CN111655475B - 金属-碳纤维强化树脂材料复合体和金属-碳纤维强化树脂材料复合体的制造方法 - Google Patents

金属-碳纤维强化树脂材料复合体和金属-碳纤维强化树脂材料复合体的制造方法 Download PDF

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CN111655475B
CN111655475B CN201980009784.5A CN201980009784A CN111655475B CN 111655475 B CN111655475 B CN 111655475B CN 201980009784 A CN201980009784 A CN 201980009784A CN 111655475 B CN111655475 B CN 111655475B
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resin
carbon fiber
metal
layer
cfrtp
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CN111655475A (zh
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郡真纯
河村保明
植田浩平
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • 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
    • B29C65/18Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • 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
    • B29C65/4805Joining 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
    • 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
    • B29C65/50Joining 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
    • 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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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • 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
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    • B29C66/40General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
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    • B29C66/45Joining of substantially the whole surface of the articles
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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
    • 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
    • B29C66/72General 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 structure of the material of the parts to be joined
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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
    • 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
    • B29C66/72General 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 structure of the material of the parts to be joined
    • B29C66/723General 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 structure of the material of the parts to be joined being multi-layered
    • B29C66/7232General 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 structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer
    • B29C66/72321General 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 structure of the material of the parts to be joined being multi-layered comprising a non-plastics layer consisting of metals or their alloys
    • 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
    • B29C66/73General 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
    • B29C66/7311Thermal properties
    • B29C66/73115Melting point
    • B29C66/73116Melting point of different melting point, i.e. the melting point of one of the parts to be joined being different from the melting point 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
    • 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
    • B29C66/73General 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
    • 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
    • B29C66/73General 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
    • B29C66/73921General 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 characterised by the materials of both parts being thermoplastics
    • 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
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    • B29C66/742Joining plastics material to non-plastics material to metals or their alloys
    • B29C66/7428Transition metals or their alloys
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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
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    • B29C66/80General aspects of machine operations or constructions and parts thereof
    • B29C66/83General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/832Reciprocating joining or pressing tools
    • B29C66/8322Joining or pressing tools reciprocating along one axis
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/90Measuring or controlling the joining process
    • B29C66/91Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • 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
    • B29C66/9141Measuring 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 temperature
    • B29C66/91421Measuring 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 temperature of the joining tools
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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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
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    • B29C66/9192Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明提供了一种金属‑碳纤维强化树脂材料复合体,具有金属构件、设置在金属构件的至少一面上的树脂层、和设置在树脂层的面上的碳纤维强化树脂材料,金属构件是钢铁材料或铁系合金,树脂层含有热塑性树脂,碳纤维强化树脂材料含有碳纤维材料和具有热塑性的基体树脂,树脂层的玻璃化转变温度Tg1或熔点Tm1比碳纤维强化树脂材料的玻璃化转变温度Tg2或熔点Tm2高,将金属‑碳纤维强化树脂材料复合体浸渍在含有5质量%氯化钠的水溶液时在频率1Hz下的交流阻抗为1×107Ω以上。

Description

金属-碳纤维强化树脂材料复合体和金属-碳纤维强化树脂材 料复合体的制造方法
技术领域
本发明涉及金属-碳纤维强化树脂材料复合体和金属-碳纤维强化树脂材料复合体的制造方法。
背景技术
使碳纤维含在基体树脂中复合化而成的碳纤维强化塑料(CFRP:Carbon FiberReinforced Plastics)重量轻且抗拉强度、加工性等优异。因此,CFRP被广泛用于民生领域到产业用途。汽车产业中,为了满足与油耗、以及其他性能提高有关的车体轻量化的需求,关注于CFRP的轻量性、抗拉强度、加工性等已经研究了将CFRP用于汽车构件。
但是、在仅是将CFRP用于汽车构件的情况,存在CFRP的压缩强度小的问题,基体树脂使用热固性树脂的CFRP有容易产生脆性破坏等问题。因此,最近开发了将金属构件与CFRP层叠一体化(复合化)的复合材料。
为了将金属构件与CFRP复合化,需要将金属构件与CFRP接合,作为接合方法已知通常的使用环氧树脂系热固性粘接剂的方法。但是、如前所述,在基体树脂中使用热固性树脂的CFRP存在容易产生脆性破坏的问题,所以开发了基体树脂使用热塑性树脂的热塑性碳纤维强化塑料(CFRTP:Carbon Fiber Reinforced Thermo Plastics)。
例如、在以下的专利文献1中提出了通过注射成型制造由金属材料、CFRTP、CFRTP的基体树脂等层叠而成的CFRTP复合体。
现有技术文献
专利文献
专利文献1:日本特开2016-150547号公报
发明内容
发明要解决的课题
但是、本发明人发现了,根据金属构件与CFRTP的接合条件不同,有金属构件与碳纤维接触的可能性,与周围的水分之类的电解液一起形成局部电池,产生金属构件腐蚀的现象(异种材料接触腐蚀)。此外,本发明人发现了,在金属构件是钢铁材料或铁系合金的情况,由于它们的表面不能形成稳定的氧化皮膜或钝化膜,是比较容易被腐蚀的材料,所以异种材料接触腐蚀发生得更为显著。
于是,本发明鉴于上述问题而完成,其目的是提供能够抑制由金属构件更具体的是钢铁材料或铁系合金与碳纤维强化树脂材料中的碳纤维之间的接触而产生的异种材料接触腐蚀的、金属-碳纤维强化树脂材料复合体。
解决课题的手段
本发明鉴于上述认识而完成,其主要思想如下。
[1].一种金属-碳纤维强化树脂材料复合体,具有金属构件、设置在所述金属构件的至少一面上的树脂层、和设置在所述树脂层的面上的碳纤维强化树脂材料,
所述金属构件是钢铁材料或铁系合金,所述树脂层含有热塑性树脂,所述碳纤维强化树脂材料含有碳纤维材料和具有热塑性的基体树脂,
所述树脂层的熔点Tm1比所述碳纤维强化树脂材料的熔点Tm2高,
将所述金属-碳纤维强化树脂材料复合体浸渍在含有5质量%氯化钠的水溶液时在频率1Hz下的交流阻抗为1×107Ω以上。
[2].如[1]所述的金属-碳纤维强化树脂材料复合体,所述树脂层中含有的热塑性树脂是与所述基体树脂不同的树脂。
[3].如[1]或[2]所述的金属-碳纤维强化树脂材料复合体,所述树脂层的熔点Tm1和所述基体树脂的熔点Tm2满足下述式(1)的关系,其中Tm1和Tm2的单位都是℃,
Tm2≤Tm1-10℃ 式(1)。
[4].如[1]~[3]的任一项所述的金属-碳纤维强化树脂材料复合体,所述树脂层的厚度为5μm以上。
[5].如[1]~[4]的任一项所述的金属-碳纤维强化树脂材料复合体,所述钢铁材料或铁系合金是具有锌系镀层的镀敷钢材。
[6].如[1]~[5]的任一项所述的金属-碳纤维强化树脂材料复合体,所述基体树脂含有选自苯氧类树脂、聚碳酸酯类树脂、聚对苯二甲酸乙二醇酯类树脂、聚2,6-萘二甲酸乙二醇酯类树脂、尼龙类树脂、聚丙烯类树脂、聚乙烯类树脂、聚环氧醚酮类树脂和聚苯硫醚类树脂中的至少1种热塑性树脂,
所述树脂层中含有的树脂含有选自聚碳酸酯类树脂、聚对苯二甲酸乙二醇酯类树脂、聚2,6-萘二甲酸乙二醇酯类树脂、尼龙类树脂、聚丙烯类树脂、聚乙烯类树脂、聚环氧醚酮类树脂和聚苯硫醚类树脂中的至少1种热塑性树脂。
[7].如[1]~[6]的任一项所述的金属-碳纤维强化树脂材料复合体,所述基体树脂含有苯氧类树脂。
[8].一种金属-碳纤维强化树脂材料复合体的制造方法,包含以下工序:
在作为钢铁材料或铁系合金的金属构件的至少一面上形成含有热塑性树脂的树脂膜的工序,
在形成了所述树脂膜的面的至少一部分上配置含有碳纤维材料和基体树脂的碳纤维强化树脂材料或碳纤维强化树脂材料成型用预浸料的工序,所述基体树脂含有热塑性树脂,以及
在加热温度T下进行热压接而形成树脂层和碳纤维强化树脂材料层的工序,以及
所述加热温度T小于所述树脂层的熔点Tm1,所述树脂层的熔点Tm1比所述基体树脂的熔点Tm2高。
[9].一种金属-碳纤维强化树脂材料复合体的制造方法,包含以下工序:
在作为钢铁材料或铁系合金的金属构件的至少一面上配置含有热塑性树脂的树脂片的工序,
在所述树脂片的、与所述金属构件相反侧的面的至少一部分上配置含有碳纤维材料和基体树脂的碳纤维强化树脂材料或碳纤维强化树脂材料成型用预浸料的工序,所述基体树脂含有热塑性树脂,以及
在加热温度T下进行热压接而形成树脂层和碳纤维强化树脂材料层的工序,以及
所述加热温度T小于所述树脂层的熔点Tm1,所述树脂层的熔点Tm1高于所述基体树脂的熔点Tm2
[10].如[8]或[9]所述的金属-碳纤维强化树脂材料复合体的制造方法,所述加热温度T为所述基体树脂的熔点Tm2以上。
发明效果
如前面所讲,通过在树脂层中使用熔点比CFRTP中含有的热塑性基体树脂的熔点高的热塑性树脂,在将金属构件、树脂层和CFRTP层接合而进行的热压接时树脂层形成比CFRTP的基体树脂更硬的状态,因此能够抑制碳纤维侵入树脂层中。
如以上说明,根据本发明,能够抑制由金属构件具体的是钢铁材料或铁系合金与碳纤维强化树脂材料中的碳纤维之间的接触而产生的异种材料接触腐蚀,即使是在作为金属构件使用比较容易被腐蚀的钢铁材料或铁系合金的情况,也能够提高金属-碳纤维强化树脂材料复合体的耐腐蚀性。
附图说明
图1是显示本发明的第1实施方式金属-CFRTP复合体的截面构造的示意图。
图2是显示本实施方式的金属-CFRTP复合体的另一方案的截面构造的示意图。
图3是对厚度测定方法进行说明的图。
图4是显示本实施方式的金属-CFRTP复合体的一例制造工序的说明图。
图5是显示本实施方式的金属-CFRTP复合体的另一方案的一例制造工序的说明图。
具体实施方式
以下参照附图对本发明的优选实施方案进行详细说明。另外,在本说明书和附图中,通过对实质上具有相同功能构成的构成要素附上相同符号来省略重复说明。
<背景>
如前所讲,本发明人发现了,根据金属构件与CFRTP的接合条件不同,会发生异种材料接触腐蚀,即成为金属构件与碳纤维接触的复合材料,与周围的水分那样的电解液一起形成局部电池而使金属构件腐蚀。例如、在使用粘接树脂将金属构件与CFRTP进行热压接而复合化的情况中,在使用将金属构件和CFRTP粘接的粘接树脂的熔点、与CFRTP的基体树脂的熔点相等的粘接构件和CFRTP时,在进行热压接时粘接树脂和CFRTP的基体树脂会软化,有时CFRTP中的碳纤维侵入软化了的粘接树脂中。侵入粘接树脂中的碳纤维有时以与金属构件接触的状态或位于金属构件附近的状态存在。在这样的碳纤维与金属构件接触的位置如果有例如含有水分等电解质的物质存在,则碳纤维与金属构件形成局部电池,电势比碳纤维贱的金属构件被腐蚀。即使在碳纤维与金属构件不直接接触的情况,当在金属构件的附近有碳纤维存在时,有时也会通过水分等导电,使金属构件腐蚀。尤其是金属构件是表面不形成稳定的氧化皮膜或钝化膜的钢铁材料或铁系合金的情况,它们比较容易被腐蚀,所以与碳纤维的接触会使异种材料接触腐蚀显著发生。进而、在表面设置含有对铁具有牺牲防腐蚀作用的锌的锌系镀层的钢铁材料或铁系合金的情况,在碳纤维与锌系镀层之间容易产生更大电位差,异种材料接触腐蚀发生更显著。
因此,本发明人想到了通过在金属构件与CFRTP的热压接时防止CFRTP中的碳纤维侵入粘接树脂中,将金属构件与碳纤维充分分开,来抑制由金属构件和碳纤维形成的局部电池导致的金属构件腐蚀。具体的,想到了通过在金属构件与CFRTP之间设置熔点比CFRTP的基体树脂高的热塑性树脂层,来防止热压接时金属构件与碳纤维接触。进而、本发明人关注CFRTP的基体树脂和粘接树脂,发明了能够抑制由金属构件与碳纤维形成的局部电池导致的金属构件腐蚀的金属-碳纤维强化树脂材料复合体。因此,通过防止金属构件与碳纤维接触,即使是金属构件比较容易被腐蚀的钢铁材料或铁系合金、或锌系镀层钢板,也可以充分抑制异种材料接触腐蚀,所以能够得到耐腐蚀性改善了的复合体。
<金属-碳纤维强化树脂材料复合体的构造>
首先,参照图1~3来对本发明的第1实施方式的金属-碳纤维强化树脂材料复合体的构造进行说明。图1~3是显示作为本实施方式的金属-碳纤维强化树脂材料复合体的金属-CFRTP复合体1的层叠方向上的截面构造的示意图。
如图1所示,金属-CFRTP复合体1具有金属构件11、CFRTP层12、树脂层13。作为代替方案,金属-CFRTP复合体1可以仅具有金属构件11、CFRTP层12和树脂层13。因此,金属构件11与CFRTP层12介由树脂层13被复合化。其中,「复合化」是指金属构件11与CFRTP层12介由树脂层13被接合(粘合)、一体化。此外,「一体化」是指金属构件11、CFRTP层12和树脂层13在加工或变形时作为一体而移动。
本实施方式中,树脂层13是热塑性树脂,以与金属构件11的至少一侧的面接触的方式设置,将金属构件11与CFRTP层12牢固粘接。其中,不仅有树脂层13和CFRTP层12设置在金属构件11的仅一面的情况,也可以是在两面都设置。此外,也可以采取2个金属构件11之间夹着含有树脂层13与CFRTP层12的层叠体的构造。
本实施方式的金属-碳纤维强化树脂材料复合体1进而可以在CFRTP层12或树脂层13上具有涂膜。该涂膜可以通过例如手涂、喷涂、辊涂、浸涂、电沉积、粉末涂装等形成。如后面所讲,在金属构件11的面上设置的树脂层13优选厚度为5μm以上,通过这样,能够有效防止碳纤维的接触,充分确保绝缘性。
本实施方式的金属-碳纤维强化树脂材料复合体1在浸渍在含有5质量%氯化钠的水溶液时频率1Hz下的交流阻抗为1×107Ω以上。为了充分抑制异种材料接触腐蚀,得到改善的耐腐蚀性,具有这样的1Hz下的交流阻抗是有效的。该交流阻抗小于1×107Ω时,异种材料接触腐蚀抑制有可能不充分。该交流阻抗优选为2×107Ω以上、例如3×107Ω以上、或5×107Ω以上。此外,为了充分得到复合体的电沉积性,该交流阻抗可以为1×109Ω以下,例如8×108Ω以下、或5×108Ω以上。该交流阻抗大于1×109Ω时,有电沉积涂层附着不充分的情况,未必能够充分抑制水、盐水等腐蚀因素的侵入。
上述交流阻抗是表示电解液存在环境下的金属-碳纤维强化树脂材料复合体的击穿电阻的指标,通过该指标能够定量预测腐蚀环境下的异种材料接触腐蚀的程度。因此,该交流阻抗的值越高,则能够越有效抑制异种材料接触腐蚀,因此能够提高复合体的耐腐蚀性。
本发明中交流阻抗测定如下。首先,将金属-碳纤维强化树脂材料复合体冲裁加工成φ15mm的圆盘状,将冲裁后的试样上的毛刺用锉除去,由此制作交流阻抗测定用试样。当在金属构件上有镀层或电沉积涂膜的情况,在冲裁加工前形成用于固定工作电极的金属构件露出部。接下来,以交流阻抗测定用试样的CFRP层侧成为与电解液接触面那样在金属构件上固定工作电极。此时,用硅橡胶密封圈覆盖交流阻抗测定用试样,调整交流阻抗测定用试样的CFRP层与电解液的接触面积(测定面积)成为1.0cm2。作为对电极使用碳电极,作为参比电极使用银-氯化银电极,作为电解液使用溶氧浓度饱和了的5%氯化钠水溶液100ml(25℃)。将交流阻抗测定用试样在电解液中静置60分钟,然后使用电位计,重叠5mV的交流电压,使频率从10mHz变到1kHz,测定交流阻抗。需要说明的是,本发明中只要没有特殊说明,交流阻抗是指在5%氯化钠水溶液浸渍时频率1Hz下的交流阻抗。
下面对金属-CFRTP复合体1的各构成要素和其他构成进行具体说明。
(金属构件11)
金属构件11的材质、形状和厚度等,只要是能够进行压制等成型加工就没有特别限定,但优选形状为薄板状。作为金属构件11的材质,可举出例如,铁、铝、镁和它们的合金等。这里,作为合金的例子,可举出例如,铁系合金(包含不锈钢)、Al系合金、Mg合金等。金属构件11的材质优选为钢铁材料(钢材)、铁系合金、钛或镁,更优选为与其它金属种类相比抗拉强度高的钢铁材料或铁系合金。如前面所讲,在金属构件11是钢铁材料或铁系合金时,在它们的表面上不会形成氧化皮膜等,所以腐蚀比较容易进行,异种材料接触腐蚀发生更为显著。因此,在使用钢铁材料或铁系合金而成的复合体中采用本发明的构造,对于抑制异种材料接触腐蚀非常有效。作为这样的钢铁材料,是例如日本工业标准(JIS)等中规定的钢铁材料,可以列举出一般结构用、机械结构用而使用的碳钢、合金钢、高张力钢等。作为这样的钢铁材料的具体例可以列举出冷轧钢材、热轧钢材、汽车构造用热轧钢板材、汽车加工用热轧高张力钢板材、汽车构造用冷轧钢板材、汽车加工用冷轧高张力钢板材、热间加工时进行了淬火的、通常被称作热压印材的高张力钢材等。钢材的情况,对成分没有特殊限定,除了Fe、C以外,还可以添加Mn、Si、P、Al、N、Cr、Mo、Ni、Cu、Ca、Mg、Ce、Hf、La、Zr、Sb中的1种或2种以上。这些添加元素可以按照要求得到的材料强度和成型性而适当选择1种或2种以上,添加量也可以适当调整。需要说明的是,金属构件11是板状的情况,其可以是被成型了的。
对作为金属构件11的材料的钢铁材料可以实施任意的表面处理。这里,所谓表面处理可举出例如,镀锌和镀铝、镀锡等各种镀敷处理、磷酸锌处理、铬酸盐处理和非铬酸盐处理等化学转化处理、以及喷砂那样的物理或化学蚀刻那样的化学表面粗化处理,但不限于此。此外,可以对钢铁材料实施上述多种表面处理。作为表面处理,优选至少进行以防锈性的赋予作为目的的处理。
作为金属构件11,尤其是因为耐腐蚀性优异,在钢铁材料中优选使用实施了镀敷处理的镀层钢材。作为金属构件11特优选的镀层钢材可以列举出热浸镀锌钢板、锌合金镀层钢板或将它们热处理使Fe在锌镀层中扩散从而合金化了的合金化热浸镀锌钢板、电镀锌钢板、电镀Zn-Ni钢板、热浸镀Zn-5%Al合金钢板、以热浸镀55%Al-Zn合金钢板为代表的热浸镀Zn-Al合金钢板、以热浸镀Zn-1~12%Al-1~4%Mg合金钢板、热浸镀55%Al-Zn-0.1~3%Mg合金钢板为代表的热浸镀Zn-Al-Mg合金钢板、以热浸镀Zn-11%Al-3%Mg-0.2%Si合金钢板代表的热浸镀Zn-Al-Mg-Si合金钢板、镀Ni钢板或将其热处理使Fe在Ni镀层中扩散而合金化了的合金化Ni镀层钢板、镀Al钢板、镀锡钢板、镀铬钢板等。锌系镀层钢板作为耐腐蚀性优异金属构件11优选。作为金属构件11,进而Zn-Al-Mg合金镀层钢板或Zn-Al-Mg-Si合金镀层钢板耐腐蚀性更优异,所以更优选。如前面所讲,含有对基底钢板具有牺牲防腐蚀作用的锌的锌系镀层钢材,如果与CFRTP层12中的碳纤维102接触,则与直接使用钢铁材料的情况相比,异种材料接触腐蚀发生更显著。这是由于锌系镀层与碳纤维102具有大的电位差的缘故。因此,将使用锌系镀层钢材的复合体形成本发明的构造,这对于抑制异种材料接触腐蚀非常有效。
为了提高与隔着树脂层13的CFRTP层12的粘接性,还可以在金属构件11的表面通过底漆进行处理。作为该处理中使用的底漆,优选例如硅烷偶联剂、三嗪硫醇衍生物。作为硅烷偶联剂可以使用通常公知的硅烷偶联剂,可以列举出例如、γ-(2-氨基乙基)氨基丙基三甲氧基硅烷、γ-(2-氨基乙基)氨基丙基甲基二甲氧基硅烷、γ-(2-氨基乙基)氨基丙基三乙氧基硅烷、γ-(2-氨基乙基)氨基丙基甲基二乙氧基硅烷、γ-(2-氨基乙基)氨基丙基甲基二甲氧基硅烷、γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧基)丙基甲基二甲氧基硅烷、γ-(甲基丙烯酰氧基)丙基三乙氧基硅烷、γ-(甲基丙烯酰氧基)丙基甲基二乙氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三甲氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基三乙氧基硅烷、N-β-(N-乙烯基苄基氨基乙基)-γ-氨基丙基甲基二乙氧基硅烷、γ-(1,2-环氧丙氧基)丙基三甲氧基硅烷、γ-(1,2-环氧丙氧基)丙基甲基二甲氧基硅烷、γ-(1,2-环氧丙氧基)丙基三乙氧基硅烷、γ-(1,2-环氧丙氧基)丙基甲基二乙氧基硅烷、γ-巯基丙基三甲氧基硅烷、γ-巯基丙基甲基二甲氧基硅烷、γ-巯基丙基三乙氧基硅烷、γ-巯基丙基甲基二乙氧基硅烷、甲基三甲氧基硅烷、二甲基二甲氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷、乙烯基三乙酰氧基硅烷、γ-氯丙基三甲氧基硅烷、γ-氯丙基甲基二甲氧基硅烷、γ-氯丙基三乙氧基硅烷、γ-氯丙基甲基二乙氧基硅烷、六甲基二硅氮烷、γ-苯氨基丙基三甲氧基硅烷、γ-苯氨基丙基甲基二甲氧基硅烷、γ-苯氨基丙基三乙氧基硅烷、γ-苯氨基丙基甲基二乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基甲基二甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二乙氧基硅烷、十八烷基二甲基〔3-(三甲氧基甲硅烷基)丙基〕氯化铵、十八烷基二甲基〔3-(甲基二甲氧基甲硅烷基)丙基〕氯化铵、十八烷基二甲基〔3-(三乙氧基甲硅烷基)丙基〕氯化铵、十八烷基二甲基〔3-(甲基二乙氧基甲硅烷基)丙基〕氯化铵、γ-氯丙基甲基二甲氧基硅烷、γ-巯基丙基甲基二甲氧基硅烷、甲基三氯硅烷、二甲基二氯硅烷、三甲基氯硅烷等,其中在使用具有缩水甘油醚基的硅烷偶联剂、例如具有缩水甘油醚基的γ-(1,2-环氧丙氧基)丙基三甲氧基硅烷和γ-(1,2-环氧丙氧基)丙基三乙氧基硅烷时,涂膜的加工密合性特别提高。进而、如果使用三乙氧基型的硅烷偶联剂,则能够提高基底处理剂的保存稳定性。这可以认为是由于三乙氧基硅烷在水溶液中比较稳定,聚合速度慢的缘故。硅烷偶联剂使用1种,但可以将2种以上合并使用。作为三嗪硫醇衍生物可以列举出6-二烯丙基氨基-2,4-二硫醇-1,3,5-三嗪、6-甲氧基-2,4-二硫醇-1,3,5-三嗪单钠、6-丙基-2,4-二硫醇氨基-1,3,5-三嗪单钠和2,4,6-三硫醇-1,3,5-三嗪等。
(CFRTP层12)
CFRTP层12具有热塑性的基体树脂101、和存在于该基体树脂101中的被复合化了的碳纤维102。作为代替方案,CFRTP层12可以仅由热塑性的基体树脂101、和在该基体树脂101中存在的被复合化了的碳纤维102构成。作为CFRTP层12可以是例如、使用CFRTP成型用预浸料形成的,或是使含有碳纤维102的基体树脂101固化而成的复合物。CFRTP层12不局限于1层,可以是例如图2所示的2层以上。CFRTP层12的厚度、以及CFRTP层12为多层时CFRTP层12的层数n,可以根据使用目的来适当设定。例如、CFRTP层12的厚度的下限可以是0.01mm、0.05mm或0.1mm。另一方面,例如、上限可以是3.0mm、2.0mm或1.0mm。CFRTP层12是多层时,各层可以是同一构成,也可以不同。即、构成CFRTP层12的基体树脂101的树脂种类,只要是具有比树脂层13的树脂组合物的熔点Tm1低的熔点Tm2的树脂即可,可以每一层都不同。此外,构成CFRTP层12的碳纤维102的种类、含有比率等也可以每层都不同。
作为CFRTP层12中使用的基体树脂101使用热塑性树脂。优选作为基体树脂101的树脂成分,相对于树脂成分100质量份含有50质量份以上、60质量份以上、70质量份以上、80质量份以上、或90质量份以上的热塑性树脂。另外,基体树脂101也可以仅含有热塑性树脂。对于可以在基体树脂101中使用的的热塑性树脂的种类没有特殊限定,可以使用选自苯氧树脂、聚烯烃及其酸改性物、聚苯乙烯、聚甲基丙烯酸甲酯、AS树脂、ABS树脂、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等热塑性芳香族聚酯、聚碳酸酯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺、聚醚酰亚胺、聚醚砜、聚苯醚及其改性物、聚苯硫醚、聚甲醛、聚芳酯、聚醚酮、聚醚醚酮、聚醚酮酮以及尼龙等中的1种以上。此外,「热塑性树脂」中也包括后述的可以变为第2固化状态交联固化物的树脂。此外,通过在基体树脂101中使用热塑性树脂,能够解决当在CFRP中使用热固性树脂时产生的、脆性导致不能进行弯曲加工的问题。
其中,在基体树脂101含有热塑性树脂的情况,可以解除在CFRP的基体树脂中使用热固性树脂时的问题,即CFRP层具有脆性、不能弯曲加工的问题,进而节拍时间(takttime)长的问题。通常、热塑性树脂熔融时的粘度比较高,不能如热固化前的环氧树脂等热固性树脂那样以低粘度的状态含浸于碳纤维102,因此与热固性树脂相比,对碳纤维102的含浸性差。因此,难以如使用了热固性树脂作为基体树脂101的情况那样提高CFRTP层12中的碳纤维密度(VF:Volume Fraction)。例如在使用热固性树脂环氧树脂作为基体树脂101的情况下,可以容易使VF为60%左右,但在使用了聚丙烯、尼龙等热塑性树脂作为基体树脂101的情况下,VF有时会被限制在50%左右。此外,如果使用聚丙烯、尼龙等热塑性树脂,则不能如使用了环氧树脂等热固性树脂时那样使CFRTP层具有充分高的耐热性。
为了消除这样的使用热塑性树脂时的问题,作为基体树脂101优选使用苯氧树脂。由于苯氧树脂分子结构与环氧树脂酷似,因此具有与环氧树脂同等程度的耐热性,此外,与树脂层13、碳纤维102的粘接性变得良好。进一步,通过在苯氧树脂中添加环氧树脂那样的固化成分使其共聚,可以制成所谓部分固化型树脂。通过使用这样的部分固化型树脂作为基体树脂101,可以制成在碳纤维102中的含浸性优异的基体树脂。进一步,通过使该部分固化型树脂中的固化成分热固化,从而可以抑制如通常的热塑性树脂那样CFRTP层12中的基体树脂101在被暴露于高温时熔融或软化。苯氧树脂中的固化成分的添加量只要考虑在碳纤维102中的含浸性、以及CFRTP层12的脆性、节拍时间和加工性等来适当决定即可。这样,通过使用苯氧树脂作为基体树脂101,能够进行自由度高的固化成分的添加和控制。
另外,例如往往在碳纤维102的表面上施与与环氧树脂溶合好的上浆剂。由于苯氧树脂与环氧树脂的化学结构酷似,因此通过使用苯氧树脂作为基体树脂101,可以直接使用环氧树脂用的上浆剂。因此,可以提高成本竞争力。
此外,在热塑性树脂中苯氧树脂也具有好的成型性,与碳纤维102、树脂层13的粘接性优异,而且通过使用酸酐、异氰酸酯化合物、己内酰胺等作为交联剂,可以在成型后具有与高耐热性的热固性树脂同样的性质。因此,本实施方式中作为基体树脂101的树脂成分,优选使用相对于树脂成分100质量份含有苯氧树脂50质量份以上的树脂组合物的硬化物或固化物。通过使用这样的树脂组合物,能够将CFRTP层12与树脂层13牢固接合。树脂组合物更优选在树脂成分100质量份中含有苯氧树脂55质量份以上,可以是例如60质量份以上、65质量份以上、70质量份以上、75质量份以上、80质量份以上、85质量份以上、90质量份以上、或95质量份以上。另一方面,树脂组合物中也可以仅含有苯氧树脂作为基体树脂101。粘接树脂组合物形态可以是例如粉末、清漆等液体、膜等固体。
再者,苯氧树脂的含量可以如以下那样使用红外光谱法(IR:InfraRedspectroscopy)测定,在通过IR从对象树脂组合物分析苯氧树脂的含有比例的情况,可以使用透射法、ATR反射法等、IR分析这些通常方法进行测定。
例如,用锐利的刃具等削出CFRTP层12,用镊子等尽可能将纤维除去,从CFRTP层12取样作为分析对象的树脂组合物。在透射法的情况下,一边将KBr粉末与成为分析对象的树脂组合物的粉末用研钵等均匀地混合一边捣碎从而制作薄膜,制成试样。在ATR反射法的情况下,可以一边与透射法同样地将粉末用研钵均匀地混合一边捣碎从而制作片剂,来制作试样,也可以用锉刀等使单晶KBr片剂(例如直径2mm×厚度1.8mm)的表面损伤,撒满成为分析对象的树脂组合物的粉末使其附着而制成试样。在任何方法中,预先测定与成为分析对象的树脂混合前的KBr单体中的背景(backgroud)都是重要的。IR测定装置可以使用市售的一般装置,但优选为作为精度具有吸收(Absorbance)可以以1%单位进行区分、波数(Wavenumber)可以以1cm-1单位进行区分的分析精度的装置,可举出例如,日本分光株式会社制的FT/IR-6300等。
在调查苯氧树脂的含量的情况下,苯氧树脂的吸收峰在例如1450~1480cm-1、1500cm-1附近、1600cm-1附近等存在,所以可以基于以上吸收峰的强度来计算含量。
所谓“苯氧树脂”,是由2价酚化合物与表卤代醇的缩合反应、或2价酚化合物与2官能环氧树脂的加聚反应获得的线形的高分子,是非晶质的热塑性树脂。苯氧树脂可以在溶液中或在无溶剂的条件下通过以往公知的方法获得,粉末、清漆和膜的任一形态都可以使用。关于苯氧树脂的平均分子量,作为质均分子量(Mw),例如为10,000以上且200,000以下的范围内,但优选为20,000以上且100,000以下的范围内,更优选为30,000以上且80,000以下的范围内。通过使苯氧树脂(A)的Mw为10,000以上的范围内,可以提高成型体的强度,该效果通过使Mw为20,000以上,进一步为30,000以上而进一步提高。另一方面,通过使苯氧树脂的Mw为200,000以下,可以使操作性、加工性优异,该效果通过使Mw为100,000以下,进一步为80,000以下而进一步提高。另外,本说明书中的Mw通过凝胶渗透色谱(GPC)测定,是使用标准聚苯乙烯标准曲线而换算的值。
本实施方式中使用的苯氧树脂的羟基当量(g/eq)例如为50以上且1000以下的范围内,但优选为50以上且750以下的范围内,更优选为50以上且500以下的范围内。通过使苯氧树脂的羟基当量为50以上,从而羟基减少而吸水率下降,因此可以使固化物的机械物性提高。另一方面,通过使苯氧树脂(A)的羟基当量为1000以下,从而可以抑制羟基变少,因此可以使与树脂层13的亲和性提高,使金属-CFRTP复合体1的机械物性提高。该效果通过使羟基当量为750以下,进一步为500以下而进一步提高。
此外,苯氧树脂的玻璃化转变温度(Tg)例如为65℃以上且150℃以下的范围内的物质是适合的,但优选为70℃以上且150℃以下的范围内。如果Tg为65℃以上,则可以确保成型性,同时抑制树脂的流动性变得过大,因此可以充分地确保树脂层13的厚度。另一方面,如果Tg为150℃以下,则熔融粘度变低,因此没有孔隙等缺陷地含浸于强化纤维基材变得容易,可以为更低温的接合工艺。另外,本说明书中的苯氧树脂的Tg是使用差示扫描量热测定装置,在10℃/分钟的升温条件下,在20~280℃的范围内的温度下测定,由第二次扫描的峰值计算的数值。
作为苯氧树脂,只要是满足上述物性的苯氧树脂,就没有特别限定,作为优选的苯氧树脂,可以举出双酚A型苯氧树脂(例如,能够作为新日铁住金化学株式会社制フェノトートYP-50、フェノトートYP-50S、フェノトートYP-55U而获得)、双酚F型苯氧树脂(例如,能够作为新日铁住金化学株式会社制フェノトートFX-316而获得)、双酚A与双酚F的共聚型苯氧树脂(例如,能够作为新日铁住金化学株式会社制YP-70而获得)、除上述举出的苯氧树脂以外的溴化苯氧树脂、含有磷的苯氧树脂、含有砜基(sulphone)的苯氧树脂等特殊苯氧树脂(例如,能够作为新日铁住金化学株式会社制フェノトートYPB-43C、フェノトートFX293、YPS-007等而获得)等。这些树脂可以单独使用1种,或混合使用2种以上。
作为基体树脂101的树脂成分使用的热塑性树脂优选为在160~250℃的范围内的任一温度区域下熔融粘度成为3,000Pa·s以下的物质,更优选为成为90Pa·s以上且2,900Pa·s以下的范围内的熔融粘度的物质,进一步优选为成为100Pa·s以上且2,800Pa·s以下的范围内的熔融粘度的物质。通过160~250℃的范围内的温度区域中的熔融粘度为3,000Pa·s以下,从而熔融时的流动性变好,在CFRTP层12中不易产生孔隙等缺陷。另一方面,在熔融粘度为90Pa·s以下的情况下,作为树脂组合物的分子量过小,如果分子量小则脆化,金属-CFRTP复合体1的机械强度降低。
◇交联性树脂组合物
通过在含有苯氧树脂(以下称作苯氧树脂(A))的树脂组合物中,配合例如酸酐、异氰酸酯、己内酰胺等作为交联剂,也可以制成交联性树脂组合物(即,树脂组合物的固化物)。交联性树脂组合物通过利用苯氧树脂(A)所包含的仲羟基进行交联反应,从而树脂组合物的耐热性提高,因此有利于对在更高温环境下使用的构件的应用。利用了苯氧树脂(A)的仲羟基的交联形成,优选使用配合了交联固化性树脂(B)和交联剂(C)的交联性树脂组合物。作为交联固化性树脂(B),可以使用例如环氧树脂等,但没有特别限定。通过使用这样的交联性树脂组合物,获得树脂组合物的Tg与苯氧树脂(A)单独的情况相比大幅提高了的第2固化状态的固化物(交联固化物)。交联性树脂组合物的交联固化物的Tg例如为160℃以上,优选为170℃以上且220℃以下的范围内。
在交联性树脂组合物中,作为配合于苯氧树脂(A)的交联固化性树脂(B),优选为2官能性以上的环氧树脂。作为2官能性以上的环氧树脂,可例示双酚A型环氧树脂(例如,能够作为新日铁住金化学株式会社制エポトートYD-011、エポトートYD-7011、エポトートYD-900而获得)、双酚F型环氧树脂(例如,能够作为新日铁住金化学株式会社制エポトートYDF-2001而获得)、二苯基醚型环氧树脂(例如,能够作为新日铁住金化学株式会社制YSLV-80DE而获得)、四甲基双酚F型环氧树脂(例如,能够作为新日铁住金化学株式会社制YSLV-80XY而获得)、双酚硫醚型环氧树脂(例如,能够作为新日铁住金化学株式会社制YSLV-120TE而获得)、氢醌型环氧树脂(例如,能够作为新日铁住金化学株式会社制エポトートYDC-1312而获得)、苯酚酚醛清漆型环氧树脂(例如,能够作为新日铁住金化学株式会社制エポトートYDPN-638而获得)、邻甲酚酚醛清漆型环氧树脂(例如,能够作为新日铁住金化学株式会社制エポトートYDCN-701、エポトートYDCN-702、エポトートYDCN-703、エポトートYDCN-704而获得)、芳烷基萘二酚酚醛清漆型环氧树脂(例如,能够作为新日铁住金化学株式会社制ESN-355而获得)、三苯基甲烷型环氧树脂(例如,能够作为日本化药株式会社制EPPN-502H而获得)等,但不限定于此。此外,这些环氧树脂可以单独使用1种,也可以混合使用2种以上。
此外,作为交联固化性树脂(B),没有特别限定,但优选为结晶性环氧树脂,更优选为熔点为70℃以上且145℃以下的范围内,且150℃下的熔融粘度为2.0Pa·s以下的结晶性环氧树脂。通过使用显示这样的熔融特性的结晶性环氧树脂,可以使作为树脂组合物的交联性树脂组合物的熔融粘度降低,可以使CFRTP层12的粘接性提高。如果熔融粘度超过2.0Pa·s,则有时交联性树脂组合物的成型性降低,金属-CFRTP复合体1的均质性降低。
作为适合作为交联固化性树脂(B)的结晶性环氧树脂,可举出例如,新日铁住金化学株式会社制エポトートYSLV-80XY、YSLV-70XY、YSLV-120TE、YDC-1312、三菱化学株式会社制YX-4000、YX-4000H、YX-8800、YL-6121H、YL-6640等、DIC株式会社制HP-4032、HP-4032D、HP-4700等、日本化药株式会社制NC-3000等。
交联剂(C)通过与苯氧树脂(A)的仲羟基形成酯键,从而使苯氧树脂(A)3维交联。因此,与热固性树脂的固化那样的牢固的交联不同,可以通过水解反应来解开交联,因此能够将金属构件11与CFRTP层12容易地剥离。因此,可以将金属构件11再循环利用。
作为交联剂(C),优选使用酸酐。酸酐在常温下为固体,只要是不太有升华性的物质,就没有特别限定,但从对金属-CFRTP复合体1的耐热性赋予、反应性的方面考虑,优选为具有2个以上与苯氧树脂(A)的羟基反应的酸酐的芳香族酸酐。特别是,如均苯四甲酸酐那样具有2个酸酐基的芳香族化合物与偏苯三甲酸酐和羟基的组合相比交联密度变高,耐热性提高,因此更适合使用。在芳香族酸二酐中,例如,4,4’-氧双邻苯二甲酸、乙二醇双偏苯三酸酐酯、4,4’-(4,4’-异亚丙基二苯氧基)二邻苯二甲酸酐这样的对苯氧树脂和环氧树脂具有相容性的芳香族酸二酐,使Tg提高的效果大,是更优选的。特别是,如均苯四甲酸酐那样具有2个酸酐基的芳香族酸二酐例如与仅具有1个酸酐基的邻苯二甲酸酐相比交联密度提高,耐热性提高,因此更适合使用。即,芳香族酸二酐由于具有2个酸酐基因此反应性良好,以短的成型时间获得对脱模而言强度充分的交联固化物,并且通过与苯氧树脂(A)中的仲羟基的酯化反应,生成4个羧基,因此可以使最终的交联密度高。
关于苯氧树脂(A)、作为交联固化性树脂(B)的环氧树脂、和交联剂(C)的反应,通过苯氧树脂(A)中的仲羟基与交联剂(C)的酸酐基的酯化反应、进一步由该酯化反应生成的羧基与环氧树脂的环氧基的反应而被交联和固化。通过苯氧树脂(A)与交联剂(C)的反应可以获得苯氧树脂交联体,但环氧树脂共存,从而使粘接树脂组合物的熔融粘度降低,因此显示与被粘物(树脂层13)的含浸性的提高、交联反应的促进、交联密度的提高、和机械强度的提高等优异的特性。
另外,可以认为在交联性树脂组合物中,虽然有作为交联固化性树脂(B)的环氧树脂共存,但以作为热塑性树脂的苯氧树脂(A)作为主成分,其仲羟基与交联剂(C)的酸酐基的酯化反应优先进行。即,作为交联剂(C)使用的酸酐、与作为交联固化性树脂(B)使用的环氧树脂的反应花费时间(反应速度慢),因此交联剂(C)与苯氧树脂(A)的仲羟基的反应先发生,接着,通过先前反应中残留的交联剂(C)、来源于交联剂(C)的残存羧基与环氧树脂反应从而交联密度进一步提高。因此,与以作为热固性树脂的环氧树脂作为主成分的树脂组合物不同,通过交联性树脂组合物而获得的交联固化物为热塑性树脂,储存稳定性也优异。
在利用苯氧树脂(A)的交联的交联性树脂组合物中,优选相对于苯氧树脂(A)100质量份,以成为5质量份以上且85质量份以下的范围内的方式含有交联固化性树脂(B)。相对于苯氧树脂(A)100质量份的交联固化性树脂(B)的含量更优选为9质量份以上且83质量份以下的范围内,进一步优选为10质量份以上且80质量份以下的范围内。通过使交联固化性树脂(B)的含量为85质量份以下,可以缩短交联固化性树脂(B)的固化时间,因此除易于在短时间获得脱模所需要的强度以外,CFRTP层12的再循环利用性提高。该效果通过使交联固化性树脂(B)的含量为83质量份以下,进一步为80质量份以下而进一步提高。另一方面,通过使交联固化性树脂(B)的含量为5质量份以上,从而易于获得由交联固化性树脂(B)的添加带来的交联密度的提高效果,交联性树脂组合物的交联固化物易于表现160℃以上的Tg,此外,流动性变得良好。另外,关于交联固化性树脂(B)的含量,通过上述那样的使用了IR的方法,对来源于环氧树脂的峰进行同样地测定,可以测定交联固化性树脂(B)的含量。
交联剂(C)的配合量通常相对于苯氧树脂(A)的仲羟基1摩尔为酸酐基0.6摩尔以上且1.3摩尔以下的范围内的量,优选为0.7摩尔以上且1.3摩尔以下的范围内的量,更优选为1.1摩尔以上且1.3摩尔以下的范围内。如果酸酐基的量为0.6摩尔以上,则交联密度变高,因此机械物性、耐热性优异。该效果通过使酸酐基的量为0.7摩尔以上,进一步为1.1摩尔以上而进一步提高。如果酸酐基的量为1.3摩尔以下,则可以抑制未反应的酸酐、羧基对固化特性、交联密度带来不良影响。因此,优选根据交联剂(C)的配合量来调整交联固化性树脂(B)的配合量。具体而言,例如,为了使通过苯氧树脂(A)的仲羟基与交联剂(C)的酸酐基的反应而产生的羧基、与作为交联固化性树脂(B)使用的环氧树脂反应,使环氧树脂的配合量与交联剂(C)的当量比为0.5摩尔以上且1.2摩尔以下的范围内为好。优选交联剂(C)与环氧树脂的当量比为0.7摩尔以上且1.0摩尔以下的范围内。
虽然只要将交联剂(C)与苯氧树脂(A)、交联固化性树脂(B)配合一起,就可以获得交联性树脂组合物,但为了确实地进行交联反应,可以进一步添加作为催化剂的促进剂(D)。促进剂(D)只要是在常温下为固体,没有升华性的物质,就没有特别限定,可举出例如,三乙二胺等叔胺、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑类、三苯基膦等有机膦类、四苯基
Figure BDA0002598111430000191
四苯基硼酸盐等四苯基硼盐等。这些促进剂(D)可以单独使用1种,也可以并用2种以上。需要说明的是,在使交联性树脂组合物为微细粉末,利用静电场通过粉末涂装法将其附着在强化纤维基材上而形成基体树脂101的情况,作为促进剂(D)优选使用催化剂活性温度为130℃以上、常温下为固体的咪唑系潜在性催化剂。在使用促进剂(D)的情况下,促进剂(D)的配合量优选相对于苯氧树脂(A)、交联固化性树脂(B)和交联剂(C)的合计量100质量份为0.1质量份以上且5重量份以下的范围内。
交联性树脂组合物在常温下为固体,关于其熔融粘度,160~250℃的范围内的温度区域中的作为熔融粘度的下限值的最低熔融粘度优选为3,000Pa·s以下,更优选为2,900Pa·s以下,进一步优选为2,800Pa·s以下。通过160~250℃的范围内的温度区域中的最低熔融粘度为3,000Pa·s以下,在采用热压等的进行热压接时可以使交联性树脂组合物在被粘物中充分地含浸,可以抑制CFRTP层12产生孔隙等缺陷,因此金属-CFRTP复合体1的各种机械物性提高。该效果通过使160~250℃的范围内的温度区域中的最低熔融粘度为2,900Pa·s以下,进一步为2,800Pa·s以下而进一步提高。
在以上用于形成基体树脂101的树脂组合物(包含交联性树脂组合物)中,在不损害其粘接性、物性的范围,可以配合例如,天然橡胶、合成橡胶、弹性体等以及各种无机填料、溶剂、体质颜料、着色剂、抗氧化剂、紫外线防止剂、阻燃剂、阻燃助剂等其它添加物。
作为基体树脂101使用的热塑性树脂,可以按照树脂层13中使用的热塑性树脂的热物性来相应选择。具体的,作为基体树脂101使用与树脂层13中含有的树脂组合物的熔点Tm1相比较为低熔点Tm2的树脂。即、以树脂层13的熔点Tm1比CFRTP层12的熔点Tm2高的方式选择基体树脂101。如果满足这样的关系,则在为了形成本发明的复合体而进行热压接时,即使是CFRTP层12软化、碳纤维102在CFRTP层12中流动的情况,树脂层13也不完全软化,树脂层13保持比CFRTP层12的基体树脂101硬的状态。换言之,根据本发明,在进行热压接时的加热温度(例如180~250℃)下树脂层13具有能够防止碳纤维102侵入该树脂层13的硬度。因此,能够防止该碳纤维102贯穿树脂层13而使金属构件11与碳纤维102接触,结果有效抑制异种材料接触腐蚀。此外,为了得到这样的效果,需要使热压接时的加热温度T小于树脂层13的熔点Tm1。通过这样设定温度,能够使CFRTP层12软化、并且以碳纤维102不贯穿树脂层13的程度适度软化。通过这样,能够使金属构件11、树脂层13和CFRTP层12充分粘接,并且、碳纤维102不贯穿树脂层13,得到抑制了异种材料接触腐蚀、耐腐蚀性优异的本发明的复合体。热压接时的加热温度T,为了得到良好的加工性而优选为基体树脂101的熔点Tm2以上。
[熔点Tm]
基体树脂101优选具有在热压接温度下保持与树脂层13的粘接性的熔点Tm2。需要说明的是,本说明书中的树脂:树脂层13和基体树脂101的熔点Tm1和Tm2是通过使用差示扫描量热测定装置、以10℃/分的升温条件、在20~280℃的范围内的温度下测定,根据第二次扫描的峰值计算出的数值。此外,在是非晶性热塑性树脂、观测不到熔点Tm1或Tm2的情况,可以利用通常已知的经验定律来适当设定熔点Tm1或Tm2。利用的经验定律,可以根据在基体树脂101中使用的热塑性树脂的性质、作为树脂层13使用的热塑性树脂的组合来适当选择。在作为树脂层13使用的热塑性树脂的熔点Tm1比较低的情况,使用了观测不到熔点的非晶性热塑性树脂的基体树脂101的熔点Tm2可以使用例如、作为经验定律之一的、熔点(K)=玻璃转变温度(K)×1.4的关系式来设定。此外,例如、在基体树脂101是在比较高温下显示流动性,观测不到熔点的非晶性热塑性树脂的情况,该基体树脂101的熔点Tm2使用熔点(K)=玻璃转变温度(K)×1.5的关系式来设定。
[纤维密度]
CFRTP内的碳纤维的密度(VF:Volume Fraction)是影响强度的因素,通常VF越高,则CFRTP的强度越高。本实施方式中、对CFRTP层12的VF没有特殊限定,可以为20体积%以上、30体积%以上、40体积%以上或50体积%以上,可以是75体积%以下、70体积%以下或65体积%以下。从基体树脂与碳纤维的密合性、和CFRTP的强度之间的均衡的观点出发,优选CFRTP层12的VF为50体积%以上65体积%以下。此外,如前面所讲、在CFRTP层12的基体树脂101使用苯氧树脂时,容易实现高于50体积%的VF。
[碳纤维102]
关于碳纤维102的种类,例如,PAN系、沥青系都可以使用,只要根据目的、用途来选择即可。此外,作为碳纤维102,上述纤维可以单独使用1种,也可以并用多个种类。
纺织物基材、使用了连续纤维的织物(cloth)材、单向强化纤维基材(UD材)等,但从增强效果方面考虑,优选作为碳纤维基材使用织物材、UD材。
(树脂层13)
树脂层13含有热塑性树脂,其设置在金属构件11的表面上,将金属构件11与CFRTP层12接合。树脂层13可以使用例如粉末、清漆等液体、片等固体来得到。此外,树脂层13中含有的树脂组合物优选是具有与金属构件11的良好粘接性的树脂。对于作为树脂层13使用的树脂组合物没有特殊限定,可以使用例如选自苯氧树脂、聚烯烃及其酸改性物、聚苯乙烯、聚甲基丙烯酸甲酯、AS树脂、ABS树脂、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等热塑性芳香族聚酯、聚碳酸酯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺、聚醚酰亚胺、聚醚砜、聚苯醚及其改性物、聚苯硫醚、聚甲醛、聚芳酯、聚醚酮、聚醚醚酮、聚醚酮酮以及尼龙等中的1种以上。在CFRTP层12的基体树脂101是苯氧树脂的情况,基于熔点之差和硬度的观点,优选作为树脂层13使用聚酰胺(例如聚酰胺66)。
[树脂层13的厚度]
本实施方式的金属-CFRTP复合体1中,树脂层13的厚度优选为5μm以上。通过使树脂层13的厚度为5μm以上,能够充分保持金属构件11与CFRTP层12的粘接性,有效抑制热压接时碳纤维102与金属构件11接触。此外,树脂层13的厚度可以为6μm以上、7μm以上、8μm以上、或9μm以上。另一方面,树脂层13的厚度,从加工性和成本面的观点为50μm以下,可以为例如40μm以下、30μm以下或20μm以下。作为树脂层13的厚度的范围优选为5μm以上50μm以下、更优选7μm以上25μm以下、进而优选9μm以上20μm以下。需要说明的是,为了更充分的确保加工性,可以根据用途,使树脂层13的厚度小于10μm。
另外,金属构件11、CFRTP层12和树脂层13的厚度可以如以下那样按照JIS K5600-1-7,5.4项的光学方法的截面法测定。即,使用不对试样带来有害的影响,没有间隙地埋入的常温固化树脂,使用リファインテック株式会社制的低粘性エポマウント27-777作为主剂,使用27-772作为固化剂,埋入试样。在要观察的位置,利用切断机以与厚度方向平行的方式将试样切断而露出截面,使用在JIS R 6252或6253中规定的号数的研磨纸(例如,280号、400号或600号)进行研磨,制作观察面。在使用研磨材的情况下,使用适当等级的金刚石糊料或类似的糊料进行研磨,制作观察面。此外,可以根据需要实施磨光研磨,将试样的表面平滑化直到经得起观察的状况。
使用具备对于提供最佳图像的对比度而言适当的照明系统、且具有充分的精度的显微镜(例如,オリンパス社制BX51等),以适当的视场大小观察试样。另外,视场的大小可以以金属构件11、CFRTP层12和树脂层13的厚度可以确认的方式改变(例如,如果CFRTP层12的厚度为1mm,则可以改变为厚度可以确认的视场的大小)。例如,在树脂层13的厚度时,将观察视场内以图3的方式4等分,在各分区点的宽度方向中央部,计测树脂层13的厚度,将其平均的厚度设为该视场中的厚度。该观察视场选择不同的5处位置进行,在各个观察视场内4等分,在各分区中测定厚度,算出平均值。相邻的观察视场彼此分离3cm以上进行选择为好。将该5处的平均值进一步进行了平均的值设为树脂层13的厚度即可。此外,在金属构件11、CFRTP层12的厚度的测定中,与上述树脂层13的厚度的测定同样地进行即可。
树脂层13中,在不损害其粘接性、物性的范围,可以配合例如,天然橡胶、合成橡胶、弹性体等,以及各种无机填料、溶剂、体质颜料、着色剂、抗氧化剂、紫外线防止剂、阻燃剂、阻燃助剂等其它添加物。
如前所述、树脂层13的树脂组合物和基体树脂101选择具有如下硬度的树脂:在树脂层13与CFRTP的热压接时金属构件11、CFRTP层12和树脂层13被良好的粘接,同时CFRTP层12中的碳纤维102不侵入树脂层13的硬度。因此,如前面所说明,作为树脂层13使用具有比基体树脂101的熔点Tm2高的熔点Tm1的树脂。通过使用满足这样关系的树脂,能够防止CFRTP层12中的碳纤维102侵入树脂层13,使得碳纤维102与金属构件11接触。结果、能够抑制由于碳纤维102与金属构件11的接触导致的金属构件11的腐蚀。此外,优选树脂层13的树脂组合物的熔点Tm1与基体树脂101的熔点Tm2的差为5℃以上。从抑制碳纤维102对树脂层13侵入的观点,更优选树脂层13和基体树脂101使用树脂层13的树脂组合物的熔点Tm1与基体树脂101的熔点Tm2满足以下式(1)关系的树脂。
Tm2≤Tm1-10℃ 式(1)
即、树脂层13的树脂组合物的熔点Tm1与基体树脂101的熔点Tm2之差优选为10℃以上,例如、该差可以是15℃以上或20℃以上。需要说明的是,本说明书中熔点Tm1和Tm2是使用差示扫描量热测定装置,以10℃/分的升温条件、20~280℃的范围内的温度下测定,根据第二次扫描的峰值计算的数值。此外,在是非晶性热塑性树脂、观察不到熔点的情况,为了方便,定义:熔点(K)=玻璃转变温度(K)×1.4。
金属-CFRTP复合体1中,构成树脂层13的树脂组合物进而优选是与CFRTP层12的基体树脂101不同的树脂。这里所谓的「不同的树脂」是指与全部树脂成分中含有率最高的成分即主成分不同的树脂。为了确保充分的熔点差、确保热压接时充分的树脂层的硬度,作为CFRTP层12和树脂层13的组合,优选选择苯氧树脂和聚酰胺树脂。
<金属-CFRTP复合体1的制造方法>
以上、对作为本实施方式的金属-碳纤维强化树脂材料复合体的金属-CFRTP复合体1的构成进行了具体说明,接下来,参照图4和图5对本实施方式的金属-CFRTP复合体1的制造方法予以说明。图4和图5是显示金属-CFRTP复合体1的制造工序例的说明图。
金属-CFRTP复合体1,可以通过将加工成所希望形状的CFRTP(或其前体CFRTP成型用预浸料21)与金属构件11(钢铁材料或铁系合金)用树脂膜20或树脂片20A粘接来得到。热压接后、上述粘接的CFRTP变为CFRTP层12,树脂膜20或树脂片20A变为树脂层13。本发明中作为树脂层13和CFRTP层12的基体树脂101,以树脂层13的熔点Tm1比CFRTP层12的熔点Tm2高的方式进行选择。作为通过将金属构件11与CFRTP用树脂膜20或树脂片20A粘接、结合而复合化的方法,可以通过例如、以下的方法1或方法2进行。
(方法1)
方法1中,在将树脂膜20(成为树脂层13)形成在金属构件11的表面后,层叠成为CFRTP层12的CFRTP或CFRTP成型用预浸料21并热压接。
在该方法中例如如图4(a)所示,在金属构件11的至少一侧的面上涂布粉状或液状、或片化的树脂组合物来形成树脂膜20。也可以将粉状的树脂组合物溶解在溶剂中后再涂布。需要说明的是,在该方法中也可以不在金属构件11侧、而是在成为CFRTP层12的CFRTP侧或CFRTP成型用预浸料侧形成树脂膜20,这里以在金属构件11侧形成树脂膜20的情况为例进行了说明。
更具体地,例如如图4(b)所示,在金属构件11的形成了树脂膜20的面上重合配置成为CFRTP层12的CFRTP成型用预浸料21,形成将金属构件11、树脂膜20和CFRTP成型用预浸料21按照该顺序层叠而成的层叠体。再者,图4(b)中,可以层叠CFRTP来代替CFRTP成型用预浸料21,但此时可以对CFRTP的粘接面进行例如采用喷射处理等的粗化、采用等离子体处理、电晕处理等的活化。接下来,通过将该叠层体进行加热和加压,从而如图4(c)所示,获得金属-CFRTP复合体1。
该方法1中、作为形成成为树脂层13的树脂膜20的方法,没有特殊限定,在使用粘性液体的树脂组合物的情况,可以通过以从狭缝射嘴、圆形状射嘴吐出的方式进行的涂布、毛刷涂、刮板涂、挂铲涂等通常公知的方法进行涂布。在将粉状树脂组合物溶解在溶剂中使用的情况,可以采用通常公知的涂布方法,例如毛刷涂、喷涂、棒涂、从各种形状的射嘴吐出的涂布、模涂、帘涂、辊涂、喷涂、丝网印刷等公知方法。在使用片化的树脂组合物的情况,作为将片化树脂组合物贴附的方法,可以用人手、机器人等通常公知的方法进行贴附。尤其是通过粉末涂装形成的树脂膜20,由于树脂组合物是微粒,所以容易熔融,并且由于在树脂膜20内具有适度空隙,所以容易去孔隙。此外,在将CFRTP或CFRTP成型用预浸料21热压接时,由于树脂组合物与金属构件11的表面浸润良好,所以不需要清漆涂布中那样的脱气工序,难以发生从片上可以看到那样程度的孔隙等、由于浸润性不足导致的不良情况。树脂膜20可以涂布在金属板整个面上,也可以仅在CFRTP贴附的位置进行局部涂布。
该方法1中,图4(a)中在金属构件11的两面上形成树脂膜20,也可以如图4(b)、在两个树脂膜20的每一个上都层叠CFRTP成型用预浸料21(或CFRTP)。此外,成为CFRTP层12的CFRTP成型用预浸料21(或CFRTP)不局限于1层,可以是多层(参照图2)。此外,可以使用2枚以上的金属构件11将成为CFRTP层12的CFRTP成型用预浸料21(或CFRTP)以夹层状夹入的方式层叠。
(方法2)
方法2中,将成为树脂层13的片化的树脂组合物(树脂片20A)、与成为CFRTP层12的CFRTP或CFRTP成型用预浸料21层叠在金属构件11上进行热压接。
该方法2中如例如图5(a)所示,在金属构件11的至少一侧的面上重叠配置将树脂组合物形成片状的树脂片20A、和成为CFRTP层12的CFRTP成型用预浸料21,形成由金属构件11、树脂片20A和CFRTP成型用预浸料21按照该顺序层叠而成的层叠体。需要说明的是,图5(a)中,可以层叠CFRTP来代替CFRTP成型用预浸料21,但此时的CFRTP的粘接面优选进行了例如、喷砂处理等粗化处理、等离子体处理、电晕处理等活化处理。接下来,对该层叠体加热和加压而得到图5(b)所示那样的金属-CFRTP复合体1。
方法2中,图5(a)中,可以在金属构件11的两面每一面上都层叠树脂片20A和CFRTP成型用预浸料21(或CFRTP)。此外,成为CFRTP层12的CFRTP成型用预浸料21(或CFRTP)不限于1层,可以是多层(参照图2)。此外,可以使用2枚以上的金属构件11,将树脂片20A和成为CFRTP层12的CFRTP成型用预浸料21(或CFRTP)以夹层状夹入的方式层叠。
(进行热压接条件)
以上说明的方法中,为了将金属构件11、以及树脂膜20或树脂片20A、和成为CFRTP层12的CFRTP成型用预浸料21(或CFRTP)复合化而热压接的条件具体说明如下。需要说明的是,本发明中、通过选择满足上述熔点关系的树脂层13和基体树脂101,在热压接工序中即使CFRTP层软化·熔融,碳纤维102能够流动,由于下层的树脂层13比基体树脂101硬,发挥阻挡层作用,所以能够有效防止碳纤维102贯穿树脂层13而与金属构件11接触。
(热压接温度)
热压接温度T小于树脂层13的熔点Tm1。在热压接温度T设定在该温度范围时,能够抑制CFRTP层12中的碳纤维102侵入树脂层13中。此外,热压接温度T,为了得到良好的加工性而优选为基体树脂101的熔点Tm2以上。更优选热压接温度T满足以下的式(2)。
Tm2+2℃≤T≤Tm1-5℃ 式(2)
通过使热压接温度T满足式(2),能够使碳纤维102不容易侵入树脂层13,从而获得碳纤维102难以与金属构件11接触的效果。此时,热压接温度T优选小于基体树脂101的分解温度。热压接温度T根据CFRTP层12的基体树脂101和树脂层13的树脂种类适当决定即可,可以为例如180℃以上或220℃以上、进而为270℃以下或250℃以下。在CFRTP层12的基体树脂101和树脂层13的树脂层分别使用苯氧树脂和聚酰胺树脂的情况,热压接温度T在235~255℃的范围较好,例如240℃。
(热压接压力)
热压接时的压力优选为例如3MPa以上、更优选为3MPa以上5MPa以下的范围。在压力高于上限时,施加了过度的压力,所以有可能发生变形和损伤,此外在低于下限时对碳纤维102的含浸性变差。
(热压接时间)
关于热压接时间,至少3分以上就能够充分热压接,优选为5分以上20分以下的范围内。
需要说明的是,热压接工序中可以通过加压成型机将金属构件11、树脂片20A、和成为CFRTP层12的CFRTP成型用预浸料21(或CFRTP)进行复合一次性成型。复合一次性成型优选通过热压进行,也可以将预先加热到预定温度的材料快速设置在低温的加压成型机上进行加工。
(前处理工序)
制造金属-CFRTP复合体1时,优选作为将金属构件11与CFRTP用树脂组合物接合的前处理工序,将金属构件11脱脂,脱脂方法可以采用:用溶剂擦的方法;水洗;使用含有表面活性剂的水溶液或洗涤剂进行洗涤,加热使油成分挥发除去的方法;碱脱脂等通常公知的方法。作为金属构件11的脱脂方法,碱脱脂是工业上通常的方式,脱脂效果高,所以优选。更优选对模具进行脱模处理和除去金属构件11表面的附着物(去垃圾)。除了无锡钢(TinFree Steel)那样的密合性非常高的钢板以外,通常如果不对附着了防锈油等的钢板等金属构件11脱脂、恢复密合力,则难以得到充分的粘接强度。于是,通过对金属构件11进行上述前处理,容易使金属-CFRTP复合体1得到高粘接强度。关于脱脂的必要性,可以事先将成为对象的金属构件在没有脱脂工序的情况下与成为对象的CFRTP利用成为对象的树脂组合物而接合一体化,测定粘接强度来判断即可。
(后工序)
对金属-CFRTP复合体1进行的后工序,除了涂装以外,还可以为了利用螺栓、铆钉等与其他构件的机械接合而进行打孔加工、或为了粘接接合而进行粘接剂的涂布等。
<本实施方式的效果>
根据上述本实施方式,能够提供金属构件11和CFRTP层12介由树脂层13被牢固接合了的金属-CFRTP复合体1。这些金属-CFRTP复合体1可以抑制由金属构件11与CFRTP层12中的碳纤维102发生的异种材料接触腐蚀。尤其是在金属构件11是容易被腐蚀的钢铁材料或铁系合金的情况,异种材料接触腐蚀更成为问题,所以本实施方式非常有效。此外,本实施方式的金属-CFRTP复合体1通过具有5μm以上厚度的树脂层13,绝缘性增加,能够更有效抑制异种材料接触腐蚀。进而由于作为CFRTP层12的基体树脂使用热塑性树脂,所以能够使CFRTP塑性变形,结果、能够将金属-CFRTP复合体1一体进行形状加工。进而、根据上述本实施方式可以得到具有电沉积膜的金属-CFRTP复合体1。
实施例
下面通过实施例来对本发明进而具体进行说明,但本发明不受这些实施例限定。
(金属板的准备)
将成分为C:0.131质量%、Si:1.19质量%、Mn:1.92质量%、P:0.009质量%、S:0.0025质量%、Al:0.027质量%、N:0.0032质量%、余量为Fe和杂质的钢热轧,酸洗,然后进行冷轧,从而得到厚度1.0mm的冷轧钢板。接下来,将制作出的冷轧钢板在连续退火装置中以最高到达板温为820℃的条件进行退火。退火工序的退火炉内的环境为含有1.0体积%H2的N2气。将制作的冷轧钢板称作CR。此外,将制作的冷轧钢板,以具有退火工序的连续热浸镀装置的退火工序中最高到达板温为820℃的条件退火,然后用镀敷工序热浸镀锌。退火工序的退火炉内的环境是含有1.0体积%H2的N2气。镀敷工序中的镀浴的成分使用Zn-0.2%Al(称作GI)、Zn-0.09%Al(称作GA)、Zn-1.5%Al-1.5%Mg(称作Zn-Al-Mg)、Zn-11%Al-3%Mg-0.2%Si(称作Zn-Al-Mg-Si)这4种,来制造镀层钢板。需要说明的是,在使用Zn-0.09%Al镀层(GA)的热浸镀浴的情况,在热浸镀浴中浸渍钢板,一边从镀层浴将钢板拉出,一边从狭缝射嘴吹N2气进行气体吹扫,调整镀液的附着量,然后用感应加热器加热到板温为480℃,使其合金化,使钢板中的Fe向镀层中扩散。关于镀敷后钢板的镀层附着量,GA为45g/m2、GA以外的镀层为60g/m2。将4种金属板都用日本パーカライジング社制碱脱脂剂「ファインクリーナーE6404」进行脱脂。需要说明的是,对制作的5种金属板测定抗拉强度,结果均为980MPa以上。
(树脂膜形成工序)
作为树脂层的原料使用聚酰胺66、聚酰胺6、聚酰胺6/66共聚物和聚酰胺6/66/12共聚物,形成分别使用了上述树脂的树脂膜或使用聚酰胺66的树脂片。以下对各树脂膜或树脂片的形成方法进行说明。
<聚酰胺66树脂膜(a)>
将東レプラスチック精工株式会社制聚酰胺66TPS(注册商标)N66NC(熔点=260℃)溶解在六氟异丙醇中成固体成分浓度(N.V.)为20重量%,通过棒涂涂布在制作的金属板上,在80℃下干燥,使溶剂挥发,由此在金属板上形成表1~3中记载的厚度(1μm、5μm、10μm、20μm、50μm)的聚酰胺66树脂膜(a)。
<聚酰胺6树脂膜(b)>
将宇部兴产株式会社制的聚酰胺6ベースグレード1020(熔点=220℃)溶解在六氟异丙醇中使固体成分浓度(N.V.)为20重量%,将其用棒涂机涂布在制作的金属板上,在80℃下干燥、使溶剂挥发,从而在金属板上形成10μm的聚酰胺6树脂膜(b)。
<聚酰胺6/66共聚物树脂膜(c)>
将宇部兴产株式会社制的聚酰胺6/66共聚物ベースグレード5033(熔点=196℃)溶解在六氟异丙醇中使固体成分浓度(N.V.)为20重量%,将其用棒涂机涂布在制作的金属板上,在80℃干燥,使溶剂挥发,从而在金属板上形成10μm的聚酰胺6/66共聚物树脂膜(c)。
<聚酰胺6/66/12共聚物树脂膜(d)>
将宇部兴产株式会社制的聚酰胺6/66/12共聚物ベースグレード6434(熔点=188℃)溶解在六氟异丙醇中使固体成分浓度(N.V.)为20重量%,将其用棒涂机涂布在制作的金属板上,在80℃干燥使溶剂挥发,从而在金属板上形成10μm的聚酰胺6/66/12共聚物树脂膜(d)。
<聚酰胺66树脂片(e)>
将東レプラスチック精工株式会社制聚酰胺66TPS(注册商标)N66NC(熔点=260℃)用加热到280℃的压机以3MPa压制3分钟,从而制作厚度50μm的聚酰胺66树脂片(e)。
(CFRTP预浸料的制作)
接下来,用以下方法制作成为CFRTP层的4种CFRTP预浸料。
<苯氧树脂CFRTP预浸料(A)的制作>
将新日铁住金化学株式会社制双酚A型苯氧树脂「フェノトートYP-50S」(玻璃化转变温度=83℃)粉碎、分级,形成平均粒径D50为80μm粉末,将其对着由碳纤维形成的强化纤维基材(织布材:东邦テナックス社制、IMS60)在静电场中以电荷70kV、喷吹空气压0.32MPa的条件进行粉末涂装。之后、在烘箱中170℃加热熔融1分钟,将树脂热熔接而制作厚度约0.6mm的苯氧树脂CFRTP预浸料(A)。需要说明的是,粉碎、分级后的苯氧树脂的平均粒径,是通过激光衍射·散射式粒径分布测定装置(マイクロトラックMT3300EX、日机装社制)测定的以体积基准计、累计体积达到50%时对应的粒径。制作的苯氧树脂CFRTP预浸料(A)的熔点使用前面说明的、熔点(K)=玻璃转变温度(K)×1.4的式子,为了方便设为225℃(498K)。
<聚酰胺6/66共聚物CFRTP预浸料(B)的制作>
将宇部兴产株式会社制的聚酰胺6/66共聚物ベースグレード5033(熔点=196℃)用加热到180℃的压机以3MPa压制3分钟,从而制作厚度100μm的尼龙树脂片。将该尼龙树脂片与由碳纤维形成的平纹组织的强化纤维基材(织布材:サカイオーベックス社制、SA-3203)交替层叠而得到层叠体。将该层叠体用加热到220℃的压机以3MPa压制3分钟而制作厚度约0.6mm的尼龙树脂CFRTP预浸料(B)。
<聚酰胺6/66共聚物CFRTP预浸料(C)的制作>
将宇部兴产株式会社制的聚酰胺6/66共聚物ベースグレード5034(熔点=192℃)用加热到180℃的压机以3MPa压制3分钟,从而制作厚度100μm的尼龙树脂片。将该尼龙树脂片与由碳纤维形成的平纹组织的强化纤维基材(织物材:サカイオーベックス社制、SA-3203)交替层叠,而得到层叠体。将该层叠体用加热到220℃的压机以3MPa压制3分钟来制作厚度约0.6mm的尼龙树脂CFRTP预浸料(C)。
<聚酰胺6/66/12共聚物CFRTP预浸料(D)的制作>
将宇部兴产株式会社制的聚酰胺6/66/12共聚物6434(熔点=188℃)用加热到180℃的压机以3MPa压制3分钟而制作厚度100μm的尼龙树脂片。将该尼龙树脂片与由碳纤维形成的平纹组织的强化纤维基材(织布材:サカイオーベックス社制、SA-3203)交替层叠而得到层叠体。将该层叠体用加热到220℃的压机以3MPa压制3分钟,从而制作厚度约0.6mm的尼龙树脂CFRTP预浸料(B)。
(金属-CFRTP复合体试样的制作)
接下来,将金属板、表面形成了树脂膜的金属板、或表面配置树脂片的金属板、与CFRTP预浸料按照表1~3记载的组合使用,而制作金属-CFRTP复合体。具体地,在形成了树脂膜的金属板上叠放制作的CFRTP预浸料,用加热到表1~3中记载的规定温度的具有平模的压机在3MPa下压制3分钟,从而制作出具有树脂层(a)~(e)和CFRTP层(A)~(D)的金属-CFRTP复合体试样。仅No.10的试样,在层叠树脂片(e)的金属板上叠放制作的预浸料,与上述同样地压制,从而制作出金属-CFRTP复合体试样。至于No.17~No.21的金属-CFRTP复合体,在金属板上不层叠树脂层或不配置树脂片,将CFRTP预浸料载置在金属板上,与上述同样进行压制而制作金属-CFRTP复合体。依照JIS K 5600-1-7、5.4项的光学方法的截面法对得到的金属-CFRTP复合体测定厚度。CFRTP层的厚度全都是0.5mm,树脂层的厚度与形成的树脂膜同样。需要说明的是,使用的CFRTP预浸料的碳纤维的密度全都是55体积%。
Figure BDA0002598111430000331
Figure BDA0002598111430000341
Figure BDA0002598111430000351
(交流阻抗的测定)
交流阻抗测定如下。首先,将得到的各试样冲裁加工成φ15mm的圆盘状,将冲裁后的试样上的毛刺用锉除去,由此制作测定用试样。当在试样上有镀层的情况,在冲裁加工前形成用于固定工作电极的钢材的露出部。接下来,以交流阻抗测定用试样的CFRP层侧成为与电解液接触面那样在金属构件上固定工作电极。此时,用硅橡胶密封圈覆盖交流阻抗测定用试样,调整交流阻抗测定用试样的CFRP层与电解液的接触面积(测定面积)成为1.0cm2。作为对电极使用碳电极,作为参比电极使用银-氯化银电极,作为电解液使用溶氧浓度饱和了的5%氯化钠水溶液100ml(25℃)。将交流阻抗测定用试样在电解液中静置60分钟,然后使用电位计、重叠5mV的交流电压,使频率从10mHz变到1kHz,测定交流阻抗。表1~3中、将在1Hz下的交流阻抗为1×107Ω以上的情况记作「〇」,将其他的情况记作「×」。需要说明的是,所有试样的1Hz下的交流阻抗都是1×109Ω以下。
<评价>
(耐腐蚀性)
在层叠了宽度70mm×长度150mm的树脂层的金属板的中央压接宽度50mm×长度100mm的CFRTP而成复合试样,对该复合试样进行脱脂、表面调整、磷酸锌处理,然后进行电沉积涂布。脱脂,采用日本パーカライジング社制脱脂剂(ファインクリーナーE6408),在60℃的条件下浸渍5分钟进行脱脂。在脱脂后的复合试样的表面调整中,采用日本パーカライジング社制(プレパレンX)在40℃的条件下浸渍5分钟。之后使用日本パーカライジング社制磷酸锌化学转化剂(パルボンドL3065)以35℃的条件浸渍3分钟从而进行磷酸锌处理。磷酸锌处理后水洗,用150℃气氛的烘箱干燥。之后、电沉积日本ペイント社制的电沉积涂料(パワーフロート1200)15μm,在170℃气氛的环境中烘烤20分烧后作为试样使用。电沉积涂料仅在没有贴CFRTP的金属部分上涂布。
使用制作出的试样进行循环腐蚀试验(CCT)。CCT的模式依照汽车工业标准JASO-M609进行。试样以CFRTP侧作为评价面,以能够对评价面喷雾盐水那样设置在试验机上进行试验。耐腐蚀性的评价中,目视观察试样的外观,30次循环(8小时为1次循环)之前每3次循环观察一次,30次循环以后每15次循环观察一次,求出产生红锈时的循环次数。产生红锈前的循环次数越多,表示耐腐蚀性越优异,能够抑制异种材料接触腐蚀。此外,由于红锈从贴在金属上的CFRTP的端部附近开始发生,所以关注这里进行目视观察。
(压制加工性)
使用V字型的凹凸模具,以将模具加热到200℃的状态进行热加工,评价V字的压制加工性。使用在宽度50mm×长度50mm的金属板整个面上贴上了CFRTP的复合材试样进行试验。使CFRTP为阴模侧、使金属材为阳模侧来设置模具,进行压制。再者,使用V字型模具的V部的角度为90°的模具进行压制加工,使用弯曲部的R(曲率半径)不同的模具进行压制加工,求出CFRTP不剥离的极限R。以更小的曲率半径也不剥离的复合材,表示压制加工性越优异。观察压制加工后的截面,将在金属板与CFRTP的粘接部分中、金属板与CFRTP相对于粘接部分全体剥离了30%以上的情况记作「剥离」。将CFRTP不剥离的极限R为30mmR以下的情况,看作是压制加工性良好。
如表1所示,金属板使用冷轧钢板CR、并且设置了树脂层的No.11的试样与没有设置树脂层的No.15的试样相比较,可以知道,设置了树脂层的金属-CFRTP复合体No.11显示出更好的耐腐蚀。此外,如表1~3所示,在作为金属板使用GA、GI、Zn-Al-Mg和An-Al-Mg-Si的情况也同样、设置了树脂层的金属-CFRTP复合体树脂层比没有设置树脂层的金属-CFRTP复合体显示出更好的耐腐蚀性。
No.13的试样和No.14的试样是对No.1的试样的制作条件改变了热压接温度而制作的试样。提高热压接温度而制作的No.13的试样比No.1的试样耐腐蚀性低,显示出与没有设置树脂层的No.16同等程度的耐腐蚀性。降低热压接温度而制作的No.14的试样具有良好的耐腐蚀性,但压制加工性不良。
将No.1的试样、No.2的试样和No.3的试样进行比较就可以知道,与No.2的试样和No.3的试样相比,No.1的试样耐腐蚀性优异。基体树脂的熔点Tm2和树脂层的熔点Tm1满足Tm2≤Tm1-10℃的关系式的金属-CFRTP复合体的耐腐蚀性大大提高。
No.6的~No.9的试样,是对No.1的试样的制作条件中树脂层的厚度进行改变而制作的试样。可知,No.6的试样比No.7~No.9的试样耐腐蚀性低。通过使金属-CFRTP复合体的树脂层的膜厚为5μm以上,能够大大提高金属-CFRTP复合体的耐腐蚀性。
如上述那样、本实施方式的金属-CFRTP复合体对碳纤维和金属之间的异种材料接触腐蚀的耐腐蚀性优异,并且及时进行热轧,CFRTP也不容易剥离、加工性优异。
以上、参照附图对本发明的优选实施方式进行了具体说明,但本发明不受这些例子限定。至于本发明所属的技术领域中具有通常知识的人在本专利的权利要求记载的技术思想的范围内可以想到的各种变更例或修正例,这些当然也属于本发明的技术范围。
附图标号说明
1 金属-CFRTP复合体
11 金属构件
12 CFRTP层
13 树脂层
20 树脂膜
20A 树脂片
21 CFRTP成型用预浸料
30 涂膜
101 基体树脂
102 碳纤维

Claims (12)

1.一种金属-碳纤维强化树脂材料复合体,具有金属构件、设置在所述金属构件的至少一面上的树脂层、和设置在所述树脂层的面上的碳纤维强化树脂材料,
所述金属构件是钢铁材料,所述树脂层含有热塑性树脂,所述碳纤维强化树脂材料含有碳纤维材料和具有热塑性的基体树脂,
所述树脂层的熔点Tm1比所述碳纤维强化树脂材料的熔点Tm2高,
将所述金属-碳纤维强化树脂材料复合体浸渍在含有5质量%氯化钠的水溶液时在频率1Hz下的交流阻抗为1×107Ω以上,
所述树脂层的熔点Tm1和所述基体树脂的熔点Tm2满足下述式(1)的关系,其中Tm1和Tm2的单位都是℃,
Tm2≤Tm1-10℃ 式(1)。
2.如权利要求1所述的金属-碳纤维强化树脂材料复合体,所述树脂层中含有的热塑性树脂是与所述基体树脂不同的树脂。
3.如权利要求1或2所述的金属-碳纤维强化树脂材料复合体,所述树脂层的厚度为5μm以上。
4.如权利要求1或2所述的金属-碳纤维强化树脂材料复合体,所述钢铁材料是具有锌系镀层的镀敷钢材。
5.如权利要求1或2所述的金属-碳纤维强化树脂材料复合体,所述基体树脂含有选自苯氧类树脂、聚碳酸酯类树脂、聚对苯二甲酸乙二醇酯类树脂、聚2,6-萘二甲酸乙二醇酯类树脂、尼龙类树脂、聚丙烯类树脂、聚乙烯类树脂、聚环氧醚酮类树脂和聚苯硫醚类树脂中的至少1种热塑性树脂,
所述树脂层中含有的树脂含有选自聚碳酸酯类树脂、聚对苯二甲酸乙二醇酯类树脂、聚2,6-萘二甲酸乙二醇酯类树脂、尼龙类树脂、聚丙烯类树脂、聚乙烯类树脂、聚环氧醚酮类树脂和聚苯硫醚类树脂中的至少1种热塑性树脂。
6.如权利要求1或2所述的金属-碳纤维强化树脂材料复合体,所述基体树脂含有苯氧类树脂。
7.如权利要求1或2所述的金属-碳纤维强化树脂材料复合体,所述钢铁材料是铁系合金。
8.如权利要求4所述的金属-碳纤维强化树脂材料复合体,所述镀敷钢材是铁系合金。
9.一种金属-碳纤维强化树脂材料复合体的制造方法,包含以下工序:
在作为钢铁材料的金属构件的至少一面上直接形成含有热塑性树脂的树脂膜的工序,
在形成了所述树脂膜的面的至少一部分上配置含有碳纤维材料和基体树脂的碳纤维强化树脂材料或碳纤维强化树脂材料成型用预浸料的工序,所述基体树脂含有热塑性树脂,以及
在加热温度T下进行热压接而形成树脂层和碳纤维强化树脂材料层的工序,
所述加热温度T小于所述树脂层的熔点Tm1,所述树脂层的熔点Tm1比所述基体树脂的熔点Tm2高,
所述树脂层的熔点Tm1和所述基体树脂的熔点Tm2满足下述式(1)的关系,其中Tm1和Tm2的单位都是℃,
Tm2≤Tm1-10℃ 式(1)。
10.一种金属-碳纤维强化树脂材料复合体的制造方法,包含以下工序:
制作含有热塑性树脂的树脂片的工序,
在作为钢铁材料的金属构件的至少一面上配置含有热塑性树脂的所述树脂片的工序,
在所述树脂片的、与所述金属构件相反侧的面的至少一部分上配置含有碳纤维材料和基体树脂的碳纤维强化树脂材料或碳纤维强化树脂材料成型用预浸料的工序,所述基体树脂含有热塑性树脂,以及
在加热温度T下进行热压接而形成树脂层和碳纤维强化树脂材料层的工序,
所述加热温度T小于所述树脂层的熔点Tm1,所述树脂层的熔点Tm1高于所述基体树脂的熔点Tm2
所述树脂层的熔点Tm1和所述基体树脂的熔点Tm2满足下述式(1)的关系,其中Tm1和Tm2的单位都是℃,
Tm2≤Tm1-10℃ 式(1)。
11.如权利要求9或10所述的金属-碳纤维强化树脂材料复合体的制造方法,所述加热温度T为所述基体树脂的熔点Tm2以上。
12.如权利要求9或10所述的金属-碳纤维强化树脂材料复合体的制造方法,所述钢铁材料是铁系合金。
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