JP4705215B2 - Paper-containing resin composition for molding process - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、射出成形や押出し成形、溶融圧縮成形等の成形加工に使用する成形加工用の紙含有樹脂組成物に関する。
【０００２】
【従来の技術】
熱可塑性合成樹脂を主成分とした成形加工用の樹脂組成物は公知である。組成物は、射出成形や押出し成形、溶融圧縮成形等の技術を利用してシートや容器等の成形品に加工される。廃棄された成形品は、清掃工場の焼却炉で焼却されるが、合成樹脂は、単位重量当たりの燃焼熱が高く、焼却炉を痛める原因となっている。成形品の燃焼熱を下げる手段として、組成物に紙を含有させる技術がある。
【０００３】
組成物に紙を含有させるものとして、特開平１０−１３８２４１号公報は、両面又は片面に主としてポリエチレン樹脂層を有する複合紙を細断して得られる細断紙成分と、低密度ポリエチレン、リニア低密度ポリエチレン、中密度ポリエチレンのうちの少なくとも１つの樹脂と高密度ポリエチレン、メタロセン−ポリエチレンのうちの少なくとも１つの樹脂とのうちのいずれか一方を細断して得られる細断樹脂成分とを混練して得られる紙含有樹脂ペレットを開示している。
【０００４】
紙含有樹脂ペレットは、５０重量％以上の紙成分含有率を有し、紙細断成分の比重と細断樹脂成分の比重との差分が±０．０５〜±０．１６ｇ／ｃｍ３の範囲にある。紙含有樹脂ペレットは、両面又は片面に樹脂層を有する細断紙成分を使用することで、紙成分と樹脂成分とを混練したときにそれら成分が均一に分散することができ、それら成分のペレットにおける偏り分散を防ぐことができる。紙含有樹脂ペレットは、１ｍｍ角〜５ｍｍ角に細断された細断紙成分と１ｍｍ角〜５ｍｍ角に細断された細断樹脂成分とが混練機で加熱、混練された後、押出し機で押し出して製造される。
【０００５】
【発明が解決しようとする課題】
同号公報に開示の紙含有樹脂ペレットは、１ｍｍ角〜５ｍｍ角の細断紙成分を使用しているために紙成分が短繊維状のまま樹脂成分と混練され、かつ、紙成分含有率が５０重量％以上と過半を占めるので、加熱しても流動性を示さない紙成分が樹脂成分の流動性を妨害してしまう。
【０００６】
ペレットの製造時では、押出し機のシリンダ内に進入した紙成分と樹脂成分とのうち、樹脂成分はシリンダ内で溶融して流動するが、紙成分が樹脂成分の流動を妨げるので、溶融した樹脂成分が円滑に押出し機からダイへ向かって流動することができない場合がある。また、紙成分と樹脂成分と混練するときに、押出し機のスクリュと紙成分との摩擦によって剪断発熱が生じ、紙成分が熱で劣化してしまうことがある。
【０００７】
製造された紙含有樹脂ペレットを射出成形に用いる場合では、紙含有樹脂の流動抵抗が高くかつ固化し易いために、紙含有樹脂を高温、高圧、高速で射出させる必要がある。しかし、樹脂の溶融温度が約１９０℃を超えると樹脂に含まれている紙成分が熱分解を起こしてしまうので、温度をそれ以上に上げることができない。樹脂を高圧、高速で型内に流入させると、射出成形機や型が損傷してしまうことがある。
【０００８】
本発明の課題は、燃焼熱が低く、かつ、良好な流動性を有し、組成物の製造時では、押出し機からダイへ円滑に流動することができ、組成物を使用した射出成形では、組成物を高温、高圧、高速で射出させる必要がなく、シートや容器等の成形品を製造することができる成形加工用の紙含有樹脂組成物を提供することにある。
【０００９】
【課題を解決するための手段】
前述した課題を解決するための本発明は、紙を主成分とする低燃焼熱成分と、燃焼熱が前記紙のそれよりも高い熱可塑性合成樹脂を主成分とする高燃焼熱成分とから構成され、それら成分を混和して得られる成形加工用の紙含有樹脂組成物を改良することにある。
【００１０】
本発明の成形加工用の紙含有樹脂組成物は、紙を主成分とする低燃焼熱成分と、燃焼熱が前記紙のそれよりも高い熱可塑性合成樹脂を主成分とする高燃焼熱成分とから構成され、それら成分を混和して得られる成形加工用の紙含有樹脂組成物において、
前記低燃焼熱成分が、５０μｍ以上かつ２００μｍ以下の粒径を有する紙パウダーを主成分とし、５μｍ以上かつ１５０μｍ以下の粒径を有する澱粉と、酸化チタン、タルク、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、カオリンのうちの少なくとも一つの粉状無機物と少なくとも澱粉とを含有し、
前記澱粉が、前記低燃焼熱成分のうちの１０重量％以上かつ２５重量％以下を占め、前記無機物が、前記低燃焼熱成分のうちの１重量％以上かつ２５重量％以下を占め、前記紙パウダーと前記澱粉と前記無機物との重量％が、紙パウダー＞澱粉、又は、紙パウダー＞澱粉＋無機物のいずれかの関係にあり、
前記組成物が、５０重量％を超過しかつ７０重量％以下の前記低燃焼熱成分と、３０重量％以上かつ５０重量％未満の前記高燃焼熱成分とを含有し、前記組成物における前記低燃焼熱成分と前記高燃焼熱成分との重量％が、低燃焼熱成分＞高燃焼熱成分の関係にあることを特徴とする。
【００１４】
【発明の実施の形態】
本発明にかかる成型加工用の紙含有樹脂組成物の詳細を説明すると、以下のとおりである。
（１）一例として示す成形加工用の紙含有樹脂組成物（以下、第１組成物という。）は、紙パウダーを主成分とする低燃焼熱成分と、燃焼熱が紙パウダーのそれよりも高い熱可塑性合成樹脂を主成分とする高燃焼熱成分とから構成されている。第１組成物には、低燃焼熱成分を形成する紙パウダーが５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂が３０重量％以上であって５０重量％未満の範囲で含まれており、第１組成物における合成樹脂と紙パウダーとの重量％が紙パウダー＞合成樹脂の関係にある。
【００１５】
紙パウダーは、広葉樹パルプと針葉樹パルプとのうちの少なくとも一方を原料としてそれらパルプを粉状に粉砕したセルロース主体のものと、古紙を粉状に粉砕したものとのうちのいずれか一方、または、両者を配合したものである。広葉樹パルプや針葉樹パルプを原料とした紙パウダーは、リグニン成分が１％以下のものを使用することが好ましく、古紙を原料とした紙パウダーは、セルロース成分が９５重量％以上含まれていることが好ましい。紙パウダーは、その粒径が５０μｍ以上であって２００μｍ以下の範囲、好ましくは、７５μｍ以上であって１５０μｍ以下の範囲にある。
【００１６】
合成樹脂は、低密度ポリエチレン、リニア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、メタロセン−ポリエチレン、ブロック重合ポリプロピレン、ランダム重合ポリプロピレン、ホモ重合ポリプロピレン、メタロセン−ポリプロピレン、オレフィン系エラストマー、エチレンビニルアセテート共重合体、エチレンエチルアクリレート共重合体、ポリスチレン、スチレン−アクリロニトリル共重合体（ＡＳ樹脂）、ポリブタジエン−スチレン−アクリロニトリルグラフト共重合体（ＡＢＳ樹脂）、ナイロンとのうちのいずれか１種類、または、それら樹脂を２種類以上配合したものである。
【００１７】
紙パウダーが７０重量％を超過し、かつ、合成樹脂が３０重量％未満の場合では、加熱しても流動性を示さない紙パウダーが合成樹脂の流動性を著しく低下させてしまうので、組成物において良好な流動性を得ることが難しい。紙パウダーが５０重量％未満、かつ、合成樹脂が５０重量％を超過する場合では、高燃焼熱成分である合成樹脂が組成物の過半を占めるので、紙パウダーの低燃焼熱成分としての作用が合成樹脂によって妨げられ、組成物の燃焼熱をわずかに低下させることができるにすぎない。
【００１８】
紙パウダーの粒径が５０μｍ未満の場合では、パルプや古紙を５０μｍ未満の粒径に加工するために複数の工程を必要とするので、紙パウダーの生産コストが高くなってしまう。その結果、組成物や組成物を使用した成形品の生産コストが上昇することになる。
【００１９】
紙パウダーの粒径が２００μｍを超過する場合では、紙パウダーが合成樹脂の中で分散不良を起こし、紙パウダーが合成樹脂中に嵩高な継粉を形成する場合があり、嵩高な継粉によって組成物の流動性が著しく低下してしまうことがある。
【００２０】
第１組成物の１００重量％のうちには、紙成分として粒径が５０μｍ≦粒径≦２００μｍの範囲にある紙パウダーを５０重量％＜紙パウダー≦７０重量％の範囲で含有しているので、組成物の燃焼熱を下げることができるとともに、組成物が良好な流動性を有する。
（２）他の一例として示す紙含有樹脂組成物（以下、第２組成物という。）は、紙パウダーを主成分とする低燃焼熱成分と、熱可塑性合成樹脂を主成分とし、熱可塑性の改質成分を含有する高燃焼熱成分とから構成されている。第２組成物には、低燃焼熱成分を形成する紙パウダーが５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂と改質成分との混合物が３０重量％以上であって５０重量％未満の範囲で含まれている。紙パウダーと合成樹脂とは、第１組成物のそれらと同一のものである。
【００２１】
改質成分は、合成樹脂と相互に親和性を有するもので、合成樹脂と混合物を形成し、合成樹脂の流動性を向上させることができる。また、改質成分は、合成樹脂と紙パウダーとを接着するバインダーとしての作用を有する。改質成分は、高燃焼熱成分の全重量％のうち、３重量％以上であって２０重量％以下を占めている。改質成分は、メルトフローインデックスが１０〜２５ｇ／１０分の範囲にある。
【００２２】
改質成分は、熱可塑性エラストマー、スチレン−ブタジエンラバー、ブタジエンラバー、水素添加スチレン−ブタジエンラバー、スチレン−エチレンブチレン・オレフィン結晶ブロックコポリマー、オレフィン結晶・エチレンブチレン・オレフィン結晶ブロックコポリマーのうちのいずれか１種類、または、それらを２種類以上配合したものである。
【００２３】
水素添加スチレン−ブタジエンラバー、スチレン−エチレンブチレン・オレフィン結晶ブロックコポリマー、オレフィン結晶・エチレンブチレン・オレフィン結晶ブロックコポリマーそれぞれは、エチレンとブテン−１とから形成されたランダム性の高い共重合体であり、ポリマー分子中に二重結合を持たず、かつ、低結晶性で柔軟性のある透明性の高いポリオレフィン系熱可塑性合成樹脂である。
【００２４】
改質成分が３重量％未満、かつ、改質成分のメルトフローインデックスが１０ｇ／１０分未満の場合は、改質成分が十分に作用せず、組成物の流動性を向上させることができない。改質成分が２０重量％を超過し、かつ、改質成分のメルトフローインデックスが２５ｇ／１０分を超過する場合は、組成物が必要以上に軟質化されてしまうので、組成物が十分な硬度を得ることができない。また、組成物の引張り強さと引裂強度とが低下してしまう。
（３）他の一例として示す紙含有樹脂組成物（以下、第３組成物という。）は、紙パウダーを主成分とし、澱粉を含有する低燃焼熱成分と、熱可塑性合成樹脂を主成分とする高燃焼熱成分とから構成されている。第３組成物には、低燃焼熱成分を形成する紙パウダーと澱粉との混合物が５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂が３０重量％以上であって５０重量％未満の範囲で含まれている。紙パウダーと合成樹脂とは、第１組成物のそれらと同一のものである。
【００２５】
澱粉は、焼却時の燃焼熱が紙パウダーのそれよりも低い。ゆえに、組成物に澱粉を加えることで、組成物の燃焼熱を一層低下させることができる。澱粉は、低燃焼熱成分の全重量％のうち、１０重量％以上であって２５重量％以下を占め、紙パウダーと澱粉との重量％が紙パウダー＞澱粉の関係にある。澱粉は、その粒径が５μｍ以上であって１５０μｍ以下の範囲にある。
【００２６】
澱粉が１０重量％未満の場合は、澱粉の組成物に及ぼす影響が十分ではなく、組成物の燃焼熱を低下させる効果が少ない。澱粉が２５重量％を超過する場合は、合成樹脂や紙パウダーの発火点よりも澱粉のそれが高いので、組成物の発火点が上昇し、組成物を燃焼させるときに強い火力を用いなければならなくなってしまう。
【００２７】
澱粉の粒径が５μｍ未満の場合では、澱粉を５μｍ未満の粒径に加工するために複数の工程を必要とするので、使用する澱粉の生産コストが高くなってしまう。澱粉の粒径が１５０μｍを超過する場合は、澱粉が合成樹脂の中で分散不良を起こし、澱粉が合成樹脂中に嵩高な継粉を形成する場合があり、嵩高な継粉によって組成物の流動性が著しく低下してしまうことがある。
（４）他の一例として示す紙含有樹脂組成物（以下、第４組成物という。）は、紙パウダーを主成分とし、粉状無機物を含有する低燃焼熱成分と、熱可塑性合成樹脂を主成分とする高燃焼熱成分とから構成されている。第４組成物には、低燃焼熱成分を形成する紙パウダーと無機物との混合物が５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂が３０重量％以上であって５０重量％未満の範囲で含まれている。紙パウダーと合成樹脂とは、第１組成物のそれらと同一のものである。
【００２８】
無機物は、低燃焼熱成分の全重量％のうち、１重量％以上であって２５重量％以下を占め、紙パウダーと無機物との重量％が、紙パウダー＞無機物の関係にある。無機物は、酸化チタン、タルク、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、カオリンのうちのいずれか１種類、または、それら無機物を２種類以上配合したものである。無機物は不燃性なので、組成物に無機物を加えることで、組成物の燃焼熱を一層低下させることができる。
【００２９】
無機物が１重量％未満の場合は、無機物が十分に作用せず、組成物の燃焼熱を低下させる効果が少ない。無機物が２５重量％を超過する場合は、組成物の塑性や延性、耐衝撃性が極端に低下してしまうことがある。
（５）他の一例として示す紙含有樹脂組成物（以下、第５組成物という。）は、紙パウダーを主成分とし、澱粉を含有する低燃焼熱成分と、熱可塑性合成樹脂を主成分とし、改質成分を含有する高燃焼熱成分とから構成されている。第５組成物には、低燃焼熱成分を形成する紙パウダーと澱粉との混合物が５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂と改質成分との混合物が３０重量％以上であって５０重量％未満の範囲で含まれている。紙パウダー、澱粉、合成樹脂、改質成分は、第１〜第３組成物のそれらと同一のものである。
【００３０】
改質成分は、高燃焼熱成分の全重量％のうち、３重量％以上であって２０重量％以下を占めている。澱粉は、低燃焼熱成分の全重量％のうち、１０重量％以上であって２５重量％以下を占め、紙パウダーと澱粉との重量％が、紙パウダー＞澱粉の関係にある。
（６）他の一例として示す紙含有樹脂組成物（以下、第６組成物という。）は、紙パウダーを主成分とし、粒状無機物を含有する低燃焼熱成分と、熱可塑性合成樹脂を主成分とし、改質成分を含有する高燃焼熱成分とから構成されている。第６組成物には、低燃焼熱成分を形成する紙パウダーと無機物との混合物が５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂と改質成分との混合物が３０重量％以上であって５０重量％未満の範囲で含まれている。紙パウダー、無機物、合成樹脂、改質成分は、第１，第２，第４組成物のそれらと同一のものである。
【００３１】
改質成分は、高燃焼熱成分の全重量％のうち、３重量％以上であって２０重量％以下を占めている。無機物は、低燃焼熱成分の全重量％のうち、１重量％以上であって２５重量％以下を占め、紙パウダーと無機物との重量％が、紙パウダー＞無機物の関係にある。
（７）他の一例として示す紙含有樹脂組成物（以下、第７組成物という。）は、紙パウダーを主成分とし、澱粉と無機物とを含有する低燃焼熱成分と、熱可塑性合成樹脂を主成分とし、改質成分を含有する高燃焼熱成分とから構成されている。第７組成物には、低燃焼熱成分を形成する紙パウダーと澱粉と無機物との混合物が５０重量％を超過しかつ７０重量％以下の範囲、高燃焼熱成分を形成する合成樹脂と改質成分との混合物が３０重量％以上であって５０重量％未満の範囲で含まれている。紙パウダー、澱粉、無機物、合成樹脂、改質成分は、第１〜第４組成物のそれらと同一のものである。
【００３２】
改質成分は、高燃焼熱成分の全重量％のうち、３重量％以上であって２０重量％以下を占めている。澱粉は、低燃焼熱成分の全重量％のうち、１０重量％以上であって２５重量％以下を占めている。無機物は、低燃焼熱成分の全重量％のうち、１重量％以上であって２５重量％以下を占めている。紙パウダーと澱粉と無機物との重量％が、紙パウダー＞澱粉＋無機物の関係にある。
【００３３】
第５〜第７組成物において、それら組成物を構成する紙パウダー、澱粉、無機物、合成樹脂、改質成分それぞれの重量％を規定する理由は、第１〜第４組成物のそれらと同一である。第５〜第７組成物において、改質成分のメルトフローインデックスは、第１〜第４組成物のそれらと同一である。
【００３４】
改質成分、澱粉または無機物を含有する第５および第６組成物と改質成分、澱粉、無機物を含有する第７組成物とは、第１、第２組成物よりも組成物の燃焼熱を一層低下させることができるとともに、第１、第３、第４組成物よりも組成物の流動性を一層向上させることができる。
【００３５】
本実施の形態にかかる組成物は、第１、第３、第４組成物が１〜１０ｇ／１０分の範囲、第２、第５〜第７組成物が３〜１２ｇ／１０分の範囲のメルトフローインデックスを有する。第２、第５〜第７組成物は、高燃焼熱成分の全重量％のうち、改質成分を３重量％＜改質成分＜２０重量％の範囲で含有しているので、改質成分を含まない第１、第３、第４組成物よりもメルトフローインデックスの値が高くなる。
【００３６】
それら組成物のメルトフローインデックスは、第１〜第７組成物の温度を１９０℃、押出し圧力を１．２６／ｋｇ、押出し時間を１０分間とし、規定の直径および長さのオリフィスから押し出して測定した。
【００３７】
第１〜第７組成物は、それら組成物を構成する高燃焼熱成分と低燃焼熱成分とが混練機で加熱、混練された後、押出し機とダイとを使用してペレット状や板状、塊状に成形される。第１〜第７組成物は、射出成形や押出し成形、溶融圧縮成形等の技術を利用してシートや容器等の成形品に加工される。
【００３８】
古紙としては、新聞古紙や雑誌古紙、印刷古紙、包装古紙、段ボール古紙、ＯＡ古紙等を使用することができる。古紙は、古紙→離解→蒸煮→精選→洗浄分離→漂白→洗浄→脱インキの工程、古紙→選別→離解→精選→洗浄の工程等を経てパルプに再生される。
【００３９】
（実施例１）
低燃焼熱成分である紙パウダーと高燃焼熱成分である熱可塑性合成樹脂とを混和して試料を作成し、燃焼時の燃焼カロリー（ｋｃａＬ／ｋｇ）および燃焼灰分（試料１００ｇと試料を燃焼させたときの燃焼後の試料残量との比％）と流動性（Ｌ／Ｔ）とを測定した。実施例１では、紙パウダーとして粒径が１５０μｍのものと７５μｍのものとの２種類を使用し、合成樹脂としてポリプロピレンを使用した。
【００４０】
実施例１の試料としては、１５０μｍの粒径の紙パウダーと合成樹脂とを混和して得られた組成物の重量％を、紙パウダー（３０重量％）／合成樹脂（７０重量％）、紙パウダー（５１重量％）／合成樹脂（４９重量％）、紙パウダー（６０重量％）／合成樹脂（４０重量％）とした３種類と、７５μｍの粒径の紙パウダーと合成樹脂とを混和して得られた組成物の重量％を、紙パウダー（３０重量％）／合成樹脂（７０重量％）、紙パウダー（５１重量％）／合成樹脂（４９重量％）、紙パウダー（粒径６０重量％）／合成樹脂（４０重量％）とした３種類との計６種類を用意した。
【００４１】
なお、流動性（Ｌ／Ｔ）は、幅１０．０ｍｍ、厚み１．０ｍｍの流動フローテスト用の型を使用し、試料の温度１８５℃、射出圧力（１０００ｋｇ／ｃｍ２）の条件で測定した。ここで、Ｌは試料の流動距離を示し、Ｔは試料の厚みを示す。測定結果を以下の表１に示す。
【００４２】
【表１】
（実施例２）
実施例２では、紙パウダーとして粒径が１５０μｍのものと７５μｍのものとの２種類を使用し、合成樹脂としてポリエチレンを使用した。実施例２の試料としては、１５０μｍの粒径の紙パウダーと合成樹脂とを混和して得られた組成物の重量％を、紙パウダー（３０重量％）／合成樹脂（７０重量％）、紙パウダー（５１重量％）／合成樹脂（４９重量％）、紙パウダー（６０重量％）／合成樹脂（４０重量％）とした３種類と、７５μｍの粒径の紙パウダーと合成樹脂とを混和して得られた組成物の重量％を、紙パウダー（３０重量％）／合成樹脂（７０重量％）、紙パウダー（５１重量％）／合成樹脂（４９重量％）、紙パウダー（６０重量％）／合成樹脂（４０重量％）とした３種類との計６種類を用意した。流動性（Ｌ／Ｔ）の測定条件は実施例１のそれと同一である。測定結果を以下の表２に示す。
【００４４】
【表２】
実施例１と実施例２とからは、紙パウダーの重量％が３０重量％、合成樹脂の重量％が７０重量％の組成物の燃焼カロリーに対して、紙パウダーの重量％が５１重量％、合成樹脂の重量％が４９重量％と紙パウダーの重量％が６０重量％、合成樹脂の重量％が４０重量％との組成物の燃焼カロリーそれぞれが低下していることがわかる。但し、組成物のうち紙パウダーの重量％が多くなるにしたがって燃焼灰分が増えるとともに、流動性が低下する。実施例１と実施例２とにおける組成物の燃焼時では、白煙は発生したが黒煙は発生しなかった。また、燃焼ガスでは、ベンゼンやアンモニアは発生していない。
【００４６】
【発明の効果】
本発明に係る成形加工用の紙含有樹脂組成物によれば、組成物の焼却時における燃焼熱を下げることができるので、焼却炉を傷めることがない。組成物は、メルトフローインデックスが１〜１０ｇ／１０分の範囲にあり、優れた流動性を有するので、組成物の製造時において押出し機からダイへ円滑に流動することができる。組成物を使用した射出成形では、型内に組成物を高温、高圧、高速で射出させる必要がなく、シートや容器等の成形品を製造することができ、射出成形機や型を傷めてしまうことや組成物に含まれる紙パウダーが熱分解してしまうことを防ぐことができる。また、型内に組成物を円滑に充填することができ、型内におけるショートモールドの発生を防ぐことができる。
【００４７】
紙パウダーと熱可塑性合成樹脂とから構成された組成物では、組成物の焼却時における燃焼熱を下げることができ、良好な流動性を有する。紙パウダーと熱可塑性合成樹脂との他に、改質成分を加えた組成物では、紙パウダーと熱可塑性合成樹脂とから構成された組成物と比較して流動性を一層向上させることができる。紙パウダーと熱可塑性合成樹脂との他に、改質成分、澱粉、無機物を加えた組成物では、紙パウダーと熱可塑性合成樹脂とから構成された組成物と比較して流動性を一層向上させることができるとともに、組成物の燃焼熱を一層低下させることができる。
【００４８】
紙パウダーとして古紙を使用し、合成樹脂として廃材を使用する場合では、環境循環社会において資源を有効に利用することができ、省資源化を図ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper-containing resin composition for molding used for molding such as injection molding, extrusion molding, and melt compression molding.
[0002]
[Prior art]
Resin compositions for molding processing which are mainly composed of a thermoplastic synthetic resin are known. The composition is processed into a molded product such as a sheet or a container using techniques such as injection molding, extrusion molding, and melt compression molding. Although the discarded molded product is incinerated in an incinerator of a cleaning factory, synthetic resin has a high combustion heat per unit weight, causing damage to the incinerator. As a means for reducing the heat of combustion of a molded article, there is a technique for incorporating paper into the composition.
[0003]
JP-A-10-138241 discloses a composition containing paper, a shredded paper component obtained by shredding a composite paper mainly having a polyethylene resin layer on both sides or one side, low density polyethylene, linear low Kneading at least one resin of density polyethylene and medium density polyethylene and a chopped resin component obtained by chopping at least one of high density polyethylene and at least one resin of metallocene-polyethylene The paper-containing resin pellets obtained are disclosed.
[0004]
The paper-containing resin pellet has a paper component content of 50% by weight or more, and the difference between the specific gravity of the paper shredding component and the specific gravity of the shredded resin component is in the range of ± 0.05 to ± 0.16 g / cm 3 . It is in. Paper-containing resin pellets use shredded paper components having a resin layer on both sides or one side, so that when the paper component and resin component are kneaded, the components can be uniformly dispersed, and the pellets of these components Can be prevented. The paper-containing resin pellets are obtained by heating and kneading a shredded paper component shredded into 1 mm square to 5 mm square and a shredded resin component shredded into 1 mm square to 5 mm square with an extruder. Extruded and manufactured.
[0005]
[Problems to be solved by the invention]
Since the paper-containing resin pellets disclosed in the same publication use a 1 mm square to 5 mm square shredded paper component, the paper component is kneaded with the resin component in a short fiber form, and the paper component content is Since it occupies a majority of 50% by weight or more, a paper component that does not exhibit fluidity even when heated interferes with the fluidity of the resin component.
[0006]
At the time of pellet production, the resin component melts and flows in the cylinder out of the paper component and the resin component that have entered the extruder cylinder, but the paper component prevents the resin component from flowing, so the molten resin Ingredients may not flow smoothly from the extruder to the die. Further, when the paper component and the resin component are kneaded, shear heat generation may occur due to friction between the screw of the extruder and the paper component, and the paper component may be deteriorated by heat.
[0007]
When the produced paper-containing resin pellets are used for injection molding, it is necessary to inject the paper-containing resin at high temperature, high pressure and high speed because the flow resistance of the paper-containing resin is high and it is easy to solidify. However, if the melting temperature of the resin exceeds about 190 ° C., the paper component contained in the resin undergoes thermal decomposition, and thus the temperature cannot be increased further. If the resin is allowed to flow into the mold at high pressure and high speed, the injection molding machine or the mold may be damaged.
[0008]
The problem of the present invention is that the heat of combustion is low and has good fluidity, and at the time of production of the composition, it can smoothly flow from the extruder to the die. In the injection molding using the composition, An object of the present invention is to provide a paper-containing resin composition for molding processing that does not require injection of the composition at high temperature, high pressure, and high speed, and can produce a molded article such as a sheet or a container.
[0009]
[Means for Solving the Problems]
The present invention for solving the above-described problems comprises a low combustion heat component mainly composed of paper and a high combustion heat component mainly composed of a thermoplastic synthetic resin whose combustion heat is higher than that of the paper. And improving the paper-containing resin composition for molding processing obtained by mixing these components.
[0010]
The paper-containing resin composition for molding processing of the present invention comprises a low combustion heat component mainly composed of paper, and a high combustion heat component mainly composed of a thermoplastic synthetic resin whose combustion heat is higher than that of the paper. In a paper-containing resin composition for molding processing obtained by mixing these components,
Starch having a particle size of 5 μm or more and 150 μm or less, titanium oxide, talc, calcium carbonate, calcium sulfate, barium sulfate, the main component of which is a low combustion heat component, a paper powder having a particle size of 50 μm or more and 200 μm or less , even without less and at least one powdered inorganic substances of the kaolin containing and starch,
The starch occupies 10% to 25% by weight of the low combustion heat component, the inorganic material occupies 1% to 25% by weight of the low combustion heat component, and the paper The weight percentage of the powder, the starch and the inorganic substance is in a relationship of either paper powder> starch or paper powder> starch + inorganic substance,
The composition contains more than 50% by weight and less than 70% by weight of the low combustion heat component and 30% by weight or more and less than 50% by weight of the high combustion heat component, The weight percent of the combustion heat component and the high combustion heat component has a relationship of low combustion heat component> high combustion heat component.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The details of the paper-containing resin composition for molding according to the present invention will be described as follows.
(1) A paper-containing resin composition for molding processing shown as an example (hereinafter referred to as a first composition) has a low combustion heat component mainly composed of paper powder and a combustion heat higher than that of paper powder. It is comprised from the high combustion heat component which has a thermoplastic synthetic resin as a main component. In the first composition, the paper powder forming the low combustion heat component exceeds 50% by weight and is in the range of 70% by weight or less, and the synthetic resin forming the high combustion heat component is 30% by weight or more and 50% by weight. The weight percentage of the synthetic resin and the paper powder in the first composition is in the relationship of paper powder> synthetic resin.
[0015]
The paper powder is either a cellulose-based material obtained by pulverizing these pulps into a powdery form using at least one of a hardwood pulp and a coniferous pulp as a raw material, and one of those obtained by pulverizing used paper, or Both are blended. The paper powder made from hardwood pulp or softwood pulp preferably uses a lignin component of 1% or less, and the paper powder made from waste paper contains 95% by weight or more of a cellulose component. preferable. The paper powder has a particle size of 50 μm or more and 200 μm or less, preferably 75 μm or more and 150 μm or less.
[0016]
Synthetic resins are low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, metallocene-polyethylene, block polymerized polypropylene, random polymerized polypropylene, homopolymerized polypropylene, metallocene-polypropylene, olefin elastomer, ethylene vinyl acetate copolymer Copolymer, ethylene ethyl acrylate copolymer, polystyrene, styrene-acrylonitrile copolymer (AS resin), polybutadiene-styrene-acrylonitrile graft copolymer (ABS resin), nylon, or these resins 2 or more types are blended.
[0017]
In the case where the paper powder exceeds 70% by weight and the synthetic resin is less than 30% by weight, the paper powder that does not exhibit fluidity even when heated significantly reduces the fluidity of the synthetic resin. In this case, it is difficult to obtain good fluidity. When the paper powder is less than 50% by weight and the synthetic resin exceeds 50% by weight, the synthetic resin, which is a high combustion heat component, occupies the majority of the composition, so that the action of the paper powder as a low combustion heat component is achieved. It is only disturbed by the synthetic resin and can only slightly reduce the heat of combustion of the composition.
[0018]
In the case where the particle size of the paper powder is less than 50 μm, a plurality of steps are required to process the pulp and waste paper into a particle size of less than 50 μm, which increases the production cost of the paper powder. As a result, the production cost of the composition or a molded product using the composition increases.
[0019]
When the particle size of the paper powder exceeds 200 μm, the paper powder may cause a dispersion failure in the synthetic resin, and the paper powder may form a bulky powder in the synthetic resin. The fluidity of the product may be significantly reduced.
[0020]
In 100% by weight of the first composition, the paper component contains paper powder having a particle size in the range of 50 μm ≦ particle size ≦ 200 μm in a range of 50% by weight <paper powder ≦ 70% by weight. In addition to reducing the heat of combustion of the composition, the composition has good fluidity.
(2) A paper-containing resin composition (hereinafter referred to as the second composition) shown as another example is a low-combustion heat component mainly composed of paper powder and a thermoplastic synthetic resin as a main component, and is a thermoplastic resin. And a high combustion heat component containing a reforming component. In the second composition, the paper powder forming the low combustion heat component exceeds 50% by weight and not more than 70% by weight, and the mixture of the synthetic resin and the reforming component forming the high combustion heat component is 30% by weight. % Or more and less than 50% by weight. The paper powder and the synthetic resin are the same as those of the first composition.
[0021]
The modifying component has an affinity for the synthetic resin and can form a mixture with the synthetic resin to improve the fluidity of the synthetic resin. Further, the modifying component acts as a binder that bonds the synthetic resin and the paper powder. The reforming component accounts for 3% by weight or more and 20% by weight or less of the total weight% of the high combustion heat component. The modifying component has a melt flow index in the range of 10 to 25 g / 10 minutes.
[0022]
The modifying component is any one of thermoplastic elastomer, styrene-butadiene rubber, butadiene rubber, hydrogenated styrene-butadiene rubber, styrene-ethylenebutylene / olefin crystal block copolymer, olefin crystal / ethylenebutylene / olefin crystal block copolymer. It is a type or a combination of two or more types.
[0023]
Each of hydrogenated styrene-butadiene rubber, styrene-ethylene butylene / olefin crystal block copolymer, and olefin crystal / ethylene butylene / olefin crystal block copolymer is a highly random copolymer formed from ethylene and butene-1. It is a polyolefin-based thermoplastic synthetic resin that does not have a double bond in the polymer molecule, is low in crystallinity, and has high flexibility.
[0024]
When the modifying component is less than 3% by weight and the melt flow index of the modifying component is less than 10 g / 10 minutes, the modifying component does not act sufficiently and the fluidity of the composition cannot be improved. If the reforming component exceeds 20% by weight and the melt flow index of the modifying component exceeds 25 g / 10 min, the composition will be softened more than necessary, so that the composition has sufficient hardness. Can't get. Further, the tensile strength and tear strength of the composition are lowered.
(3) A paper-containing resin composition (hereinafter referred to as a third composition) shown as another example is mainly composed of paper powder, a low combustion heat component containing starch, and a thermoplastic synthetic resin as a main component. And high combustion heat components. In the third composition, the mixture of paper powder and starch that forms a low combustion heat component exceeds 50% by weight and is less than 70% by weight, and the synthetic resin that forms a high combustion heat component is 30% by weight or more. And is contained in the range of less than 50% by weight. The paper powder and the synthetic resin are the same as those of the first composition.
[0025]
Starch has a lower heat of combustion during incineration than that of paper powder. Therefore, the combustion heat of the composition can be further reduced by adding starch to the composition. Starch is 10% by weight or more and 25% by weight or less of the total weight% of the low combustion heat component, and the weight% of paper powder and starch is in the relationship of paper powder> starch. Starch has a particle size of 5 μm or more and 150 μm or less.
[0026]
When the starch is less than 10% by weight, the influence of the starch on the composition is not sufficient, and the effect of reducing the combustion heat of the composition is small. If the starch exceeds 25% by weight, it will be higher than the ignition point of synthetic resin or paper powder, so the ignition point of the composition will rise and a strong heating power must be used when burning the composition. Will not be.
[0027]
In the case where the particle size of the starch is less than 5 μm, a plurality of steps are required to process the starch into a particle size of less than 5 μm, which increases the production cost of the starch used. When the particle size of the starch exceeds 150 μm, the starch may cause poor dispersion in the synthetic resin, and the starch may form a bulky splice in the synthetic resin. May be significantly reduced.
(4) The paper-containing resin composition (hereinafter referred to as the fourth composition) shown as another example is mainly composed of paper powder, a low combustion heat component containing a powdered inorganic substance, and a thermoplastic synthetic resin. It consists of a high combustion heat component as a component. In the fourth composition, the mixture of the paper powder and the inorganic material forming the low combustion heat component is more than 50% by weight and not more than 70% by weight, and the synthetic resin forming the high combustion heat component is 30% by weight or more. And is contained in the range of less than 50% by weight. The paper powder and the synthetic resin are the same as those of the first composition.
[0028]
The inorganic substance accounts for 1% by weight or more and 25% by weight or less of the total weight% of the low combustion heat component, and the weight% of the paper powder and the inorganic substance has a relationship of paper powder> inorganic substance. The inorganic substance is one of titanium oxide, talc, calcium carbonate, calcium sulfate, barium sulfate, and kaolin, or a mixture of two or more of these inorganic substances. Since the inorganic substance is nonflammable, the heat of combustion of the composition can be further reduced by adding the inorganic substance to the composition.
[0029]
When the inorganic substance is less than 1% by weight, the inorganic substance does not act sufficiently, and the effect of reducing the combustion heat of the composition is small. If the inorganic content exceeds 25% by weight, the plasticity, ductility and impact resistance of the composition may be extremely lowered.
(5) The paper-containing resin composition (hereinafter referred to as the fifth composition) shown as another example is mainly composed of paper powder, a low combustion heat component containing starch, and a thermoplastic synthetic resin as the main component. And a high combustion heat component containing a reforming component. The fifth composition includes a mixture of paper powder and starch forming a low combustion heat component in a range of more than 50% by weight and 70% by weight or less, a synthetic resin and a modifying component forming a high combustion heat component, In a range of 30% by weight or more and less than 50% by weight. The paper powder, starch, synthetic resin, and modifying component are the same as those of the first to third compositions.
[0030]
The reforming component accounts for 3% by weight or more and 20% by weight or less of the total weight% of the high combustion heat component. Starch is 10% by weight or more and 25% by weight or less of the total weight% of the low combustion heat component, and the weight% of paper powder and starch is in the relationship of paper powder> starch.
(6) A paper-containing resin composition (hereinafter referred to as a sixth composition) shown as another example has a paper powder as a main component, a low-combustion heat component containing a particulate inorganic substance, and a thermoplastic synthetic resin as a main component. And a high combustion heat component containing a reforming component. The sixth composition includes a synthetic resin and a reforming component that form a high combustion heat component in a range where the mixture of the paper powder and the inorganic material forming the low combustion heat component exceeds 50% by weight and 70% by weight or less. In a range of 30% by weight or more and less than 50% by weight. The paper powder, inorganic substance, synthetic resin, and modifying component are the same as those of the first, second, and fourth compositions.
[0031]
The reforming component accounts for 3% by weight or more and 20% by weight or less of the total weight% of the high combustion heat component. The inorganic substance accounts for 1% by weight or more and 25% by weight or less of the total weight% of the low combustion heat component, and the weight% of the paper powder and the inorganic substance has a relationship of paper powder> inorganic substance.
(7) A paper-containing resin composition (hereinafter referred to as the seventh composition) shown as another example includes a low-combustion heat component containing paper powder as a main component, starch and inorganic substances, and a thermoplastic synthetic resin. The main component is a high combustion heat component containing a reforming component. In the seventh composition, a mixture of paper powder, starch and inorganic material forming a low combustion heat component exceeds 50% by weight and is less than 70% by weight. A mixture with the components is contained in the range of 30% by weight or more and less than 50% by weight. The paper powder, starch, inorganic substance, synthetic resin, and modifying component are the same as those of the first to fourth compositions.
[0032]
The reforming component accounts for 3% by weight or more and 20% by weight or less of the total weight% of the high combustion heat component. Starch is 10% by weight or more and 25% by weight or less of the total weight% of the low combustion heat component. The inorganic substance accounts for 1% by weight or more and 25% by weight or less of the total weight% of the low combustion heat component. The weight percent of paper powder, starch and inorganic matter is in the relationship of paper powder> starch + inorganic matter.
[0033]
In the fifth to seventh compositions, the reasons for prescribing the weight percentages of the paper powder, starch, inorganic substance, synthetic resin, and modifying component constituting the compositions are the same as those of the first to fourth compositions. is there. In the fifth to seventh compositions, the melt flow index of the modifying component is the same as those of the first to fourth compositions.
[0034]
The fifth and sixth compositions containing the modifying component, starch or inorganic substance, and the seventh composition containing the modifying component, starch, or inorganic substance have a higher heat of combustion than the first and second compositions. While being able to reduce further, the fluidity | liquidity of a composition can be improved further than the 1st, 3rd, 4th composition.
[0035]
In the composition according to the present embodiment, the first, third and fourth compositions are in the range of 1 to 10 g / 10 minutes, and the second, fifth to seventh compositions are in the range of 3 to 12 g / 10 minutes. It has a melt flow index. The second, fifth to seventh compositions contain the reforming component in the range of 3 wt% <reforming component <20 wt% of the total weight% of the high combustion heat component. The melt flow index value is higher than that of the first, third, and fourth compositions that do not contain.
[0036]
The melt flow index of these compositions is measured by extruding from an orifice having a specified diameter and length, with the temperature of the first to seventh compositions being 190 ° C., the extrusion pressure being 1.26 / kg, and the extrusion time being 10 minutes. did.
[0037]
In the first to seventh compositions, the high combustion heat component and the low combustion heat component constituting the composition are heated and kneaded in a kneader, and then pelletized or plate-shaped using an extruder and a die. It is formed into a lump shape. The first to seventh compositions are processed into molded articles such as sheets and containers using techniques such as injection molding, extrusion molding, and melt compression molding.
[0038]
As the used paper, newspaper used paper, magazine used paper, printed used paper, packaging used paper, cardboard used paper, OA used paper, and the like can be used. Waste paper is recycled into pulp through the steps of waste paper → separation → steaming → selection → washing separation → bleaching → washing → deinking, wastepaper → selection → separation → selection → washing.
[0039]
Example 1
A sample is prepared by mixing paper powder, which is a low combustion heat component, and thermoplastic synthetic resin, which is a high combustion heat component, and burns calories during combustion (kcaL / kg) and combustion ash (100 g of the sample and the sample are burned) (Ratio% of the remaining amount of the sample after combustion) and fluidity (L / T). In Example 1, two types of paper powder having a particle size of 150 μm and 75 μm were used as paper powder, and polypropylene was used as a synthetic resin.
[0040]
As a sample of Example 1, the weight% of the composition obtained by mixing paper powder having a particle diameter of 150 μm and synthetic resin was used as paper powder (30 wt%) / synthetic resin (70 wt%), paper Three types of powder (51% by weight) / synthetic resin (49% by weight) and paper powder (60% by weight) / synthetic resin (40% by weight) were mixed with paper powder having a particle diameter of 75 μm and synthetic resin. % By weight of the composition thus obtained was paper powder (30% by weight) / synthetic resin (70% by weight), paper powder (51% by weight) / synthetic resin (49% by weight), paper powder (particle size 60% by weight). %) / Synthetic resin (40 wt%) and a total of 6 types were prepared.
[0041]
The fluidity (L / T) was measured using a flow flow test mold with a width of 10.0 mm and a thickness of 1.0 mm under the conditions of a sample temperature of 185 ° C. and an injection pressure (1000 kg / cm 2 ). . Here, L indicates the flow distance of the sample, and T indicates the thickness of the sample. The measurement results are shown in Table 1 below.
[0042]
[Table 1]
(Example 2)
In Example 2, two types of paper powder having a particle size of 150 μm and 75 μm were used, and polyethylene was used as a synthetic resin. As a sample of Example 2, the weight% of the composition obtained by mixing paper powder having a particle diameter of 150 μm and synthetic resin was used as paper powder (30 wt%) / synthetic resin (70 wt%), paper Three types of powder (51% by weight) / synthetic resin (49% by weight) and paper powder (60% by weight) / synthetic resin (40% by weight) were mixed with paper powder having a particle diameter of 75 μm and synthetic resin. % By weight of the composition thus obtained was paper powder (30% by weight) / synthetic resin (70% by weight), paper powder (51% by weight) / synthetic resin (49% by weight), paper powder (60% by weight). / A total of 6 types including 3 types of synthetic resin (40% by weight) were prepared. The measurement conditions for fluidity (L / T) are the same as those in Example 1. The measurement results are shown in Table 2 below.
[0044]
[Table 2]
From Example 1 and Example 2, the weight percentage of paper powder is 51% by weight with respect to the burned calories of the composition where the weight percentage of paper powder is 30% by weight and the weight percentage of synthetic resin is 70% by weight. It can be seen that the burned calories of the composition of 49% by weight of the synthetic resin, 60% by weight of the paper powder, and 40% by weight of the synthetic resin are reduced. However, as the weight percentage of the paper powder in the composition increases, the combustion ash content increases and the fluidity decreases. When the compositions in Examples 1 and 2 were burned, white smoke was generated but black smoke was not generated. Moreover, benzene and ammonia are not generated in the combustion gas.
[0046]
【The invention's effect】
According to the paper-containing resin composition for molding processing according to the present invention, since the heat of combustion at the time of incineration of the composition can be lowered, the incinerator is not damaged. Since the composition has a melt flow index in the range of 1 to 10 g / 10 minutes and has excellent fluidity, it can smoothly flow from the extruder to the die during the production of the composition. In injection molding using the composition, it is not necessary to inject the composition into the mold at high temperature, high pressure, and high speed, and a molded product such as a sheet or a container can be manufactured, which may damage the injection molding machine or the mold. And the paper powder contained in the composition can be prevented from being thermally decomposed. In addition, the composition can be filled smoothly into the mold, and the occurrence of a short mold in the mold can be prevented.
[0047]
In a composition composed of paper powder and a thermoplastic synthetic resin, the heat of combustion at the time of incineration of the composition can be lowered, and the composition has good fluidity. In addition to the paper powder and the thermoplastic synthetic resin, the composition added with the modifying component can further improve the fluidity as compared with the composition composed of the paper powder and the thermoplastic synthetic resin. In addition to paper powder and thermoplastic synthetic resin, the composition with modified ingredients, starch, and inorganics further improves fluidity compared to the composition composed of paper powder and thermoplastic synthetic resin. And the combustion heat of the composition can be further reduced.
[0048]
When waste paper is used as the paper powder and waste material is used as the synthetic resin, resources can be used effectively in an environmentally circulating society, and resource saving can be achieved.
Claims (1)
前記低燃焼熱成分が、５０μｍ以上かつ２００μｍ以下の粒径を有する紙パウダーを主成分とし、５μｍ以上かつ１５０μｍ以下の粒径を有する澱粉と、酸化チタン、タルク、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、カオリンのうちの少なくとも一つの粉状無機物とを含有し、
前記澱粉が、前記低燃焼熱成分のうちの１０重量％以上かつ２５重量％以下を占め、前記無機物が、前記低燃焼熱成分のうちの１重量％以上かつ２５重量％以下を占め、前記紙パウダーと前記澱粉と前記無機物との重量％が、紙パウダー＞澱粉、又は、紙パウダー＞澱粉＋無機物のいずれかの関係にあり、
前記組成物が、５０重量％を超過しかつ７０重量％以下の前記低燃焼熱成分と、３０重量％以上かつ５０重量％未満の前記高燃焼熱成分とを含有し、前記組成物における前記低燃焼熱成分と前記高燃焼熱成分との重量％が、低燃焼熱成分＞高燃焼熱成分の関係にあることを特徴とする成形加工用の紙含有樹脂組成物。A molding process that is composed of a low-combustion heat component mainly composed of paper and a high-combustion heat component whose main component is a thermoplastic synthetic resin whose combustion heat is higher than that of the paper. In the paper-containing resin composition for
Starch having a particle size of 5 μm or more and 150 μm or less, titanium oxide, talc, calcium carbonate, calcium sulfate, barium sulfate, the main component of which is a low combustion heat component, a paper powder having a particle size of 50 μm or more and 200 μm or less , Containing at least one powdered inorganic substance of kaolin,
The starch occupies 10% by weight or more and 25% by weight or less of the low combustion heat component, the inorganic substance occupies 1% by weight or more and 25% by weight or less of the low combustion heat component, and the paper The weight percentage of the powder, the starch and the inorganic substance is in a relationship of either paper powder> starch or paper powder> starch + inorganic substance,
The composition contains more than 50% by weight and less than 70% by weight of the low combustion heat component and 30% by weight or more and less than 50% by weight of the high combustion heat component, A paper-containing resin composition for molding, wherein the weight percent of the combustion heat component and the high combustion heat component is in the relationship of low combustion heat component> high combustion heat component.
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| JP2006265346A (en) * | 2005-03-23 | 2006-10-05 | Hokuetsu Paper Mills Ltd | Paper-crushed material for mixing with resin, environment-considering type resin composition containing the same and environment-considering type resin molded article by using the same |
| EP2308599B1 (en) | 2009-11-02 | 2014-01-08 | Kankyokeieisogokenkyusho Co, Inc. | Method for producing fine paper powder |
| US8835539B2 (en) | 2011-06-22 | 2014-09-16 | Kankyokeieisogokenkyusho Co., Inc. | Manufacturing method for resin composition containing fine paper powder |
| US9169397B2 (en) | 2011-06-22 | 2015-10-27 | Kankyokeieisogokenkyusho Co., Inc. | Manufacturing method for resin composition containing fine paper powder |
| JP6437391B2 (en) | 2015-07-07 | 2018-12-12 | 東洋ゴム工業株式会社 | Rubber composition for tire, tire and method for producing the same |
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| JPH05345842A (en) * | 1992-06-16 | 1993-12-27 | Calp Corp | Compound resin composition for bent sheet |
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| JPH0680888A (en) * | 1992-09-01 | 1994-03-22 | Tokuyama Soda Co Ltd | Base material for hanger |
| JP3095298B2 (en) * | 1992-10-20 | 2000-10-03 | 富士写真フイルム株式会社 | Molded products for photographic photosensitive materials |
| JPH07285544A (en) * | 1994-04-12 | 1995-10-31 | O G K Giken Kk | Container |
| JPH08157645A (en) * | 1994-12-05 | 1996-06-18 | Kowa Kogyo:Kk | Stock for biodegradable molded product and its production |
| JP3123011B2 (en) * | 1994-12-28 | 2001-01-09 | 有限会社環境クリエイト | Resin composition and film |
| JP3605947B2 (en) * | 1996-06-18 | 2004-12-22 | 三井化学株式会社 | Polyolefin-based resin composition, composite material and manufacturing method |
| JPH10101942A (en) * | 1996-10-02 | 1998-04-21 | Kuraray Co Ltd | Thermoplastic resin composition |
| JPH10251523A (en) * | 1997-03-17 | 1998-09-22 | Cci Corp | Production of woody molded product |
| JPH11255871A (en) * | 1998-03-12 | 1999-09-21 | Japan Atom Energy Res Inst | Lactone-containing resin, lactone-containing resin composition, molded part and film thereof |
| JPH11269326A (en) * | 1998-03-23 | 1999-10-05 | Eco Polymer Kk | Woody resin composition |
| JP2000129136A (en) * | 1998-10-27 | 2000-05-09 | Showa Denko Plastic Products Kk | Resin composition having improved moldability |
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