CN108136684A - 粘接两种不同塑料的方法 - Google Patents

粘接两种不同塑料的方法 Download PDF

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Publication number
CN108136684A
CN108136684A CN201680060617.XA CN201680060617A CN108136684A CN 108136684 A CN108136684 A CN 108136684A CN 201680060617 A CN201680060617 A CN 201680060617A CN 108136684 A CN108136684 A CN 108136684A
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China
Prior art keywords
priming paint
polymer
weight
plastic material
joined
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Pending
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CN201680060617.XA
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English (en)
Inventor
M·哈姆
P·沃尔特
D·卡斯珀
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of CN108136684A publication Critical patent/CN108136684A/zh
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4895Solvent bonding, i.e. the surfaces of the parts to be joined being treated with solvents, swelling or softening agents, without adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/02Preparation of the material, in the area to be joined, prior to joining or welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/02Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/026Chemical pre-treatments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/71General 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/71General 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
    • B29C66/712General 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 the composition of one of the parts to be joined being different from the composition of the other part
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
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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
    • B29C66/731General 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 intensive physical properties of the material of the parts to be joined
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
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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
    • B29C65/06Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C65/06Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding
    • B29C65/0609Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding characterised by the movement of the parts to be joined
    • B29C65/0618Linear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C65/06Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding
    • B29C65/0609Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding characterised by the movement of the parts to be joined
    • B29C65/0627Angular, i.e. torsional
    • BPERFORMING OPERATIONS; TRANSPORTING
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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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    • B29C65/0609Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding characterised by the movement of the parts to be joined
    • B29C65/0636Orbital
    • BPERFORMING OPERATIONS; TRANSPORTING
    • 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
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    • B29C65/1664Laser beams characterised by the way of heating the interface making use of several radiators
    • B29C65/1667Laser beams characterised by the way of heating the interface making use of several radiators at the same time, i.e. simultaneous laser welding
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    • B29C65/5057Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like positioned between the surfaces to be joined
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Abstract

本发明涉及使用底漆粘接两种不同塑料的方法。待彼此接合的所述两种塑料的汉森参数之间的加权二次方距离(Ra)2大于22MPa,并且所述底漆包含与待接合的两种塑料的汉森参数的加权二次方距离(Ra)2均小于22MPa的聚合物。本发明还涉及相应粘接的产品。

Description

粘接两种不同塑料的方法
技术领域
本发明涉及一种使用底漆来焊接两种不同塑料材料的方法,其中待接合的两种塑料材料彼此之间的汉森参数的加权二次方距离(weighted quadratic distance)(Ra)2大于22MPa,并且该底漆包含与待接合的两个塑料材料的汉森参数的加权二次方距离(Ra)2小于22MPa的聚合物。本发明还涉及相应的焊接产品。
背景技术
现有技术已知用于将两个以上由塑料材料(例如聚乙烯(PE)、聚丙烯酸酯或聚酰胺(PA))构成的基材相互连接的各种方法。在这种情况下,存在两种机械连接选择,例如锁合或螺合,或粘合剂粘接法。或者,塑料材料也可以焊接在一起。焊接是一种用于不可拆卸地、整体地、物理地连接通常为相同类型的塑料材料(例如PE和PE,或PA和PA)的接合方法。相同类型的热塑性塑料是在其分子结构、其熔点、其熔融粘度和其热膨胀系数方面没有实质性差异的聚合物,并且原则上可以在一定程度上相互混合。相同类型的塑料材料通常是具有相同聚合物基体和/或相同塑料材料的塑料材料。
已知多种用于将两种以上相同类型的塑料材料焊接在一起的方法。在这种情况下,可以使用多种焊接方法,例如红外焊接、红外/摩擦焊接或超声波焊接。这些用于焊接相同类型的塑料材料的方法基于在焊接区域中熔化的相关塑料材料以及在所述区域中以整体粘接和摩擦方式相互连接的材料。
在使相同类型的塑料材料相互连接的情况下,这些焊接方法可以很好地工作。但是,当将不同类型和/或不相容的两种塑料材料(例如聚酰胺和聚苯乙烯塑料材料)焊接在一起时,不可能在两个基材之间产生具有足够高机械强度的永久连接。如果尝试使用现有技术中已知的焊接方法直接焊接彼此不能混合的两种完全不同的塑料材料,则不能获得强度或者仅获得非常低的强度。
迄今为止,仅通过机械连接或粘合剂粘接法可以将相应的不同塑料材料相互连接。机械连接的缺点是复杂的连接、点状材料应力以及需要使用额外的机械连接装置。此外,在机械连接的情况下,很难实现整体结合的连接。然而,粘合剂粘接法的缺点在于连接的最终强度只能在可能长达几周的长时间后才能达到。此外,粘合剂粘接低能量表面通常需要对接合对象(partner)进行费力的预处理。另外,因为外部天气条件,粘合剂连接通常不是无限期地稳定的。而且,提供清洁的粘合剂连接往往复杂且耗时。因此,通过焊接方法进行的连接对塑料材料而言是最清洁、最快速和最简单的技术方案。
发明内容
因此,本发明的一个目的是提供一种用于焊接两种不同塑料材料的简单方法。在这种情况下,所述不同塑料材料之间借助于焊缝的连接意欲尽可能地稳定并且持久。
令人惊讶地发现,这个目的通过使用底漆来焊接两种不同塑料材料的方法实现,待接合的两种塑料材料彼此之间的汉森参数的加权二次方距离(Ra)2大于22MPa,并且底漆包含与待接合的两种塑料材料的汉森参数的加权二次方距离(Ra)2小于22MPa的聚合物。
令人惊讶地发现,通过基于汉森参数的加权二次方距离(Ra)2来选择塑料材料和底漆,可以对底漆进行选择,从而使得两种不同的塑料材料可以焊接在一起。使用相应的底漆可以在焊接两种不同的塑料材料时于塑料材料之间实现特别稳定和不老化的连接。
具体实施方式
汉森参数的加权二次方距离(Ra)2根据以下公式确定:
(Ra)2=4(ΔδD)2+(ΔδP)2+(ΔδH)2
在该公式中,δD是分散力的汉森参数,δP是极性的汉森参数,并且δH是氢桥键的汉森参数。ΔδD、ΔδP和ΔδH各自表示待比较的塑料材料或聚合物的这些汉森参数的差,例如,聚合物1和2的ΔδD=(δD1D2)。相关塑料材料或聚合物的各个汉森参数δD、δP和δH的值根据Charles M.Hansen的书籍“Hansen Solubility Parameters:A User's Handbook”(第二版;Taylor&Francis Group;2007;ISBN-10 0-8493-7248-8)确定。在该来源中已经可以找到各聚合物的许多值。根据本书描述的方法,汉森参数可以优选地使用程序HSPIP(第4版,4.1.07)从所附的数据库获得,或者如果不可获得,可以使用该程序包含的“DIY”功能(functionality)来确定,优选使用所附的神经网络,如“帮助”部分所述。HSPIP程序可从Steven Abbott TCNF Ltd.公司获得。
待接合的塑料材料是两种不同的塑料材料,其原则上可选自所有已知的塑料材料,只要待接合的塑料材料彼此之间的汉森参数的加权二次方距离(Ra)2大于22MPa、优选大于25MPa、特别是大于30MPa、特别优选大于35MPa。当(Ra)2相当时,这两种塑料不能相互混合,因此是不相容的;因此,在没有其它助剂的情况下不能焊接这两种塑料材料,或者难以焊接。
待接合的塑料材料优选各自至少基于聚合物,即聚酰胺塑料材料基于聚酰胺聚合物。各自基于待接合的塑料材料的聚合物含量(不含填料的全部塑料材料),80重量%以上、特别是90重量%以上、优选95重量%以上、特别优选98重量%以上的待接合的塑料材料优选由这种聚合物或聚合物混合物组成。除了聚合物之外,塑料材料还可以含有其它组分,例如,填料(例如玻璃纤维)、颜料、矿物颗粒、染料、流变助剂、脱模助剂或稳定剂。各自基于全部塑料材料(包含填料),待接合的塑料材料优选40重量%以上、特别是60重量%以上、优选70重量%以上、优选90重量%以上由该聚合物组成。各自基于全部塑料材料(包含填料),塑料材料优选具有50~90重量%、特别是60~80重量%的该聚合物含量。
待接合的塑料材料和/或这些塑料材料所基于的聚合物可以选自以下物质:塑料材料优选为热塑性塑料,例如提及了以下物质作为合适的热塑性聚合物:聚氧化烯烃、聚碳酸酯(PC)、聚酯(例如聚对苯二甲酸丁二醇酯(PBT)或聚对苯二甲酸乙二醇酯(PET))、聚烯烃(例如聚乙烯或聚丙烯)、聚(甲基)丙烯酸酯、聚酰胺、乙烯基芳香族(共)聚合物(例如聚苯乙烯、抗冲击改性聚苯乙烯(如HI-PS、或者ASA、ABS或AES聚合物))、聚亚芳基醚(例如聚苯醚(PPE))、聚砜、聚苯硫醚(PPS)、聚氨酯、聚乳酸、含卤素聚合物(例如聚氯乙烯(PVC))、含酰亚胺基团的聚合物、纤维素酯、有机硅聚合物和热塑性弹性体。也可以使用不同热塑性聚合物的混合物作为塑料模制部件的材料。这些混合物可以是单相或多相聚合物共混物。待相互连接的模制部件可由相同或不同的热塑性聚合物或热塑性聚合物共混物组成,优选塑料材料具有热塑性聚合物作为主要组分;各自基于塑料材料的聚合物含量、特别是各自基于全部塑料材料(包含填料),塑料材料特别是40重量%以上、特别是60重量%以上、优选70重量%以上、优选90重量%以上由所述一种热塑性聚合物组成。
例如,聚酰胺塑料材料适合作为待接合的塑料材料。聚酰胺塑料材料优选为热塑性聚酰胺。酰胺类热塑性聚合物包括例如聚酰胺6,ε-己内酰胺的均聚物(聚己内酰胺);聚酰胺11,11-氨基十一烷酸的缩聚物——聚(11-氨基十一烷酰胺);聚酰胺12,ω-月桂基内酰胺的均聚物(聚月桂基内酰胺);聚酰胺6.6,六亚甲基二胺和己二酸的均缩聚物(聚己二酰己二胺);聚酰胺6.10,六亚甲基二胺和癸二酸的均缩聚物(聚(癸二酰己二胺));聚酰胺6.12,六亚甲基二胺和十二烷二酸的均缩聚物(聚十二烷二酰己二胺);或聚酰胺6-3-T,三甲基1,6-己二胺与对苯二甲酸的均缩聚物(聚三甲基六亚甲基二胺)、苯二胺和对苯二甲酸的聚(对苯二甲酰对苯二胺)或聚(间苯二甲酰对苯二胺)、不同二胺和对苯二甲酸的聚邻苯二甲酰胺(PPA);以及它们的混合物。
光学透明聚酰胺包括含有线性脂肪族二羧酸和脂环族二胺的单晶聚酰胺、含有线性脂肪族二羧酸和脂环族二胺以及任选存在的内酰胺或氨基酸的非晶聚酰胺、含有对苯二甲酸和脂环族或支化脂肪族二胺和任选存在的内酰胺或氨基酸的非晶聚酰胺、或含有间苯二甲酸和脂环族或线性或支化脂肪族二胺和任选存在的内酰胺或氨基酸的非晶聚酰胺。合适的光学透明聚酰胺例如是十二烷二酸的酰胺,以及4,4'-二氨基二环己基甲烷的异构体、对苯二甲酸的混合物,以及2,2,4-三甲基六亚甲基二胺和2,4,4-三甲基六亚甲基二胺的异构体、十二烷二酸的混合物,和3,3'-二甲基-4,4'-二(氨基环己基)甲烷的异构体、月桂基内酰胺、间苯二甲酸的混合物,以及3,3'-二甲基-4,4'-二(氨基环己基)甲烷的异构体、或十四烷二酸的混合物,以及3,3'-二甲基-4,4'-二(氨基环己基)甲烷的异构体、或ε-己内酰胺或ω-月桂基内酰胺的混合物。
优选的聚酰胺选自聚酰胺6、聚酰胺6.6、聚酰胺6.10、聚酰胺6.12、聚酰胺10.10、聚酰胺11、聚酰胺12、聚酰胺10.12、聚邻苯二甲酰胺、光学透明聚酰胺或基于所述聚酰胺的混合物。特别优选的聚酰胺选自聚酰胺6、聚酰胺6.6、聚酰胺12、聚邻苯二甲酰胺、光学透明聚酰胺及它们的混合物,特别是聚酰胺6、聚酰胺6.6及它们的混合物。
聚(甲基)丙烯酸酯是合成的——优选透明的——热塑性塑料。优选的聚(甲基)丙烯酸酯由50~100重量%、特别是70~100重量%的丙烯酸酯和/或甲基丙烯酸酯构成,其中所述(甲基)丙烯酸酯单元优选用C1-C12烷基官能团(特别是C1-C4烷基官能团,优选甲基官能团)酯化。该书面形式(written form)的聚(甲基)丙烯酸酯是指该聚合物由丙烯酸酯和/或甲基丙烯酸酯构成。也就是说,该书面形式的(甲基)丙烯酸酯是指:其可以是丙烯酸酯或甲基丙烯酸酯。特别优选的是,聚(甲基)丙烯酸酯为聚甲基丙烯酸甲酯(PMMA,又俗称为丙烯酸玻璃或有机玻璃)。优选的聚甲基丙烯酸甲酯由50~100重量%、特别是70~100重量%的甲基丙烯酸甲酯构成。
主要地,(甲基)丙烯酸(特别是丙烯酸),及其烷基官能团中具有1~12个碳原子、特别是1~4个碳原子的烷基酯,以及丙烯腈和/或甲基丙烯腈、丙烯酰胺和/或甲基丙烯酰胺、苯乙烯和/或马来酸酐可作为用于制备聚(甲基)丙烯酸酯、特别是聚甲基丙烯酸甲酯的共聚单体。热塑性和热弹性可变形的塑料材料是优选的。优选的热塑性聚甲基丙烯酸甲酯塑料材料的重量平均摩尔质量(重均Mw)大于50,000g/mol,特别是大于100,000g/mol。热塑性聚(甲基)丙烯酸酯——特别是聚甲基丙烯酸甲酯——塑料材料的重量平均摩尔质量(重均Mw)优选小于2,000,000g/mol,特别是小于1,000,000g/mol,优选小于500,000g/mol。对于注射成型而言,特别优选的热塑性聚(甲基)丙烯酸酯——特别是聚甲基丙烯酸甲酯——塑料材料的重量平均摩尔质量(重均Mw)为50,000g/mol~250,000g/mol,例如为约100,000g/mol~约180,000g/mol。
合适的聚烯烃塑料特别是热塑性聚烯烃塑料。聚烯烃塑料材料基于聚烯烃聚合物,例如α-烯烃的均聚物和共聚物。聚烯烃聚合物可以选自基于乙烯、丙烯和/或丁烯的聚α-烯烃均聚物(特别是乙烯或丙烯的均聚物)、以及基于乙烯、丙烯、1-丁烯、1-己烯和1-辛烯的聚α-烯烃共聚物(特别是乙烯/α-烯烃和丙烯/α-烯烃共聚物,优选乙烯或丙烯与1-丁烯、1-己烯和1-辛烯的共聚物)或它们的组合。特别地,聚烯烃塑料选自聚乙烯(特别是高密度/HD-聚乙烯、中密度/MD-聚乙烯、低密度/LD-聚乙烯、超高分子量/UHMW-聚乙烯和线性低密度/LLD-聚乙烯,优选HD-聚乙烯、MD-聚乙烯或LD-聚乙烯)和聚丙烯塑料。聚烯烃塑料特别优选为聚丙烯塑料材料。
聚烯烃聚合物——特别是聚丙烯聚合物——的重量平均摩尔质量(重均Mw)优选大于10,000g/mol,特别是大于20,000g mol,优选大于50,000g/mol,特别优选大于100,000g/mol。聚烯烃聚合物——特别是聚丙烯聚合物——的重量平均摩尔质量(重均Mw)优选小于2,000,000g/mol,特别是小于1,000,000g/mol,优选小于500,000g/mol。特别优选的聚乙烯聚合物的重量平均摩尔质量(重均Mw)为50,000g/mol~1,000,000g/mol,特别是200,000g/mol~500,000g/mol。其它优选的聚乙烯聚合物(UHMW-PE聚合物)的重量平均摩尔质量大于2,000,000g/mol,特别是4,000,000g/mol~6,000,000g/mol。特别优选的聚烯烃聚合物——特别是聚丙烯聚合物——的重量平均摩尔质量(重均Mw)为50,000g/mol~250,000g/mol。
合适的聚酯塑料材料也是本身已知的并且被记载于文献中。优选的聚酯塑料材料包含在主链中具有芳香环的聚酯,该环来源于芳香族二羧酸。芳香环也可以被取代,例如被卤素(例如氯或溴)取代,或被C1~C4烷基(例如甲基、乙基、异丙基、正丙基或正丁基、异丁基或叔丁基)取代。聚酯可以以本身已知的方式通过使芳香族二羧酸、其酯或其其它成酯衍生物与脂肪族二羟基化合物反应来制备。萘二甲酸、邻苯二甲酸、对苯二甲酸和间苯二甲酸或它们的混合物是优选的二羧酸。至多30摩尔%的芳香族二羧酸可以被脂肪族或脂环族二羧酸(例如己二酸、壬二酸、癸二酸、十二烷二酸和环己烷二羧酸)替代。具有2~8个碳原子的二醇——特别是1,2-乙二醇、1,4-丁二醇、1,6-己二醇、1,4-己二醇、1,4-环己烷二甲醇、新戊二醇和它们的混合物——是优选的脂肪族二羟基化合物。可衍生自具有2~6个C原子的链烷二醇的聚对苯二甲酸亚烷基酯是特别优选的聚酯。
聚酯塑料材料优选选自聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯和聚对苯二甲酸丁二醇酯(PBT)塑料材料及它们的混合物,特别是聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)塑料材料及它们的混合物。
合适的聚碳酸酯塑料材料优选为形式上可描述为碳酸的聚酯的热塑性塑料。聚碳酸酯原则上可以通过碳酰氯与二醇、优选双酚的缩聚来制备。芳香族聚碳酸酯是优选的聚碳酸酯。芳香族聚碳酸酯是至少由芳香族单体构成的那些。优选的聚碳酸酯塑料是基于双酚——特别是双酚A和双酚F——的聚碳酸酯塑料。在基于双酚的聚碳酸酯中,二醇组分优选50重量%、特别是70重量%、优选90重量%、优选100重量%由双酚——特别是双酚A和/或双酚F——构成。
包含选自苯乙烯、氯苯乙烯、α-甲基苯乙烯和对甲基苯乙烯中的单体的至少一种乙烯基芳香族聚合物——特别是共聚物——的塑料材料也是合适的塑料材料。以较小的量,乙烯基芳香族共聚物也可以包含(优选不超过20重量%的,特别是不超过8重量%的)共聚单体——例如(甲基)丙烯腈或(甲基)丙烯酸酯——作为一部分构成单元。特别优选的乙烯基芳香族聚合物是聚苯乙烯、苯乙烯-丙烯腈共聚物(SAN)、聚苯乙烯-甲基丙烯酸甲酯(SMMA)和抗冲击改性聚苯乙烯(HIPS=高抗冲聚苯乙烯)。当然,也可以使用所述聚合物的混合物。
最特别优选的乙烯基芳香族聚合物是ASA、ABS和AES聚合物(ASA=丙烯腈-苯乙烯-丙烯酸酯,ABS=丙烯腈-丁二烯-苯乙烯,AES=丙烯腈-EPDM橡胶-苯乙烯)。这些高抗冲乙烯基芳香族聚合物含有至少一种橡胶弹性接枝聚合物和热塑性聚合物(基质聚合物)。通常,使用苯乙烯/丙烯腈聚合物(SAN)作为基质材料。优选地,使用包含以下物质作为橡胶的接枝聚合物:基于二烯(如丁二烯或异戊二烯)的二烯橡胶(ABS),基于丙烯酸烷基酯(如丙烯酸正丁酯和丙烯酸2-乙基己酯)的丙烯酸烷基酯橡胶,基于乙烯、丙烯和二烯的EPDM橡胶,或者所述橡胶或橡胶单体的混合物。
所述乙烯基芳香族聚合物的重均分子量特别地为1,500~2,000,000g/mol,优选为70,000~1,000,000g/mol。
另外,塑料材料可以是至少一种聚碳酸酯和至少一种乙烯基芳香族聚合物(优选为上述乙烯基芳香族聚合物)的混合物。所述混合物的聚碳酸酯含量优选高于乙烯基芳香族聚合物(特别是SMMA、SAN、ASA、ABS和/或AES,优选为ABS)的含量。聚碳酸酯(特别是芳香族聚碳酸酯)与乙烯基芳香族聚合物(特别是SMMA、SAN、ASA、ABS和/或AES,优选ABS)的比例优选为1:1~100:1,特别是2:1~50:1,优选为3:1~10:1。
聚氧化烯烃均聚物或共聚物——特别是(共)聚甲醛(POM)——也适合于制备塑料材料。极其一般而言,所述聚合物在聚合物主链中包含至少50摩尔%的-CH2O重复单元。均聚物通常由甲醛或三氧杂环己烷通过聚合来制备,其优选在合适催化剂的存在下进行。聚甲醛共聚物和聚甲醛三元共聚物是优选的。优选的聚甲醛(共)聚合物具有至少150℃的熔点和5,000~200,000、优选7,000~150,000g/mol的分子量(重均分子量)Mw。特别优选的是在链端部具有C-C键的经端基稳定的聚甲醛聚合物。
聚亚芳基醚优选被理解为聚亚芳基醚本身和聚亚芳基醚硫化物、聚亚芳基醚砜或聚亚芳基醚酮。其亚芳基可以相同或不同,并且彼此独立地表示具有6~18个C原子的芳香族官能团。合适的亚芳基官能团的实例为亚苯基、亚联苯基(biphenylene)、亚三联苯基(terphenylene)、1,5-亚萘基、1,6-亚萘基、1,5-亚蒽基、9,10-亚蒽基或2,6-亚蒽基。在所述基团中,优选的是1,4-亚苯基和4,4-亚联苯基。所述芳香族官能团优选未被取代。然而,其可以带有一个或多个取代基。
此外,聚氨酯、聚异氰脲酸酯和聚脲是适合于制备塑料模制部件的材料。通常已知的是柔性、半刚性或刚性的热塑性或交联聚异氰酸酯加聚产物,例如聚氨酯、聚异氰脲酸酯和/或聚脲。其制备已被广泛描述,并且通常通过使异氰酸酯与在通常已知条件下与异氰酸酯反应的化合物反应来进行。该反应优选在催化剂和/或助剂的存在下进行。
本身已知的芳香族、芳基脂肪族、脂肪族和/或脂环族有机异氰酸酯(优选二异氰酸酯)可作为异氰酸酯。
分子量为60~10,000g/mol且关于异氰酸酯的官能度为1~8、优选2~6(在热塑性聚氨酯的情况下,官能度为约2)的通常已知化合物可以用作与异氰酸酯反应的化合物,其中所述化合物为例如多元醇,如分子量为500~10,000g/mol的聚醚多元醇、聚酯多元醇和聚醚聚酯多元醇以及/或者分子量小于500g/mol的二醇、三醇和/或多元醇。
聚交酯(即乳酸的聚合物)是本身已知的并且可以根据本身已知的方法制备。
除了聚交酯,也可以使用基于乳酸和其它单体的共聚物或嵌段共聚物。通常使用线性聚交酯。但是,也可以使用支化乳酸聚酯。例如,可以使用多官能的酸或醇作为支化剂。
氯乙烯的聚合物(例如,特别是聚氯乙烯(PVC),如刚性PVC和柔性PVC;和氯乙烯的共聚物,如uPVC模制化合物)是合适的含卤素聚合物。此外,还可行的是含氟聚合物,特别是聚四氟乙烯(PTFE)、四氟乙烯-全氟丙烯共聚物(FEP)、四氟乙烯与全氟烷基乙烯基醚的共聚物、乙烯-四氟乙烯共聚物(ETFE)、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、聚氯三氟乙烯(PCTFE)和乙烯-氯三氟乙烯共聚物(ECTFE)。
含酰亚胺基团的聚合物特别是聚酰亚胺、聚醚酰亚胺和聚酰胺-酰亚胺。
合适的纤维素酯是例如乙酸纤维素、乙酸丁酸纤维素和丙酸纤维素。
另外,有机硅聚合物也可以作为热塑性聚合物。硅橡胶尤其适合。这些聚合物通常是包含能够进行交联反应的基团的聚有机硅氧烷。
最后,也可以使用热塑性弹性体(TPE)的化合物类别。可以将TPE以热塑性聚合物的方式加工,但其具有橡胶弹性。由两种以上单体单元组成的TPE嵌段共聚物、TPE接枝共聚物和多嵌段(segmented)TPE共聚物是合适的。特别合适的TPE是:热塑性聚氨酯弹性体(TPE-U或TPU),苯乙烯-低聚嵌段共聚物(TPE-S)如SBS(苯乙烯-丁二烯-苯乙烯嵌段共聚物)和SEBS(苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物,其可通过氢化SBS获得),热塑性聚烯烃弹性体(TPE-O),热塑性聚酯弹性体(TPE-E),热塑性聚酰胺弹性体(TPE-A),以及特别是热塑性硫化橡胶(TPE-V)。
下面将描述优选的各种实施方案,其为以下方案中的单独一种或两种以上的组合:优选地,待接合的塑料材料均不由聚氧乙烯构成。优选地,待接合的塑料材料均不由聚碳酸酯(PC)构成。优选地,待接合的塑料均不由聚对苯二甲酸丁二醇酯(PBT)和/或聚对苯二甲酸乙二醇酯(PET)——特别是聚酯——构成。优选地,待接合的塑料材料均不由聚乙烯和/或聚丙烯——特别是聚烯烃——构成。优选地,待接合的塑料材料均不由聚酰胺构成。优选地,待接合的塑料均不由聚苯乙烯——特别是乙烯基芳香族(共)聚合物——构成。优选地,待接合的塑料材料均不由ASA、ABS或AES聚合物构成。优选地,待接合的塑料材料均不由聚亚芳基醚构成。优选地,待接合的塑料材料均不由聚砜构成。优选地,待接合的塑料材料均不由聚苯硫醚构成。优选地,待接合的塑料材料均不由聚氨酯构成。优选地,待接合的塑料材料均不由聚交酯构成。优选地,待接合的塑料材料均不由含卤素聚合物构成。优选地,待接合的塑料材料均不由含酰亚胺基团的聚合物构成。优选地,待接合的塑料材料均不由纤维素酯构成。优选地,待接合的塑料材料均不由有机硅聚合物构成。优选地,待接合的塑料材料均不由热塑性弹性体构成。
如上所述,以上提及的聚合物(由其可以制备待接合的塑料材料)的汉森参数是已知的或可以确定。为了确定汉森参数的加权二次方距离(Ra)2,可以使用如上定义的以下公式:
(Ra)2=4(ΔδD)2+(ΔδP)2+(ΔδH)2
对于待接合的不同塑料材料,构成相关塑料材料的不同聚合物的汉森参数的加权二次方距离(Ra)2应当大于22MPa,优选大于25MPa,特别是大于30MPa,特别优选大于35MPa。
本发明的另一主要部分是至少一种底漆——优选恰好一种底漆——的使用。所述底漆包含至少一种第一聚合物,其与待接合的两种塑料材料(特别是该塑料材料所基于的聚合物)的汉森参数的加权二次方距离(Ra)2小于22MPa、特别是小于17MPa、优选小于15MPa、特别优选小于12MPa。因为(Ra)2具有相应的值,所以底漆的聚合物与待接合的塑料材料和/或其聚合物相容并可与其混合,其中各组分的相容性越好则(Ra)2值越小。由此可以实现特别稳定且持久的焊接连接。
底漆是焊接助剂,其优选作为预处理层而被施加到待焊接的基材表面中的至少一个上的接合区的区域中。底漆不应被理解为粘合剂、清洁剂或类似物;相反,底漆是用于焊接的辅助剂,由此使接合对象在接合区(或焊接区)中彼此相容,并且由此在接合区中在待焊接的基材之间进行接合时实现整体粘接和摩擦连接。
使用含有本发明聚合物的相应底漆使得不同的塑料材料可以在焊接时在接合缝中相容,由此实现稳定且持久的连接。如果不使用相应的底漆,则不能实现焊接连接或仅可实现极低的焊接连接强度。优选地,接合的基材的拉伸强度大于2MPa,特别是大于5MPa,优选大于7MPa。拉伸强度在5mm/s的牵引速度下测定,其中待测量的样品具有130mm×68mm×3mm的几何形状并且使用底漆被端对端地焊接至130mm×3mm表面。
上面已经提到的用于塑料材料的所有聚合物都可以作为用于底漆的合适聚合物。
下面将描述优选的各种实施方案,其为以下方案中的单独一种或两种以上的组合:优选地,底漆基本上不含聚氧化烯烃。优选地,底漆基本上不含聚碳酸酯(PC)。优选地,底漆基本上不含聚对苯二甲酸丁二醇酯(PBT)和/或聚对苯二甲酸乙二醇酯(PET)。优选地,底漆基本上不含聚乙烯和/或聚丙烯,特别是聚烯烃。优选地,底漆基本上不含聚酰胺。优选地,底漆基本上不含聚苯乙烯,特别是由乙烯基芳香族(共)聚合物构成的聚苯乙烯。优选地,底漆基本上不含ASA、ABS和/或AES聚合物。优选地,底漆基本上不含聚亚芳基醚。优选地,底漆基本上不含聚砜。优选地,底漆基本上不含聚苯硫醚。优选地,底漆基本上不含聚氨酯。优选地,底漆基本上不含聚交酯。优选地,底漆基本上不含含卤素聚合物。优选地,底漆基本上不含含有酰亚胺基团的聚合物。优选地,底漆基本上不含纤维素酯。优选地,底漆基本上不含有机硅聚合物。优选地,底漆基本上不含热塑性弹性体。根据本发明,术语“基本上不含”应理解为表示底漆含有少于5重量%、优选少于1重量%、最特别优选少于0.1重量%的相关物质,尤其是不含相关物质。
除了本发明聚合物之外,底漆优选还可以含有不同于本发明第一聚合物(特别是在其聚合物结构方面)的至少一种其它聚合物。所述至少一种其它聚合物优选与待焊接的两种塑料材料中的至少一种以及与底漆中的本发明第一聚合物相容。优选地,所述其它聚合物特别是与待接合的两种塑料材料的汉森参数的加权二次方距离(Ra)2且特别是其与以上提及的本发明第一聚合物的汉森参数的加权二次方距离(Ra)2小于22MPa,特别是小于17MPa,优选小于15MPa,特别优选小于12MPa。
各自基于底漆的总重量,其它聚合物占底漆的含量优选为1~40重量%、特别是5~30重量%、特别优选10~20重量%。各自基于底漆的总聚合物含量(不含溶剂和填料的底漆),其它聚合物占底漆聚合物含量的含量优选为5~70重量%、特别是20~60重量%、特别优选30~50重量%。在一个优选实施方案中,底漆不含有其它聚合物,而是仅包含本发明第一聚合物。
在一个优选实施方案中,底漆中所含的本发明第一聚合物——特别是底漆中的每种聚合物、优选底漆——基本上不含马来酸酐基团。在另一优选实施方案中,底漆中所含的本发明第一聚合物——特别是底漆中的每种聚合物、优选是底漆——基本上不含马来酸酐基团和/或胺基团,特别是基本上不含酸基团、酸酐基团、胺基团和/或羟基基团,优选基本上不含酸基团、酸酐基团、羟基基团、硫醇基团、胺基团、环氧基团和/或异氰酸酯基团,优选基本上不含任何反应性基团。上述基团应理解为这样的基团,其通过聚合引入/反应进入聚合物中以便仍是游离的并且处于在焊接条件下能够反应的形式(例如游离酸或OH基团)而存在。根据本发明,术语“基本上不含”应理解为意指底漆中所含的本发明第一聚合物——特别是底漆中的每种聚合物、优选底漆——含有少于1重量%、优选少于0.1重量%、最特别优选少于0.01重量%的所述基团,最特别优选不含所述基团。
除本发明第一聚合物和其它聚合物之外,底漆还可以包含溶剂、特别是有机溶剂。各自基于底漆的总重量,底漆的溶剂含量优选为10~90重量%、特别是50~85重量%、特别优选60~80重量%。
合适的溶剂为所有常规溶剂,例如:水;醇类;酮类,例如甲基异丁基酮(MIBK)或环己酮(CH);醚类,例如乙醚或四氢呋喃(THF);酯类,例如乙酸乙酯;或碳酸酯类,例如碳酸二甲酯或碳酸二丙酯;甲苯;二甲苯;或它们的混合物。
在一个优选实施方案中,底漆含有有机溶剂。特别优选的溶剂是在20℃下蒸气压为1~600hPa、特别是2~200hPa、特别优选5~20hPa的溶剂。在这种情况下,已发现具有相应蒸气压的溶剂对于最小化或防止蒸发时底漆层中气泡形成而言是特别有利的。特别优选地,底漆含有选自四氢呋喃、甲基异丁基酮、环己酮及它们的混合物中的溶剂;特别优选地,底漆含有四氢呋喃或甲基异丁基酮和环己酮的混合物。如果使用甲基异丁基酮和环己酮的混合物作为溶剂,则各自基于全部溶剂混合物,所述混合物优选含有10~50重量%、特别是20~35重量%的环己酮。
如果使用有机溶剂,则各自基于底漆的总重量,底漆的总聚合物含量优选为10~90重量%、特别是15~50重量%、特别优选20~40重量%。总聚合物含量对应于在底漆中使用的所有聚合物的含量,特别是本发明共聚物和上述其它聚合物的含量。
在另一优选实施方案中,底漆以含水分散体或乳液的形式存在。在这种情况下,本发明的聚合物和任选存在的其它聚合物被乳化或分散于水中。在这种情况下,各自基于底漆的总重量,底漆的总聚合物含量优选为5~90重量%、特别是20~70重量%、特别优选30~55重量%。对于含水分散体/乳液而言,有利的是,聚合物组分基本上仅由本发明聚合物和上述任选存在的其它聚合物构成,特别是仅由本发明聚合物构成。根据本发明,术语“基本上”应理解为表示聚合物组分95重量%以上、优选97重量%以上、最特别优选99重量%以上由本发明聚合物和上述任选存在的其它聚合物构成,特别是仅由本发明聚合物构成。
在另一优选实施方案中,底漆基本上不含溶剂。
除本发明共聚物、上述其它聚合物和溶剂之外,底漆还可以含有其它组分,例如填料、(荧光)染料和颜料、流变助剂、消泡剂、润湿剂、稳定剂或增塑剂。然而,除了染料和颜料之外,底漆优选基本上不含其它组分,特别是基本上不含任何其它组分。根据本发明,术语“基本上不含”应理解为表示底漆含有少于5重量%、优选少于1重量%、最特别优选少于0.1重量%的相关物质,特别是不含相关物质。
在本发明的用于使用底漆焊接两种不同塑料材料的方法中,待接合的两种塑料材料彼此之间的汉森参数的加权二次方距离(Ra)2大于22MPa,并且该底漆包含与待接合的两种塑料材料的汉森参数的加权二次方距离(Ra)2小于22Mpa的聚合物。
在这种方法中,在各种情况下,底漆通过熔化而起到用于焊接两种不同塑料材料的辅助剂的作用。所使用的相容性底漆可以在两个接合对象之间产生相容性,由此可以在两种塑料材料之间产生稳定且持久的整体粘接连接。
可以使用多种方法将底漆施加到一个或两个接合对象的表面上。因此,例如,所述底漆可以使用计量装置、使用针和计量机器人(a needle and metering robot)、通过注射成型、通过挤出、通过薄膜涂覆、通过热熔体施加、通过喷涂、通过铺展或通过浸渍而施加。
当施加底漆时,所述底漆可以施加到待焊接的基材的仅一个表面或两个表面上。底漆优选施加到仅一个表面上。在使用薄膜进行焊接的情况下,薄膜必须放置在基材之间。
在底漆含有溶剂的情况下,在施加到一个或两个表面之后,优选对底漆进行干燥直至溶剂蒸发到达到不粘的、尺寸稳定的底漆层的程度。特别地,底漆在仅几秒钟后可焊接并在不长于数周的时间内可焊接。施加后,对底漆优选干燥至少1小时、优选至少12小时。
对待焊接的基材的一个或两个表面的施加优选如此进行,从而使得底漆具有1μm~5,000μm、特别是10~3,000μm、优选50~1,000μm、特别优选100~500μm的层厚度。如果底漆中含有溶剂,则层厚度是指已经干燥除去溶剂的底漆。
在将底漆施加到待焊接的基材的一个或两个表面上之后,并且任选地在底漆已经干燥之后,待焊接的基材可以使用常规的焊接方法相互连接。塑料材料的焊接通常通过接合对象在接合面中的局部塑化以及在压力下的接合来进行。应该对工艺参数进行选择,从而使得熔体的显著挤压流动导致接合对象在接合面中的最佳连接。加热可以通过对流、接触加热、辐射或摩擦进行。用于塑化的不同能量输入可以以一系列方式进行,并产生用于焊接塑料材料的不同过程。
合适的焊接方法例如是:
·热气焊接[HG]
采用热气流(一般为空气)的对流加热,两阶段过程
·热板焊接[HP]
接触加热,两阶段过程
·超声波焊接[US]
通过摩擦进行的加热,超声范围内的横波导致边界层中的加热,单阶段过程
·高频焊接[HF]
通过内摩擦进行的加热,极性分子根据高频磁场排列,单阶段,仅用于极性塑料材料和薄膜
·摩擦焊接[FRW]:线性;轨道;自旋;角度
通过摩擦进行的加热,单阶段过程
·激光焊接[LW]:轮廓,同步,准同步,掩模
通过辐射进行的加热,相干辐射,激光传输焊接,一般为单阶段(可以是两阶段)
·红外焊接[IR]
通过辐射进行的加热,非相干辐射,两阶段
上面列出的焊接方法也可以任选地组合,例如红外焊接和摩擦焊接。聚酰胺塑料材料特别优选通过使用选自以下方法中的焊接方法而被焊接到聚(甲基)丙烯酸酯塑料材料上:热板焊接、热接触或热脉冲焊接、温气或热气焊接、摩擦焊接、微波或感应焊接、激光对缝或激光照射焊接、红外焊接、超声波焊接及它们的组合,特别是选自热板焊接、红外焊接、超声波焊接、摩擦焊接及它们的组合。
特别优选的是包括以下步骤的使用底漆整体接合两种塑料材料的方法:
·提供包含第一接合区的第一塑料材料,
·提供包含第二接合区的第二塑料材料,
·预热所述第一接合区,
·将底漆施加到经预热的第一接合区,特别是在不含溶剂的底漆的情况下,
·使提供有底漆的第一接合区与所述第二接合区接触,
·将所述第一接合区与所述第二接合区整体连接,特别是通过使用常规塑料材料焊接方法(例如红外焊接、热板焊接、热气焊接、摩擦焊接、超声波焊接)进行。
通常,可以将DIN 1910-3:1977-09应用于焊接塑料材料。因此,在上下文中可以理解使用热和/或压力整体接合热塑性塑料材料。加热可以例如基于接触加热(使用固体的焊接)、对流加热(使用热气体的焊接)、辐射加热(使用波束的焊接)和通过摩擦进行的加热(通过运动进行的焊接)以及通过电力进行的焊接来进行。
在有利的发展方案(development)中,对所使用的底漆进行选择并使其匹配该方法,从而使得将其在低于底漆中聚合物的分解温度的温度下施加到经加热的且/或热的接合区对底漆的内部化学交联没有任何影响。
有利的是,预热第一塑料材料的第一接合区。可以使用本领域技术人员已知并且适用于该目的的辅助剂和技术来预热。特别是,使用热气体或等离子体适合预热。还可想到的是通过辐射——特别是红外辐射或激光辐射——进行的预热。加热元件或加热工具也可用于预热第一接合区。最后,还可想到在烘箱或加热室内预热。可以想到预热整个塑料材料以及由此也预热所述接合区。然而,替代性地或另外地,也可以仅预热接合区本身。
在有利的发展方案中,在预热期间,加热装置与塑料材料(特别是与待预热的第一接合区)的间距——特别是加热装置的发热区域或加热装置的待预热的有效表面或加热装置的与第一接合区相对的区域的间距——为0.5mm~100mm、优选地1mm~60mm。或者,也可以想到通过在特别是第一接合区和加热装置的加热元件之间进行接触来进行加热以及/或者在所述接触期间进行加热。
另一优势是:选择用于第一接合对象的塑料材料并调整第一塑料材料的方法参数,从而使得第一接合区在预热时熔化以及使得在预热时在第一接合区中产生熔融层。在特别优选实施方案中,熔融层的厚度优选为0.05mm~6mm、特别优选为0.1mm~5mm。这种熔融层可以导致分子更好的粘附和/或扩散和/或相互作用,并且与特定流动相结合,可以得到改善的连接层。如果第一塑料材料的边界层处于熔融状态,则只要与底漆化学结合就可以进行相互作用。熔融层可以特别取决于部件的几何形状和相关的部件设计。优选地,调整和/或选择方法参数从而使得不导致部件变形。优选,使用合适的手段和/或方法步骤使接合区与待施加的底漆之间的温度差相等。在这种情况下,可以特别想到预热底漆以降低优选热塑性底漆与第一接合区之间的温度差。这可以例如抵消第一接合区在方法步骤之间的快速冷却。
任选地,对第一接合区进行预处理,优选在预热第一接合区的步骤之前对第一接合区进行预处理。替代性地或另外地,也可以对第二接合区进行预处理。例如,可以想到使用溶剂或例如碱性塑料清洁剂进行的清洁作为可能的预处理。还可以使用机械预处理,特别是通过刮擦、抛光、刷涂或辐射来预处理。可以想到的化学预处理特别是酸洗或使用反应性气体。此外,使用热、化学和/或物理预处理可证明是有利的,特别是通过气体火焰或等离子弧进行的。替代性地或另外地,通过电晕放电进行的电预处理可以使第一接合区和/或第二接合区在该过程中经受电晕放电以便在相应的表面处产生极性分子。另一种选择是用于预处理接合区——特别是为了活化和/或清洁相应的表面——的等离子体处理(优选使用等离子体喷嘴的)。尽管如此,通过等离子体进行的涂覆也证明是有利的。另一种选择是烧红接合区以增加合适塑料材料中的表面张力。另一种预处理是使用紫外线、电子束、放射线或通过激光进行的辐射。最后,预处理也可以以涂布的形式进行,特别是通过涂漆或使用助粘剂进行。也可以想到在预热之前较长时间地预处理第一塑料材料或第一塑料材料的接合区。因此可以想到:例如在制造第一塑料材料的过程中已经进行了预处理,以便能够在本发明的方法中进一步加工经预处理的塑料材料。
可以想到以各种方式施加底漆。例如,并且特别是在工业领域中,可以想到使用自动施加辅助进行的施加,特别是通过计量机器人进行的施加。在这种情况下,所述机器人可以配备针(needle)和/或高度传感器,以便能够执行复杂的计量过程。底漆也可通过注射成型施加,其中将底漆在注射成型机中塑化并在压力下注入容纳有含第一接合区的第一塑料材料的模具中。或者,可以想到薄膜施加,其中首先由底漆通过薄膜吹塑或平膜挤出而制备薄膜。随后,可以将薄膜切割成任何所需的形状,例如通过切割或冲压方法进行切割;并且在所述预热之后,可以在另一步骤中将其施加于第一接合区。在这种情况下,已经发现使用厚度为1μm~5,000μm的薄膜/薄板是有利的。另外可想到的可能的施加是挤压焊接,在此期间底漆以焊丝的形式存在或在挤压机中熔化并且可以以熔融形式施加到第一接合区。底漆也可以以焊丝的形式提供,以便可通过热空气焊接进行施加。另一种选择是通过喷涂方法施加底漆。在注射成型期间施加的情况下,也可以进行注塑工具的预处理和/或预热和/或局部变化的温度控制。当然,也可以想到本领域技术人员已知的并且适合于特定用途的其它类型的施加。
另一优势是:进一步加热或加热第一接合区,同时施加底漆,特别是以便防止第一接合区的温度在预热和施加底漆之间下降。这可以通过上述的预热方法步骤来进行;为了简便起见,其可以在施加期间继续进行。替代性地或者另外地,可以进行另外的加热,特别是借助于另外的方法步骤进行。因此,可以证明有利的是,例如在底漆施加期间同时加热第一接合区(例如通过在底漆施加期间同时将第一接合区暴露于辐射、强制对流或接触加热),以防止第一接合区的温度在预热后下降。
在有利的发展方案中,施加底漆从而使得在第一接合区上布置厚度为1μm~5mm、优选为10μm~3mm的连接层。在这种情况下,连接层的厚度应理解为第一接合区上的连接层的材料厚度。
另一优势是:当将第一接合区和计量装置相对于彼此移动时,将底漆通过计量装置施加到第一接合区上,其中当将第一接合区和加热装置相对于彼此移动时,对施加底漆的第一接合区在施加底漆前通过加热装置进行预热,并且当第一接合区处于经预热的状态下时通过计量装置施加底漆。
在这种情况下,已经发现特别有利的是:在预热期间,加热装置以10mm/min~100mm/min、优选为10mm/min~30mm/min的速度移动通过第一接合区。
还可有利的是,加热装置领先于计量装置,优选以限定的恒定间距领先。尤其是,有利的是以下述方式实施该方法,即:在计量装置和第一接合区相对于彼此以10mm/min~100mm/min、优选10mm/min~30mm/min移动时,将底漆通过计量装置施加到第一接合区,其中当将加热装置和第一接合区相对于彼此移动时,对施加底漆的所述接合区在施加底漆之前通过加热装置进行预热,并且加热装置优选同时以0.1~10s的时间间隔领先于用于施加底漆的计量装置或计量装置的喷嘴。
在这种情况下,已经发现特别有利的是,使用由计量装置和加热装置组成的涂布单元。在这种情况下,涂布单元尤其可以理解为在加热装置和计量装置之间提供刚性连接的单元,从而使得在相对运动期间加热装置——优选以限定且恒定的间距——领先于计量装置,以确保在施加底漆之前立即预热第一接合区。当然,也可以想到:在这种情况下,间距是可以调整的;或者在对流预热的情况下,调节介质的体积流量和/或喷嘴直径,特别是通过合适的机械、机电或气动方式运行的调节器来调节。
与之不同,涂布单元也可以理解为是两个完全隔离或分离的模块的形式的加热装置和计量装置;然而,所述加热装置和计量装置执行相同或基本上相同的相对于塑料材料的相对运动,以确保在施加底漆之前立即预热底漆的施加位置。
在有利的发展方案中,虽然加热装置和计量装置相对于塑料材料执行基本上相同的主相对运动或具有基本上相同的基本方向,但是,除了所述主相对运动外,两个所提及的装置中的至少一个经历另外的相对于塑料材料的相对运动。因此,例如,加热装置和/或计量装置除了主相对运动之外还可以执行一个或多个副相对运动,在该副相对运动期间例如也可以施加底漆。例如,特别地,加热装置和/或计量装置可以执行或经历在主相对运动周围环绕移动或曲折移动的副相对运动。
在这种情况下,一方面塑料材料可以移动,或者另一方面加热装置和计量装置或者作为涂布单元在一起的这两个装置可以移动。在这种情况下,一方面加热装置和计量装置或者作为涂布单元在一起的两个装置可固定不动,另一方面塑料材料可固定不动;或者在各个情况下其运动部分可以在不同方向上运动。
在有利的发展方案中,主相对运动以10mm/min~100m/min、优选10mm/min~30m/min的速度进行,从而(例如特别地还由于加热装置的合适设计)使得塑料材料在加热装置的加热表面内的停留时间尽可能短、特别是为1~60秒。这可以理解为这样的加热装置周围的区域或空间,其在提高第一塑料材料的第一接合区的温度(即第一塑料材料的第一接合区的预热)的意义上影响温度。由此,可以避免例如对塑料材料的过度加热和损坏或塑料材料的降解。
此外,可证明有利的是:特别是为了将计量装置和/或加热装置连接至现有生产线,或将计量装置和/或加热装置连接到现有生产线中,可使加热装置配备总线接口,特别是用于PROFIBUS的总线接口,或配备实时以太网接口。
在施加所述底漆之后,使第二接合区与底漆层接触。在这种情况下,可证明有利的是:将两种塑料材料固定在一起,特别是通过本领域技术人员已知的夹紧装置或类似的固定助剂进行固定。
当然,任选地可以对第二接合区在使第二接合区与底漆层接触的步骤之前进行预处理。在这种情况下,特别是可以想到所有上述的预处理技术。也可以想到,对第二塑料材料或第二塑料材料的接合区在接触之前进行较长时间的预处理。由此,可以想到例如:在制造第二塑料材料的过程中已经进行预处理,以便能够在本发明方法中进一步加工经预处理的塑料材料。第二塑料材料的预处理也可以包括将底漆施加到第二接合区。在这种情况下,优选地,也可以想到,在施加底漆之前预热第二接合区。上述实施方案在此也是优选的。
如上所述,使第二接合区和底漆接触,然后是接合过程,其中通过供热使已处理和/或涂布的接合对象塑化并且整体地相互连接,优选在压力的作用下进行。可以想到:对于第二接合区和底漆之间的这种整体连接,供热可通过以下手段进行:热传导,例如热板焊接和/或热接触焊接和/或热脉冲焊接;摩擦,特别是超声波、摩擦或高频焊接;微波或感应焊接;对流,例如温气体或热气体焊接;辐射,例如红外、激光对缝或激光照射焊接;或两种以上所述技术的组合。
本发明还涉及根据本发明方法生产的物品或产品。
此外,本发明涉及本发明的底漆用于焊接两种不同塑料材料的用途。
实施方案
所选的材料和汉森参数
对于聚酰胺12和苯乙烯-丁二烯-丙烯酸酯共聚物这两种塑料材料,根据4(δD1D2)2+(δP1P2)2+(δH1–δH2)2得到的(Ra)2值为23.3MPa。
对于底漆-聚合物(聚苯醚)和塑料材料1(聚酰胺12),(Ra)2值为8.9MPa。
对于底漆-聚合物(聚苯醚)和塑料材料2(苯乙烯-丁二烯-丙烯酸酯共聚物),(Ra)2值为7.1MPa。
使用底漆-聚合物(聚苯醚)使得两种所提到的塑料材料可以彼此相容,以使所述材料能够焊接。

Claims (11)

1.使用底漆来焊接两种不同塑料材料的方法,其特征在于,待接合的所述两种塑料材料彼此之间的汉森参数的加权二次方距离(Ra)2大于22MPa,并且所述底漆包含与待接合的所述两种塑料材料的汉森参数的加权二次方距离(Ra)2小于22MPa的聚合物。
2.如权利要求1所述的焊接方法,其特征在于,所述两种不同的塑料材料彼此之间的汉森参数的加权二次方距离(Ra)2大于25MPa,特别地大于30MPa,特别优选大于35MPa。
3.如权利要求1或2所述的焊接方法,其特征在于,各自基于全部塑料材料,所述待接合的塑料材料各自40重量%以上、特别是60重量%以上、优选70重量%以上、优选90重量%以上由至少一种聚合物组成。
4.如权利要求1~3中任一项所述的焊接方法,其特征在于,所述底漆的聚合物与所述两种塑料材料的汉森参数的加权二次方距离(Ra)2小于17MPa,优选小于15MPa,特别优选小于12MPa。
5.如权利要求1~4中任一项所述的焊接方法,其特征在于,所述底漆包含其它聚合物,优选其与待接合的一种塑料材料的汉森参数的加权二次方距离(Ra)2、特别是其与待接合的两种塑料材料的汉森参数的加权二次方距离(Ra)2、且特别是其与所述底漆的第一聚合物的汉森参数的加权二次方距离(Ra)2小于22MPa,特别是小于17MPa,优选小于15MPa,特别优选小于12MPa。
6.如权利要求5所述的焊接方法,其特征在于,各自基于所述底漆的总重量,所述其它聚合物占所述底漆的含量为1~40重量%、特别是5~30重量%、特别优选10~20重量%,或者所述底漆不包含任何其它聚合物。
7.如权利要求1~6中任一项所述的焊接方法,其特征在于,所述底漆中所含的聚合物、特别是所述底漆中的每种聚合物、优选所述底漆基本上不含马来酸酐基团和/或胺基团,特别是基本上不含酸基团、酸酐基团、胺基团和/或羟基基团,优选基本上不含酸基团、酸酐基团、羟基基团、硫醇基团、胺基团、环氧基团和/或异氰酸酯基团,优选基本上不含任何反应性基团。
8.如权利要求1~7中任一项所述的焊接方法,其特征在于,所述底漆包含至少一种溶剂、特别是至少一种有机溶剂;各自基于所述底漆的总重量,所述底漆的溶剂含量优选为10~90重量%、特别是50~85重量%、特别优选60~80重量%。
9.如权利要求8所述的焊接方法,其特征在于,所述至少一种溶剂在20℃下的蒸气压为1~600hPa、特别是2~200hPa、特别优选5~20hPa;优选地,所述溶剂选自四氢呋喃、甲基异丁基酮、环己酮及它们的混合物。
10.根据权利要求1~9中任一项所述的焊接方法生产的物品。
11.权利要求1~9中任一项所述的方法中的底漆用于焊接两种不同的塑料材料的用途。
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Application publication date: 20180608