CN1970277A - 利用电磁辐射的熔接方法 - Google Patents

利用电磁辐射的熔接方法 Download PDF

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Publication number
CN1970277A
CN1970277A CNA2006101605577A CN200610160557A CN1970277A CN 1970277 A CN1970277 A CN 1970277A CN A2006101605577 A CNA2006101605577 A CN A2006101605577A CN 200610160557 A CN200610160557 A CN 200610160557A CN 1970277 A CN1970277 A CN 1970277A
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China
Prior art keywords
moulded parts
film
electromagnetic radiation
laser
welding
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CNA2006101605577A
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CN1970277B (zh
Inventor
R·格林
M·维尔皮茨
F·-E·鲍曼
K·库曼
S·蒙谢默
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Evonik Operations GmbH
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Degussa GmbH
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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
    • 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
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11Joint 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
    • B29C66/112Single lapped joints
    • B29C66/1122Single lap to lap joints, i.e. overlap joints
    • 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
    • B29C65/14Joining 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
    • B29C65/1429Joining 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 characterised by the way of heating the interface
    • B29C65/1435Joining 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 characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. transmission welding
    • 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
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    • B29C65/14Joining 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
    • B29C65/1477Joining 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 making use of an absorber or impact modifier
    • B29C65/148Joining 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 making use of an absorber or impact modifier placed at the interface
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/4805Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/481Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/4815Hot melt adhesives, e.g. thermoplastic adhesives
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    • 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
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    • B29C66/90Measuring or controlling the joining process
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    • B29C66/914Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9161Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/93Measuring or controlling the joining process by measuring or controlling the speed
    • B29C66/934Measuring or controlling the joining process by measuring or controlling the speed by controlling or regulating the speed
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0822Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
    • 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
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0855Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
    • 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
    • B29C65/14Joining 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
    • B29C65/1403Joining 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 characterised by the type of electromagnetic or particle radiation
    • B29C65/1412Infrared [IR] radiation
    • 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
    • B29C65/14Joining 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
    • B29C65/1403Joining 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 characterised by the type of electromagnetic or particle radiation
    • B29C65/1425Microwave radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
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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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    • B29C65/00Joining 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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    • B29C65/1654Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/1658Laser 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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    • BPERFORMING OPERATIONS; TRANSPORTING
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Abstract

可借助于膜C相互熔接两种不可相互直接熔接的模制件A和B,只要该膜的第一表面的材料与模制件A的材料相容且该膜的第二表面的材料与模制件B的材料相容以及只要膜C或与其相接触的表面区吸收电磁辐射。熔接如此进行,即使膜C的第一表面与模制件A相接触,并使膜C的第二表面与模制件B相接触,并入射电磁辐射。

Description

利用电磁辐射的熔接方法
技术领域
本发明涉及一种利用电磁辐射以单层膜或多层膜熔接模制件的方法。
背景技术
塑料模制件可用不同的塑料熔接方法相互连接,如通过高频熔接法、热脉冲熔接法、热接触熔接法、加热楔形熔接法或利用电磁辐射如激光、IR或微波辐射。在激光透射熔接时,通常应用透射激光的接合件和吸收激光的对接件。激光辐射穿过透射体并与相邻的吸收性模制体相遇,该模制体经局部受热而熔化。但该穿过透射接合件的激光束在接合时不能透入吸收对接件太深,而是在表面区域即已导致该吸收模制件熔化。由此导致在接合区内该激光束有利的局部转变成热。该扩展的熔体与透射对接件接触,并也使其局部熔化。压紧力有助于该接合连接的实现。热按需引入,并不可过早向外逸散。未经充填的热塑性塑料对在通常用于激光透射熔接的波长下的激光是相当透明的。与其它熔接方法相比,其优点是有非常好的连接光学外观和接合区的限于局部的加热。这同样适用于利用IR辐射或其它电磁辐射的熔接。
已知可利用置于中间的吸收激光的膜来相互熔接可透过激光的两个模制件(WO 00/20157;WO 02/38677;F. Krause等人,“MehrFreiheiten bei der Farbwahl”,Kunststoffe 10/2003,第196-199页)。但还不知应用两个由于其不相容性而不可直接相互熔接的模制件的这类方法。
此外,还已知一种制备由激光熔接的复合模制件的方法,该法中两塑料模制件A和B通过另一模制件C相互熔接,该模制件C含透射激光辐射的材料层C1和吸收激光辐射的材料层C2。该层C2与模制体A和B重叠,并在重叠区与A和B相连接。但以此方法得不到本发明所需几何形状的复合件。
发明内容
本发明的目的在于利用电磁辐射制备由两互不相容的模制件组成的复合件。
该目的是通过具有下列步骤的方法实现的:
a)制备模制件A,
b)制备模制件B,其材料与模制件A是不相容的,该摸制件A和B至少之一是可透电磁辐射的,
c)制备膜C,其第一表面的材料与模制件A的材料相容,其第二表面的材料与模制件B的材料相容,该膜C或与其相接触的表面区吸收电磁辐射,
d)使膜C的第一表面与模制件A接触,膜C的第二表面与模制件B接触,
e)入射电磁辐射,熔化膜C,和
f)使熔化区冷却。
具体实施方式
在本发明的一个可能的实施方案中,步骤d)如下进行,即:使膜C置于模制件A和B之间。随后在步骤e)中,在A和C之间以及在B和C之间同时进行熔接。
在本发明的另一个可能的实施方案中,步骤d)如下进行,即:使膜C与模制件A和B之一例如通过层叠预先连接。在特定情况下,该相关模制件在与膜接触时才形成。这可通过用熔融的模塑料注塑置于模中的膜以形成模制件,并同时与膜形成复合材料而进行。接着使该复合件与另一模制件接触。
本发明另一些可能的实施方案例如如下:
·模制件A和B之一或膜C吸收所用波长范围的电磁辐射,不需添加剂;
·电磁辐射的吸收通过加入吸收性添加剂引起;
·吸收电磁辐射的添加剂存在于模制件A和B之一中,位于整个模制件中、表面层中或就在表面上。例如该模制件可全部或在表面区中由例如填充有炭黑的模制料构成。该膜C需要时仅含少量或不含添加剂;
·吸收电磁辐射的添加剂存在于膜中。该实施方案是优选的,因为与上述实施方案相比,可更好地确保在熔接时形成膜与两模制件的牢固连接;
·所述膜是单层的;在此情况下其由与两模制件的材料具有强粘附性的材料制成;
·所述膜是双层的;其一层材料与模制件A呈最佳粘附,而另一层材料与模制件B呈最佳粘附。两膜层相互强粘附;
·所述膜是三层的,第一外层材料与模制件A呈最佳粘附,需要时其类似于模制件A的材料或与模制件A的材料相同;第二外层的材料与模制件B同样也是如此。两外层通过粘附促进剂层相互连接。以此方法在材料配对上得到很大程度的自由度。如果需要,该膜还可含四层或更多层;但这也增加制备成本。也必须要确保膜不太厚,以在辐照时整个厚度熔化;
·吸收电磁辐射的添加剂存在于所有膜层中。这样,可设想但不必需的是,例如在双层膜或三层膜情况下,每层膜均由含这种添加剂的模塑料形成。任选地,在不同区域存在吸收不同波长范围的不同的添加剂。如果在一侧需相互熔接不同深度区域时这是特别有利的;
·吸收电磁辐射的添加剂存在于膜C的一层中或视需要存在于多层中,但非所有层中。在不太厚的膜情况下,单吸收层足以在辐照时使膜在整个厚度区熔化。在三层膜情况下,添加剂因此可存在于所述外层的一层中或存在于中间层中或例如存在于外层的一层中以及中间层中;
·所述复合件在最简单情况下呈A/C/B结构。如果A和B对电磁辐射均是足够透射的,则入射可选择性地通过A或通过B进行;
·所述复合件含多于一个模制件A、多于一个模制件B和/或多于一层膜C。该模制件A或模制件B或模C可在形状、结构和组成上是不同的。例如按本发明可制备结构为A/C/B/C/A或A1/C1/B/C2/A2的复合件。在这些情况下,通过从两侧入射进行双倍熔接。
这些和其它的可设想的实施方案只要合适可相互组合。
作为模制件A和B可首先考虑以注塑、挤压、吹塑成型或通过其它原型或变型工艺(压制、模压、烧结、浇注)制备的模制件,包括膜和半成品(板、管、薄板、棒等)。这些模制件可按已知方法制备。该模制件也可由多部件如多层形成。至少该模制件之一必需是透激光的。
该模制件通常由热塑性聚合物构成,但也可由热固性塑料构成。
作为热塑性聚合物可考虑本领域技术人员已知的所有热塑性塑料。适用的热塑性聚合物例如描述于Kunststoff-Taschenbuch,Hrsg.Saechtling,25.Ausgabe,Hanser-Verlag,München,1992,特别是第四章以及其中引用的参考文献,以及Kunststoff-Taschenbuch,Hrsg.G.Becker und D.Braun,Bnde 1-11,Hanser-Verlag,Mǔnchen,1966-1996。
适用的热塑性塑料的实例为:聚氧化烯、聚碳酸酯(PC)、聚酯如聚对苯二甲酸丁二醇酯(PBT)或聚对苯二甲酸乙二醇酯(PET)、聚烯烃如聚乙烯或聚丙烯、聚(甲基)丙烯酸酯、聚酰胺、乙烯基芳族(共)聚合物如聚苯乙烯、经冲击韧性改性的聚苯乙烯如HI-PS、或ASA聚合物、ABS聚合物或AES聚合物、聚芳撑醚如聚亚苯醚(PPE)、聚砜、聚氨酯、聚交酯、含卤素聚合物、含亚酰氨基的聚合物、纤维素酯、硅氧烷聚合物和热塑性弹性体。也可使用不同热塑性塑料的混合物作为塑料模制件的材料。该混合物包括单相聚合物混合物或多相聚合物混合物。
待相互连接的模制件可由相同的或不同的热塑性塑料或热塑性塑料混合物组成。
聚氧化烯均聚物或共聚物特别是(共)聚甲醛(POM)以及其制备方法是本领域技术人员已知的,并在文献中有所描述。适用的材料例如以牌号Ultraform(BASF AG)可市购。最通常的是该聚合物在聚合物主链中含至少50摩尔%的重复单元-CH2O-。均聚物一般通过甲醛或三烷聚合,优选在合适的催化剂存在下进行制备。优选聚甲醛共聚物和聚甲醛三聚物。优选的聚甲醛(共)聚物的熔点至少为150℃,分子量(重均值)Mw为5000-200000,优选7000-150000g/mol。特别优选在链端有C-C-键的端基稳定化的聚甲醛聚合物。
适用的聚碳酸酯是已知的,例如按DE-B-1300266通过界面缩聚反应或按DE-A-1495730通过碳酸二苯酯与双酚的反应制得。优选的双酚是2,2-二(4-羟苯基)丙烷,通常称为双酚A。适用的聚碳酸酯可以牌号Lexan(GE Plastics B.V.,Holland)市购。
适用的聚酯也是已知的,并在文献中有所描述。其在主链中含芳环,该芳环来自芳族二羧酸。该芳环也可是取代的,例如通过卤素如氯或溴取代或通过C1-C4-烷基如甲基、乙基、异丙基或正丙基或正丁基、异丁基或叔丁基取代。该聚酯可以已知方法通过芳族二羧酸、其酯或其它生成酯的衍生物与脂族二羟基化合物的反应而制备。优选的二羧酸是萘二羧酸、对苯二酸和间苯二酸或其混合物。不超过30摩尔%的芳族二羧酸可用脂族或环脂族的二羧酸如己二酸、壬二酸、癸二酸、十二烷二酸和环己二羧酸替代。脂族二羟基化合物优选是含2-6个碳原子的二元醇,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-环己二甲醇和新戊二醇或其混合物。特别优选的聚酯是由含2-6个碳原子的链烷二醇衍生的聚对苯二酸亚烷基酯。其中特别优选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)。
适用的聚烯烃主要是聚乙烯和聚丙烯以及基于乙烯或丙烯的共聚物,任选还含高级α-烯烃。聚烯烃也应意指乙烯-丙烯弹性体和乙烯-丙烯三聚物。
聚(甲基)丙烯酸酯特别是指聚甲基丙烯酸甲酯(PMMA)以及基于甲基丙烯酸甲酯与不超过40重量%其它可共聚单体如丙烯酸正丁酯、丙烯酸叔丁酯或丙烯酸-2-乙基己酯的共聚物,如其可以牌号Lucryl(BASF AG)或Plexiglas(Rhm GmbH)市购。在本发明中,其也意指经冲击韧性改性的聚(甲基)丙烯酸酯以及经聚丙烯酸酯橡胶进行冲击韧性改性的聚(甲基)丙烯酸酯和SAN聚合物的混合物(如BASF AG公司的牌号为Terlux的市售产品)。
本发明中的聚酰胺应意指所有已知的聚酰胺,包括聚醚酰胺和聚醚嵌段酰胺以及它们的混合物。其实例是由含7-13个环的内酰胺衍生的聚酰胺,如聚己内酰胺、聚辛内酰胺和聚月桂内酰胺,以及通过二羧酸与二胺反应得到的聚酰胺。该聚酰胺也可是全芳族的或部分芳族的,部分芳族的通常称为PPA。
作为二羧酸可使用含6-14,特别是6-12个碳原子的链烷二羧酸和芳族二羧酸。这里可提及己二酸、壬二酸、癸二酸、十二烷二羧酸和对苯二酸和/或间苯二酸。
适合作二胺的特别是含6-12,特别是6-8个碳原子的链烷二胺以及间二甲苯二胺、二-(4-氨基苯基)甲烷、二-(4-氨基环己基)甲烷、2,2-二-(4-氨基苯基)丙烷或2,2-二-(4-氨基环己基)丙烷。
优选的聚酰胺是聚六亚甲基己二酰胺(PA 66)、聚六亚甲基癸二酰胺(PA 610)、聚六亚甲基十二烷二羧酸酰胺(PA 612)、聚己内酰胺(PA 6)、共聚酰胺6/66,特别是含5-95重量%己内酰胺单元的共聚酰胺6/66,以及聚月桂内酰胺(PA12)和PA 11,此外还有基于己内酰胺、对苯二酸和六亚甲基二胺的共聚酰胺或基于对苯二酸、己二酸和六亚甲基二胺的共聚酰胺。
此外还要提及如通过1,4-二氨基丁烷与己二酸在高温下的缩合反应得到的聚酰胺(PA 46)。这种结构的聚酰胺的制备方法例如描述于EP-A 0038094、EP-A 0038582和EP-A 0039524。
聚酰胺的其它实例是通过两种或多种前述单体的共聚反应得到的共聚酰胺,或多种聚酰胺的混合物,其中混合比是任意的。
下面的非最终的列表包括本发明中所述的以及其它的聚酰胺(括号中是单体);PA 46(四亚甲基二胺、己二酸)、PA 66(六亚甲基二胺、己二酸)、PA 69(六亚甲基二胺、壬二酸)、PA 610(六亚甲基二胺、癸二酸)、PA 612(六亚甲基二胺、癸烷二羧酸)、PA 613(六亚甲基二胺、十一烷二羧酸)、PA 614(六亚甲基二胺、十二烷二羧酸)、PA 1212(1,12-十二烷二胺、癸烷二羧酸)、PA 1313(1,13-二氨基十三烷、十一烷二羧酸)、PA MXD6(间二甲苯二胺、己二酸)、PATMDT(三甲基六亚甲基二胺、对苯二甲酸)、PA 4(吡咯烷酮)、PA 6(ε-己内酰胺)、PA 7(乙内酰胺)、PA 8(辛内酰胺)、PA 9(9-氨基壬酸)、PA 11(11-氨基十一烷酸)、PA 12(月桂内酰胺)。这些聚酰胺及其制备方法是已知的。关于其制备的详情,本领域技术人员可参阅Ullmanns Encyklopdie der Technischen Chemic,第4版,第19卷,第39-54页,Verlag Chemie,Weinheim 1980,和UllmannsEncyclopedia of Industrial Chemistry,Vol.A21,第179-260页,VCHVerlag,Weinheim 1992以及Stoeckhert,Kunststofflexikon,第8版,425-428页,Hanser Vershlag München 1992(词条“Polyamide”和以下)。
其它适用的热塑性材料是乙烯基芳族(共)聚合物。这种已知的市购聚合物的分子量通常为1500-2000000,优选70000-1000000g/mol。
这里苯乙烯、氯苯乙烯、α-甲基苯乙烯和对甲基苯乙烯的乙烯基芳族(共)聚合物仅是代表性的;共聚单体如(甲基)丙烯腈或(甲基)丙烯酸酯也可以小的比例(优选不大于20,特别是不大于8重量%)参与结构中。特别优选的乙烯基芳族(共)聚合物是聚苯乙烯、苯乙烯-丙烯腈共聚物(SAN)和冲击韧性改性的聚苯乙烯(HIPS=高冲击韧性聚苯乙烯)。当然也可使用这些聚合物的混合物。可按EP-A-0302485中所述方法制备。
此外,特别优选ASA聚合物、ABS聚合物和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)。这些冲击韧性的乙烯基芳族聚合物含至少一种橡胶弹性接枝聚合物和热塑性的聚合物(复制聚合物)。作为基质材料通常用苯乙烯/丙烯腈聚合物(SAN)。优选应用接枝聚合物,该接枝聚合物含基于二烯例如丁二烯或异戊二烯(ABS)的二烯橡胶、基于丙烯酸的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橡胶或这些橡胶或橡胶单体的混合物作为橡胶。
适用的ABS聚合物的制备例如已详述于DE-A 10026858或DE-A19728629中。ASA聚合物的制备可例如参阅EP-A 0099532。AES聚合物的制备例如公开在US 3055859或US 4224419中。
聚芳撑醚优选意指聚芳撑醚本身、聚芳撑醚硫化物、聚芳撑醚砜或聚芳撑醚酮。其芳撑基可以是相同的或不同的,并各自独立为具有6-18个碳原子的芳基。适用的芳撑基实例是亚苯基、亚联苯基、亚三联苯基、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。其中优选1,4-亚苯基和4,4’-亚联苯基。这些芳基宜为未取代的。但它们也可带一个或多个取代基。适用的聚亚苯基醚可以牌号Noryl(GE Plastics B.V.,Holland)市购。
聚芳撑醚本身是已知的或可按已知方法制备。
用于合成聚芳撑醚砜或聚芳撑醚酮的优选工艺条件例如描述于EP-A 0113112和EP-A 0135130中。适用的聚亚苯醚砜例如可以牌号UltrasonE(BASF AG)市购,适用的聚亚苯醚酮可以牌号Victrex市购。
此外,聚氨酯、聚异氰脲酸酯和聚脲类也是制备塑料模制件的适用材料。软性、半硬性或硬性的热塑性或交联的聚异氰酸酯加聚产物如聚氨酯、聚异氰脲酸酯和/或聚脲类通常是已知的。其制备有大量描述,并且通常由异氰酸酯与在一般已知条件下对异氰酸酯呈反应性的化合物的反应来制备。优选该反应在有催化剂和/或助剂条件下进行。
作为异氰酸酯可使用已知的芳族、芳脂族、脂族和/或环脂族的有机异氰酸酯,优选二异氰酸酯。
作为对异氰酸酯呈反应性的化合物可使用例如通常已知的分子量为60-10000g/mol和对异氰酸酯的官能度为1-8,优选2-6的化合物(在热塑性聚氨酯情况下官能度约为2),例如多元醇如分子量为500-10000g/mol的聚醚多元醇、聚酯多元醇和聚醚聚酯多元醇和/或分子量小于500g/mol的二元醇、三元醇和/或多元醇。
聚交酯即乳酸的聚合物是已知的,并可按已知的方法制备。
除聚交酯外,也可应用基于乳酸和其它单体的共聚物或嵌段共聚物。大多使用线性聚交酯。但也可应用分支的乳酸聚合物。例如多官能酸或醇可用作支化剂。
适用的含卤素的聚合物例如可提及氯乙烯的聚合物,特别是聚氯乙烯(PVC)如硬PVC和软PVC和氯乙烯的共聚物如PVC-U-模塑料。
此外,还可考虑含氟的聚合物,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醚的共聚物、乙烯-四氟乙烯共聚物(ETFE)、聚偏-1,1-二氟乙烯(PVDF)、聚乙烯氟化物(PVF)、聚氯三氟乙烯(PCTFE)和乙烯-氯三氟乙烯共聚物(ECTFE)。
含亚酰胺基的聚合物特别是聚亚酰胺、聚醚亚酰胺和聚酰胺亚酰胺。
适用的纤维素酯例如是乙酸纤维素、乙酰丁酸纤维素和丙酸纤维素。
此外,还可用硅氧烷聚合物作为热塑性塑料。特别适用的是硅橡胶。其中通常包括具有能进行交联反应的基团的聚有机硅氧烷。这类聚合物例如描述于Rmpp Chemie Lexikon,CD-ROM-Version 1.0,Thieme Verlag Stuttgart 1995。
最后,还可使用热塑性弹性体(TPE)类化合物。TPE可如热塑性塑料一样加工,但又有橡胶弹性特性。适用的有由两种或多种单体结构单元组成的TPE嵌段共聚物、TPE接枝共聚物和链段TPE共聚物。特别适用的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-丁烯-苯乙烯嵌段共聚物,通过SBS氢化而得)、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)和特别是热塑性硫化橡胶(TPE-V)。TPE详情可参阅G.Holden等人,ThermoplasticElastomers,2.Auflage,Hanser Verlag,München 1996。
此外,模制件A和B还可含通常的添加剂和加工助剂。
适用的添加剂和加工助剂例如是润滑剂或脱模剂、橡胶、抗氧化剂、耐光作用稳定剂、抗静电剂、防火剂或纤维状或粉末状填料或增强剂以及其它添加剂或它们的混合物。
适用的润滑剂和脱模剂例如是硬脂酸、十八烷醇、硬脂酸酯或硬脂酸酰胺、硅油、金属硬脂酸盐、褐煤蜡和基于聚乙烯和聚丙烯的蜡。
适用的抗氧化剂(热稳定剂)是如位阻酚、氢醌、芳基胺、亚磷酸盐、其各种取代物及其混合物。
适用的耐光作用稳定剂例如是各种取代的间苯二酚、水杨酸盐、苯并三唑、二苯酮和HALS(位阻胺光稳定剂)。
适用的抗静电剂例如是胺衍生物如N,N-双(羟烷基)烷基胺或N,N-双(羟烷基)亚烷基胺、聚乙二醇酯或甘油单硬脂酸酯和甘油二硬脂酸酯以及其混合物。
适用的防火剂例如是本领域技术人员已知的单独用或与三氧化锑组合用的含卤素的化合物或含磷化合物、氢氧化镁、红磷以及其它通用的化合物或其混合物。包括如在DE-A 19632675或在Encyclopedia ofChemical Technology,Hrsg.R.Kirk和D.Othmer,Vol.10,3.Aufl.,Wiley,New York,1980,第340-420页中所公开的磷化合物如磷酸酯,例如磷酸三芳基酯如三羟甲苯基磷酸酯、亚磷酸酯例如亚磷酸三芳酯,或亚膦酸酯。作为亚膦酸酯通常可应用双(2,4-二-叔丁基苯基)-苯基膦酸酯、三(2,4-二-叔丁基苯基)-膦酸酯、四(2,4-二-叔丁基-6-甲基苯基)-4,4’-亚联苯基二膦酸酯、四(2,4-二-叔丁基苯基)-4,4’-亚联苯基二膦酸酯、四(2,4-二甲基苯基)-1,4-亚联苯基二膦酸酯、四(2,4-二-叔丁基苯基)-1,6-亚己基二膦酸酯和/或四(3,5-二甲基-4-羟苯基)-4,4’-二亚联苯基二膦酸酯或四(3,5-二-叔丁基-4-羟苯基)-4,4’-二亚联苯基二膦酸酯。
此外,基于氢氧化物或碳酸盐,特别是镁的氢氧化物或碳酸盐的无机防火剂、无机和有机硼化合物如硼酸、硼酸钠、氧化硼、四苯基硼酸钠和硼酸三苄酯、含氮的防火剂如亚氨基磷烷、密胺氰脲酸酯和聚磷酸铵以及密胺磷酸酯(参见Encyclopedia of ChemicalTechnology,出处同上)也是适用的。此外也可考虑用含抗滴剂如特氟隆或高分子聚苯乙烯的混合物作为防火剂。
纤维状或粉末状的填料和增强物质的实例是碳纤维或呈玻璃织物、玻璃毡或玻璃粗纱、碎玻璃以及玻璃珠形式的玻璃纤维,特别优选玻璃纤维。所用的玻璃纤维可以由E-玻璃、A-玻璃或C-玻璃制成,并优选用例如基于环氧树脂、硅烷、氨基硅烷或聚氨酯的粘料和基于官能化的硅烷的粘附促进剂处理。该玻璃纤维可以短玻璃纤维或无限长线条(粗钞)形式引入。
适用的细粒填料例如是无定形二氧化硅、须晶、氧化铝纤维、碳酸镁(白垩)、粉化石英、云母、膨润土、滑石、长石或特别是硅酸钙如硅灰石和高岭土。
纤维状、粉末状或细粒状的填料和增强物质的用量按模制件计通常为1-60,优选10-50重量%。
此外,模制件A或B还可含有着色剂。由此该模制件A和B可以是相同颜色的或不同颜色的。
由聚合物模塑料、添加剂、加工助剂和/或着色剂制备模制件可按已知的混合方法进行,例如在熔融下于挤压机、Banbury混合机、捏和机、滚压机或延压机中进行。但所述组分也可“冷”态使用,且粉末状混合物或由颗粒组成的混合物在加工时才熔融和匀质化。
任选地含有所述添加剂、加工助剂和/或着色剂的所述组分优选在挤压机或另一混合设备中于100-320℃、热塑性聚合物熔融情况下进行混合和排料。应用挤压机是特别优选的,特别是应用同向旋转的密啮合双杆挤压机。
或者,两模制件之一可由不是塑料的材料如木材、金属(如铝、镁、钢)、陶瓷或石料制成。该另一模制件则对电磁辐射是透射的。
模制件A的材料与模制件B的材料是不相容的。结果两模制件不能直接熔接,因为不产生粘附性或没有足够的粘附性。
当本领域技术人员通过入射电磁辐射熔接可通透电磁辐射的模制件A和含有有效量的吸收电磁辐射的添加剂的模制件B而得到一个模制件,其中断开该熔接所需的拉应力(按DIN EN ISO 527的拉伸试验测定)小于2N/mm2,优选最大为1.5N/mm2和特别优选最大为1N/mm2时,可达到的粘附性是不足够的。
对膜C的材料基本上可利用前述的热塑性塑料或模塑料。在材料选用方面,本领域技术人员可在已知是相容的宽材料对范围内选择。
通常膜厚为最大500μm,最大400μm,最大300μm,最大250μm或最大200μm,而最小厚度为10μm,15μm,20μm,25μm或30μm。
适用的材料组合的典型实例如下:
a)将由市售聚酰胺模塑料(如基于PA 6、PA 66、PA 610、PA612、PA 1010、PA 11、PA 12或上面提及过的聚酰胺之一)制成的模制件A通过例如由基于以密胺酸酐接枝的聚丙烯(如AdmerQB 520E)的模塑料制成的含有如炭黑作为添加剂的模与由市售的聚丙烯模塑料制成的模制件B相连接。所达到的粘附性是合格的。
b)在a)中提及的模制件A和B可实现较牢固连接,只要应用置于其间的双层膜,并且该膜邻接模制件A的层由含如炭黑作添加剂的聚酰胺模塑料制成(最好是基于与模制件A相同的聚酰胺),而邻接模制件B的层由基于以密胺酸酐接枝的聚丙烯(如AdmerQB 520E)的模塑料制成。
c)还可由b)开始额外增加模制件强度,只要利用置于其间的三层模,并且该膜邻接模制件A的层由聚酰胺模塑料制成(最好是基于与模制件A相同的聚酰胺),而邻接模制件B的层由市售的聚丙烯模塑料制成;该两层通过置于其间的基于以密胺酸酐接枝的聚丙烯(如AdmerQB 520E)制成的粘附促进层相连接。添加剂(如炭黑)可选择性地含于聚酰胺层中、粘附促进层中和/或聚丙烯层中。
上述三层膜,还有如b)中使用的双层膜,均可用已知方法制备,如通过共挤压制备。
d)另一实例是由PA 12模塑料制成的模制件(例如盖)与由PBT模塑料制成的模制件(例如外壳)借助于置于其间的双层膜熔接,其中邻接PBT模制件的层(层厚如为50μm)由PA 12、PBT和相容性促进剂(如按E-A-0509211或EP-A-1065048)的混合物制成,而邻接PA 12模制件的层(层厚如为50μm)由PA 12模塑料制成。添加剂如炭黑可选择性地含于一层或另一层中。
吸收电磁辐射的添加剂可以是炭黑。其它适用的吸附性添加剂是骨炭、石墨、其它碳颗粒、碱式磷酸铜(KHP)、染料、颜料或金属粉末。如EP-A-0797511中所述的干扰颜料也是很适合的;相应的产品以牌号Iriodin销售。在WO 00/20157和WO 02/38677中所述的添加剂也是很适用的(如ClearWeld)。
此外,还适用的有:云母或云母颜料、二氧化钛、高岭土、氧化锑(III)、金属颜料、基于氯氧化铋的颜料(如Merck的Biflair系列,高亮颜料)、氧化铟锡(纳米ITO粉末,来自Nanogate TechnologiesGmbH或Degussa的AdNanoITO)、AdNano氧化锌(Degussa)、六氯化镧似及市售的防火剂,其含氰脲酸密胺或磷,优选磷酸盐、亚磷酸盐、膦酸盐或元素(红)磷。
如果应避免其特性色受干扰,吸收利优选含干扰颜料,特别优选Merck的Iriodin LS系列或ClearWeld
可按炉炭黑法、煤气炭黑法或火焰炭黑法制备炭黑,优选按炉炭黑法制备。初始粒度为10-100nm,优选为20-60nm,粒度分布可窄可宽。按DIN 53601测定的BET表面积为10-600m2/g,优选70-400m2/g。该炭黑颗粒可经氧化性后处理以调节表面官能度。其可调节成疏水性的(如Degussa的Printex 55或Flammruβ 101)或亲水性的(如Degussa的Farbruβ FW20或Printex 150 T)。其可为高结构化的或低结构化的;由此可描述原始主颗粒的集结度。通过应用特定的导电炭黑可调节由本发明粉末制备的构件的导电性。通过应用珠粒状炭黑可利用在湿混合工艺和干混合工艺下的较好的可分散性。应用炭黑分散体也是有利的。
骨炭是一种含元素碳的矿物质黑颜料。其由达70-90%的磷酸钙和达30-10%的碳所组成。密度通常为2.3-2.8g/ml。
吸收剂也可含有机和/或无机颜料的混合物、防火剂或其它着色剂,其中每一种本身在100-3000nm波长范围内均不吸收或很少吸收入射的电磁能,但成组合后可足够好地用于本发明方法中吸收入射的电磁能。
在膜或膜层中的吸收性添加剂的浓度通常为0.05-20重量%,优选0.1-5重量%,特别优选0.2-1.5重量%。
电磁辐射入射下的熔接可相应于现有技术所建议的在压紧压力下进行。
该电磁辐射的频率范围无限制。例如可以是微波辐射、IR辐射或优选激光辐射。
在本发明方法中所用的激光辐射的波长通常为150-11000nm,优选700-2000nm,特别优选800-1100nm。
原则上所有通常的激光器均适用,例如气体激光器和固体激光器。气体激光器例如是(括号中是辐射光束的典型波长):CO2激光器(10600nm),氩气体激光器(488nm和514.5nm),氦-氖气体激光器(543nm,632.8nm,1150nm),氪气体激光器(330-360nm,420-800nm),氢气体激光器(2600-3000nm),氮气体激光器(337nm);固体激光器例如是(括号中是辐射光束的典型波长):Nd:YAG激光器(Nd3+:Y3Al5O12)(1064nm),高功率二极管激光器(800-1000nm),红宝石激光器(694nm),F2准分子激光器(157nm),ArF准分子激光器(193nm),KrCl准分子激光器(222nm),KrF准分子激光器(248nm),XeCl准分子激光器(308nm),XeF准分子激光器(351nm)以及波长为532nm(频率倍增)、355nm(频率增至三倍)或266nm(频率增至四倍的频率增大Nd:YAG-激光器。
所用激光器的功率通常为1-200瓦,优选5-100瓦,特别是10-50瓦。
所用激光器的能量密度在文献中作为所谓的“单位长度能量输入(Streckenenergien)”给出,在本发明中通常为0.1-50J/mm。实际的能量密度定义为入射功率/产生的熔接面积。该值相当于单位长度能量输入/产生的熔接缝宽之比值。所用激光器的实际能量密度通常为0.01-25J/mm2
要选用的能量密度除该透明体的反射特性外还尤其与待连接的塑料模制件是否含填料或增强物质或其它强吸收激光的或强散射激光的物质有关。对小反射的和不含填料或增强物质的聚合物,该能量密度通常为1-20J/mm,特别是3-10J/mm。对含填料或增强物质的聚合物,该能量密度通常为3-50J/mm,特别是5-20J/mm。
可在本发明中使用的相应激光器是市购可得的。
特别优选的激光器在短波的红外范围发射。这种特别优选的激光器是固体激光器,特别是Nd:YAG激光器(1064nm)和高功率二极管激光器(800-1000nm)。
激光辐射可以是位置固定(不动)的,而待连接的模制件可移动通过激光源。也可以是模制件位置固定(静止),而激光源可移动通过模制件。
在激光源可移动情况下,可通过光学或光学-机械设备移动整个激光器、仅移动激光器头、或仅移动由激光器射出的激光辐射。这种设备例如可以是棱镜、反射镜、导光电缆特别是玻璃纤维电缆、和其它在激光技术中常用的设备,以及这些设备的组合。也可既移激光源也移动模制件。
激光源相对于模制件的移动速度(下面简称“速度”)在例如外形熔接情况下通常为1-10000mm/s,优选5-5000mm/s,特别是50-1000mm/s。
关于激光器功率和速度,存在上述的上限和下限,这尤其是因为在太高激光器功率或太低速度下,在模制件的待连接位置上的聚合物材料会发生分解(热损伤),而在太低激光器功率或太高速度下,不再产生高质量(即耐久牢固和密实)的熔接缝,因为该熔接所需的扩散过程需要一定的热作用时间。
在某些情况下,在激光熔接前对待连接的模制件进行干燥是有利的,以避免由于蒸发的水产生熔接缝缺陷。
该激光透射熔接可以各种实施方式进行。最重要的例举如下:轮廓熔接是一种顺序熔接工艺,其中激光束沿自由可编程控制的缝轮廓行进或构件相对于固定安装的激光器移动。熔接缝宽按激光器类型、光学装置和透激光的模制件的散射不同而强烈变化,通常为0.6-5mm。
同时熔接:各高功率二极管的呈线状发射的光束沿待熔接的缝轮廓排布。整个外形的熔化和熔接同时完成。
准同时熔接或扫描熔接:该方案是轮廓熔接和同时熔接的组合。激光束通过电流计镜(扫描器)以高速度沿熔接缝轮廓来回移动。由此待连接区逐渐受热并完全熔化。
掩模熔接:线状激光束横向于待连接的部件移动。激电束被处于激光器和构件之间的掩模有选择性地遮蔽,并仅在应熔接的部位射到构件上。掩模中的最精细结构可达高分辨率,并且熔接缝宽仅为10μm。
按本发明方法得到的复合模制件特别是例如家用设备和电气设备或用于汽车、飞机或轮船外用或内用的外壳、容器例如燃料罐、包装、常用制品、构件、紧固件等。
该复合件的主要特征在于,熔接缝是不透液体和气体的。
本发明方法也特别适于制备含另外构件的组合模制件。这些另外的构件可以是例如由金属、玻璃、陶瓷、聚合物、橡胶或其它材料制成的机械(包括精密机械)、电气、电子、光学、声学或其它构件。
按本发明制备的复合件也是本发明的目的。
所达到的熔接强度可通过按DIN EN ISO 527的拉伸试验直接对模制件或在锯下的部分上进行测定。使熔接裂开所需的拉伸应力通常最小为2N/mm2,优选最小为3N/mm2,最小为4N/mm2,最小为5N/mm2,最小为6N/mm2,最小为7N/mm2,最小为8N/mm2,最小为9N/mm2,最小为10N/mm2

Claims (10)

1.一种用于由至少两个互相不可直接熔接的模制件制备复合件的方法,其具有下列步骤:
a)制备模制件A,
b)制备模制件B,其材料与模制件A的材料不相容,
c)制备膜C,其第一表面的材料与模制件A的材料相容,其第二表面的材料与模制件B的材料相容,其中膜C或与其相接触的表面区吸收电磁辐射,
d)使膜C的第一表面与模制件A接触,膜C的第二表面与模制件B接触,
e)入射电磁辐射,熔化膜C,和
f)使熔化区冷却。
2.权利要求1的方法,其特征在于,在步骤d)中将所述膜置于模制件A和B之间。
3.权利要求1的方法,其特征在于,在步骤d)中使膜C首先与模制件A和B之一相连接。
4.上述权利要求之一的方法,其特征在于,膜C由两层、三层、四层或多层组成。
5.上述权利要求之一的方法,其特征在于,膜C或与其相接触的表面区含有吸收电磁辐射的添加剂。
6.权利要求5的方法,其特征在于,所述吸收电磁辐射的添加剂仅存在于由两层、三层、四层或多层组成的膜C的一层中。
7.上述权利要求之一的方法,其特征在于,所述复合件含一个以上的模制件A、一个以上的模制件B和/或一层以上的膜C。
8.上述权利要求之一的方法,其特征在于,膜C的厚度为10-500μm。
9.上述权利要求之一的方法,其特征在于,使用微波辐射、IR辐射或激光辐射作为电磁辐射。
10.一种按权利要求1-9之一制备的复合件。
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CN102112294B (zh) * 2008-08-05 2015-01-28 弗雷泽纽斯医疗保健德国有限公司 通过激光透射焊接方法生产复合体的方法
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CN101912196B (zh) * 2010-07-01 2011-09-07 深圳创怡兴实业有限公司 电磁熔接式清洁刷、密封刷的生产方法
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CN106462111B (zh) * 2014-06-03 2019-08-09 斯沃奇集团研究和开发有限公司 由焊接材料制成的用于钟表的由外部零件组成的构件
CN108136681A (zh) * 2015-10-16 2018-06-08 汉高股份有限及两合公司 焊接两种聚酰胺塑料的方法
CN108136682A (zh) * 2015-10-16 2018-06-08 汉高股份有限及两合公司 焊接两种不同的聚烯烃塑料的方法
CN108136683A (zh) * 2015-10-16 2018-06-08 汉高股份有限及两合公司 焊接聚酰胺和聚(甲基)丙烯酸酯塑料的方法
CN106313519A (zh) * 2016-08-17 2017-01-11 江苏大学 一种提高激光透射焊接强度的方法

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