体积平均粒径45μm
(B)-1:羟丙基纤维素(HPC-M)Mw620000
(B)-2:羟丙基纤维素(HPC-L)Mw140000
(B)-3:聚丙烯酸
(B)-4:聚乙烯醇缩丁醛,Mw38000
(B)-5:膨润土
(B)-6:聚乙烯醇缩丁醛,Mw60000
(B)-7:聚乙烯醇缩丁醛,Mw14000
(S)-1:甘油
(S)-2:乙醇
(S)-3:丙二醇单甲醚
(C)-1:碳粉末,体积平均粒径40nm
<评价>
使用以下所示的金属基材及树脂部件,进行金属/树脂接合部件的制造。
金属基材:长度5cm×宽度2cm×厚度1mm的A5052铝板
树脂部件:长度5cm×宽度2cm×厚度1mm的尼龙66构成的片材
[对金属基材面形成焊缝(合金的突起物)的试验]
工序(i):
分别将上述实施例4、比较例4、比较例9、比较例11的覆层用组合物以厚度100μm且宽度方向1.2mm×长度方向1.5cm的图案状涂布至作为金属基材的所述铝板。
工序(ii):
接着,对所述铝板中的覆层用组合物的涂布部照射激光,在所述铝板表面形成焊缝(合金的突起物)。
在本实施例中,使用了使用光学系统整形为直径1.2mm的点光束且波长970nm的半导体激光。点光束的扫描速度为20mm/s。使点光束以宽度16mm进行扫描并照射20mm2以上的区域。
将分别使用实施例4、比较例4、比较例9、比较例11的覆层用组合物而形成的焊缝的状态示出在图1~图4。
图1是示出使用实施例4的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
图2是示出使用比较例4的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
图3是示出使用比较例9的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
图4是示出使用比较例11的覆层用组合物形成的焊缝的状态的光学显微镜图像(5倍)。
在图1中,在使用实施例4的覆层用组合物的情况下,能够确认金属粉末与碳粉末的混合粉末的熔融凝固物密集并形成突起物10。此外,在突起物10之间存在空隙12,空隙12与突起物10所形成的显著的凹凸在金属基材面的整体上均匀地存在。
在图2中,使用比较例4的覆层用组合物的情况下,几乎确认不到金属粉末与碳粉末的混合粉末的熔融凝固物密集而成的突起物,也未确认到突起物与空隙所形成的凹凸。
在图3中,使用比较例9的覆层用组合物的情况下,仅略微确认到金属粉末与碳粉末的混合粉末的熔融凝固物密集而成的突起物30,也几乎确认不到突起物30与空隙32所形成的凹凸。
在图4中,与使用了实施例4的覆层用组合物的情况相比,在使用比较例11的覆层用组合物的情况下,金属粉末与碳粉末的混合粉末的熔融凝固物形成更密集的较大的突起物40。该突起物40在金属基材表面不均匀地存在。
[接合强度的评价]
工序(i):
分别将上述实施例6~17、实施例19~24及比较例11的各覆层用组合物以厚度100μm且宽度方向2mm×长度方向1.5cm的图案状涂布至作为金属基材的所述铝板。
工序(ii):
接着,对所述铝板中的覆层用组合物的涂布部照射激光,在所述铝板面形成焊缝(合金的突起物)。
此处的激光照射使用了使用光学系统整形为直径2mm的点光束且波长970nm的半导体激光。使点光束的扫描速度为30mm/s。使点光束以宽度20mm进行扫描并照射40mm2以上的区域。
工序(iii):
接着,将由作为树脂部件的尼龙6,6构成的片材配置并按压于形成在所述铝板面的焊缝上。按压是如下所述地进行的:利用金属制的背衬板从金属基材侧进行背衬,由玻璃板(TEMPAX玻璃,厚度5mm)夹住树脂部件,用油压泵施加在油压泵上显示为1.4MPa的压力。
工序(iv):
接着,从所述树脂部件侧对形成在所述铝板面的焊缝与由所述尼龙6,6构成的片材的界面照射整形为点状的半导体激光的激光光点从而进行加热,得到铝板与由尼龙6,6构成的片材的接合部件。
这里的激光光点的照射条件是使平均输出为150W,重复频率为1000Hz,占空比(Duty)为50%,扫描速度为10mm/s。
对于得到的铝板与由尼龙6,6构成的片材的接合部件,通过进行拉伸剪切强度试验来测量接合强度。将其结果示出在表7~表8。
【表7】
Figure BDA0002716181060000151
【表8】
Figure BDA0002716181060000152
根据表7~表8的结果能够确认,通过应用本发明,能够不使用粘接剂地制造金属基材与树脂部件的接合强度更加提高的金属/树脂接合部件。
实施例6与实施例19的有机溶剂不同。确认到与使用了实施例6的覆层用组合物的情况相比,使用了实施例19的覆层用组合物的情况下的接合强度稍高。
实施例17、实施例20与实施例21中,作为粘合剂使用的聚乙烯醇缩丁醛的Mw不同。确认到存在聚乙烯醇缩丁醛的Mw越大接合强度越高的倾向。
此外,根据本发明的覆层用组合物,能够更加提高接合强度,并且能够稳定地将金属基材和树脂部件接合。
附图标记说明
10 突起物
12 空隙
30 突起物
32 空隙
40 突起物。

Claims (9)

1.一种用于将金属基材与树脂部件接合的覆层用组合物,其特征在于,含有包含两种以上金属的金属粉末、粘合剂、有机溶剂与碳粉末,
所述金属粉末的含量相对于所述覆层用组合物的总量为50~70质量%。
2.如权利要求1所述的用于将金属基材与树脂部件接合的覆层用组合物,其特征在于,所述金属粉末分散在所述粘合剂与所述有机溶剂的混合液中。
3.如权利要求1所述的用于将金属基材与树脂部件接合的覆层用组合物,其特征在于,所述粘合剂的含量相对于所述覆层用组合物的总量为0.000001~10质量%。
4.如权利要求1所述的用于将金属基材与树脂部件接合的覆层用组合物,其特征在于,所述粘合剂包含纤维素化合物。
5.如权利要求1所述的用于将金属基材与树脂部件接合的覆层用组合物,其特征在于,所述有机溶剂包含醇。
6.如权利要求1所述的用于将金属基材与树脂部件接合的覆层用组合物,其特征在于,所述金属粉末包含钛。
7.一种金属/树脂接合部件的制造方法,该金属/树脂接合部件是金属基材与树脂部件接合而得的,该金属/树脂接合部件的制造方法的特征在于,具有:
工序(i),将权利要求1~6的任一项所述的覆层用组合物涂布至所述金属基材的至少一部分;
工序(ii),对所述金属基材中的所述覆层用组合物的涂布部照射激光;
工序(iii),在所述金属基材中的激光照射部上配置所述树脂部件;
工序(iv),加热所述激光照射部与所述树脂部件的界面,将所述金属基材与所述树脂部件接合。
8.如权利要求7所述的金属/树脂接合部件的制造方法,其特征在于,在所述工序(iv)中,通过照射激光对所述激光照射部与所述树脂部件的界面进行加热从而将所述金属基材与所述树脂部件接合。
9.如权利要求7或8所述的金属/树脂接合部件的制造方法,其特征在于,使用1种以上的与构成所述金属基材的金属相同的金属与除此以外的金属的混合金属粉末作为所述金属粉末。
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