JP2010076141A - Method for manufacturing different kind of thermoplastic resin molded body and the same - Google Patents

Method for manufacturing different kind of thermoplastic resin molded body and the same Download PDF

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JP2010076141A
JP2010076141A JP2008244466A JP2008244466A JP2010076141A JP 2010076141 A JP2010076141 A JP 2010076141A JP 2008244466 A JP2008244466 A JP 2008244466A JP 2008244466 A JP2008244466 A JP 2008244466A JP 2010076141 A JP2010076141 A JP 2010076141A
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thermoplastic resin
layer
electron beam
beam irradiation
molded body
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JP5253065B2 (en
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Yoshitake Nishi
義武 西
Keisuke Iwata
圭祐 岩田
Hironori Sato
浩則 佐藤
Hiroaki Takei
廣明 武井
Akira Tonegawa
昭 利根川
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Tokai University
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a molded body excellent in interlayer bond strength of the layer comprising a different kind of thermoplastic resin, and a molded body obtained thereby. <P>SOLUTION: In the method for manufacturing the different kind of thermostatic resin molded body, a laminated body having a layer (A) comprising an adjacent thermoplastic resin (A) and a layer (B) comprising a thermoplastic resin (B) (where the thermoplastic resin (A) and the thermoplastic resin (B) are the different kind of thermoplastic resin) is irradiated with an electron beam having an acceleration voltage with a range of 50-300 keV from the layer (A) toward the layer (B) or from the layer (B) toward the layer (A). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は異種熱可塑性樹脂成型体の製造方法、および異種熱可塑性樹脂成型体に関する。   The present invention relates to a method for producing a different type thermoplastic resin molded body and a different type thermoplastic resin molded body.

熱可塑性樹脂は、軽量で機械的強度が高いことから、一般産業用途、土木・建築用途、輸送用機器分野など、幅広い分野で多量に使用されている。また、熱可塑性樹脂は、熱硬化性樹脂を用いた場合と比べて、成形性が非常に良好であり成形材料として有用である。さらに熱可塑性樹脂は生体適合性も良好であるため、人工血管、人工臓器、人工靱帯等の医療分野での応用が有望視され、その際には性質の異なった異種の樹脂を組み合わせて使用することが考えられている。   Thermoplastic resins are lightweight and have high mechanical strength, and are therefore used in large quantities in a wide range of fields, including general industrial applications, civil engineering / architecture applications, and transportation equipment. In addition, the thermoplastic resin has a very good moldability compared to the case where a thermosetting resin is used, and is useful as a molding material. Furthermore, since thermoplastic resins have good biocompatibility, they are expected to be applied in medical fields such as artificial blood vessels, artificial organs, and artificial ligaments. In that case, different types of resins with different properties are used in combination. It is considered.

しかしながら、従来の異種熱可塑性樹脂を接合する技術では、一般に熱可塑性樹脂どうしのぬれ性が乏しく、また結晶性熱可塑性樹脂は非晶性樹脂と比べて融点が高いため、融着等による接合は難しい等の欠点がある。そのため、熱可塑性樹脂間の接着性不良が起こり、充分な物性向上が図れなかった。   However, conventional techniques for joining different types of thermoplastic resins generally have poor wettability between thermoplastic resins, and crystalline thermoplastic resins have a higher melting point than amorphous resins. There are drawbacks such as difficulties. As a result, poor adhesion between thermoplastic resins occurred, and sufficient physical properties could not be improved.

熱可塑性樹脂間のぬれ性を改良した熱可塑性樹脂間の接合としては、例えばレーザー加熱処理による熱可塑性樹脂の接合技術が提案されている（例えば、特許文献１参照）。また、接着剤を含有する熱可塑性樹脂を用いた熱可塑性樹脂間の接合が提案されている（例えば、特許文献２参照）。さらに、紫外線照射を用いた、熱可塑性樹脂間の接合が提案されている（例えば、特許文献３参照）。   As joining between thermoplastic resins with improved wettability between thermoplastic resins, for example, a joining technique of thermoplastic resins by laser heat treatment has been proposed (see, for example, Patent Document 1). Further, bonding between thermoplastic resins using a thermoplastic resin containing an adhesive has been proposed (see, for example, Patent Document 2). Furthermore, joining between thermoplastic resins using ultraviolet irradiation has been proposed (see, for example, Patent Document 3).

上記特許文献１〜３に開示された技術は、熱処理（加熱温度、および加熱時間等）や、熱可塑性樹脂や接着剤の組成を規定することにより、熱可塑性樹脂間の界面近傍の異種高分子材料を改質、または、第三高分子層の形成により接合するものであって、熱可塑性樹脂層間の接合強度が十分でなかったり、生体への影響が不明な物質の混入が懸念されたり、あるいは殺菌処理が難しい場合があった。
特開２００４−２２３７１９号公報 特開平０９―２７７４５９号公報 特開平７−９０２２８号公報 The techniques disclosed in Patent Documents 1 to 3 described above are different types of polymers in the vicinity of the interface between the thermoplastic resins by defining the composition of the heat treatment (heating temperature, heating time, etc.) and the thermoplastic resin or adhesive. The material is modified or bonded by forming a third polymer layer, and the bonding strength between the thermoplastic resin layers is not sufficient, or there is a concern about the mixing of substances whose influence on the living body is unknown, Alternatively, sterilization may be difficult.
JP 2004-223719 A Japanese Patent Application Laid-Open No. 09-277459 Japanese Patent Laid-Open No. 7-90228

本発明は上記従来技術の有する課題に鑑みてなされたものであり、異種の熱可塑性樹脂からなる層の層間接合強度に優れた成形体の製造方法および該製造方法により得られた成形体を提供することを目的とする。   The present invention has been made in view of the above-described problems of the prior art, and provides a method for producing a molded article having excellent interlayer bonding strength between layers of different types of thermoplastic resins, and a molded article obtained by the production method. The purpose is to do.

本発明者らは上記課題を達成するために鋭意研究を重ねた結果、異種の熱可塑性樹脂からなる層を、隣接して配置した積層体に、特定の加速電圧の範囲で、電子線を照射することにより、層間の界面接合強度に優れた異種熱可塑性樹脂成形体が得られることを見出し、本発明を完成させた。   As a result of intensive studies to achieve the above-mentioned problems, the inventors of the present invention irradiate an electron beam within a specific acceleration voltage range on a laminated body in which layers made of different types of thermoplastic resins are arranged adjacent to each other. As a result, it was found that a different kind of thermoplastic resin molded article having excellent interlaminar interface bonding strength was obtained, and the present invention was completed.

すなわち、本発明の異種熱可塑性樹脂成形体の製造方法は、隣接した、熱可塑性樹脂（Ａ）からなる層（Ａ）および熱可塑性樹脂（Ｂ）（ただし、熱可塑性樹脂（Ａ）と、熱可塑性樹脂（Ｂ）とは異種の熱可塑性樹脂である）からなる層（Ｂ）を有する積層体に、層
（Ａ）から層（Ｂ）に向かって、または層（Ｂ）から層（Ａ）に向かって、加速電圧が５０〜３００ｋｅＶの範囲で電子線照射を行うことを特徴とする。 That is, the manufacturing method of the different type | mold thermoplastic resin molding of this invention WHEREIN: The layer (A) and thermoplastic resin (B) (however, thermoplastic resin (A) which consists of an adjacent thermoplastic resin (A), and heat A laminate having a layer (B) made of a thermoplastic resin different from the thermoplastic resin (B) is applied to the layer (A) from the layer (A) to the layer (B) or from the layer (B) to the layer (A). The electron beam irradiation is performed in an acceleration voltage range of 50 to 300 keV.

前記積層体に電子線照射を行う前、後または電子線照射中に、前記積層体を一体化することが好ましい。
前記電子線照射における電子線照射線量が、０．０５〜０．５ＭＧｙの範囲であることが好ましい。 It is preferable that the laminate is integrated before, after or during electron beam irradiation of the laminate.
The electron beam irradiation dose in the electron beam irradiation is preferably in the range of 0.05 to 0.5 MGy.

また本発明には、上記記載の製造方法により得られることを特徴とする異種熱可塑性樹脂成型体が含まれる。   Further, the present invention includes a heterogeneous thermoplastic resin molded article obtained by the production method described above.

本発明の異種熱可塑性樹脂成型体の製造方法により得られる、異種熱可塑性樹脂成型体は、異種の熱可塑性樹脂からなる層の層間の界面が高い接着強度で接合されている。
また、本発明の異種熱可塑性樹脂成型体の製造方法により得られる、異種熱可塑性樹脂成型体は、同時に殺菌・滅菌効果も得られることから特に人工血管、人工靱帯等の医療機器分野の使用に適しており、さらには、一般産業用途、土木、建築、輸送用機器、電子機器分野等の各種産業分野における、軽量化や強靭化を必要とされる製品や、接合・複合部品等として用いることができる。 In the heterogeneous thermoplastic resin molding obtained by the method for producing a heterogeneous thermoplastic resin molding of the present invention, the interface between layers of different thermoplastic resins is bonded with high adhesive strength.
In addition, the heterogeneous thermoplastic resin molded body obtained by the method for producing a heterogeneous thermoplastic resin molded body of the present invention is also effective for use in the field of medical equipment such as artificial blood vessels and artificial ligaments because it can also have a sterilizing and sterilizing effect. In addition, it is used as a product that requires weight reduction and toughness in various industrial fields such as general industrial use, civil engineering, construction, transportation equipment, and electronic equipment, and as a joined / composite part. Can do.

次に本発明について具体的に説明する。
本発明の異種熱可塑性樹脂成形体の製造方法は、隣接した、熱可塑性樹脂（Ａ）からなる層（Ａ）および熱可塑性樹脂（Ｂ）（ただし、熱可塑性樹脂（Ａ）と、熱可塑性樹脂（Ｂ）とは異種の熱可塑性樹脂である）からなる層（Ｂ）を有する積層体に、層（Ａ）から層（Ｂ）に向かって、または層（Ｂ）から層（Ａ）に向かって、加速電圧が５０〜３００ｋｅＶの範囲で電子線照射を行うことを特徴とする。 Next, the present invention will be specifically described.
The manufacturing method of the different type | mold thermoplastic resin molded object of this invention is the layer (A) and thermoplastic resin (B) (however, thermoplastic resin (A) and thermoplastic resin which consist of the adjacent thermoplastic resin (A). (B) is a laminate having a layer (B) made of a different kind of thermoplastic resin), and is directed from the layer (A) to the layer (B) or from the layer (B) to the layer (A). Thus, electron beam irradiation is performed in an acceleration voltage range of 50 to 300 keV.

本発明の異種熱可塑性樹脂成型体の製造方法では、熱可塑性樹脂（Ａ）からなる層（Ａ）および熱可塑性樹脂（Ｂ）からなる層（Ｂ）が隣接した状態で配置された積層体、すなわち異種の熱可塑性樹脂からなる層が互いに隣接した積層体に電子線を照射することにより、層間の接着強度を高めることができる。   In the method for producing a heterogeneous thermoplastic resin molded body of the present invention, a laminate in which the layer (A) made of the thermoplastic resin (A) and the layer (B) made of the thermoplastic resin (B) are arranged adjacent to each other, That is, by irradiating an electron beam to a laminated body in which layers made of different types of thermoplastic resins are adjacent to each other, the adhesive strength between the layers can be increased.

本発明の製造方法においては、前述のように層（Ａ）および層（Ｂ）が隣接した積層体の層（Ａ）から層（Ｂ）に向かって、または層（Ｂ）から層（Ａ）に向かって、電子線を照射する。   In the production method of the present invention, as described above, the layer (A) and the layer (B) are adjacent to each other from the layer (A) to the layer (B) or from the layer (B) to the layer (A). Irradiate with an electron beam.

前記積層体の層（Ａ）を構成する熱可塑性樹脂（Ａ）および層（Ｂ）を構成する熱可塑性樹脂（Ｂ）としては、熱可塑性を有する樹脂であれば特に限定はなく、汎用樹脂、耐熱性樹脂、耐衝撃性樹脂、エンジニアリング樹脂等様々な熱可塑性樹脂を用いることができる。また、熱可塑性樹脂（Ａ）および熱可塑性樹脂（Ｂ）の組み合わせとしては、特に限定はなく、異なる種類の熱可塑性樹脂であればよい。   The thermoplastic resin (A) that constitutes the layer (A) of the laminate and the thermoplastic resin (B) that constitutes the layer (B) are not particularly limited as long as they are thermoplastic resins. Various thermoplastic resins such as a heat resistant resin, an impact resistant resin, and an engineering resin can be used. Moreover, there is no limitation in particular as a combination of a thermoplastic resin (A) and a thermoplastic resin (B), What is necessary is just a different kind of thermoplastic resin.

熱可塑性樹脂としては、例えば、ポリエチレンやポリプロピレン等のポリオレフィン；ポリスチレン、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸メチル、ポリアクリル酸エチル等のポリ（メタ）アクリル酸エステル等のビニル系重合体；ナイロン６、ナイロン６６、ナイロン１１、ナイロン１２、ナイロン６１０、ナイロン６１２、ナイロン６１、ナイロン６Ｔ、ナイロン９Ｔ等のポリアミド、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリカーボネート、ポリイミド等の縮合系重合体；ポリアセタール；ポリフェニレンオキサイド；ポリフェニレンサルフ
ァイド；ポリエーテルスルホン等が挙げられる。上記樹脂は一種単独で用いてもよく、二種以上をブレンドして用いてもよい。また、これらの樹脂には必要に応じて、熱安定剤、帯電防止剤、滑剤、造核剤、充填剤などを添加してもよい。 Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene; vinyl heavy resins such as poly (meth) acrylates such as polystyrene, polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, and polyethyl acrylate. Combined; Nylon 6, Nylon 66, Nylon 11, Nylon 12, Nylon 610, Nylon 612, Nylon 61, Nylon 6T, Nylon 9T, etc. Polyamide, Polyethylene terephthalate, Polybutylene terephthalate, etc. Polyester, Polycarbonate, Polyimide, etc. Polyacetal; Polyphenylene oxide; Polyphenylene sulfide; Polyethersulfone and the like. The said resin may be used individually by 1 type, and may blend and use 2 or more types. Moreover, you may add a heat stabilizer, an antistatic agent, a lubricant, a nucleating agent, a filler etc. to these resin as needed.

熱可塑性樹脂（Ａ）および熱可塑性樹脂（Ｂ）としては、目的の用途に応じて、異種の熱可塑性樹脂を選択して組み合わせる。例えば、実施例に示したようにポリアミドの薄層とポリメタクリル酸メチル、ポリプロピレン、またはポリカーボネートの比較的厚いシート層とを組み合わせた積層体を用いて製造された異種熱可塑性樹脂成型体は、各層が有する物性に加えて、熱可塑性樹脂の層間に高い接合強度を持ち、全体として機械的強度、生体適合性、加工性に優れる。   As the thermoplastic resin (A) and the thermoplastic resin (B), different types of thermoplastic resins are selected and combined depending on the intended use. For example, as shown in the examples, different types of thermoplastic resin moldings manufactured using a laminate in which a thin layer of polyamide and a relatively thick sheet layer of polymethyl methacrylate, polypropylene, or polycarbonate are combined are In addition to the physical properties possessed by the resin, it has high bonding strength between the layers of the thermoplastic resin, and as a whole is excellent in mechanical strength, biocompatibility, and processability.

本発明に用いる積層体は、フィルムまたはシート状であると、電子線が均一に照射されるため好ましい。また、本発明に用いる積層体は、前述の互いに隣接した層（Ａ）および層（Ｂ）を有していれば良く、他の層がさらに被覆されていてもよい。   The laminate used in the present invention is preferably a film or a sheet because the electron beam is uniformly irradiated. Moreover, the laminated body used for this invention should just have the above-mentioned mutually adjacent layer (A) and layer (B), and the other layer may be further coat | covered.

他の層の一例としては、例えばゴム状体を挙げることができる。
本発明に用いる積層体において、前記層（Ａ）および層（Ｂ）の厚さとしては特に限定はなく、通常は層（Ａ）および層（Ｂ）の厚さは０．０１〜５００μｍの範囲にある。本発明においては、層（Ａ）および層（Ｂ）の厚さとしては、どちらが厚くてもよい。 As an example of another layer, a rubber-like body can be mentioned, for example.
In the laminate used in the present invention, the thickness of the layer (A) and the layer (B) is not particularly limited, and the thickness of the layer (A) and the layer (B) is usually in the range of 0.01 to 500 μm. It is in. In the present invention, either the layer (A) or the layer (B) may be thicker.

本発明の異種熱可塑性樹脂成型体の製造方法においては、通常、前記積層体に電子線照射を行う前、後または電子線照射中に、前記積層体を一体化する。すなわち、予め一体化させてから電子線を照射してもよく、一体化させながら電子線を照射してもよく、電子線を照射した後に一体化させてもよい。一体化することにより、本発明の製造方法により得られる異種熱可塑性樹脂成型体は、より高い層間接着強度を有する。ここで一体化処理とは、層（Ａ）と層（Ｂ）とを固定する処理であれば特に限定はなく、熱可塑性樹脂のフィルムないしシートを積層して得られた前記積層体に圧縮等の加圧操作を加える処理や、層（Ａ）または層（Ｂ）上に、熱可塑性樹脂（Ｂ）または熱可塑性樹脂（Ａ）を押し出し、層（Ｂ）または層（Ａ）を形成し、積層体の形成と同時に一体化を行う処理や、熱可塑性樹脂（Ａ）および熱可塑性樹脂（Ｂ）を共押出しすることにより、積層体の形成と同時に一体化を行う処理が挙げられる。加圧操作を行う処理としては、例えば図２に示す簡易な加圧装置や、既存のプレス成形機を用いる方法であってもよいし、また一対のロール間を通過させたりする方法でもよい。また、大量生産する場合には、層（Ａ）または層（Ｂ）上に、熱可塑性樹脂（Ｂ）または熱可塑性樹脂（Ａ）を押し出して、層（Ｂ）または層（Ａ）を形成させて、積層体の形成と同時に一体化を行う処理や、熱可塑性樹脂（Ａ）および熱可塑性樹脂（Ｂ）を共押出しすることにより、積層体の形成と同時に一体化を行う処理が簡便である。   In the method for producing a molded article of different thermoplastic resins according to the present invention, usually, the laminate is integrated before, after or during electron beam irradiation of the laminate. That is, the electron beam may be irradiated after being integrated in advance, or may be irradiated while being integrated, or may be integrated after being irradiated with the electron beam. By integrating, the dissimilar thermoplastic resin molding obtained by the production method of the present invention has higher interlayer adhesion strength. Here, the integration treatment is not particularly limited as long as it is a treatment for fixing the layer (A) and the layer (B), and compression or the like is performed on the laminate obtained by laminating a thermoplastic resin film or sheet. A process of applying a pressing operation of, or extruding the thermoplastic resin (B) or the thermoplastic resin (A) on the layer (A) or the layer (B) to form the layer (B) or the layer (A), The process which integrates simultaneously with formation of a laminated body, and the process which integrates simultaneously with formation of a laminated body by coextruding a thermoplastic resin (A) and a thermoplastic resin (B) are mentioned. The processing for performing the pressing operation may be, for example, a method using a simple pressing device shown in FIG. 2 or an existing press molding machine, or a method of passing between a pair of rolls. In mass production, the thermoplastic resin (B) or the thermoplastic resin (A) is extruded onto the layer (A) or the layer (B) to form the layer (B) or the layer (A). Thus, the process of integrating at the same time as the formation of the laminated body and the process of integrating at the same time as the formation of the laminated body are easy by co-extruding the thermoplastic resin (A) and the thermoplastic resin (B). .

なお一体化処理が、加圧操作を行う処理である場合には、好ましくは大気中、室温で、４〜３０００ｋＰａの印加圧力下で保持することにより行われる。
図２は、簡易な加圧装置例の概念図を示す。図２では、フィルムまたはシート状の熱可塑性樹脂からなる積層体（１１および１２）を、スプリングバネ１４を備えた台座１３の上に載せて配置し、それら全体を加圧補助フィルム１０で覆い、そのフィルムの周囲から強い力で積層体を押さえ込むことにより、結果的に積層体の上下面から強い圧力を加えている。 In the case where the integration process is a process of performing a pressurizing operation, the integration process is preferably performed by holding in air at room temperature under an applied pressure of 4 to 3000 kPa.
FIG. 2 shows a conceptual diagram of a simple pressurizing device example. In FIG. 2, the laminates (11 and 12) made of a film or sheet-like thermoplastic resin are placed on the pedestal 13 provided with the spring spring 14, and the whole is covered with the pressure assisting film 10, As a result, a strong pressure is applied from the upper and lower surfaces of the laminate by pressing the laminate from the periphery of the film with a strong force.

本発明において、積層体に電子線照射を行うには、加速電圧が５０〜３００ｋｅＶの範囲で行われる。本発明においては、熱可塑性樹脂の放射線損傷や、Ｘ線の発生を防ぐため、また加熱による熱可塑性樹脂の変形、融解、劣化を防ぐために加速電圧は低い方が望ましく、好ましくは加速電圧が１００〜３００ｋｅＶ、より好ましくは１２０〜２００ｋｅ
Ｖ、さらに好ましくは１５０〜１８０ｋｅＶの範囲で電子線照射を行う。電子線の照射時間は、通常０．０１〜３．０秒であり、電子線照射時の温度は通常室温〜５０℃の範囲である。 In this invention, in order to perform electron beam irradiation to a laminated body, acceleration voltage is performed in the range of 50-300 keV. In the present invention, in order to prevent radiation damage of the thermoplastic resin and generation of X-rays, and to prevent deformation, melting and deterioration of the thermoplastic resin due to heating, it is desirable that the acceleration voltage is low, preferably the acceleration voltage is 100. -300 keV, more preferably 120-200 ke
The electron beam irradiation is performed in the range of V, more preferably in the range of 150 to 180 keV. The irradiation time of the electron beam is usually 0.01 to 3.0 seconds, and the temperature at the time of electron beam irradiation is usually in the range of room temperature to 50 ° C.

電子線照射装置は、特に限定されるものではなく、図１に本発明に使用可能な電子線照射装置の一例を示す。該電子線照射装置は、マルチ電子銃７を備えた真空室２と、その下部に積層体（試料）６が供給される筐体１とが設置され、真空室２と筐体１とが接するように構成されている。筐体１の内部は、窒素ガスのような不活性ガス雰囲気に保たれ、駆動ロール３および従動ロール４に懸架されたコンベヤ５が配置されている。該コンベヤ５の上を試料６が搬送される。前記真空室２内には、カソードとなるマルチ電子銃７が配置され、真空室２の下部でかつ筺体１と接する箇所にアノードとなる窓８がチタン膜によって形成され配置されている。真空室２内のマルチ電子銃７から、筐体１中の試料６に向かって電子線が窓８を通して照射されるので、筐体１の内部がプロセス領域９を構成している。   The electron beam irradiation apparatus is not particularly limited, and FIG. 1 shows an example of an electron beam irradiation apparatus that can be used in the present invention. In the electron beam irradiation apparatus, a vacuum chamber 2 having a multi-electron gun 7 and a casing 1 to which a laminated body (sample) 6 is supplied are installed below the vacuum chamber 2, and the vacuum chamber 2 and the casing 1 are in contact with each other. It is configured as follows. The interior of the housing 1 is maintained in an inert gas atmosphere such as nitrogen gas, and a conveyor 5 suspended from the driving roll 3 and the driven roll 4 is disposed. A sample 6 is conveyed on the conveyor 5. A multi-electron gun 7 serving as a cathode is disposed in the vacuum chamber 2, and a window 8 serving as an anode is formed of a titanium film at a position below the vacuum chamber 2 and in contact with the housing 1. Since the electron beam is irradiated from the multi-electron gun 7 in the vacuum chamber 2 toward the sample 6 in the housing 1 through the window 8, the inside of the housing 1 constitutes the process region 9.

なお、前記試料６とは、電子線が照射される対象であり、具体的には前記積層体である。本発明において、電子線の照射は、層（Ａ）から層（Ｂ）に向かって、または層（Ｂ）から層（Ａ）に向かって行われる。すなわち、積層体の一方の表面側から積層体の深さ方向に向かって電子線が照射される。なお、電子線の照射は一般に層（Ａ）と層（Ｂ）との厚さに差がある場合には、厚さの薄い層から、厚い層に向かって電子線を照射することが低い加速電圧によって有効な電子線を照射する観点から好ましい。   In addition, the sample 6 is a target to be irradiated with an electron beam, specifically, the laminate. In the present invention, the electron beam irradiation is performed from the layer (A) to the layer (B) or from the layer (B) to the layer (A). That is, an electron beam is irradiated from the one surface side of a laminated body toward the depth direction of a laminated body. In general, when there is a difference in thickness between the layer (A) and the layer (B), electron beam irradiation is accelerated by irradiating an electron beam from a thin layer toward a thick layer. It is preferable from the viewpoint of irradiating an effective electron beam with voltage.

すなわち、図２に示す装置を用いて一体化した積層体（１１および１２）に電子線を照射する場合には、通常１１から１２に向かって電子線が照射される。
ここで電子線照射量Ｄ（ＭＧｙ）は、Ｉ（Irradiation current（ｍＡ））、Ｓ（Conveyor speed(ｍ／ｍｉｎ.)）、ｎ（Number of Irradiation）との間の関係式（下記式
１）から算出される。
Ｄ＝０．２１６×（Ｉ／Ｓ）×ｎ (式１) That is, when irradiating an electron beam to the integrated laminated body (11 and 12) using the apparatus shown in FIG.
Here, the electron beam dose D (MGy) is a relational expression between I (Irradiation current (mA)), S (Conveyor speed (m / min.)), And n (Number of Irradiation) (the following formula 1). Is calculated from
D = 0.216 × (I / S) × n (Formula 1)

本発明では、前記照射における電子線照射線量が、０．０５〜０．５ＭＧｙの範囲であることが好ましく、０．１〜０．４５ＭＧｙの範囲であることがより好ましく、０．２〜０．３ＭＧｙの範囲であることが特に好ましい。   In this invention, it is preferable that the electron beam irradiation dose in the said irradiation is the range of 0.05-0.5MGy, It is more preferable that it is the range of 0.1-0.45MGy, 0.2-0. A range of 3MGy is particularly preferred.

この範囲であれば、電子線照射によって各層の機械的強度が損なわれることなく、高い接着強度で層間の接合がなされるので、得られる異種樹脂成型体の引張強度や曲げ強度、さらには衝撃強度等の機械的な物性が、従来の異種樹脂成型体と比べて向上するために好ましい。   Within this range, the mechanical strength of each layer is not impaired by electron beam irradiation, and the layers are joined with high adhesive strength, so the tensile strength and bending strength of the resulting dissimilar resin molded product, and even impact strength The mechanical properties such as the above are preferable because they are improved as compared with the conventional different resin moldings.

なお、電子線照射に際して、少なくとも電子線は接着すべき層間の界面にまで到達することが望ましいことから、電子線の進入深さを考慮して、電子線が照射され侵入する側の層を形成する素材の密度や厚さ、照射環境等を適宜制御することが必要になる。例えば、複合体に組み込まれているフィルムやシートの厚さが増すと、一般に電子線が内部にまで充分に進入しないため、照射電圧の変化に伴い、透過可能なフィルムの厚さが決まる。そこで、電子線が照射され侵入される側の熱可塑性樹脂層の厚さは、電子線の加速電圧によって影響を受け、少なくとも両層の界面にまで電子線が侵入することが望ましい。   In addition, since it is desirable that at least the electron beam reaches the interface between the layers to be bonded during electron beam irradiation, the layer on the side where the electron beam is irradiated is formed in consideration of the penetration depth of the electron beam. It is necessary to appropriately control the density and thickness of the material to be processed, the irradiation environment and the like. For example, when the thickness of the film or sheet incorporated in the composite increases, the electron beam generally does not sufficiently enter the inside, so that the thickness of the transmissive film is determined according to the change of the irradiation voltage. Therefore, the thickness of the thermoplastic resin layer on which the electron beam is irradiated and penetrated is affected by the acceleration voltage of the electron beam, and it is desirable that the electron beam penetrates at least to the interface between both layers.

実施例で示したように、厚さ２５μｍのポリアミドフィルムと、異種の熱可塑性樹脂（ポリプロピレン、ポリメタクリル酸メチル、ポリカーボネート）シートとを組み合わせて用いた場合、ポリアミドフィルム側から加速電圧（Ｖ）を１７０ｋｅＶの条件で電子線照射したときには、電子線は１００〜２００μｍの深さへと侵入する。そこで１００〜２０
０ｋｅＶの電子線が内部まで充分に侵入させるためには、電子線が照射される側の層の厚さは０．０１〜２００μｍであることが好ましく、加速電圧が５０〜３００ｋｅＶの範囲の電子線で、内部まで充分に侵入させるためには、電子線が照射される側の層の厚さが０．０１〜５００μｍであることが好ましい。なお、電子線が直接照射されない他方の層は、主に機械的な強度を保つ役割を担う基材層として使われることが多いので、実用的な厚さを有していればよい。 As shown in the examples, when a polyamide film having a thickness of 25 μm and a different kind of thermoplastic resin (polypropylene, polymethyl methacrylate, polycarbonate) sheet are used in combination, an acceleration voltage (V) is applied from the polyamide film side. When an electron beam is irradiated under the condition of 170 keV, the electron beam penetrates to a depth of 100 to 200 μm. So 100-20
In order for the 0 keV electron beam to sufficiently penetrate into the inside, the thickness of the layer on the side irradiated with the electron beam is preferably 0.01 to 200 μm, and the acceleration voltage is in the range of 50 to 300 keV. And in order to fully penetrate | invade to the inside, it is preferable that the thickness of the layer by which the electron beam is irradiated is 0.01-500 micrometers. Note that the other layer that is not directly irradiated with the electron beam is often used as a base material layer that mainly plays a role of maintaining mechanical strength, so that it has only to have a practical thickness.

このようにして製造された異種熱可塑性樹脂成型体は、さらに真空成型や圧空成型等の様々な二次成形を加えて、希望する各種の形状へと変更させることができる。
本発明の製造方法により得られる、異種熱可塑性樹脂成型体は、層（Ａ）に由来する層（Ａ’）および層（Ｂ）に由来する層（Ｂ’）を有しており、層間の接合強度に優れる。層間の接合強度に優れる理由については明らかではないが、本発明者らは積層体に電子線を照射することにより、異種熱可塑性樹脂にダングリングボンドが形成し、それによって相互のぬれ性が改良されて、熱可塑性樹脂間の界面接着性が向上し、高い接合強度が得られたと推定している。 The heterogeneous thermoplastic resin molded body thus produced can be changed into various desired shapes by further performing various secondary molding such as vacuum molding and pressure molding.
The heterogeneous thermoplastic resin molding obtained by the production method of the present invention has a layer (A ′) derived from the layer (A) and a layer (B ′) derived from the layer (B), Excellent bonding strength. The reason why the bonding strength between the layers is excellent is not clear, but the present inventors formed dangling bonds in different types of thermoplastic resins by irradiating the laminate with an electron beam, thereby improving the wettability of each other. Thus, it is presumed that the interfacial adhesion between the thermoplastic resins is improved and a high bonding strength is obtained.

本発明の異種熱可塑性樹脂成型体は、人工血管、人工靱帯などの幅広い医療用材料、あるいは医療器具部品等としての使用に好適である。もちろん各種産業分野における接合・複合部品や製品にも応用することができる。   The heterogeneous thermoplastic resin molding of the present invention is suitable for use as a wide range of medical materials such as artificial blood vessels and artificial ligaments, or medical instrument parts. Of course, it can also be applied to joint / composite parts and products in various industrial fields.

次に本発明について実施例を示してさらに詳細に説明するが、本発明はこれらによって限定されるものではない。
〔実施例１〕
下記２種類の熱可塑性樹脂のフィルムを準備した。フィルムの大きさは、共に長さ１０．０ｍｍで、幅が１０．０ｍｍであった。
（１）ポリアミドフィルム(ナイロン−６、ユニチカ製 EMBLEM ON、厚さ２５μｍ)
（２）ポリプロピレンシート(ニッコー株式会社製 ポリプロピレンフィルムシート、厚
さ０．２ｍｍ)
ポリプロピレンシートの上に、ポリアミドフィルムを重ねて敷き、積層体を得た。 EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
[Example 1]
The following two types of thermoplastic resin films were prepared. The film size was 10.0 mm in length and 10.0 mm in width.
(1) Polyamide film (Nylon-6, EMBLEM ON made by Unitika, thickness 25μm)
(2) Polypropylene sheet (produced by Nikko Corporation, polypropylene film sheet, thickness 0.2 mm)
A polyamide film was laminated and spread on a polypropylene sheet to obtain a laminate.

その後、図２に記載の加圧装置を用いて、常温、印加圧力０．２７ＭＰａ、大気雰囲気の条件で積層体をプレスして、長さ１０．０ｍｍ、幅１０．０ｍｍの、ポリアミド層／ポリプロピレン層からなる２層が一体化した積層体（複合体）を得た。なお、該複合体の厚さは２２５．０μｍ、体積は２２．５ｍｍ3であった。 Thereafter, using the pressurizing apparatus shown in FIG. 2, the laminate was pressed under the conditions of normal temperature, applied pressure of 0.27 MPa, and atmospheric atmosphere, and a polyamide layer / polypropylene having a length of 10.0 mm and a width of 10.0 mm. A laminate (composite) in which two layers composed of layers were integrated was obtained. The composite had a thickness of 225.0 μm and a volume of 22.5 mm 3 .

次いで、図２の加圧装置に設置された状態にある前記複合体をそのまま図１に示した電子線照射装置にセットし、室温、窒素ガス雰囲気中（１０１３ｈＰａ）で電子線を照射して、シート状の異種熱可塑性樹脂成型体を得た。なお、電子線の照射は、ポリアミド層からポリプロピレン層に向かって行った。照射条件は、Acceleration voltage（加速電圧
）が１７０ｋｅＶ、Irradiation currentがＩ＝２ｍＡ、Conveyor speedがＳ＝１０ｍ
／ｍｉｎ、真空室の真空度が３×１０-4Ｐａ以下、Ｔｉ箔窓の厚さが１５μｍ、窓から試料までの距離が１０ｍｍ、試料にかかる電圧が約１３０ｋｅＶで、1回当たりの照射量は
、４３．２ｋＧｙで、1回当たりの照射時間は０．２３秒であった。また、電子線の照射
回数は３回であり、電子線照射量は０．１３ＭＧｙ（４３．２ｋＧｙ×３）であった。 Next, the composite in a state of being installed in the pressurizing apparatus of FIG. 2 is set as it is in the electron beam irradiation apparatus shown in FIG. 1, and irradiated with an electron beam at room temperature in a nitrogen gas atmosphere (1013 hPa). A sheet-like dissimilar thermoplastic resin molding was obtained. The electron beam was irradiated from the polyamide layer toward the polypropylene layer. Irradiation conditions are Acceleration voltage 170 keV, Irradiation current I = 2 mA, Conveyor speed S = 10 m
/ Min, the vacuum degree of the vacuum chamber is 3 × 10 −4 Pa or less, the thickness of the Ti foil window is 15 μm, the distance from the window to the sample is 10 mm, the voltage applied to the sample is about 130 keV, and the irradiation amount per time Was 43.2 kGy, and the irradiation time per irradiation was 0.23 seconds. The number of electron beam irradiations was 3, and the electron beam irradiation amount was 0.13 MGy (43.2 kGy × 3).

得られた、異種熱可塑性樹脂成型体を、その後図３に示すように２個のステンレス鋼棒(泰豊トレーディングス製 ＪＩＳ Ｇ４３１８相当 ＳＵＳ３０４、厚さ５．０ｍｍ、幅５．０ｍｍ、長さ１０．０ｍｍの角棒形)の間に挟み、その際に試料の平坦な両表面と角
棒端面との間を接着剤（セメダイン製品 商品名ＳＵＰＥＲ Ｘ）を用いて接着し、それ
を引張試験用試験片として利用した。 As shown in FIG. 3, the obtained heterogeneous thermoplastic resin molding was then divided into two stainless steel bars (SUS304, equivalent to JIS G4318 manufactured by Taiho Trading Co., Ltd., thickness 5.0 mm, width 5.0 mm, length 10 . Between the flat surfaces of the sample and the end face of the square bar using an adhesive (Cemedine product name SUPER X), which is used for tensile testing. Used as a test piece.

前記引張試験用試験片を用いて、引張試験をＪＩＳ Ｋ７０７３に準拠して行い、測定した引張強度値から各試験片における両層の接着面に対する接着強度を評価した。すなわち、インストロン引張試験機（型番３３６７）を用い、引張速度１ｍｍ／ｍｉｎ．で引張試験を行い、下記式より引張強度を算出した。
σ＝Ｆ／Ｓ
（σ：引張強度（ＭＰａ）、Ｆ：引張荷重（Ｎ）、Ｓ：試験片の断面積（ｍ2）） Using the tensile test specimen, a tensile test was conducted in accordance with JIS K7073, and the adhesive strength of each test specimen to the adhesive surfaces of both layers was evaluated from the measured tensile strength value. That is, using an Instron tensile tester (model number 3367), a tensile speed of 1 mm / min. A tensile test was performed, and the tensile strength was calculated from the following formula.
σ = F / S
(Σ: tensile strength (MPa), F: tensile load (N), S: cross-sectional area of test piece (m 2 ))

〔実施例２〕
前記（２）ポリプロピレンシート(ニッコー株式会社製 ポリプロピレンフィルムシー
ト、厚さ０．２ｍｍ)を、（３）ポリメタクリル酸メチルシート(日東樹脂工業製 クラレ
ックス、厚さ１．０ｍｍ)に代えた以外は実施例１と同様に行い、ポリアミド層／ポリメ
タクリル酸メチル層からなる２層が一体化した積層体（複合体）、異種熱可塑性樹脂成型体および引張試験用試験片を得た。 [Example 2]
(2) The polypropylene sheet (Nikko Co., Ltd., polypropylene film sheet, thickness 0.2 mm) was replaced with (3) polymethyl methacrylate sheet (Nitto Jushi Kogyo Clarex, thickness 1.0 mm). The same procedure as in Example 1 was performed to obtain a laminate (composite) in which two layers composed of a polyamide layer / polymethyl methacrylate layer were integrated, a dissimilar thermoplastic resin molded body, and a tensile test specimen.

実施例１と同様に引張試験を行い、引張強度を算出した。
なお、該複合体の厚さは１０２５μｍ、体積は１０２．５ｍｍ3であった。また、電子
線の照射は、ポリアミド層からポリメタクリル酸メチル層に向かって行った。 A tensile test was performed in the same manner as in Example 1 to calculate the tensile strength.
The composite had a thickness of 1025 μm and a volume of 102.5 mm 3 . Moreover, the electron beam irradiation was performed from the polyamide layer toward the polymethyl methacrylate layer.

〔実施例３〕
前記（２）ポリプロピレンシート(ニッコー株式会社製 ポリプロピレンフィルムシー
ト、厚さ０．２ｍｍ)を、（４）ポリカーボネートシート(ゼネラル・エレクトリック社製
レキサンシート、厚さ１．０ｍｍ)に代えた以外は実施例１と同様に行い、ポリアミド
層／ポリカーボネート層からなる２層が一体化した積層体（複合体）、異種熱可塑性樹脂成型体および引張試験用試験片を得た。 Example 3
Example except that (2) polypropylene sheet (polypropylene film sheet, thickness 0.2 mm, manufactured by Nikko Corporation) was replaced with (4) polycarbonate sheet (lexan sheet, thickness 1.0 mm, manufactured by General Electric Co., Ltd.) In the same manner as in No. 1, a laminate (composite) in which two layers composed of a polyamide layer / polycarbonate layer were integrated, a dissimilar thermoplastic resin molded body, and a tensile test specimen were obtained.

実施例１と同様に引張試験を行い、引張強度を算出した。
なお、該複合体の厚さは１０２５μｍ、体積は１０２．５ｍｍ3であった。また、電子
線の照射は、ポリアミド層からポリカーボネート層に向かって行った。 A tensile test was performed in the same manner as in Example 1 to calculate the tensile strength.
The thickness of the complex 1025Myuemu, volume was 102.5mm 3. Further, the electron beam irradiation was performed from the polyamide layer toward the polycarbonate layer.

〔実施例４、５〕
電子線の照射回数を３回から５回（実施例４）、１０回（実施例５）へと増加させた以外は実施例１と同様に行い、異種熱可塑性樹脂成型体および引張試験用試験片を得た。なお、電子線照射線量は０．２２ＭＧｙ（実施例４）、０．４３ＭＧｙ（実施例５）であった。
実施例１と同様に引張試験を行い、引張強度を算出した。 [Examples 4 and 5]
Except that the number of electron beam irradiations was increased from 3 times to 5 times (Example 4) and 10 times (Example 5), it was carried out in the same manner as in Example 1, and a different thermoplastic resin molding and a test for tensile test I got a piece. The electron beam irradiation dose was 0.22 MGy (Example 4) and 0.43 MGy (Example 5).
A tensile test was performed in the same manner as in Example 1 to calculate the tensile strength.

〔実施例６、７〕
電子線の照射回数を３回から５回（実施例６）、１０回（実施例７）へと増加させた以外は実施例２と同様に行い、異種熱可塑性樹脂成型体および引張試験用試験片を得た。なお、電子線照射線量は０．２２ＭＧｙ（実施例６）、０．４３ＭＧｙ（実施例７）であった。
実施例２と同様に引張試験を行い、引張強度を算出した。 [Examples 6 and 7]
Except that the number of electron beam irradiations was increased from 3 times to 5 times (Example 6) and 10 times (Example 7), it was carried out in the same manner as in Example 2, and a thermoplastic resin molded body and a test for tensile test I got a piece. The electron beam irradiation dose was 0.22 MGy (Example 6) and 0.43 MGy (Example 7).
A tensile test was performed in the same manner as in Example 2 to calculate the tensile strength.

〔実施例８、９〕
電子線の照射回数を３回から５回（実施例８）、１０回（実施例９）へと増加させた以外は実施例３と同様に行い、異種熱可塑性樹脂成型体および引張試験用試験片を得た。なお、電子線照射線量は０．２２ＭＧｙ（実施例８）、０．４３ＭＧｙ（実施例９）であった。 [Examples 8 and 9]
Except that the number of electron beam irradiations was increased from 3 times to 5 times (Example 8) and 10 times (Example 9), it was carried out in the same manner as in Example 3, and different thermoplastic resin moldings and tests for tensile tests. I got a piece. The electron beam irradiation doses were 0.22 MGy (Example 8) and 0.43 MGy (Example 9).

実施例３と同様に引張試験を行い、引張強度を算出した。
電子線の照射回数が５回および１０回である異種熱可塑性樹脂成型体から得られた引張試験用試験片（実施例４〜９）に関して、引張応力と伸び歪との関係を図４に示した。
また、実施例１〜９および後述する比較例１〜３より、電子線照射線量と引張応力との関係、電子線照射線量と引張歪との関係を図５および６に示した。 A tensile test was performed in the same manner as in Example 3 to calculate the tensile strength.
FIG. 4 shows the relationship between tensile stress and elongation strain for tensile test specimens (Examples 4 to 9) obtained from different types of thermoplastic resin moldings with electron beam irradiation times of 5 and 10. It was.
Further, from Examples 1 to 9 and Comparative Examples 1 to 3 to be described later, the relationship between the electron beam irradiation dose and the tensile stress, and the relationship between the electron beam irradiation dose and the tensile strain are shown in FIGS.

〔比較例１〕
前記実施例１と同様の複合体を用いて、電子線を照射することなく引張試験用試験片を作成した。実施例１と同様に引張試験を行い、引張強度を算出した。 [Comparative Example 1]
A tensile test specimen was prepared using the same composite as in Example 1 without irradiating the electron beam. A tensile test was performed in the same manner as in Example 1 to calculate the tensile strength.

〔比較例２〕
前記実施例２と同様の複合体を用いて、電子線を照射することなく引張試験用試験片を作成した。実施例２と同様に引張試験を行い、引張強度を算出した。 [Comparative Example 2]
A tensile test specimen was prepared using the same composite as in Example 2 without irradiating the electron beam. A tensile test was performed in the same manner as in Example 2 to calculate the tensile strength.

〔比較例３〕
前記実施例３と同様の複合体を用いて、電子線を照射することなく引張試験用試験片を作成した。実施例３と同様に引張試験を行い、引張強度を算出した。 [Comparative Example 3]
Using the same composite as in Example 3, a test specimen for tensile test was prepared without irradiating an electron beam. A tensile test was performed in the same manner as in Example 3 to calculate the tensile strength.

実施例１〜９と比較例１〜３とを比較することにより、電子線を照射することによって得られた異種熱可塑性樹脂成型体は、高い引張強度および高い弾性率を有することがわかった。すなわち、異種熱可塑性樹脂成型体は、各層が強い強度で接着されている。   By comparing Examples 1 to 9 and Comparative Examples 1 to 3, it was found that the heterogeneous thermoplastic resin moldings obtained by irradiating with an electron beam had high tensile strength and high elastic modulus. That is, in the different type thermoplastic resin molded body, each layer is bonded with strong strength.

図１は、電子線照射装置の一例を示す概略図である。FIG. 1 is a schematic view showing an example of an electron beam irradiation apparatus. 図２は、異種熱可塑性樹脂層を重ねて、加圧積層（一体化）を行う装置の一例を示す概略図である。FIG. 2 is a schematic diagram illustrating an example of an apparatus for performing pressure lamination (integration) by stacking different thermoplastic resin layers. 図３は、引張試験用試験片の構造を示す概略図である。FIG. 3 is a schematic view showing the structure of a tensile test specimen. 図４は、実施例４〜９で行った引張試験で得られた引張応力と伸び歪との関係を示す図である。FIG. 4 is a diagram showing the relationship between the tensile stress and the elongation strain obtained in the tensile tests performed in Examples 4 to 9. 図５は、実施例１〜９、および比較例１〜３で行った引張試験において、引張応力と電子線照射線量との関係を示す図である。FIG. 5 is a diagram illustrating a relationship between tensile stress and electron beam irradiation dose in the tensile tests performed in Examples 1 to 9 and Comparative Examples 1 to 3. 図６は、実施例１〜９、および比較例１〜３で行った引張試験において、伸び歪と電子線照射線量との関係を示す図である。FIG. 6 is a diagram showing the relationship between the elongation strain and the electron beam irradiation dose in the tensile tests conducted in Examples 1 to 9 and Comparative Examples 1 to 3.

符号の説明Explanation of symbols

１・・・筐体
２・・・真空室
３・・・駆動ロール
４・・・従動ロール
５・・・コンベヤ
６・・・試料
７・・・マルチ電子銃（カソード）
８・・・窓（アノード）
９・・・プロセス領域
１０・・・加圧補助フィルム
１１・・・熱可塑性樹脂(実施例においては、ポリアミドフィルム)
１２・・・熱可塑性樹脂(実施例においては、ポリカーボネート、アクリル樹脂、または
ポリプロピレン)
１３・・・台座(例えば、ウレタン樹脂)
１４・・・スプリングバネ１４
１５・・・ステンレス角材
１６・・・熱可塑性樹脂(ポリアミドフィルム)
１７・・・熱可塑性樹脂(ポリカーボネート、アクリル樹脂、ポリプロピレン) DESCRIPTION OF SYMBOLS 1 ... Housing 2 ... Vacuum chamber 3 ... Drive roll 4 ... Follower roll 5 ... Conveyor 6 ... Sample 7 ... Multi electron gun (cathode)
8 ... Window (Anode)
9 ... Process region 10 ... Pressure assisting film 11 ... thermoplastic resin (polyamide film in the embodiment)
12 ... thermoplastic resin (in the embodiment, polycarbonate, acrylic resin, or polypropylene)
13 ... Base (for example, urethane resin)
14 ... Spring spring 14
15 ... Stainless steel square 16 ... thermoplastic resin (polyamide film)
17 ... thermoplastic resin (polycarbonate, acrylic resin, polypropylene)

Claims (4)

隣接した、熱可塑性樹脂（Ａ）からなる層（Ａ）および熱可塑性樹脂（Ｂ）（ただし、熱可塑性樹脂（Ａ）と、熱可塑性樹脂（Ｂ）とは異種の熱可塑性樹脂である）からなる層（Ｂ）を有する積層体に、
層（Ａ）から層（Ｂ）に向かって、または層（Ｂ）から層（Ａ）に向かって、加速電圧が５０〜３００ｋｅＶの範囲で電子線照射を行うことを特徴とする異種熱可塑性樹脂成型体の製造方法。 From the adjacent layer (A) made of the thermoplastic resin (A) and the thermoplastic resin (B) (however, the thermoplastic resin (A) and the thermoplastic resin (B) are different types of thermoplastic resins). In the laminate having the layer (B)
Heterogeneous thermoplastic resin characterized in that electron beam irradiation is performed in the range of 50 to 300 keV in acceleration voltage from layer (A) to layer (B) or from layer (B) to layer (A) A method for producing a molded body. 前記積層体に電子線照射を行う前、後または電子線照射中に、前記積層体を一体化することを特徴とする請求項１に記載の異種熱可塑性樹脂成型体の製造方法。   The method for producing a different type thermoplastic resin molded body according to claim 1, wherein the laminate is integrated before, after or during electron beam irradiation of the laminate. 前記電子線照射における電子線照射線量が、０．０５〜０．５ＭＧｙの範囲であることを特徴とする請求項１または２に記載の異種熱可塑性樹脂成型体の製造方法。   The method for producing a heterogeneous thermoplastic resin molding according to claim 1 or 2, wherein an electron beam irradiation dose in the electron beam irradiation is in a range of 0.05 to 0.5 MGy. 請求項１〜３のいずれかに記載の製造方法により得られることを特徴とする異種熱可塑性樹脂成型体。   A heterogeneous thermoplastic resin molded article obtained by the production method according to claim 1.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011136492A (en) * 2009-12-28 2011-07-14 Dainippon Printing Co Ltd Method for bonding film base material
JP2012158050A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2012158049A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2012158054A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate, and method for manufacturing the same
JP2012158056A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate, and method for manufacturing the same
JP2012254591A (en) * 2011-06-09 2012-12-27 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2012254592A (en) * 2011-06-09 2012-12-27 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2013018168A (en) * 2011-07-08 2013-01-31 Dainippon Printing Co Ltd Laminate and method for producing the same
JP2013180431A (en) * 2012-02-29 2013-09-12 Dainippon Printing Co Ltd Laminate and method of manufacturing the same
JP2014218086A (en) * 2014-07-22 2014-11-20 大日本印刷株式会社 Laminated body and method for manufacturing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002316362A (en) * 2001-04-20 2002-10-29 Toyo Kohan Co Ltd Method for manufacturing laminate
JP2003509251A (en) * 1999-09-23 2003-03-11 アクララ バイオサイエンシーズ， インコーポレイテッド Method for joining two workpieces made of plastic without using foreign matter
JP2004273238A (en) * 2003-03-07 2004-09-30 Kuraray Co Ltd Method of manufacturing surface lighting source element member
JP2004268383A (en) * 2003-03-07 2004-09-30 Kuraray Co Ltd Plastic bonding method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003509251A (en) * 1999-09-23 2003-03-11 アクララ バイオサイエンシーズ， インコーポレイテッド Method for joining two workpieces made of plastic without using foreign matter
JP2002316362A (en) * 2001-04-20 2002-10-29 Toyo Kohan Co Ltd Method for manufacturing laminate
JP2004273238A (en) * 2003-03-07 2004-09-30 Kuraray Co Ltd Method of manufacturing surface lighting source element member
JP2004268383A (en) * 2003-03-07 2004-09-30 Kuraray Co Ltd Plastic bonding method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011136492A (en) * 2009-12-28 2011-07-14 Dainippon Printing Co Ltd Method for bonding film base material
JP2012158050A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2012158049A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2012158054A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate, and method for manufacturing the same
JP2012158056A (en) * 2011-01-31 2012-08-23 Dainippon Printing Co Ltd Laminate, and method for manufacturing the same
JP2012254591A (en) * 2011-06-09 2012-12-27 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2012254592A (en) * 2011-06-09 2012-12-27 Dainippon Printing Co Ltd Laminate and method for manufacturing the same
JP2013018168A (en) * 2011-07-08 2013-01-31 Dainippon Printing Co Ltd Laminate and method for producing the same
JP2013180431A (en) * 2012-02-29 2013-09-12 Dainippon Printing Co Ltd Laminate and method of manufacturing the same
JP2014218086A (en) * 2014-07-22 2014-11-20 大日本印刷株式会社 Laminated body and method for manufacturing the same

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