CN108136679A - 焊接聚烯烃塑料和基于含有羰基基团的聚合物的塑料的方法 - Google Patents

焊接聚烯烃塑料和基于含有羰基基团的聚合物的塑料的方法 Download PDF

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Publication number
CN108136679A
CN108136679A CN201680059675.0A CN201680059675A CN108136679A CN 108136679 A CN108136679 A CN 108136679A CN 201680059675 A CN201680059675 A CN 201680059675A CN 108136679 A CN108136679 A CN 108136679A
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China
Prior art keywords
priming paint
polymer
plastic material
welding
polyolefin
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CN201680059675.0A
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English (en)
Inventor
P·沃尔特
N·费里德里克
L·冈萨雷斯
H·吕岑
T·黑蒂希
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 CN108136679A publication Critical patent/CN108136679A/zh
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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
    • B29C65/40—Applying molten plastics, e.g. hot melt
    • B29C65/405—Applying molten plastics, e.g. hot melt characterised by the composition of the applied molten plastics
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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Abstract

本发明涉及使用底漆焊接聚烯烃塑料和基于至少一种含有羰基基团的聚合物的塑料的方法，相对于所述底漆中的聚合物的比例，所述底漆含有至少20wt.％的包含马来酸酐单元或马来酸酐衍生物单元的聚合物。本发明还涉及相应的焊接产品。

Description

焊接聚烯烃塑料和基于含有羰基基团的聚合物的塑料的方法
本发明涉及使用底漆将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的方法，所述底漆含有至少20wt.％的包含马来酸酐单元或马来酸酐衍生物单元的聚合物，基于所述底漆的聚合物比例。本发明还涉及相应的焊接产品。
现有技术已知各种方法用于将由塑料材料如聚乙烯(PE)、聚丙烯酸酯或聚酰胺(PA)组成的两个或更多个基材相互连接。对于此，同时存在机械连接选择，如闩接或螺钉连接，和粘接方法。或者，塑料材料也可以彼此焊接。焊接是用于通常在类似塑料材料之间如PE与PE或PA与PA之间建立不可分离的实质上物理连接的接合工艺。类似的热塑性材料是在其分子结构、熔融温度、熔融粘度和热膨胀系数方面彼此之间基本上没有差别的聚合物，并且所述聚合物原则上能够仅在有限程度上彼此混合。通常，类似的塑料材料为具有相同聚合物基质的塑料材料，或相同的塑料材料。
已知非常广泛的方法用于将两种或更多种类似的塑料材料焊接在一起。可使用非常广泛的焊接方法，如红外焊接、红外/振动焊接或超声焊接。用于焊接类似塑料材料的这些方法基于相关塑料材料在焊接区的区域中熔化，并且所述材料在所述区域中彼此整体结合且摩擦连接。
只要意欲将类似的塑料材料相互连接，这些焊接方法就是有效的。然而，一旦彼此不同或不相容的两种塑料材料意欲焊接到一起，例如由聚酰胺和聚烯烃组成的塑料材料，就不再可能在两种基材之间建立具有高度机械强度的持久连接。在借助于现有技术已知的焊接方法将两种塑料材料聚酰胺和聚烯烃(例如聚乙烯或聚丙烯和聚酰胺6)彼此直接焊接的试验中，没有获得强度或仅获得非常低的强度。
直到现在，相应的不同塑料材料仅能够借助于机械连接或粘接方法相互连接。机械连接是不利的，因为连接是复杂的，在某些点处存在材料应力并且需要额外的机械连接装置。此外，在机械连接中，很少可以实现整体结合连接。然而，粘接方法是不利的，因为连接的最终强度只能在长时间之后实现，可能长达几周。此外，低能量表面的结合通常要求接合构件经受复杂的预处理过程。另外，由于外部风化，粘合连接通常仅在有限的时间内是稳定的。此外，提供清洁的粘合连接往往复杂且耗时。因此，通过焊接塑料材料的方法建立连接是最清洁、最快速和最简单的解决方案。
因此，本发明的目标是提供将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的简单方法。由于焊缝，这些不同塑料材料之间的连接应是尽可能稳定且永久的。
已经令人惊讶地发现，该目标是通过使用底漆将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的方法来实现，所述底漆含有至少20wt.％的至少一种包含马来酸酐单元或马来酸酐衍生物单元的聚合物，基于所述底漆的聚合物比例。
当将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料时，使用含有至少一种相应聚合物的底漆导致可以在所述塑料材料之间获得特别稳定的整体结合的连接。
使用底漆进行焊接的第一接合构件是聚烯烃塑料材料，特别是聚烯烃热塑性材料。聚烯烃塑料材料基于聚烯烃类聚合物，如α-烯烃的均聚物和共聚物。所述聚烯烃类聚合物可选自由下述组成的组：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，和基于乙烯、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、1-辛烯的共聚物，或它们的组合。特别是，所述聚烯烃塑料材料选自聚乙烯塑料材料(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聚乙烯塑料材料)和聚丙烯塑料材料。所述聚烯烃塑料材料特别优选为聚丙烯塑料材料。
所述聚烯烃聚合物，特别是聚丙烯聚合物，优选具有大于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的重均分子量(重均Mw)。所述聚烯烃聚合物，特别是聚丙烯聚合物，优选具有小于2,000,000g/mol、特别是小于1,000,000g/mol、优选小于500,000g/mol的重均分子量(重均Mw)。特别优选的聚乙烯聚合物具有50,000g/mol至1,000,000g/mol、特别是200,000g/mol至500,000g/mol的重均分子量(重均Mw)。其它优选的聚乙烯聚合物(UHMW-PE聚合物)具有大于2,000,000g/mol、特别是4,000,000-6,000,000g/mol之间的重均分子量。特别优选的聚烯烃聚合物(特别是聚丙烯聚合物)具有50,000g/mol至250,000g/mol的重均分子量(重均Mw)。
聚烯烃塑料材料(特别是聚丙烯塑料材料)也可含有其他组分，例如填料例如玻璃纤维、颜料、染料、流变助剂、脱模助剂或稳定剂。在各种情况下基于聚烯烃塑料材料的聚合物比例(不含填料的整个聚烯烃塑料材料)，大于80wt.％、特别是大于90wt.％、优选大于98wt.％的聚烯烃塑料材料(特别是聚乙烯和/或聚丙烯塑料材料、优选聚丙烯塑料材料)优选由所提及的聚烯烃聚合物、特别是所提及的聚乙烯和/或聚丙烯聚合物、优选聚丙烯聚合物组成。在各种情况下基于整个聚烯烃塑料材料(含有填料)，大于50wt.％、特别是大于70wt.％、优选大于90wt.％、更优选大于95wt.％、特别优选大于98wt.％的聚烯烃塑料材料(优选聚丙烯塑料材料)优选由所提及的聚烯烃聚合物、特别是聚丙烯组成。
使用底漆进行焊接的第二接合构件是基于含有羰基基团的聚合物的塑料材料。在本发明的范围内，"基于含有羰基基团的聚合物"表示塑料材料的聚合物比例的至少50wt.％、优选70wt.％由含有羰基基团的聚合物组成。含有羰基基团的聚合物优选是聚酰胺或聚酯，特别是聚对苯二甲酸酯。
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-氨基十一酸的缩聚物(聚-11-氨基十一烷酰胺)；聚酰胺12，ω-月桂内酰胺的均聚物(聚月桂内酰胺)；聚酰胺6.6，己二胺与己二酸的均缩聚物(homopolycondensate)(聚己二酰己二胺)；聚酰胺6.10，己二胺与癸二酸的均缩聚物(聚癸二酰己二胺)；聚酰胺6.12，己二胺与十二烷二酸的均缩聚物(聚十二烷酰己二胺)或聚酰胺6-3-T，三甲基六亚甲基二胺与对苯二甲酸的均缩聚物(聚三甲基六亚甲基对苯二甲酰胺)，苯二胺与对苯二甲酸的聚(对亚苯基-对苯二甲酰胺)或聚(间亚苯基对苯二甲酰胺)，不同二胺与对苯二甲酸的聚邻苯二甲酰胺PPA，和它们的混合物。
光学透明的聚酰胺包含含有直链脂族二羧酸和脂环族二胺的微晶聚酰胺、含有直链脂族二羧酸和脂环族二胺以及任选含有内酰胺或氨基羧酸的无定形聚酰胺、含有对苯二甲酸和脂环族或支化脂族二胺以及任选含有内酰胺或氨基羧酸的无定形聚酰胺，或含有间苯二甲酸和脂环族二胺或直链或支化脂族二胺以及任选含有内酰胺或氨基羧酸的无定形聚酰胺。适合的光学透明的聚酰胺例如为：十二烷二酸与4,4'-双(氨基环己基)-甲烷的异构体混合物的酰胺，对苯二甲酸与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混合物的酰胺，十二烷二酸与3,3'-二甲基-4,4'-双(氨基环己基)-甲烷的异构体混合物的酰胺，月桂内酰胺、间苯二甲酸与3,3'-二甲基-4,4'-双(氨基环己基)-甲烷的异构体混合物的酰胺，或十四烷二酸与3,3'-二甲基-4,4'-双(氨基环己基)-甲烷的异构体混合物的酰胺，或ε-己内酰胺或ω-月桂内酰胺的酰胺。
优选的聚酰胺选自由下述组成的组：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、光学透明的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下述组：聚酰胺6、聚酰胺6.6、聚酰胺12、聚邻苯二甲酰胺、光学透明的聚酰胺和它们的混合物，特别是聚酰胺6、聚酰胺6.6、聚酰胺12、聚邻苯二甲酰胺和它们的混合物。所述聚酰胺塑料材料还可含有其他组分，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。在各种情况下基于整个聚酰胺塑料材料(含有填料)，大于40wt.％、特别是大于60wt.％、优选大于70wt.％、更优选大于90wt.％的聚酰胺塑料材料优选由所提及的聚酰胺组成。在各种情况下基于聚酰胺塑料材料的聚合物比例(不含填料的整个聚酰胺塑料材料)，大于90wt.％、特别是大于95wt.％、优选大于98wt.％的聚酰胺塑料材料优选由所提及的聚酰胺组成。在各种情况下基于整个聚酰胺塑料材料(含有填料)，所述聚酰胺塑料材料优选具有50-90wt.％、特别是60-80wt.％的所提及聚酰胺的含量。
适合的聚酯塑料材料本身同样是已知的，并且在文献中有描述。优选的聚酯塑料材料包含在主链上具有衍生自芳族二羧酸的芳环的聚酯。所述芳环也可以被取代，例如被卤素如氯或溴或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。聚酯可通过使芳族二羧酸、其酯或其其他成酯衍生物与脂族二羟基化合物反应以本身已知的方式来制备。优选的二羧酸包括萘二甲酸、邻苯二甲酸、对苯二甲酸和间苯二甲酸或它们的混合物。至多30mol.％的芳族二羧酸可被脂族或脂环族二羧酸如己二酸、壬二酸、癸二酸、十二烷二酸和环己烷二羧酸取代。脂族二羟基化合物之中，优选具有2至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-环己烷二甲醇和新戊二醇或它们的混合物。特别优选的聚酯包括衍生自具有2至6个C原子的烷烃二醇的聚对苯二甲酸亚烷基酯。
所述聚酯塑料材料优选选自下述的组：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)塑料材料和它们的混合物，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)塑料材料和它们的混合物。所述聚酯塑料材料还可含有其他组分，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。在各种情况下基于整个聚酯塑料材料(含有填料)，大于40wt.％、特别是大于60wt.％、优选大于70wt.％、更优选大于90wt.％的聚酯塑料材料、特别是PET或PBT塑料材料优选由所提及的聚酯组成。在各种情况下基于聚酯塑料材料的聚合物比例(不含填料的整个聚酯塑料材料)，大于90wt.％、特别是大于95wt.％、优选大于98wt.％的聚酯塑料材料优选由所提及的聚酯组成。在各种情况下基于整个聚酯塑料材料(含有填料)，所述聚酯塑料材料优选具有50-90wt.％、特别是60-80wt.％的所提及聚酯的含量。
本发明的另一个必要部分是使用至少一种底漆，优选恰好是一种底漆。所述底漆含有至少20wt.％、特别是至少50wt.％、优选至少70wt.％的至少一种含有马来酸酐单元或马来酸酐衍生物单元、特别是马来酸酐单元的聚合物，基于所述底漆的聚合物比例。
所述底漆是在接合区域范围内优选作为预处理层施加至待焊接的基材的至少一个表面的焊接助剂。所述底漆不应被理解为粘合剂、清洁剂等，而是底漆是焊接助剂，借助于该焊接助剂，接合区域(或焊接区域)中的连接构件彼此相容，从而在接合期间在接合区域中待焊接的基材之间产生整体结合和摩擦连接。
试验表明，通过使用含有根据本发明的聚合物的相应底漆，待接合的塑料材料在焊接期间在接合焊接中能够相容，因而能够获得稳定且持久的连接。不使用相应的底漆，无法获得焊接连接强度或仅获得非常低的焊接连接强度。接合基材优选具有大于2MPa、特别是大于5MPa的拉伸强度。根据关于试验描述的程序，使用5mm/s的牵引速度来测定拉伸强度。
至少一种第一聚合物为在其聚合物骨架中含有已经在其中反应或聚合的马来酸酐基团的聚合物，特别是共聚物。所述聚合物可在骨架中以聚合形式含有马来酸酐基团，例如至少一种马来酸酐单体与丙烯酸酯和/或α-烯烃单体的共聚物形式，或接枝形式，如马来酸酐接枝的聚烯烃形式。马来酸酐或马来酸酐衍生物、特别是马来酸酐可反应或聚合到聚合物中。马来酸酐衍生物的实例为包含相关5元酸酐基团的1,2,3,6-四氢邻苯二甲酸酐。
所述底漆的至少一种聚合物特别优选为马来酸酐接枝的聚烯烃，特别是马来酸酐接枝的聚乙烯或马来酸酐接枝的聚丙烯。
在另一个特别优选的实施方式中，除马来酸酐或马来酸酐衍生物之外所述底漆优选还含有包含选自下述的组的一种或多种聚合的单体的共聚物：丙烯酸酯和甲基丙烯酸酯(合一起为(甲基)丙烯酸酯)、特别是具有含有1至12个碳原子、优选1至4个碳原子的烷基官能团的(甲基)丙烯酸酯，优选(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸；和α-烯烃，特别是乙烯、丙烯、1-丁烯、1-己烯和1-辛烯，优选乙烯。此外，也可以使用具有官能团例如环氧化物或异氰酸酯基、羧基或氨基以及烷氧基硅烷基团的功能性单体。所述至少一种共聚物在聚合物中特别优选含有至少一种马来酸酐(衍生物)、至少一种(甲基)丙烯酸酯和至少一种α-烯烃，优选马来酸酐、具有C1至C4烷基官能团的(甲基)丙烯酸酯和乙烯或丙烯。
所述聚合物可通过已知的方式由所述单体来合成。另外，所述聚合物可在类似聚合物的反应中被接枝。特别优选的用于接枝目的的反应伴侣为醇、硫醇、胺、异氰酸酯、酸酐、羧酸，特别是醇，优选具有1至6个碳原子的醇，如甲醇和异丁醇。为了接枝，马来酸酐单体或马来酸酐单元可在聚合物中与反应伴侣反应，特别是被醇酯化。优选仅一些马来酸酐基团被反应或被酯化，特别是小于70％的马来酸酐基团。特别优选马来酸酐基团是未反应的，并且仍作为酸酐基团存在。在优选的实施方式中，马来酸酐基团也可以以部分水解的形式存在。完全反应的马来酸酐基团会导致所得到的焊接连接的强度的降低。
基于聚合物，具有大于或等于0.001wt.％、特别是大于或等于0.01wt.％、优选大于或等于0.02wt.％、特别优选大于或等于0.05wt.％的马来酸酐含量的聚合物是特别有利的。基于聚合物，所述聚合物有利地具有0.01-15wt.％、特别是0.02-10wt.％、优选0.5-5wt.％的马来酸酐含量。在另一个优选实施方式中，基于聚合物，所述聚合物具有2-30wt.％、特别是5-15wt.％的马来酸酐含量。使用具有相应马来酸酐含量的聚合物，焊接连接的强度特别高。
所述聚合物有利地具有大于或等于5,000g/mol、特别是大于或等于50,000g/mol、优选大于或等于100,000g/mol的重均分子量Mw。所述聚合物优选具有在5,000-2,000,000g/mol、特别是50,000-1,000,000g/mol、优选100,000-500,000g/mol范围内的重均分子量Mw。具有相应重均分子量的聚合物对获得的连接的脆性和强度具有积极效果。重均分子量可借助于GPC，通过与聚苯乙烯标准物比较来测定。
除第一聚合物之外，所述底漆可优选含有至少一种其他聚合物。所述至少一种其他聚合物优选与待焊接的两种塑料材料的至少一种相容，并且与底漆共聚物相容。特别优选所述底漆含有至少一种聚烯烃和/或聚酰胺聚合物，在各种情况下优选以上规定的那些。除根据本发明的共聚物之外，在底漆中使用另外的聚合物可进一步提高强度。
作为相容的其他聚合物，优选使用相对于待接合的塑料材料之一，特别是两种，特别是还相对于根据本发明的上述第一聚合物，具有小于22MPa、特别是小于17MPa、优选小于15MPa、特别优选小于12MPa的Hansen参数的加权二次方(weighted quadratic distance)(Ra)2的聚合物。
Hansen参数的加权二次方(Ra)2根据下式来求出：
(Ra)2＝4(ΔδD)2+(ΔδP)2+(ΔδH)2
在该式中，δD是伦敦色散力的Hansen参数，δP是极性的Hansen参数和δH是氢键的Hansen参数。ΔδD、ΔδP和ΔδH各自表示相比较的塑料材料或聚合物的这些Hansen参数的差值，例如ΔδD＝聚合物1和2的(δD1-δD2)。有关塑料材料或聚合物的单独的Hansen参数δD、δP和δH的值根据书籍Charles M.Hansen的"Hansen Solubility Parameters：AUser′sHandbook"(第二版；Taylor&Francis Group；2007；ISBN-10 0-8493-7248-8)来确定。在该来源中能够找到单个聚合物的各自值。根据该书中描述的方法，Hansen参数可优选使用HSPIP程序(第4版4.1.07)从随其提供的数据库中导出，或如果无法获得，如所述指南中描述的，可使用所述程序含有的"DIY"功能，优选使用随其提供的神经网络来确定。HSPIP程序可从Steven Abbott TCNF Ltd获得。
在各种情况下基于底漆的总重量，在所述底漆中，其他聚合物、特别是聚烯烃聚合物和/或聚酰胺聚合物的含量优选为1-40wt.％，特别是5-30wt.％，特别优选10-20wt.％。在各种情况下基于底漆的总聚合物比例(不含溶剂且不含填料的底漆)，在所述底漆的聚合物含量中，所述其他聚合物的含量优选为5-70wt.％，特别是20-60wt.％，特别优选30-50wt.％。
除根据本发明的聚烯烃聚合物和所述其他聚合物之外，所述底漆还可以含有溶剂，特别是有机溶剂。在各种情况下基于底漆的总重量，所述底漆优选具有10-95wt.％、特别是50-90wt.％、特别优选70-85wt.％的溶剂含量。
适合的溶剂为所有常规溶剂，如水、醇如乙醇、烷烃如异辛烷、酮如甲基异丁基酮(MIBK)或环己酮(CH)、醚如二乙基醚或四氢呋喃(THF)、酯如乙酸乙酯、或碳酸酯如碳酸二甲酯或碳酸二丙酯、甲苯、二甲苯或它们的混合物。
如果使用有机溶剂，则在各种情况下基于底漆的总重量，底漆的全部聚合物含量优选为1-90wt.％，特别是2-50wt.％，特别优选5-15wt.％。总聚合物含量对应于用于所述聚合物中的所有聚合物的含量，特别是根据本发明的聚合物和以上描述的其他聚合物。
在另一个优选实施方式中，底漆以水分散体或水乳液形式存在。在这种情况下，根据本发明的聚合物或(如果存在的)其他聚合物在水中乳化或分散。在这种情况下，在各种情况下基于底漆的总重量，底漆的全部聚合物含量优选为5-90wt.％，特别是20-70wt.％，特别优选30-55wt.％。对于水分散体/乳液，有利的是所述聚合物组分基本上仅由根据本发明的聚合物和任选存在的上述其他聚合物组成，特别是基本上仅由根据本发明的聚合物或其混合物组成。根据本发明，术语"基本上"理解为表示大于95wt.％、优选大于97wt.％、非常特别优选大于99wt.％的聚合物组分由根据本发明的聚合物和任选存在的上述其他聚合物组成，特别是仅由根据本发明的聚合物组成。
在特别优选的实施方式中，底漆基本上不含溶剂。
除根据本发明的聚合物、上述其他聚合物和溶剂之外，底漆可含有其他组分，如填料、(荧光)染料和颜料、流变助剂、消泡助剂、湿润助剂、稳定剂或增塑剂。然而，除染料和颜料之外，底漆优选基本上不含其他组分，特别是基本上不含任何其他组分。根据本发明，表述"基本上不含"应理解为表示所述底漆含有小于5wt.％、优选小于1wt.％、非常特别优选小于0.1wt.％的相应物质，并且特别是完全不含有相应物质。
在根据本发明的将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的方法中，使用底漆，所述底漆含有至少20wt.％的包含马来酸酐单元或马来酸酐衍生物单元的聚合物，基于所述底漆的聚合物比例。
在该方法中，底漆用作助剂在各种情况下通过熔融使两种不同塑料材料焊接。所使用的含有根据本发明的聚合物的底漆使得能够在两种接合构件之间建立相容性，作为其结果，可以在两种塑料材料之间建立稳定、持久且整体结合的连接。
所述底漆可使用各种各样的方法施加至接合构件之一或两者的表面。例如，它可以通过以下方式施加：借助于定量给料装置，借助于针和定量给料机器人，通过注射成型，通过挤出，通过以膜形式施加，通过以热熔体形式施加，通过喷射，通过铺展或通过浸渍。所述底漆可仅被施加至待焊接的基材的一个表面或两个表面。所述底漆优选仅施加到一个表面，特别是聚酰胺表面。
如果底漆含有溶剂，则在施加到一个或两个表面之后，干燥所述底漆，优选直到溶剂已经蒸发到出现非粘性的、尺寸稳定的底漆层的程度。特别是，所述底漆可在几秒和至多几周后被焊接。所述底漆优选在施加后进行干燥至少一个小时、优选至少12小时。
所述底漆优选被施加到待焊接的基材的一个表面或两个表面，以使所述底漆具有1μm至10,000μm、特别是100-5,000μm、优选500-3,000μm、特别优选1,000-2,000μm的层厚度。特别是，大于100μm的层厚度是优选的。如果底漆中含有溶剂，则层厚度是指通过溶剂干燥的底漆。
在底漆已经施加到待焊接的基材的一个表面或两个表面之后和在所述底漆任选已被干燥之后，可使用传统焊接方法将待焊接的基材互相连接。通常通过在接合平面中局部塑化的接合构件将塑料材料焊接并在压力下接合。选择工艺参数，以使熔体的显著压缩屈服导致接合平面中接合构件之间的最佳连接。加热可以通过对流、接触加热、辐射或摩擦来发生。用于塑化的不同能量输入可以通过多种方式实现，并导致用于焊接塑料材料的不同工艺。适合的焊接方法包括：
·热风焊接[HG]
借助于热气流的对流加热，通常是空气；两阶段工艺
·热板焊接[HE]
接触加热；两阶段工艺
·超声焊接[US]
通过摩擦加热；超声波范围内的横波导致在接触面加热，一阶段工艺
·高频焊接[HF]
通过内摩擦加热；根据高频磁场使极性分子取向；一阶段；仅用于极性塑料材料和膜
·振动焊接[VIB](摩擦焊接：直线；轨道；旋转；角度)
通过摩擦加热；一阶段工艺
·激光焊接[LW](轮廓(contour)；同时；准同时；掩模)
通过辐射加热；相干辐射；激光传输焊接；通常是一阶段(二阶段也可以)
·红外焊接[IR]
通过辐射加热；非相干辐射；两阶段
以上提及的焊接方法也可任选组合，例如红外焊接与振动焊接组合。塑料材料特别优选通过选自下述的焊接方法焊接：热板焊接、热接触焊接或热脉冲焊接、暖风焊接或热风焊接、振动焊接、微波或感应焊接、激光拼焊(laser butt welding)或激光传输焊接(laser transmission welding)、红外焊接、超声焊接、和它们的组合，特别是选自：红外焊接、热板焊接、振动焊接、超声焊接、和它们的组合。
预期用于将两种塑料材料使用底漆整体结合且包括下述步骤的方法是特别优选的：
·提供具有第一接合区域的第一塑料材料，
·提供具有第二接合区域的第二塑料材料，
·预加热所述第一接合区域，
·将底漆施加至预加热的第一接合区域，特别是不含溶剂的底漆，
·使设置有所述底漆的第一接合区域与第二接合区域接触，
·将所述第一接合区域整体结合至第二接合区域，特别是通过使用用于焊接塑料材料的常规方法，如红外焊接、热板焊接、暖风焊接、振动焊接和超声焊接。
根据DIN 1910-3：1977-09的说明通常可用于焊接塑料材料。因此，焊接塑料材料可理解为表示使用热和/或压力将热塑性材料整体结合。加热可例如基于接触加热(通过固体焊接)、对流加热(通过暖风焊接)、辐射加热(通过光束焊接)、摩擦加热(通过运动焊接)和电流焊接来进行。
在有利的方案(development)中，使用经选择且适合于所述方法的底漆，以使在具有低于底漆中聚合物的分解温度的温度的加热的和/或热的接合区域的施加不影响底漆的内部化学交联。
将第一塑料材料的第一接合区域预加热是有利的。对于预加热，可使用本领域技术人员已知且适合于预定目的的辅助装置和技术。特别是，使用暖风或等离子适合于预加热。借助于辐射、特别是红外辐射或激光照射的预加热也是想得到的。加热板或加热的工具也可以用于预加热第一接合区域。最后，在炉或加热的室中预加热也是想得到的。预加热整个塑料材料，从而也预加热所述接合区域，也是想得到的。然而，作为替代或另外，仅预加热所述接合区域本身也是可以的。
在有利的方案中，在预加热期间从加热装置到塑料材料(特别是待预加热的第一接合区域)的间距、特别是加热装置的热散发区域或加热装置的热释放区域或待预加热的加热装置的有效表面或加热装置与第一接合区域相对的区域至塑料材料的间距，在0.5mm至100mm的范围内，优选在1mm至60mm的范围内。或者，也可以想到借助于通过加热装置的加热元件与第一接合区域接触进行加热，和/或特别是在通过加热装置的加热元件与第一接合区域接触期间进行加热。
另一个优点是选择用于第一接合构件的塑料材料和调节第一塑料材料的方法参数，以使第一接合区域在预加热期间熔融和在预加热期间在第一接合区域中产生熔融层。在优选的实施方式中，熔融层的厚度优选在0.05mm至6mm的范围内，特别优选在0.1mm至5mm的范围内。这种熔融层能够导致分子之间改进的粘合性和/或扩散和/或相互作用，并且与某种流动结合，能够导致改进的连接层。如果第一塑料材料的界面层处在熔融状态下，则可能发生与底漆的相互作用或甚至化学结合。所述熔融层特别可取决于组件几何结构和特定的组件设计。优选调节和/或选择方法参数，以使不发生组件变形。接合区域与待施加的底漆之间的温度差优选通过适合的措施和/或方法步骤来平衡。在这种情况下，特别可想得到的是，将底漆预加热，以缩小优选的热塑性底漆与第一接合区域之间的温度差。例如，这可以抵消工艺步骤之间的第一接合区域的快速冷却。
优选在预加热第一接合区域的步骤之前，任选预处理所述第一接合区域。作为替代或另外，也可以预处理第二接合区域。例如，作为可能的预处理，借助于溶剂或塑料清洁剂(例如碱)的清洁也是想得到的。也可以使用机械预处理，特别是通过刮擦、砂光、刷涂或喷砂。想得到的化学预处理特别是酸清洁或使用反应性气体。此外，使用热、化学和/或物理预处理已证明是适当的，特别是借助于气体火焰或等离子弧。作为替代或另外，借助于电晕放电的电预处理，其中将第一接合区域和/或第二接合区域暴露于电晕放电，从而可导致在相应表面上形成极性分子。另一个可能性是等离子处理，优选使用用于预处理接合区域的等离子喷嘴，特别是为了实现相应表面的活化和/或清洁。同时，借助于等离子提供涂层也可证明是适当的。另一个可能性是火焰处理接合区域，以增大适合的塑料材料中的表面张力。另一类预处理是暴露至UV辐射、电子辐射、放射性辐射或借助于激光的辐射。最后，预处理可以是提供涂层、特别是涂料或粘合促进剂的涂层。在预加热之前以更长的时间间隔预处理第一塑料材料或第一塑料材料的接合区域，也是想得到的。因此，例如可想得到的是，进行作为第一塑料材料的制造方法的一部分的预处理，以便可以在根据本发明的方法中进一步处理预处理的塑料材料。
其中施加底漆的方式存在各种可能性。例如，特别是在工业领域中，借助于自动化辅助装置，特别是借助于定量给料机器人的施加，是想得到的。所述机器人可配备有针和/或高度传感器，以便能够进行复杂的定量给料工艺。底漆也可以通过注射成型来施加，通过底漆在注射成型机中塑化并且在压力下注入含有具有第一接合区的第一塑料材料的模具中来施加。或者，膜施加是想得到的，首先在第一步中，借助于吹膜或平膜挤出，制备由底漆组成的膜。然后，可以例如通过切割或冲压工艺将膜切割成任何形状，并在所提及的预加热之后的另一步骤中将膜施加到第一接合区域。在这种情况下，使用具有在1μm至5,000μm范围内的厚度的膜/片材已证明是适当的。其他可想到的施加选择包括挤出焊接，其中底漆以焊丝的形式存在或可以在挤出机中熔化并以熔融形式施加到第一接合区域。也可以以焊丝的形式提供所述底漆，以便使得能够借助于热风焊接施加所述底漆。另一个选择是借助于喷雾法施加底漆。在借助于注射成型施加过程中，预处理和/或预加热和/或局部改变注射模具的温度控制也是可以的。当然，本领域技术人员已知且适合于具体应用的其他类型施加也是想得到的。
另一个优点是在施加底漆的同时进一步加热第一接合区域，特别是以防止预加热与底漆施加之间的第一接合区域的温度下降。这可通过以上描述的用于预加热的方法步骤来进行，为了方便，其可在施加期间继续。作为替代或另外，补充加热(特别是借助于其他方法步骤)是可以的。例如，可证明适当的是在施加过程中同时加热第一接合区域，例如通过将第一接合区域同时暴露于辐射、强制对流或接触加热，以防止预加热后第一接合区域的温度下降。
在有利的方案中，施加底漆以使在第一接合区域上设置厚度在1μm至5mm范围内、优选在10μm至3mm范围内的连接层。连接层的厚度理解为表示第一接合区域上的连接层的材料厚度。
另一个优点是借助于定量给料装置将底漆施加至第一接合区域，同时第一接合区域与定量给料装置之间相对运动，在施加底漆之前，借助于加热装置将要施加底漆的第一接合区域预加热，同时所述第一接合区域与加热装置之间相对运动，当第一接合区域处于预加热状态下时，借助于所述定量给料装置施加底漆。
在这种情况下，已证明特别有利的是，加热装置在预加热期间以10mm/min至100m/min范围内、优选以10mm/min至30m/min范围内的速度在第一接合区域上被引导。
将加热装置优选以规定和恒定的间距领先定量给料装置，也可以是有利的。特别有利的是，进行所述方法以使底漆通过定量给料装置被施加至第一接合区域，所述定量给料装置与第一接合区域以10mm/min至100m/min范围内、优选10mm/min至30m/min范围的速度相对运动，在施加底漆之前，借助于加热装置将要施加底漆的所述接合区域预加热，所述加热装置与第一接合区域进行相对运动，所述加热装置优选同时领先所述定量给料装置或定量给料装置的喷嘴，以便在0.1-10s范围内的时间间隔施加所述底漆。
在这种情况下，使用由定量给料装置和加热装置组成的涂布单元已证明是特别有利的。涂布单元可特别理解为表示以下单元：在加热装置与定量给料装置之间提供固定连接以使加热装置在相对运动期间以规定和恒定的间距领先定量给料装置，以确保在施加底漆之前立即预加热第一接合区域。当然，能够调节间距或者在对流预加热的情况下，特别是借助于适合的机械、机电或甚至气动操作的调节器来调节体积流量或所述装置的喷嘴直径，在此也是可以想到的。
然而，涂布单元也可以理解为作为两个组件的加热装置和定量给料装置，它们彼此完全分离但相对于塑料材料参与相同或基本相同的相对运动，以确保在施加所述底漆之前即刻预加热待施加所述底漆的位置。
在有利的方案中，尽管加热装置和定量给料装置相对于塑料材料参与基本相同的主要相对运动或基本方向，但除所述主要相对运动之外，两种提及的装置中的至少一种相对于塑料材料进行附加的相对运动。因此，例如除其中也可以施加底漆的主要相对运动之外，例如，加热装置和/或定量给料装置可参与一种或多种次要的相对运动。例如，特别是加热装置和/或定量给料装置可参与或进行围绕主要相对运动的环绕或曲折的次要相对运动。
在这种情况下，一方面，可移动塑料材料，或另一方面，可移动加热装置和定量给料装置或一起作为涂布单元的两个装置。在这种情况下，一方面，加热装置和定量给料装置或者一起作为涂布单元的两个装置可以空转或与相关的运动部件一起沿不同的方向移动，或者另一方面，塑料材料可以空转或与相关的运动部件一起沿不同的方向移动。
在有利的方案中，以10mm/min至100m/min范围内、优选10mm/min至30m/min范围内的速度产生主要相对运动，例如特别是还借助于加热装置的适当设计，导致塑料材料在加热装置的加热区域内的停留时间尽可能短，特别是在1s至60s范围内。所述加热区域可理解为表示在温度升高的意义上对温度有影响(即第一塑料材料的第一接合区域的预加热)的围绕加热装置的区域或空间。因此，例如可防止对塑料材料的太多的加热和破坏或损害。
另外，特别是对于现有生产线上/中连接定量给料装置和/或加热装置，为加热装置配备总线接口、特别是Profibus或实时以太网接口，可以证明是有利的。
在已经施加所述底漆之后，将第二接合区域与底漆层接触。在此，将两种塑料材料彼此固定可以证明是有利的，特别是使用本领域技术人员已知的夹持装置或类似的固定辅助装置。
在将第二接合区域与底漆层接触的步骤之前，第二接合区域当然任选可以进行预处理。在这种情况下，特别是，所有以上描述的预处理技术是想得到的。在接触之前以更长的时间间隔预处理第二塑料材料或第二塑料材料的接合区域，也是想得到的。因此，例如可想得到的是，进行作为第二塑料材料的制造方法的一部分的预处理，以便可以在根据本发明的方法中进一步加工预处理的塑料材料。第二塑料材料的预处理还可以包括将底漆施加至第二接合区域。在这种情况下，可想得到的是，还优选在施加底漆之前预加热第二接合区域。在此时，以上实施方式同样是优选的。
在第二接合区域与底漆之间的上述接触后，进行接合工艺，其中通过供热将经处理和/或涂布的接合构件塑化，并优选在压力作用下将彼此整体结合。对于所述第二接合区域与底漆之间的整体结合连接，可想得到的是，借助于热传导提供加热，例如借助于热板焊接和/或热接触焊接和/或热脉冲焊接；借助于摩擦，特别是超声焊接、摩擦/振动焊接或高频焊接、微波或感应焊接；借助于对流，例如暖风焊接或热风焊接；借助于辐射，例如红外焊接、激光拼焊或激光传输焊接，或甚至借助于两种或更多种这些技术的组合。
本发明的其它主题涉及使用根据本发明的方法制造的物品或产品。
本发明还涉及根据本发明的底漆用于将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的用途。
实施例
使用的材料和缩写：
PA＝聚酰胺
PA 6＝聚己内酰胺
PA 6.6＝聚(N,N'-己二酰己二胺)
PA 12＝聚月桂内酰胺
PA 6.12＝聚(十二烷二酰己二胺)
PPA＝聚邻苯二甲酰胺
PP＝聚丙烯
PE＝聚乙烯
PET＝聚对苯二甲酸乙二醇酯
PBT＝聚对苯二甲酸丁二醇酯
MAH＝马来酸酐
底漆1＝PP-MAH，其MFR(230℃；2.16kg)＝7-12
底漆2＝PE-(MD)-MAH，其MFR(190℃；21.6kg)＝12-22
底漆3＝PE-(LD)-MAH，其MFR(190℃；21.6kg)＝1.6
底漆4＝PE-(LLD)-MAH，其MFR(190℃；21.6kg)＝2.5
底漆5＝乙烯、丙烯酸丁酯和马来酸酐的三元共聚物
底漆6＝乙烯、丙烯酸乙酯和马来酸酐的三元共聚物
底漆7＝聚烯烃；丙烯酸酯和MAH改性的；Mw＝67,500g/mol
试验燃料组成：
FAM B(体积％)
甲醇 15.00
水 0.50
甲苯 42.25
异辛烷 25.35
二异丁烯 12.68
乙醇 4.23
总计 100.00
IR：红外焊接；IR-VIB：红外/振动焊接；US：超声焊接
试验件的制备：
为了制备试验件，将底漆、聚合物1至4和待焊接的塑料材料在注射成型机的塑化单元中熔融(230℃)，并处理，以便形成130mm×68mm×3mm的板。
为了测试与这些材料的相容性，在各种情况下，通过IR焊接和振动焊接，将板的130mm×3mm表面边缘对边缘焊接到相同表面积的PE、PP、PA和PPA。在焊接24小时后，锯开焊接板两侧的8mm，将板剩下的分成两半(垂直于接合平面切割)，并在室温下使用拉伸试验在5mm/s的测试速度下测试。
下表显示，对于底漆与使用的塑料材料以及焊接方法的每种组合，焊接的试验件可以获得的拉伸强度(MPa)：
该表显示所述底漆对于PA、PPA和PP的优异强度。没有底漆的纯PP和纯PE对于PA和PPA仅显示出非常低的强度，并在焊接之后不施加显著量的力的情况下分解。
在多组分注射成型工艺中，将底漆注射到聚酰胺或PE上。为此，首先将150mm×66.2mm×4mm的聚酰胺和PE板注射成型，并插入到150mm×75mm×4mm的空腔中，并在进一步的注射成型工艺中将底漆聚合物注射到PA或PE塑料材料上。将注入的底漆层机械加工至1.8mm的厚度。将底漆层焊接至另一塑料材料，并如上所述，将焊接的板锯开并进行测试。
下表显示，对于底漆与使用的塑料材料以及焊接方法的每种组合，焊接的试验件可以获得的拉伸强度(MPa)：
使用底漆层焊接的塑料材料显示出优异的强度。没有底漆的情况下，塑料材料在焊接之后在没有施加显著量的力的情况下分解。
焊接的塑料材料的老化：
下表显示使用的聚合物和相关的底漆。根据上述方法，将底漆聚合物板和在多组分注射成型工艺中施加到塑料材料的底漆VIB焊接到另一塑料材料。在室温下，在试验燃料FAM-B中，和在两种不同的交替气候试验中，进行老化。在室温和5mm/s牵引速度下得到的强度给出在下表中，以MPa计：
在使用的试验装置中，在使用的试验条件下，包含底漆的焊接的塑料材料显示出优异的耐老化性。
作为底漆的三元共聚物：
在另一个工艺中，测试底漆5(乙烯、丙烯酸丁酯和马来酸酐的三元共聚物)和底漆6(乙烯、丙烯酸乙酯和马来酸酐的三元共聚物)。将底漆5在热压机中220℃下挤压以形成0.5mm厚的膜，并借助于暖风熔融到PE上，并IR-VIB焊接至PA。将底漆6在280℃下熔融，并借助于热板焊接焊接至PE和PA。
下表显示，对于底漆与使用的塑料材料以及焊接方法的每种组合，焊接的试验件可以获得的拉伸强度(MPa)：
使用底漆层焊接的塑料材料显示出优异的强度。没有底漆的情况下，塑料材料在焊接之后在没有施加显著量的力的情况下分解。
使用聚合物底漆1和7的PET和PBT的热板焊接：
在310℃下，将PP、PET和PBT分别在加热板上的30mm×4mm表面上熔融20s、15s和30s，将待接合的两种塑料材料浸渍到底漆聚合物的熔体中，并在低压下将涂有底漆的聚合物接合。对于该目的，使用底漆聚合物1和7。在室温下24小时后，在室温下，在拉伸试验机中，以5mm/s的试验速度测试焊接的试样。聚合物组合和使用的底漆聚合物以及相关的强度一起示出在下表中：
使用规定的底漆聚合物，可以得到焊接的试样的良好强度。没有底漆，使用热板焊接的样品仅具有低强度。

Claims (10)

1.使用底漆将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的方法，其中，基于所述底漆的聚合物比例，所述底漆含有至少20wt.％的至少一种包含马来酸酐单元或马来酸酐衍生物单元的聚合物。
2.根据权利要求1所述的焊接方法，其特征在于，所述聚烯烃塑料材料选自下述的组：聚乙烯塑料材料，特别是HD聚乙烯、MD聚乙烯、LD聚乙烯、UHMW聚乙烯或LLD聚乙烯塑料材料，和聚丙烯塑料材料。
3.根据权利要求1或2之一所述的焊接方法，其特征在于，所述基于至少一种含有羰基基团的聚合物的塑料材料选自聚酯塑料材料，特别是聚对苯二甲酸酯塑料材料，或聚酰胺塑料材料。
4.根据权利要求1至3之一所述的焊接方法，其特征在于，所述底漆的至少一种聚合物选自下述的组：至少一种马来酸酐单体和至少一种丙烯酸酯单体和/或α-烯烃单体的共聚物，和马来酸酐接枝的聚烯烃。
5.根据权利要求1至4之一所述的焊接方法，其特征在于，所述底漆的至少一种聚合物具有0.01-35wt.％、特别是0.02-25wt.％、优选0.05-20wt.％，特别优选0.05-15wt.％的马来酸酐含量，基于所述聚合物。
6.根据权利要求1至5之一所述的焊接方法，其特征在于，所述底漆的至少一种聚合物具有在5,000-2,000,000g/mol、特别是50,000-1,000,000g/mol、优选100,000-500,000g/mol范围内的重均分子量Mw。
7.根据权利要求1至6之一所述的焊接方法，其特征在于，除第一聚合物之外，所述底漆含有至少一种与待焊接的两种塑料材料中的至少一种相容的其他聚合物，优选至少一种聚酰胺聚合物和/或至少一种聚烯烃聚合物。
8.根据权利要求1至7之一所述的焊接方法，其特征在于，所述底漆含有至少一种溶剂，特别是水，在各种情况下基于底漆的总重量，所述底漆优选具有10-95wt.％、特别是50-85wt.％、特别优选60-80wt.％的溶剂含量。
9.使用根据权利要求1至8之一的焊接方法制造的物品。
10.根据权利要求1至8之一的底漆用于将聚烯烃塑料材料焊接至基于至少一种含有羰基基团的聚合物的塑料材料的用途。
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