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JP2013018167A - Laminate and method of manufacturing the same - Google Patents

Laminate and method of manufacturing the same Download PDF

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Publication number
JP2013018167A
JP2013018167A JP2011152246A JP2011152246A JP2013018167A JP 2013018167 A JP2013018167 A JP 2013018167A JP 2011152246 A JP2011152246 A JP 2011152246A JP 2011152246 A JP2011152246 A JP 2011152246A JP 2013018167 A JP2013018167 A JP 2013018167A
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Japan
Prior art keywords
liquid crystal
film
crystal polymer
polyolefin resin
resin film
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JP2011152246A
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Japanese (ja)
Inventor
Izumi Yagi
木 泉 八
Takayuki Ueki
木 貴 之 植
Junichi Kuroki
木 潤 一 黒
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority to JP2011152246A priority Critical patent/JP2013018167A/en
Publication of JP2013018167A publication Critical patent/JP2013018167A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—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
    • B29C65/14—Joining 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
    • B29C65/1429—Joining 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
    • B29C65/1432—Joining 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 direct heating of the surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—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
    • B29C65/14—Joining 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
    • B29C65/1429—Joining 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
    • B29C65/1435—Joining 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—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
    • B29C65/14—Joining 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
    • B29C65/1429—Joining 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
    • B29C65/1445—Joining 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 heating both sides of the joint
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—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
    • B29C65/14—Joining 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
    • B29C65/1429—Joining 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
    • B29C65/1454—Joining 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 scanning at least one of the parts to be joined
    • B29C65/1458—Joining 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 scanning at least one of the parts to be joined once, i.e. contour welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—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
    • B29C65/14—Joining 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
    • B29C65/1429—Joining 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
    • B29C65/1464—Joining 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 making use of several radiators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—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
    • B29C65/14—Joining 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
    • B29C65/1429—Joining 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
    • B29C65/1464—Joining 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 making use of several radiators
    • B29C65/1467—Joining 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 making use of several radiators at the same time, i.e. simultaneous welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—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
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint 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
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General 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
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General 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
    • B29C66/71—General 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General 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
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B29C66/712—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined the composition of one of the parts to be joined being different from the composition of the other part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General 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
    • B29C66/73—General 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
    • B29C66/735—General 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 extensive physical properties of the parts to be joined
    • B29C66/7352—Thickness, e.g. very thin
    • B29C66/73521—Thickness, e.g. very thin of different thickness, i.e. the thickness of one of the parts to be joined being different from the thickness of the other part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General 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
    • B29C66/73—General 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
    • B29C66/739—General 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
    • B29C66/7392—General 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
    • B29C66/73921—General 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/836—Moving relative to and tangentially to the parts to be joined, e.g. transversely to the displacement of the parts to be joined, e.g. using a X-Y table
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/001—Joining in special atmospheres
    • B29C66/0012—Joining in special atmospheres characterised by the type of environment
    • B29C66/0014—Gaseous environments
    • B29C66/00141—Protective gases

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

【課題】液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを接着剤を使用せずに接着した積層体であって、異物や残留溶剤等が滲出することがなく、優れた強度、耐熱性、誘電特性、電気絶縁性、ヒートシール性を有する積層体を提供する。
【解決手段】液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが積層した積層体であって、前記液晶ポリマーフィルムおよび前記ポリオレフィン樹脂フィルムの少なくとも一部で、前記液晶ポリマーフィルム中の原子と、前記ポリオレフィン樹脂フィルム中の原子との間に結合が形成されており、前記液晶ポリマーフィルムおよび前記ポリオレフィン樹脂フィルムとが接着剤を介さずに接着されている。
【選択図】図２A laminate in which a liquid crystal polymer film and a polyolefin resin film are bonded to each other without using an adhesive, and does not exude foreign matter or residual solvent, and has excellent strength, heat resistance, dielectric properties, electrical Provided is a laminate having insulating properties and heat sealing properties.
A laminate in which a liquid crystal polymer film and a polyolefin resin film are laminated, wherein at least part of the liquid crystal polymer film and the polyolefin resin film, the atoms in the liquid crystal polymer film, and the polyolefin resin film A bond is formed between the liquid crystal polymer film and the polyolefin resin film without using an adhesive.
[Selection] Figure 2

Description

本発明は、積層体に関し、さらに詳細には、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを、接着剤を介さずに接着した積層体およびその製造方法に関する。   The present invention relates to a laminate, and more particularly, to a laminate in which a liquid crystal polymer film and a polyolefin resin film are bonded without using an adhesive and a method for producing the same.

液晶ポリマーは、耐湿性、耐熱性、柔軟性に優れ、誘電特性においても高周波における低比誘電率および低誘電正接を示すことから、耐熱性絶縁材料や高強度繊維として種々の用途に使用されている。例えば、液晶ポリマーからなるフィルムを用いたフレキシブル基材は、金属層の伝送損失を低下させることができることから、フレキシブルフラットケーブル用途への適用が期待されている。また、液晶ポリマーフィルム他の樹脂フィルムで被覆したような構造のフレキシブルフラットケーブルも提案されている。   Liquid crystal polymers are excellent in moisture resistance, heat resistance, and flexibility, and have low dielectric constant and low dielectric loss tangent at high frequencies in dielectric properties, so they are used in various applications as heat resistant insulating materials and high strength fibers. Yes. For example, a flexible base material using a film made of a liquid crystal polymer can reduce transmission loss of a metal layer, and thus is expected to be applied to flexible flat cable applications. In addition, a flexible flat cable having a structure covered with a resin film such as a liquid crystal polymer film has been proposed.

液晶ポリマーフィルムと他の樹脂フィルムとの積層体として、例えば、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを接着剤を介して積層することが試みられている。ポリオレフィン樹脂フィルム等のヒートシール性を有する樹脂フィルムを液晶ポリマーフィルムに貼り合わせて積層体とすることにより、この積層体を他の部材に貼り合わせる際に、樹脂フィルム側をヒートシールすることにより、液晶ポリマーフィルムからなる積層体を他の部材に容易に貼り合わせることができる。しかしながら、ラミネート接着して積層体としたものは、積層体の使用環境によっては、接着剤成分が徐々に積層体から溶出または揮発する場合があり、接着剤成分による汚染の問題がある。また、長期使用により接着剤自体が劣化することもあり、特に屋外等で使用される外装用途においては、積層体の耐候性が問題となることもあった。また、接着剤を用いたラミネート技術においては、一般的に溶剤に希釈した樹脂成分を塗布することが行われるため、ラミネートして包装体等のような最終製品となった後にも溶剤が残留してしまうことがあった。さらに、使用する接着剤によっては、低誘電特性を犠牲にしてしまうことがあった。   As a laminate of a liquid crystal polymer film and another resin film, for example, it has been attempted to laminate a liquid crystal polymer film and a polyolefin resin film via an adhesive. By laminating a resin film having heat sealing properties such as a polyolefin resin film to a liquid crystal polymer film to form a laminate, when laminating this laminate to another member, heat sealing the resin film side, A laminate composed of a liquid crystal polymer film can be easily bonded to another member. However, in a laminate obtained by laminating and bonding, depending on the use environment of the laminate, the adhesive component may gradually elute or volatilize from the laminate, and there is a problem of contamination by the adhesive component. In addition, the adhesive itself may deteriorate due to long-term use, and the weather resistance of the laminate may be a problem particularly in exterior applications used outdoors. In addition, in the laminating technique using an adhesive, since a resin component diluted in a solvent is generally applied, the solvent remains after laminating to form a final product such as a package. There was a case. Furthermore, depending on the adhesive used, low dielectric properties may be sacrificed.

また、液晶ポリマーフィルムに、ヒートシールにより直接ポリオレフィン樹脂フィルムを貼り合わせることも考えられるが、液晶ポリマーは、全芳香族系もしくは半芳香族系の液晶ポリエステル等からなるため、溶融したポリオレフィン樹脂フィルムが液晶ポリマーフィルムに融着せず、両フィルムが強固に密着した積層体とすることができない。   In addition, it is conceivable that the polyolefin resin film is directly bonded to the liquid crystal polymer film by heat sealing. However, since the liquid crystal polymer is made of a wholly aromatic or semi-aromatic liquid crystal polyester, the molten polyolefin resin film is It is not possible to make a laminate in which both films are firmly adhered without being fused to the liquid crystal polymer film.

ところで、放射線や電子線を用いて材料の表面改質を行うことが従来から行われている。例えば、特開２００３−１１９２９３号公報（特許文献１）には、フッ素系樹脂に放射線を照射することにより架橋複合フッ素系樹脂が得られることが提案されている。また、Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127（非特許文献１）には、ポリテトラフルオロエチレンフィルムとポリイミドフィルムとを積層させて高温下で電子線（以下、ＥＢと略す場合もある）を照射することにより、互いを接着することが提案されている。また、Material Transactions Vol.50, No.7 (2009), pp1859-1863（非特許文献２）には、ポリカーボネート樹脂の表面をナイロンフィルムで覆い、その上から電子線（以下、ＥＢと略す場合もある）を照射することにより、ポリカーボネート樹脂表面にナイロンフィルムを接着する技術が提案されている。さらに、日本金属学会誌第７２巻第７号（２００８）、ｐｐ５２６−５３１（非特許文献３）には、シリコーンゴム上に置いたナイロンフィルムの上からＥＢを照射することにより、互いを接着できることが記載されている。   By the way, surface modification of a material using radiation or an electron beam has been conventionally performed. For example, Japanese Patent Application Laid-Open No. 2003-119293 (Patent Document 1) proposes that a crosslinked composite fluororesin can be obtained by irradiating the fluororesin with radiation. In Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 (Non-patent Document 1), a polytetrafluoroethylene film and a polyimide film are laminated and an electron beam ( In the following, it has been proposed to bond each other by irradiating EB. In Material Transactions Vol.50, No.7 (2009), pp1859-1863 (Non-patent Document 2), the surface of the polycarbonate resin is covered with a nylon film, and an electron beam (hereinafter abbreviated as EB) may be applied from above. A technique for adhering a nylon film to a polycarbonate resin surface has been proposed. Furthermore, the Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531 (Non-patent Document 3) can be bonded to each other by irradiating EB from a nylon film placed on silicone rubber. Is described.

特開２００３−１１９２９３号公報JP 2003-119293 A

Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 Material Transactions Vol.50, No. 7(2009), pp1859-1863Material Transactions Vol.50, No. 7 (2009), pp1859-1863 日本金属学会誌第７２巻第７号（２００８）、ｐｐ５２６−５３１Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531

本発明者らは、今般、異種材料どうしを接着する場合であっても、フィルムに電子線を照射することにより、ラミネート樹脂等を用いることなく、互いを強固に接着できることを見いだした。そして、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとの積層体のように、従来、接着剤により互いを接着していた積層体であっても、電子線照射によれば、接着剤を使用しなくても、液晶ポリマーフィルム側の原子とポリオレフィン樹脂フィルム側の原子との間に結合が形成されるか、または酸素原子、窒素原子または水酸基を介して結合が形成されて、互いが強固に接着できる、との知見を得た。本発明はかかる知見によるものである。   The present inventors have now found that even when different types of materials are bonded to each other, they can be bonded firmly to each other without using a laminate resin or the like by irradiating the film with an electron beam. And even if it is a laminate that has been conventionally bonded to each other with an adhesive, such as a laminate of a liquid crystal polymer film and a polyolefin resin film, according to electron beam irradiation, no adhesive is used. A bond is formed between an atom on the liquid crystal polymer film side and an atom on the polyolefin resin film side, or a bond is formed through an oxygen atom, a nitrogen atom or a hydroxyl group, and can be firmly bonded to each other. I got the knowledge. The present invention is based on this finding.

したがって、本発明の目的は、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを接着剤を使用せずに接着した積層体であって、優れた強度、耐熱性、誘電特性、電気絶縁性、ヒートシール性を有する積層体を提供することである。   Therefore, an object of the present invention is a laminate in which a liquid crystal polymer film and a polyolefin resin film are bonded without using an adhesive, and has excellent strength, heat resistance, dielectric properties, electrical insulation, and heat sealability. It is providing the laminated body which has.

本発明による積層体は、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが積層した積層体であって、
前記液晶ポリマーフィルムおよび前記ポリオレフィン樹脂フィルムの少なくとも一部で、前記液晶ポリマーフィルム中の原子と、前記ポリオレフィン樹脂フィルム中の原子との間に結合が形成されており、前記液晶ポリマーフィルムおよび前記ポリオレフィン樹脂フィルムとが接着剤を介さずに接着されていることを特徴とするものである。 The laminate according to the present invention is a laminate in which a liquid crystal polymer film and a polyolefin resin film are laminated,
In at least a part of the liquid crystal polymer film and the polyolefin resin film, a bond is formed between an atom in the liquid crystal polymer film and an atom in the polyolefin resin film, and the liquid crystal polymer film and the polyolefin resin The film is bonded to the film without using an adhesive.

また、本発明の態様として、前記液晶ポリマーフィルムと前記ポリオレフィン樹脂フィルムとの界面の少なくとも一部で、前記液晶ポリマーフィルム中の原子と、前記ポリオレフィン樹脂フィルム中の原子との間で、酸素原子、窒素原子または水酸基を介して結合が形成されていることが好ましい。   Further, as an aspect of the present invention, at least part of the interface between the liquid crystal polymer film and the polyolefin resin film, between atoms in the liquid crystal polymer film and atoms in the polyolefin resin film, oxygen atoms, A bond is preferably formed through a nitrogen atom or a hydroxyl group.

また、本発明の態様として、前記液晶ポリマーが、エチレンテレフタレートとパラヒドロキシ安息香酸とが重縮合したポリマー、フェノールと、フタル酸およびパラヒドロキシ安息香酸とが重縮合したポリマー、２，６−ヒドロキシナフトエ酸とパラヒドロキシ安息香酸とが重縮合したポリマーからなる群から選択されるものであることが好ましい。   Further, as an aspect of the present invention, the liquid crystal polymer may be a polymer obtained by polycondensation of ethylene terephthalate and parahydroxybenzoic acid, a polymer obtained by polycondensation of phenol, phthalic acid and parahydroxybenzoic acid, or 2,6-hydroxynaphthoic acid. Preferably, the acid is selected from the group consisting of polymers obtained by polycondensation of parahydroxybenzoic acid.

また、本発明の態様として、前記ポリオレフィン樹脂フィルムが、ポリプロピレン、ポリエチレン、またはポリメチルペンテンからなる樹脂フィルムであることが好ましい。   Moreover, as an aspect of the present invention, the polyolefin resin film is preferably a resin film made of polypropylene, polyethylene, or polymethylpentene.

また、本発明の別の態様としての製造方法は、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが積層した積層体を製造する方法であって、
液晶ポリマーフィルムおよび／またはポリオレフィン樹脂フィルムの少なくとも一方の面、に電子線を照射し、
前記電子線が照射された前記液晶ポリマーフィルム面および／またはポリオレフィン樹脂フィルム面を重ね合わせて接着する、ことを含んでなることを特徴とするものである。 Moreover, the production method as another aspect of the present invention is a method for producing a laminate in which a liquid crystal polymer film and a polyolefin resin film are laminated,
Irradiating at least one surface of the liquid crystal polymer film and / or polyolefin resin film with an electron beam,
The liquid crystal polymer film surface and / or the polyolefin resin film surface irradiated with the electron beam are superposed and bonded together.

また、本発明の態様として、前記液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを重ね合わせる前および／または重ね合わせた後に電子線照射を行うことが好ましい。   As an aspect of the present invention, it is preferable to perform electron beam irradiation before and / or after the liquid crystal polymer film and the polyolefin resin film are overlapped.

また、本発明の別の態様として、前記液晶ポリマーフィルムとポリオレフィン樹脂フィルムとの接着を加圧して行うことが好ましく、また、前記液晶ポリマーフィルムとポリオレフィン樹脂フィルムとの接着を加熱して行うことが好ましい。   Moreover, as another aspect of the present invention, it is preferable to press the adhesion between the liquid crystal polymer film and the polyolefin resin film, and the adhesion between the liquid crystal polymer film and the polyolefin resin film is performed by heating. preferable.

本発明によれば、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが積層した積層体において、液晶ポリマーフィルム中の原子と、ポリオレフィン樹脂フィルム中の原子との間に結合が形成されているか、または酸素原子、窒素原子または水酸基を介して結合が形成されているため、接着剤を介して接着していなくても、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが強固に接着した積層体が得られる。その結果、強度、耐熱性、誘電特性、電気絶縁性、ヒートシール性に優れた積層体を実現することができる。   According to the present invention, in the laminate in which the liquid crystal polymer film and the polyolefin resin film are laminated, a bond is formed between an atom in the liquid crystal polymer film and an atom in the polyolefin resin film, or an oxygen atom, Since a bond is formed through a nitrogen atom or a hydroxyl group, a laminate in which the liquid crystal polymer film and the polyolefin resin film are firmly bonded can be obtained even if the bonding is not performed through an adhesive. As a result, a laminate excellent in strength, heat resistance, dielectric properties, electrical insulation, and heat sealability can be realized.

本発明の積層体の一実施形態を示した概略断面図である。It is the schematic sectional drawing which showed one Embodiment of the laminated body of this invention. 積層体の界面（接着面）を拡大した模式断面図である。It is the schematic cross section which expanded the interface (adhesion surface) of the laminated body. 本発明による積層体の製造方法の一実施形態を示した概略模式図である。It is the schematic diagram which showed one Embodiment of the manufacturing method of the laminated body by this invention. 製造工程の一部を拡大した概略模式図である。It is the schematic schematic diagram which expanded a part of manufacturing process. 本発明による積層体の製造方法の別の実施形態を示した概略模式図である。It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. 本発明による積層体の製造方法の別の実施形態を示した概略模式図である。It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. 本発明による積層体の製造方法の別の実施形態を示した概略模式図である。It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention.

以下、本発明による積層体を、図面を参照しながら説明する。本発明による積層体は、図１に示すように、液晶ポリマーフィルム２とポリオレフィン樹脂フィルム１とが、接着剤を介さずに積層した構造を有する。   Hereinafter, the laminated body by this invention is demonstrated, referring drawings. As shown in FIG. 1, the laminate according to the present invention has a structure in which a liquid crystal polymer film 2 and a polyolefin resin film 1 are laminated without using an adhesive.

ポリオレフィン樹脂フィルム１および液晶ポリマーフィルム２の接着面の少なくとも一部で、ポリオレフィン樹脂フィルム１の原子と液晶ポリマーフィルム２の原子との間に結合が形成されることにより、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とが強固に接着されている。通常、ポリオレフィン樹脂フィルムの表面に液晶ポリマーフィルムを積層しても、両者の間に水素結合や共有結合が形成されないため接着剤を使用しなければ両者を接着することはできない。また、ヒートシールでは、上記したように両フィルムが強固に密着した積層体とすることができない。本発明においては、後記するように、ポリオレフィン樹脂フィルム１および／または液晶ポリマーフィルム２の表面に電子線を照射してラジカルを発生させて、図２に示すように、ポリオレフィン樹脂フィルム１表面の原子と液晶ポリマーフィルム２表面の原子との間に結合を形成する、ないしはポリオレフィン樹脂フィルム１表面の原子と、液晶ポリマーフィルム２表面の原子との間に、酸素原子および／または窒素原子を介して結合を形成することにより、接着剤を介することなくポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを強固に接着したものである。また、電子線照射により発生したラジカルと空気中の酸素とが結合して、ポリオレフィン樹脂フィルム１および／または液晶ポリマーフィルム２の表面にはＯＨ基が存在することがあり、その場合、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２との間で水素結合が形成される場合もある。なお、電子線照射によりラジカルの発生は、電子スピン共鳴装置（以下、ＥＳＲともいう。）を用いて、電子線照射後のフィルムに存在するフリーラジカル種を同定することにより、その発生を確認することができる。   A bond is formed between the atoms of the polyolefin resin film 1 and the atoms of the liquid crystal polymer film 2 on at least a part of the adhesive surfaces of the polyolefin resin film 1 and the liquid crystal polymer film 2, whereby the polyolefin resin film 1 and the liquid crystal polymer The film 2 is firmly bonded. Usually, even if a liquid crystal polymer film is laminated on the surface of a polyolefin resin film, hydrogen bonds and covalent bonds are not formed between the two, so that the two cannot be bonded unless an adhesive is used. Moreover, in heat sealing, as mentioned above, it cannot be set as the laminated body which both films adhered firmly. In the present invention, as will be described later, the surface of the polyolefin resin film 1 and / or the liquid crystal polymer film 2 is irradiated with an electron beam to generate radicals. As shown in FIG. A bond is formed between an atom on the surface of the liquid crystal polymer film 2 or an atom on the surface of the polyolefin resin film 1 and an atom on the surface of the liquid crystal polymer film 2 through an oxygen atom and / or a nitrogen atom. By forming the film, the polyolefin resin film 1 and the liquid crystal polymer film 2 are firmly bonded without using an adhesive. Further, radicals generated by electron beam irradiation and oxygen in the air are bonded to each other, and OH groups may be present on the surface of the polyolefin resin film 1 and / or the liquid crystal polymer film 2, in which case the polyolefin resin film A hydrogen bond may be formed between 1 and the liquid crystal polymer film 2. The generation of radicals by electron beam irradiation is confirmed by identifying the free radical species existing in the film after electron beam irradiation using an electron spin resonance apparatus (hereinafter also referred to as ESR). be able to.

また、電子線照射により液晶ポリマーフィルム２とポリオレフィン樹脂フィルム１とを接着した積層体は、図２に示すように、液晶ポリマーフィルム中の原子とポリオレフィン樹脂フィルム中の原子との間で結合が形成されているため、接着剤を全く使用しなくても、剥離を生じない積層体とすることができる。水素結合の存在の確認は、積層体を水またはアルコール溶液中に浸積して剥離の有無を確認することにより行うことができる。水素結合のみによって液晶ポリマーフィルム２とポリオレフィン樹脂フィルム１とが接着している場合、積層体を水またはアルコール溶液中に浸積すると、両者の間に形成されていた水素結合が破壊されて水またはアルコールの水素原子または酸素原子と水素結合が再形成されるため、接着力がなくなり両フィルムが剥離する。よって、接着が、共有結合および水素結合によるものなのか、水素結合のみによるものなのかを、確認することができる。   In addition, in the laminate in which the liquid crystal polymer film 2 and the polyolefin resin film 1 are bonded by electron beam irradiation, as shown in FIG. 2, a bond is formed between the atoms in the liquid crystal polymer film and the atoms in the polyolefin resin film. Therefore, even if no adhesive is used, a laminate that does not peel can be obtained. The presence of hydrogen bonds can be confirmed by immersing the laminate in water or an alcohol solution and confirming the presence or absence of peeling. When the liquid crystal polymer film 2 and the polyolefin resin film 1 are bonded only by hydrogen bonds, when the laminate is immersed in water or an alcohol solution, the hydrogen bonds formed between the two are broken and water or Since hydrogen bonds with alcohol hydrogen atoms or oxygen atoms are reformed, the adhesive force is lost and both films are peeled off. Therefore, it can be confirmed whether the adhesion is due to a covalent bond and a hydrogen bond or only due to a hydrogen bond.

以下、本発明による積層体を構成する液晶ポリマーフィルムおよびポリオレフィン樹脂フィルムについて、説明する。   Hereinafter, the liquid crystal polymer film and the polyolefin resin film constituting the laminate according to the present invention will be described.

＜液晶ポリマーフィルム＞
本発明において使用される液晶ポリマーフィルムは、液晶ポリマーをフィルム状に製膜したものである。本発明に使用できる液晶ポリマーとしては、全芳香族系もしくは半芳香族系の液晶ポリエステル、ポリエステルイミド、ポリエステルアミド等が挙げられる。これらのなかでも、ポリアリレート系液晶ポリマーが好ましく、例えば、エチレンテレフタレートとパラヒドロキシ安息香酸とが重縮合したポリマー、フェノールと、フタル酸およびパラヒドロキシ安息香酸とが重縮合したポリマー、２，６−ヒドロキシナフトエ酸とパラヒドロキシ安息香酸とが重縮合したポリマー等が挙げられる。 <Liquid crystal polymer film>
The liquid crystal polymer film used in the present invention is obtained by forming a liquid crystal polymer into a film. Examples of the liquid crystal polymer that can be used in the present invention include wholly aromatic or semi-aromatic liquid crystal polyesters, polyester imides, and polyester amides. Among these, a polyarylate-based liquid crystal polymer is preferable, for example, a polymer obtained by polycondensation of ethylene terephthalate and parahydroxybenzoic acid, a polymer obtained by polycondensation of phenol, phthalic acid and parahydroxybenzoic acid, 2,6- Examples thereof include a polymer obtained by polycondensation of hydroxynaphthoic acid and parahydroxybenzoic acid.

液晶ポリマーには、性能を損なわない範囲で必要に応じて、熱安定剤、難燃剤等の各種添加剤を製造工程中あるいはその後の加工工程において添加することができる。   Various additives such as a heat stabilizer and a flame retardant can be added to the liquid crystal polymer during the manufacturing process or in the subsequent processing steps as necessary within a range not impairing the performance.

上記した液晶ポリマーからフィルムを製造する方法は、特に制限はなく公知の方法を採用でき、例えば、液晶ポリマーを溶媒に溶解させた溶液からフィルムを得るキャスト法、Ｔダイから溶融樹脂を押出し巻き取るＴダイ法、環状ダイスを設置した押出機から溶融樹脂を円筒状に押出し、冷却し巻き取るインフレーション成形法、熱プレス法、カレンダーもしくはロールを用いた成形法等が挙げられ、好ましくは、Ｔダイ法、インフレーション成形法であり、インフレーション成形法が挙げられる。フィルムの厚みは、使用用途に応じて適宜決定できるが、概ね２０〜３００μｍ程度である。   The method for producing a film from the above liquid crystal polymer is not particularly limited, and a known method can be employed. For example, a casting method for obtaining a film from a solution in which a liquid crystal polymer is dissolved in a solvent, a molten resin is extruded and wound from a T die. Examples thereof include a T-die method, an inflation molding method in which a molten resin is extruded into a cylindrical shape from an extruder provided with an annular die, cooled and wound, a hot press method, a molding method using a calendar or a roll, etc. Method, inflation molding method, and inflation molding method. Although the thickness of a film can be suitably determined according to a use application, it is about 20-300 micrometers in general.

液晶ポリマーフィルムは、市販のものを使用してもよく、例えば、ベクトラ（ポリグラステックス社製）やノバキュレート三菱化学社製）、ベクスター（クラレ社製）などを好適に使用できる。   A commercially available liquid crystal polymer film may be used. For example, Vectra (manufactured by Polygrastex), Novacurate Mitsubishi Chemical Co., Ltd., Bexter (manufactured by Kuraray Co., Ltd.) and the like can be suitably used.

＜ポリオレフィン樹脂フィルム＞
本発明の積層体を構成するポリオレフィン樹脂フィルムとしては、低密度ポリエチレン、直鎖状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリメチルペンテン等の単体、または、ポリプロピレンと低密度ポリエチレンとの混合物や、ポリプロピレンと高密度ポリエチレンとの混合物からなるフィルムを用いることができる。また、ポリメチルペンテンは、ガス透過性、耐薬品性、耐油性などに優れた性能を有するものである。このような樹脂フィルムとしては、市販のものを使用してもよく、例えばＴＰＸフィルム（三井化学株式会社製）等を好適に使用することができる。フィルムの厚みは、使用用途に応じて適宜決定できるが、概ね２０〜３００μｍ程度である。 <Polyolefin resin film>
As the polyolefin resin film constituting the laminate of the present invention, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polymethylpentene and the like alone, or polypropylene and low density polyethylene And a film made of a mixture of polypropylene and high-density polyethylene can be used. Polymethylpentene has excellent performance in gas permeability, chemical resistance, oil resistance, and the like. As such a resin film, you may use a commercially available thing, for example, a TPX film (made by Mitsui Chemicals) etc. can be used conveniently. Although the thickness of a film can be suitably determined according to a use application, it is about 20-300 micrometers in general.

ポリオレフィン樹脂フィルムには、必要に応じて、光安定剤、紫外線吸収剤、酸化防止剤、充填剤、滑剤等、従来公知の各種添加剤を適宜添加することができる。光安定剤、紫外線吸収剤としては、従来公知のものを使用でき、例えば、フェノール系、リン系、ヒンダードアミン系の光吸収剤や、ベンゾトリアゾール系、ベンゾフェノン系、サリチル酸エステル系の紫外線吸収剤が使用できる。   Various conventionally known additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, a lubricant, and the like can be appropriately added to the polyolefin resin film as necessary. Conventionally known light stabilizers and ultraviolet absorbers can be used. For example, phenol-based, phosphorus-based, hindered amine-based light absorbers, benzotriazole-based, benzophenone-based, and salicylic acid ester-based ultraviolet absorbers are used. it can.

上記したような液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを重ね合わせて接着した積層体は、積層体を使用する際にも異物や残留溶剤等が滲出することがなく、また強度、耐熱性、誘電特性、電気絶縁性、ヒートシール性にも優れている。   A laminate in which a liquid crystal polymer film and a polyolefin resin film are laminated and bonded as described above does not exude foreign matter or residual solvent even when the laminate is used, and has strength, heat resistance, and dielectric properties. Excellent electrical insulation and heat sealability.

＜積層体の製造方法＞
次に、上記したような積層体を製造する方法を、図面を参照しながら説明する。先ず、上記したポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを準備し（図３（１））、両者のいずれか一方または両方の、接着しようとする部分に電子線を照射する（図３（２））。その結果、図３（３）に示すように、電子線が照射された部分のみ、互いのフィルムが接着される。 <Method for producing laminate>
Next, a method for producing the laminate as described above will be described with reference to the drawings. First, the polyolefin resin film 1 and the liquid crystal polymer film 2 described above are prepared (FIG. 3 (1)), and one or both of them are irradiated with an electron beam (FIG. 3 (2)). )). As a result, as shown in FIG. 3 (3), only the portions irradiated with the electron beam are bonded to each other.

本発明においては、フィルムに電子線を照射した直後に、図４に示すようにローラー６等を用いて、重ね合わせたポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを押圧することが好ましい。両フィルム１，２の表面は、図４に示すようにミクロレベルで凹凸があるため、互いのフィルムを重ね合わせても完全に密着しておらず、両フィルムの接触界面での接触面積が小さい。本発明においては、電子線を照射した直後にローラー６等でポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２を押圧することにより、両フィルムの接着面での接触面積が増加するため、密着性が向上する。   In the present invention, immediately after irradiating the film with an electron beam, it is preferable to press the overlapped polyolefin resin film 1 and liquid crystal polymer film 2 using a roller 6 or the like as shown in FIG. Since the surfaces of both films 1 and 2 are uneven at the micro level as shown in FIG. 4, even if the films are overlapped, they are not completely adhered to each other, and the contact area at the contact interface between both films is small. . In the present invention, immediately after irradiating the electron beam, pressing the polyolefin resin film 1 and the liquid crystal polymer film 2 with the roller 6 or the like increases the contact area on the bonding surface of both films, so that the adhesion is improved. .

ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを重ね合わせた後、両フィルム１，２を押圧する際には、加熱しながら両フィルム１，２を押圧することが好ましい。加熱しながら押圧することにより、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２の柔軟性が向上し、両フィルム１，２の界面（接着面）での接触面積をより増加させることができるため、密着性がより向上する。加熱する温度は、使用する材料の種類にもよるが、フィルムが熱変形できる温度であればよく、例えば、フィルムを構成する樹脂のガラス転移温度以上に加熱することができる。例えば、ポリオレフィン樹脂フィルムと液晶ポリマーフィルムとを重ね合わせる場合には、加熱温度は８０〜１８０℃、好ましくは１００〜１６０℃である。加熱温度を高くしすぎると、発生したラジカルが失活してしまい、強固な結合を実現できなくなる。なお、押圧の力（接圧）を高くしてもよく、接圧を高くすることにより、加熱温度を低くすることができる。   After the polyolefin resin film 1 and the liquid crystal polymer film 2 are overlapped, when the both films 1 and 2 are pressed, it is preferable to press both the films 1 and 2 while heating. By pressing while heating, the flexibility of the polyolefin resin film 1 and the liquid crystal polymer film 2 is improved, and the contact area at the interface (adhesive surface) between the films 1 and 2 can be further increased. Will be improved. The heating temperature may be any temperature at which the film can be thermally deformed, depending on the type of material used. For example, the heating can be performed at a temperature higher than the glass transition temperature of the resin constituting the film. For example, when superposing a polyolefin resin film and a liquid crystal polymer film, the heating temperature is 80 to 180 ° C, preferably 100 to 160 ° C. If the heating temperature is too high, the generated radicals are deactivated, and a strong bond cannot be realized. The pressing force (contact pressure) may be increased, and the heating temperature can be lowered by increasing the contact pressure.

ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを重ね合わせて押圧するには、上記したようにヒートローラ６等を好適に使用できる。また、図４に示すように、重ね合わせた積層物がヒートローラ６と支持ローラー７との間で圧接可能となるように、ヒートローラ６と対向する位置に支持ローラー７を載置してもよい。このようにヒートローラ６と対向する位置に支持ローラー７を載置することにより、積層体（フィルム１とフィルム２の積層物）とヒートローラ６との接触を線接触に近づけて、ヒートローラ６からの熱により積層体に発生する変形を最小限に抑えることができる。   In order to overlap and press the polyolefin resin film 1 and the liquid crystal polymer film 2, the heat roller 6 or the like can be suitably used as described above. Further, as shown in FIG. 4, even if the support roller 7 is placed at a position facing the heat roller 6 so that the stacked laminate can be pressed between the heat roller 6 and the support roller 7. Good. In this way, by placing the support roller 7 at a position facing the heat roller 6, the contact between the laminate (the laminate of the film 1 and the film 2) and the heat roller 6 is brought close to the line contact, and the heat roller 6. It is possible to minimize the deformation that occurs in the laminated body due to the heat from the.

図５は、本発明による別の製造方法の実施形態を示した概略図である。ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを重ね合わせて接着する工程において、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを、それぞれガイドローラにより電子線照射位置３まで導き、電子線４を両フィルム１，２に照射した後にヒートローラ６により互いの両フィルム１，２を押圧する工程を連続的に行うものである。ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２のそれぞれはロール状形態として供給されてもよい。   FIG. 5 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In the process of laminating and adhering the polyolefin resin film 1 and the liquid crystal polymer film 2, the polyolefin resin film 1 and the liquid crystal polymer film 2 are respectively guided to the electron beam irradiation position 3 by the guide rollers, and the electron beam 4 is connected to both the films 1. , 2 is continuously performed by pressing the two films 1 and 2 with the heat roller 6 after irradiation. Each of the polyolefin resin film 1 and the liquid crystal polymer film 2 may be supplied in a roll form.

電子線照射装置３から、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２のそれぞれに電子線４を照射する場合、厚みがより小さい方の材料側から電子線４を照射することが好ましい。電子線は加速電圧が増加するほどその透過力も増大する性質を有しているため、何れか一方の材料側から電子線を照射した場合に、材料の厚さによっては、他方のフィルムまたはフィルムまで電子線が届かないことがある。その場合には、電子線の加速電圧を増加させることにより、他方の材料の深部まで電子線を到達させることができるが、電子線エネルギーが高くなるにしたがって、樹脂からなる材料（フィルム）自体に不必要な照射が行われ劣化させてしまう。そのため、厚肉のフィルムと薄肉のフィルムとを重ね合わせて接着する際には、電子線エネルギーをそれほど増大させることなく、薄肉のフィルム側から電子線を照射するのが好ましい。例えば、ポリオレフィン樹脂フィルムの厚みが２５μｍ以下であり、液晶ポリマーフィルムの厚みが５０μｍ以上である場合は、ポリオレフィン樹脂フィルム側から電子線を照射する。このような電子線照射方法を採用することにより、フィルムの劣化を最小限に留めることができる。   When the electron beam irradiation device 3 irradiates the polyolefin resin film 1 and the liquid crystal polymer film 2 with the electron beam 4, it is preferable to irradiate the electron beam 4 from the material side having the smaller thickness. Since the electron beam has the property that its transmission power increases as the acceleration voltage increases, depending on the thickness of the material, it can reach the other film or film when the electron beam is irradiated from either material side. The electron beam may not reach. In that case, the electron beam can reach the deep part of the other material by increasing the acceleration voltage of the electron beam. However, as the electron beam energy increases, the material (film) itself made of resin Unnecessary irradiation is performed and deteriorates. Therefore, when a thick film and a thin film are laminated and bonded, it is preferable to irradiate an electron beam from the thin film side without increasing the electron beam energy so much. For example, when the thickness of the polyolefin resin film is 25 μm or less and the thickness of the liquid crystal polymer film is 50 μm or more, the electron beam is irradiated from the polyolefin resin film side. By adopting such an electron beam irradiation method, deterioration of the film can be minimized.

重ね合わせるフィルム１，２が両方とも厚肉である場合には、図５に示すように両方から電子線が照射できるように、電子線照射装置３と対向する位置に、別の電子線照射装置３’を設けてもよい。この態様によれば、フィルムの厚みに応じて電子線の照射エネルギーを調整することができるため、フィルムを劣化させることなく互いを接着することができる。   When both the films 1 and 2 to be superimposed are thick, as shown in FIG. 5, another electron beam irradiation device is placed at a position facing the electron beam irradiation device 3 so that the electron beam can be irradiated from both. 3 'may be provided. According to this aspect, since the irradiation energy of the electron beam can be adjusted according to the thickness of the film, the films can be bonded to each other without deteriorating the film.

図６は、本発明による別の製造方法の実施形態を示した概略図である。この実施態様においては、電子線の照射が、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを重ね合わせる前に行われる。先ず、供給されてきた一対のフィルム（ポリオレフィン樹脂フィルム１および液晶ポリマー２）は、両フィルム１，２が重ね合わされる前に、電子線照射装置３（３’）により、フィルム１（２）へ電子線４（４’）が照射される。図５に示した実施形態では、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２の電子線照射側と反対側の面どうしが対向するように両フィルム１，２を重ね合わせたのに対し、図６に示す実施態様では、両フィルム１，２の電子線照射側の面どうしが対向するように両フィルム１，２を重ね合わせる点が相違している。このように、フィルム１へ電子線を照射した側の面に他方のフィルム２を重ね合わせることにより、フィルムの厚みによらず、電子線の照射エネルギーをより小さくすることができ、その結果、フィルムの電子線照射による劣化をより低減することができる。   FIG. 6 is a schematic view showing an embodiment of another manufacturing method according to the present invention. In this embodiment, the electron beam irradiation is performed before the polyolefin resin film 1 and the liquid crystal polymer film 2 are overlapped. First, a pair of supplied films (polyolefin resin film 1 and liquid crystal polymer 2) are transferred to film 1 (2) by electron beam irradiation device 3 (3 ′) before both films 1 and 2 are overlapped. The electron beam 4 (4 ′) is irradiated. In the embodiment shown in FIG. 5, both the films 1 and 2 are overlapped so that the surfaces opposite to the electron beam irradiation side of the polyolefin resin film 1 and the liquid crystal polymer film 2 face each other. The embodiment shown is different in that the films 1 and 2 are overlapped so that the surfaces on the electron beam irradiation side of the films 1 and 2 face each other. Thus, by superimposing the other film 2 on the surface of the film 1 irradiated with the electron beam, the irradiation energy of the electron beam can be made smaller regardless of the thickness of the film. As a result, the film Degradation due to electron beam irradiation can be further reduced.

また、図６に示した実施態様においても、一対の電子線照射装置３，３’を設けて、図５に示した実施態様と同様に、ポリオレフィン樹脂フィルム１および液晶ポリマーフィルム２のそれぞれへ電子線４，４’を照射してもよい。これらの組み合わせにより、よりフィルムの劣化を少なくして接着強度を向上させることができる。   Also in the embodiment shown in FIG. 6, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and in the same manner as in the embodiment shown in FIG. Lines 4 and 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

図７は、本発明による別の製造方法の実施形態を示した概略図である。この実施形態においては、ポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２とを重ね合わせてヒートローラ６により押圧した後に電子線照射を行うものである。先ず、供給されてきた一対のフィルム１，２は、ガイドローラに導かれて重ね合わされる。続いて、ヒートローラ６と支持ローラー７とにより両フィルム１，２が押圧されるとともに、ヒートローラ６により加熱が行われる。その後、電子線照射装置３によりポリオレフィン樹脂フィルム１と液晶ポリマーフィルム２の表面に電子線４が照射されて両フィルム１，２の接着が連続的に行われる。また、図７に示した実施形態においても、一対の電子線照射装置３，３’を設けて、図５及び６に示した実施態様と同様に両フィルム１，２へそれぞれ電子線４，４’を照射してもよい。これらの組み合わせにより、よりフィルム劣化を少なくして接着強度を向上させることができる。   FIG. 7 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In this embodiment, the polyolefin resin film 1 and the liquid crystal polymer film 2 are superposed and pressed by the heat roller 6 and then irradiated with an electron beam. First, the pair of supplied films 1 and 2 are led to a guide roller and overlapped. Subsequently, both the films 1 and 2 are pressed by the heat roller 6 and the support roller 7, and heating is performed by the heat roller 6. Thereafter, the electron beam irradiation device 3 irradiates the surface of the polyolefin resin film 1 and the liquid crystal polymer film 2 with the electron beam 4 so that the films 1 and 2 are continuously bonded. Also in the embodiment shown in FIG. 7, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and the electron beams 4 and 4 are respectively applied to both films 1 and 2 in the same manner as the embodiment shown in FIGS. You may irradiate. By these combinations, the film deterioration can be further reduced and the adhesive strength can be improved.

電子線の照射エネルギーは、上記したようにフィルム厚み等に応じて適宜調整する必要がある。本発明においては、２０〜７５０ｋＶ、好ましくは３０〜４００ｋＶ、より好ましくは４０〜２００ｋＶ程度の照射エネルギー範囲で電子線を照射するが、より低い照射エネルギーとすることが好ましい。このように低い照射エネルギーとすることにより、フィルムの劣化を抑制できるだけでなく、フィルム表面のラジカル発生がより効率的におこるため、より強固な結合を実現することができる。また、電子線の吸収線量は、５〜２０００ｋＧｙ、好ましくは２０〜１０００ｋＧｙの範囲で行う。   The irradiation energy of the electron beam needs to be appropriately adjusted according to the film thickness and the like as described above. In the present invention, the electron beam is irradiated in an irradiation energy range of about 20 to 750 kV, preferably 30 to 400 kV, and more preferably about 40 to 200 kV, but it is preferable that the irradiation energy be lower. Thus, by setting it as low irradiation energy, not only deterioration of a film can be suppressed, but since radical generation | occurrence | production of a film surface occurs more efficiently, stronger bond can be implement | achieved. The absorbed dose of the electron beam is 5 to 2000 kGy, preferably 20 to 1000 kGy.

このような電子線照射装置としては、従来公知のものを使用でき、例えばカーテン型電子照射装置（ＬＢ１０２３、株式会社アイ・エレクトロンビーム社製）やライン照射型低エネルギー電子線照射装置（ＥＢ−ＥＮＧＩＮＥ、浜松ホトニクス株式会社製）等を好適に使用することができる。   As such an electron beam irradiation apparatus, conventionally known ones can be used. For example, a curtain type electron irradiation apparatus (LB1023, manufactured by I. Electron Beam Co., Ltd.) or a line irradiation type low energy electron beam irradiation apparatus (EB-ENGINE). , Manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used.

電子線を照射する際には、酸素濃度を１００ｐｐｍ以下とすることが好ましい。酸素存在下で電子線を照射するとオゾンが発生するため環境に悪影響を及ぼす場合があるからである。酸素濃度を１００ｐｐｍ以下とするには、真空下または窒素やアルゴン等の不活性ガス雰囲気下において、フィルムに電子線を照射すればよく、例えば、電子線照射装置内を窒素充填することにより、酸素濃度１００ｐｐｍ以下を達成することができる。   When irradiating with an electron beam, the oxygen concentration is preferably 100 ppm or less. This is because irradiation with an electron beam in the presence of oxygen generates ozone and may adversely affect the environment. In order to reduce the oxygen concentration to 100 ppm or less, the film may be irradiated with an electron beam in a vacuum or in an inert gas atmosphere such as nitrogen or argon. For example, by filling the electron beam irradiation apparatus with nitrogen, A concentration of 100 ppm or less can be achieved.

上記した接着方法によって得られた、ポリオレフィン樹脂フィルムと液晶ポリマーフィルムと積層した積層体は、従来のラミネート樹脂を用いて接着した場合と同等またはそれ以上の接着強度を実現できる。また、ラミネート樹脂等を全く用いていないため、積層体を使用する際にも異物や残留溶剤等が滲出することがなく、また強度、耐熱性、誘電特性、電気絶縁性にも優れている。   The laminate obtained by laminating the polyolefin resin film and the liquid crystal polymer film obtained by the above-described adhesion method can realize an adhesive strength equal to or higher than that obtained by using a conventional laminate resin. In addition, since no laminate resin or the like is used, foreign matter or residual solvent does not ooze out when the laminate is used, and the strength, heat resistance, dielectric properties, and electrical insulation are excellent.

＜フィルムの準備＞
液晶ポリマーフィルムとして、厚み５０μｍの液晶ポリマーフィルム（ベクトラＡ９５０（ポリプラスチックス社製）を準備した。また、ポリオレフィン樹脂フィルムとして、下記の下２種類のフィルムを準備した。
Ａ：エチレン−プロピレンブロック共重合体（ＰＦ３８０Ａ、サンアロマー株式会社製）を厚み７０μｍに製膜したフィルム
Ｂ：直鎖状低密度ポリエチレン（エボリューＳＰ２０２０、プライムポリマー社製）を厚み７０μｍに製膜したフィルム <Preparation of film>
A liquid crystal polymer film (Vectra A950 (manufactured by Polyplastics)) having a thickness of 50 μm was prepared as the liquid crystal polymer film, and the following two types of films were prepared as the polyolefin resin film.
A: Film obtained by forming an ethylene-propylene block copolymer (PF380A, manufactured by Sun Allomer Co., Ltd.) to a thickness of 70 μm B: Film formed by forming a linear low density polyethylene (Evolu SP2020, manufactured by Prime Polymer Co., Ltd.) to a thickness of 70 μm

実施例１
＜積層体の作製＞
上記したフィルムを、それぞれ１５０ｍｍ×７５ｍｍの大きさに切り出した試料を準備し、電子線照射装置（ライン照射型低エネルギー電子線照射装置ＥＥＳ−Ｌ−ＤＰ０１、浜松ホトニクス株式会社製）のサンプル台に並置した。この際、電子線が試料に照射されない部分を設けるために、両試料の一方の端部５〜１０ｍｍ程度にマスキングしておいた。 Example 1
<Production of laminate>
Samples obtained by cutting each of the above films into a size of 150 mm × 75 mm are prepared and placed on a sample stage of an electron beam irradiation apparatus (line irradiation type low energy electron beam irradiation apparatus EES-L-DP01, manufactured by Hamamatsu Photonics Co., Ltd.). Juxtaposed. At this time, in order to provide a portion where the sample is not irradiated with the electron beam, masking is performed on one end portion of both samples of about 5 to 10 mm.

次いで、電子照射線装置のチャンバー内の酸素濃度が１００ｐｐｍ以下となるように窒素ガスでパージした後、下記の電子線照射条件により、試料の表面に電子線を照射した。
電圧：４０ｋＶ
吸収線量：２００ｋＧｙ
装置内酸素濃度：１００ｐｐｍ以下 Next, after purging with nitrogen gas so that the oxygen concentration in the chamber of the electron irradiation apparatus becomes 100 ppm or less, the surface of the sample was irradiated with an electron beam under the following electron beam irradiation conditions.
Voltage: 40 kV
Absorbed dose: 200kGy
In-device oxygen concentration: 100 ppm or less

電子線を照射した後、試料を装置内から取り出し、すぐに両者の電子線照射面側が対向するようにして重ね合わせ、熱ラミネート法により、両フィルムを接着して積層体を得た。   After irradiating the electron beam, the sample was taken out from the apparatus, immediately overlapped so that both electron beam irradiation surface sides face each other, and both films were bonded by a thermal laminating method to obtain a laminate.

実施例２
実施例１において、電子線の照射条件を表１に示す吸収線量に変更した以外は、実施例１と同様にして積層体を得た。 Example 2
In Example 1, a laminate was obtained in the same manner as in Example 1 except that the electron beam irradiation condition was changed to the absorbed dose shown in Table 1.

実施例３
実施例１において、使用したポリオレフィン樹脂フィルムをＢのフィルムに変更した以外は、実施例１と同様にして積層体を得た。 Example 3
In Example 1, the laminated body was obtained like Example 1 except having changed the used polyolefin resin film into the film of B.

比較例１
電子照射を行わなかった以外は実施例１と同様にして積層体を得た。しかしながら、得られた積層体は液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが接着していなかった。 Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that electron irradiation was not performed. However, in the obtained laminate, the liquid crystal polymer film and the polyolefin resin film were not adhered.

比較例２
実施例１で用いた２種の樹脂フィルムを、２液硬化型芳香族エステル系接着剤（タケラックＡ−３、三井化学株式会社製）を介して貼り合わせるドライラミネート法により積層体を得た。しかしながら、得られた積層体は液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが接着していなかった。 Comparative Example 2
A laminate was obtained by a dry laminating method in which the two types of resin films used in Example 1 were bonded together via a two-component curable aromatic ester adhesive (Takelac A-3, manufactured by Mitsui Chemicals, Inc.). However, in the obtained laminate, the liquid crystal polymer film and the polyolefin resin film were not adhered.

＜積層体の接着強度の評価＞
得られた積層体を幅１５ｍｍの短冊状になるように切り出し、引張試験機（テンシロン万能材料試験機ＲＴＣ−１３１０Ａ、ＯＲＩＥＮＴＥＣ社製）を用いて、５０ｍｍ／分の速度で、９０度剥離試験を行った。なお、上記したように比較例１の積層体は、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが接着しておらず、積層体の接着強度を測定することができなかった。評価結果は、下記の表１に示される通りであった。 <Evaluation of adhesive strength of laminate>
The obtained laminate was cut into a strip shape with a width of 15 mm, and a 90 ° peel test was performed at a rate of 50 mm / min using a tensile tester (Tensilon Universal Material Tester RTC-1310A, manufactured by ORIENTEC). went. As described above, in the laminate of Comparative Example 1, the liquid crystal polymer film and the polyolefin resin film were not adhered, and the adhesion strength of the laminate could not be measured. The evaluation results were as shown in Table 1 below.

Figure 2013018167
Figure 2013018167

表１の評価結果からも明らかなように、実施例１〜３の積層体は、水中保管後であっても、接着性を維持している。この結果から、実施例１〜３の積層体は、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが水素結合や分子間力のみによって接着しているものではないことがわかる。したがって、間接的にではあるが、液晶ポリマーフィルムの原子とポリオレフィン樹脂フィルム中の原子との間で共有結合が形成されていると推認できる。   As is clear from the evaluation results in Table 1, the laminates of Examples 1 to 3 maintain adhesiveness even after storage in water. From this result, it can be seen that in the laminates of Examples 1 to 3, the liquid crystal polymer film and the polyolefin resin film are not bonded only by hydrogen bonding or intermolecular force. Therefore, although indirectly, it can be inferred that a covalent bond is formed between the atom of the liquid crystal polymer film and the atom in the polyolefin resin film.

１ ポリオレフィン樹脂フィルム
２ 液晶ポリマーフィルム
３、３’ 電子線照射装置
４、４’ 電子線
５ フィルム基材接触界面
６ ヒートローラ
７ 支持ローラー DESCRIPTION OF SYMBOLS 1 Polyolefin resin film 2 Liquid crystal polymer film 3, 3 'Electron beam irradiation apparatus 4, 4' Electron beam 5 Film base-material contact interface 6 Heat roller 7 Support roller

Claims (8)

液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが積層した積層体であって、
前記液晶ポリマーフィルムおよび前記ポリオレフィン樹脂フィルムの少なくとも一部で、前記液晶ポリマーフィルム中の原子と、前記ポリオレフィン樹脂フィルム中の原子との間に結合が形成されており、前記液晶ポリマーフィルムおよび前記ポリオレフィン樹脂フィルムとが接着剤を介さずに接着されていることを特徴とする、積層体。 A laminate in which a liquid crystal polymer film and a polyolefin resin film are laminated,
In at least a part of the liquid crystal polymer film and the polyolefin resin film, a bond is formed between an atom in the liquid crystal polymer film and an atom in the polyolefin resin film, and the liquid crystal polymer film and the polyolefin resin A laminate, wherein the film is bonded without using an adhesive. 前記液晶ポリマーフィルムと前記ポリオレフィン樹脂フィルムとの界面の少なくとも一部で、前記液晶ポリマーフィルム中の原子と、前記ポリオレフィン樹脂フィルム中の原子との間で、酸素原子、窒素原子または水酸基を介して結合が形成されている、請求項１に記載の積層体。   At least part of the interface between the liquid crystal polymer film and the polyolefin resin film, bonded between an atom in the liquid crystal polymer film and an atom in the polyolefin resin film via an oxygen atom, a nitrogen atom, or a hydroxyl group The laminate according to claim 1, wherein 前記液晶ポリマーが、エチレンテレフタレートとパラヒドロキシ安息香酸とが重縮合したポリマー、フェノールと、フタル酸およびパラヒドロキシ安息香酸とが重縮合したポリマー、２，６−ヒドロキシナフトエ酸とパラヒドロキシ安息香酸とが重縮合したポリマーからなる群から選択されるものである、請求項１または２に記載の積層体。   The liquid crystal polymer is a polymer obtained by polycondensation of ethylene terephthalate and parahydroxybenzoic acid, a polymer obtained by polycondensation of phenol, phthalic acid and parahydroxybenzoic acid, 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid. The laminate according to claim 1 or 2, which is selected from the group consisting of polycondensed polymers. 前記ポリオレフィン樹脂フィルムが、ポリプロピレン、ポリエチレン、またはポリメチルペンテンからなる樹脂フィルムである、請求項１〜３のいずれか一項に記載の積層体。   The laminate according to any one of claims 1 to 3, wherein the polyolefin resin film is a resin film made of polypropylene, polyethylene, or polymethylpentene. 請求項１〜４のいずれか一項に記載の、液晶ポリマーフィルムとポリオレフィン樹脂フィルムとが積層した積層体を製造する方法であって、
液晶ポリマーフィルムおよび／またはポリオレフィン樹脂フィルムの少なくとも一方の面、に電子線を照射し、
前記電子線が照射された前記液晶ポリマーフィルム面および／またはポリオレフィン樹脂フィルム面を重ね合わせて接着する、ことを含んでなることを特徴とする、方法。 A method for producing a laminate in which a liquid crystal polymer film and a polyolefin resin film are laminated according to any one of claims 1 to 4,
Irradiating at least one surface of the liquid crystal polymer film and / or polyolefin resin film with an electron beam,
A method comprising superimposing and adhering the liquid crystal polymer film surface and / or the polyolefin resin film surface irradiated with the electron beam. 前記液晶ポリマーフィルムとポリオレフィン樹脂フィルムとを重ね合わせる前および／または重ね合わせた後に電子線照射を行う、請求項５に記載の方法。   The method according to claim 5, wherein the electron beam irradiation is performed before and / or after the liquid crystal polymer film and the polyolefin resin film are overlapped. 前記液晶ポリマーフィルムとポリオレフィン樹脂フィルムとの接着を加圧して行う、請求項５または６に記載の方法。   The method according to claim 5 or 6, wherein adhesion between the liquid crystal polymer film and the polyolefin resin film is performed under pressure. 前記液晶ポリマーフィルムとポリオレフィン樹脂フィルムとの接着を加熱して行う、請求項５〜７のいずれか一項に記載の方法。   The method according to claim 5, wherein the adhesion between the liquid crystal polymer film and the polyolefin resin film is performed by heating.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014237769A (en) * 2013-06-07 2014-12-18 株式会社プライマテック High heat resistant liquid crystal polymer film and production method thereof
JP2021115708A (en) * 2020-01-22 2021-08-10 大日本印刷株式会社 Laminated body and its manufacturing method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014237769A (en) * 2013-06-07 2014-12-18 株式会社プライマテック High heat resistant liquid crystal polymer film and production method thereof
JP2021115708A (en) * 2020-01-22 2021-08-10 大日本印刷株式会社 Laminated body and its manufacturing method
JP7484179B2 (en) 2020-01-22 2024-05-16 大日本印刷株式会社 Laminate and method for producing same

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