JP6928679B2 - 積層シート及び積層体、並びにそれらの製造方法 - Google Patents
積層シート及び積層体、並びにそれらの製造方法 Download PDFInfo
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- JP6928679B2 JP6928679B2 JP2019569111A JP2019569111A JP6928679B2 JP 6928679 B2 JP6928679 B2 JP 6928679B2 JP 2019569111 A JP2019569111 A JP 2019569111A JP 2019569111 A JP2019569111 A JP 2019569111A JP 6928679 B2 JP6928679 B2 JP 6928679B2
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/56—Winding and joining, e.g. winding spirally
- B29C53/562—Winding and joining, e.g. winding spirally spirally
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/56—Winding and joining, e.g. winding spirally
- B29C53/58—Winding and joining, e.g. winding spirally helically
- B29C53/581—Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/56—Winding and joining, e.g. winding spirally
- B29C53/58—Winding and joining, e.g. winding spirally helically
- B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
- B29C53/62—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels rotatable about the winding axis
- B29C53/64—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels rotatable about the winding axis and moving axially
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/80—Component parts, details or accessories; Auxiliary operations
- B29C53/84—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Description
第1の色素含有層、中間層及び第2の色素含有層がこの順に積層された構成の多層体を形成する工程、並びに、その多層体を延伸する工程を含む積層シートの製造方法。
本発明における第1の色素含有層及び第2の色素含有層は、波長300nm以上3000nm以下の光を吸収する色素を含有する熱可塑性樹脂組成物からなる。本発明の積層シートにレーザーを照射するとこの色素がレーザー光を吸収して発熱し、色素含有層が溶融する。すなわち、各色素含有層がこのような色素を含有することにより、レーザー融着法を良好に実施することが可能になる。色素の種類は特に限定されず、レーザー光を吸収して発熱し色素含有層が溶融できるような種類の色素であれば良く、公知の様々な色素を使用できる。具体例としては、カーボン系の色素、シアニン色素、フタロシアニン色素、ナフタロシアニン化合物、ニッケルジチオレン錯体、スクアリウム色素、キノン系化合物、ジインモニウム化合物、アゾ化合物が挙げられる。中でも、カーボン系の色素が好ましく、カーボンブラックがより好ましい。
本発明における中間層は、熱可塑性樹脂又は熱可塑性樹脂組成物からなる。熱可塑性樹脂の具体例としては、先に各色素含有層の説明において挙げた熱可塑性樹脂が挙げられる。中間層における熱可塑性樹脂と各色素含有層における熱可塑性樹脂は、同一であっても良いし、異なっていても良い。
本発明の積層シートは、以上説明した第1の色素含有層、中間層及び第2の色素含有層をこの順に積層した積層シートである。つまり、波長300nm以上3000nm以下の光を吸収する色素を含有する色素含有層が表層となり、この表層がレーザー照射により溶融して接着性が向上する。したがって、本発明の積層シートは、レーザー融着法に好適に使用でき、レーザーテープワインディング成形用積層シートとして特に有用である。なお本発明において「第1の色素含有層、中間層及び第2の色素含有層をこの順に積層した」とは、この3層の相互の位置関係のみを意味するものである。すなわち、製造工程における各層の層形成の順番は何ら制限されず、製造後に3層がこのような位置関係にあれば良い。また3層のみの相互の位置関係を意味するものなので、本発明の効果を損なわない範囲内において、第1の色素含有層と中間層の間あるいは中間層と第2の色素含有層の間にその他の層が介在していても構わない。
本発明の積層シートは、例えば、第1の色素含有層、中間層及び第2の色素含有層がこの順に積層された構成の多層体を形成する工程、並びに、その多層体を延伸する工程を含む方法により製造できる。ここで、「第1の色素含有層、中間層及び第2の色素含有層がこの順に積層された構成の多層体」とは、多層体における3層の相互の位置関係のみを意味するものである。すなわち、製造工程における各層の層形成の順番は何ら制限されず、形成後の多層体における3層がこのような位置関係にある構成を有していれば良い。また3層のみの相互の位置関係を意味するものなので、本発明の効果を損なわない範囲内において、第1の色素含有層と中間層の間あるいは中間層と第2の色素含有層の間にその他の層が介在していても構わない。
本発明の積層体は、本発明の積層シートが1層以上(好ましくは2層以上、より好ましくは6層以上)融着された積層体である。すなわち、本発明の積層体は、複数の本発明の積層シート同士が融着により積層された構成からなる積層体であっても良いし、本発明の積層シートが他の物質に対して融着により積層された構成を有する積層体であっても良い。前者の具体例としては、本発明の積層シートをレーザーテープワインディング法によりパイプ状に積層した積層型パイプが挙げられる。後者の具体例としては、本発明の積層シートを、圧力容器、既存のパイプ、建築材料などの被補強材に対して融着により積層して補強した積層体が挙げられる。
本発明の積層体は、本発明の積層シートを、例えばレーザーテープワインディング法により積層することによって好適に得られる。レーザーテープワインディング法により得られる積層体としては、例えば、複数の本発明の積層シート同士がレーザーテープワインディング法により積層された構成からなる積層型パイプが挙げられる。また、本発明の積層シートを、圧力容器、既存のパイプ、円柱状又は円筒状の建築材料などの被補強材に対してレーザーテープワインディング法により積層して補強した積層体が挙げられる
(積層シートの作製)
Bruckner社製3種3層フィルム押出成形装置に幅600mmのマルチマニーホールド型3層ダイスを用いて、第1の色素含有層、中間層、第2の色素含有層の厚さの比が1:8:1の3層フィルムを成形した。中間層には、ポリプロピレン樹脂(プライムポリマー社製、プライムポリプロ(登録商標)F113G、メルトフローレート(ASTM D1238、190℃、荷重2.16kg)=3.0g/10分、融点=160℃)を用いた。各色素含有層には、ポリプロピレン樹脂(プライムポリプロ(登録商標)F113G)に対してカーボンブラックを含有するマスターバッチ(株式会社DIC製、PEONY(登録商標)BLACK BMB−16117、カーボンブラック含有量=40%、カーボンブラックの平均粒径=20nm(ASTM D3849))を3%添加した樹脂組成物を用いた。押出機及びTダイの設定温度を260℃として製膜し、2m/minの条件で、40℃の冷却ロールにキャストし、次いで縦延伸装置の20m/minの延伸ロールで長さ方向に10倍に延伸して積層シートを作製した。延伸後の積層シートの厚さは250μmであった。これを25mm幅にスリットして3層テープを作製した。
出力3kW、波長960〜1070nmのダイオードレーザーをクローズドループ制御するAFPT社製“STWH INB”型巻取りヘッドを装着したロボットを使用して、3層テープを内径φ100mmのマンドレルにレーザーで設定温度180℃で融着しながら3層テープの延伸方向にワインディングして熱可塑性樹脂層を形成した。次いで、マンドレルを抜き取って、ワインディングパイプを得た。ワインディングにおける3層テープの巻き付けの角度については、マンドレルの長さ方向を0°として、3層テープを+80°の角度で巻き付け、その上に−80°の角度で巻き付け、さらに+80°と−80°の角度で巻き付けを繰り返し、合計2mmの厚さになるよう巻き付けた。
試験片(100×100mm)を、中央部分に撃芯が激突する様にASTM規格の高速面衝撃試験装置に固定し、以下の条件で最大衝撃力、最大荷重点の変位及びエネルギー、パンクチャー点の変位及びエネルギーを測定した。また同時に破壊様式も確認した。結果を表1に示す。
撃芯径:1/2インチ
受け側リング径:2インチ
測定温度:室温、−40℃
撃芯速度:1.0m/s
試験片の中間層(カーボンブラックを含まない層)の部分を切り出し、DSC測定用の試験サンプルとした。測定装置としてパーキンエルマー社Pylisを用い、昇温速度10℃/minで30℃から230℃まで昇温した時のピーク温度を融点とした。その融点(Tm1)は169.76℃であった。
各色素含有層を構成する樹脂として、ポリプロピレン樹脂(プライムポリプロ(登録商標)F113G)の代わりに、ポリプロピレン系ランダム共重合樹脂(プライムポリマー社製、プライムポリプロ(登録商標)F327、メルトフローレート(ASTM D1238、190℃、荷重2.16kg)=7.0g/10分、融点=138℃)を用いたこと以外は、実施例1と同様にして3層テープを作製した。
第1の色素含有層及び第2の色素含有層にカーボンブラックを含有するマスターバッチを添加しない(すなわち中間層と同じ樹脂で構成した)こと以外は、実施例1と同様にして3層テープを作製した。この3層テープを用いて、実施例1と同様に、マンドレルにレーザーで融着しながらワインディングしたが、テープとテープとの界面が融着せず、ワインディングパイプは得られなかった。
Bruckner社製3種3層フィルム押出成形装置を用いて、ポリプロピレン樹脂(プライムポリプロ(登録商標)F113G)から厚さ250μmのキャストフィルムを成形し、これを25mm幅にスリットして単層テープを得た。この単層テープを用いて、実施例1と同様に、マンドレルにレーザーで融着しながらワインディングしたが、テープとテープとの界面が融着せず、ワインディングパイプは得られなかった。
ポリプロピレン樹脂(プライムポリプロ(登録商標)F113G)をホットプレスすることにより、2mm厚の平板を成形した。この平板に対して実施例1と同様のハイレートインパクト試験を行った。結果を表1に示す。
第1の色素含有層及び第2の色素含有層のうち一方に、カーボンブラックを含有するマスターバッチを添加しない(すなわち一方は中間層と同じ樹脂で構成した)こと以外は、実施例1と同様にして3層テープを作製した。この3層テープを用いて、実施例1と同様に、マンドレルにレーザーで融着しながらワインディングしたが、テープとテープとの界面が融着せず、ワインディングパイプは得られなかった。
比較例1で作製した3層テープの表面両面を、黒色の油性マーカー(寺西化学工業株式会社製、商品名マジックインキ大型)を用いて着色した。この着色後の3層テープを用いて、実施例1と同様にマンドレルにレーザーで融着しながらワインディングしたが、テープとテープとの界面が融着せず、ワインディングパイプは得られなかった。
縦横250mm×250mmで厚さ2.5mmのステンレス板の上に、離型フィルムとして50μmのポリイミドフィルム(宇部興産製、商品名ユーピレックスー50S)を乗せた。その上に、比較例1で作製した3層テープを、ステンレス板の縁に対して+80°の角度で設置し、さらにその上に−80°の角度で設置し、これを繰り返して合計8枚の3層テープ(+80°/−80°/+80°/−80°/+80°/−80°/+80°/−80°)を設置した。その上に、同じ離型フィルムとステンレス板を乗せて、8枚の3層テープを挟み込んだ。
2 積層シート
3 レーザー照射装置
Claims (16)
- 第1の色素含有層、中間層及び第2の色素含有層がこの順に積層されたレーザーテープワインディング成形用積層シートであって、中間層は延伸した熱可塑性樹脂又は延伸した熱可塑性樹脂組成物からなり、各色素含有層は波長300nm以上3000nm以下の光を吸収する色素を含有する延伸した熱可塑性樹脂組成物からなることを特徴とする積層シート。
- 色素がカーボンブラックである請求項1に記載の積層シート。
- 色素の含有量が、各色素含有層を構成する熱可塑性樹脂組成物中0.01質量%以上7質量%以下である請求項1に記載の積層シート。
- 第1の色素含有層の厚さと、中間層の厚さと、第2の色素含有層の厚さの比が、0.2:9.6:0.2〜2.5:5:2.5である請求項1に記載の積層シート。
- 中間層を構成する延伸した熱可塑性樹脂又は延伸した熱可塑性樹脂組成物の融点(Tm1)と、その熱可塑性樹脂又は熱可塑性樹脂組成物の延伸前の融点(Tm2)との差(Tm1−Tm2=ΔTm)が、5℃以上20℃以下である請求項1に記載の積層シート。
- 請求項1に記載の積層シートが1層以上融着された積層体。
- −40℃におけるハイレートインパクト試験の最大衝撃力が0.5kN以上であり、23℃におけるハイレートインパクト試験の最大衝撃力(E1)と、−40℃におけるハイレートインパクト試験の最大衝撃力(E2)との差(E1−E2=ΔE)が、0.2kN以下である請求項6に記載の積層体。
- ハイレートインパクト試験後の試験片の破壊面が繊維状構造を有する請求項6に記載の積層体。
- 請求項1に記載の積層シートの製造方法であって、
第1の色素含有層、中間層及び第2の色素含有層がこの順に積層された構成の多層体を形成する工程、並びに、その多層体を延伸する工程を含む積層シートの製造方法。 - 延伸する工程における延伸倍率が7倍以上15倍以下である請求項9に記載の積層シートの製造方法。
- 中間層を構成する延伸した熱可塑性樹脂又は延伸した熱可塑性樹脂組成物の融点(Tm1)と、その熱可塑性樹脂又は熱可塑性樹脂組成物の延伸前の融点(Tm2)との差(Tm1−Tm2=ΔTm)が、5℃以上20℃以下である請求項9に記載の積層シートの製造方法。
- 請求項1に記載の積層シートを、レーザーテープワインディング法により積層する積層体の製造方法。
- マンドレルの表面に、請求項1に記載の積層シートを、レーザーテープワインディング法によりワインディングして熱可塑性樹脂層を形成した後、前記マンドレルを抜き取る工程を含む請求項12に記載の積層体の製造方法。
- 熱可塑性樹脂層の厚さが300μm以上100000μm以下である請求項13に記載の積層体の製造方法。
- 熱可塑性樹脂層を、フープ巻き及び/又はヘリカル巻きによって形成する請求項13に記載の積層体の製造方法。
- 積層シートの積層角度が、マンドレルの長さ方向を0°として、10°以上85°以下である請求項13に記載の積層体の製造方法。
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US5077109A (en) * | 1987-08-31 | 1991-12-31 | Viskase Corporation | Oriented multilayer film and process for making same |
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