JP2004277622A - Method for producing high-concentration vegetable cellulose composition - Google Patents
Method for producing high-concentration vegetable cellulose composition Download PDFInfo
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- JP2004277622A JP2004277622A JP2003073048A JP2003073048A JP2004277622A JP 2004277622 A JP2004277622 A JP 2004277622A JP 2003073048 A JP2003073048 A JP 2003073048A JP 2003073048 A JP2003073048 A JP 2003073048A JP 2004277622 A JP2004277622 A JP 2004277622A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、高濃度植物セルロース組成物の製造法および調整法に関する。
【０００２】
【従来の技術】
従来から植物セルロース熱可塑性樹脂組成物および植物セルロース熱可塑性樹脂組成物からなる成形体の開発は種々行われ、多くの植物セルロース熱可塑性樹脂組成物およびその組成物よりなる成形体が知られている。（例えば特許文献１〜１１参照。）
また、植物セルロース熱可塑性樹脂組成物の調整法および製法に関しても開示されている。（例えば特許文献１１〜１７参照。）
上記で開示されている調整法および製法は、バンバリーミキサー、ヘンシェルミキサーなどの高速混合機を用い、原料を高速で撹拌して、この時に生ずるせん断力により、原料を熱可塑性樹脂の融点以上の温度まで加熱し、組成物中、特に植物セルロース中の水分などの揮発分を除去するとともに、原料を溶融して植物セルロース熱可塑性樹脂組成物を製造する方法である。
【０００３】
上記の調整法および製法では、溶融した植物セルロース熱可塑性樹脂組成物は、非常に高粘度のゲル状物質になり、これを冷却すると塊状となる。溶融時に生じるゲル状の植物セルロース熱可塑性樹組成物は非常に高粘度の融体であるため、撹拌する際に大きな応力が発生し、混合機に大きな付加を及ぼす。また、上記の調整法および製法で得た植物セルロース熱可塑性樹組成物を押出成形加工、射出成形加工に用いるためには、冷却後にできた塊状の組成物を粉砕することが必要であり、生産性や生産設備上の問題があった。
従って、従来の調整法および製法に関する開示技術は、生産設備の耐久性への影響や生産性に問題があり、植物セルロース熱可塑性樹組成物の製法および調整法として広く展開されるには至っていない。
【０００４】
【特許文献１】
特開昭５５−１３１０３１号公報
【特許文献２】
特開昭５７−１１５４３７号公報
【特許文献３】
特開昭６２−３９６４２号公報
【特許文献４】
特開２０００−３１６３５２号公報
【特許文献５】
特開昭５７−１８５３５１号公報
【特許文献６】
特開平１１−２６９３１６号公報
【特許文献７】
特開平１１−４３５６２号公報
【特許文献８】
特開平９−２８６８８０号公報
【特許文献９】
特開２０００−３８４６７号公報
【特許文献１０】
特開２０００−２７１９０９号公報
【特許文献１１】
特開２００２−１１８１６号公報
【特許文献１２】
特開昭６０−３０３０４号公報
【特許文献１３】
特公平４−４８６０６号公報
【特許文献１４】
特開平８−２１６１２２号公報
【特許文献１５】
特開平８−３１０１４７号公報
【特許文献１６】
特開平８−３２３７１０号公報
【特許文献１７】
特開２０００−１０９５６６号公報
【０００５】
【発明が解決しようとする課題】
本発明は、上記従来の問題に鑑み、混合機に大きな付加を及ぼさず且つ冷却後に組成物を粉砕する必要がなく、効率的に植物セルロース組成物を製造する方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者等は、前記課題を解決するため鋭意研究を重ねた結果、特定比率の植物セルロースと熱可塑性樹脂よりなる高濃度植物セルロース組成物を製造する際に、熱可塑性樹脂の融点以上２２０℃以下の温度の範囲になるよう混合物を撹拌することで、ゲル状の組成物の発生を抑制でき、効率的に高濃度植物セルロース組成物を乾燥できることを見出した。
【０００７】
さらに、この方法で得られる高濃度植物セルロース組成物は、冷却後に粉砕せずにそのまま押出成形加工、射出成形加工の原料として用いることができることを見出し、本発明をなすに至った。
すなわち本発明は以下の通りである。
１．植物セルロース８０〜９８重量％および熱可塑性樹脂２０〜２重量％よりなる高濃度植物セルロース組成物を製造する際に、熱可塑性樹脂の融点以上２２０℃以下の温度の範囲になるよう混合物を撹拌することを特徴とする高濃度植物セルロース組成物の製造方法。
【０００８】
２．植物セルロース８５〜９５重量％および熱可塑性樹脂１５〜５重量％よりなる高濃度植物セルロース組成物を製造する際に、熱可塑性樹脂の融点より１０℃高い温度以上２１０℃以下の温度範囲になるよう混合物を撹拌することを特徴とする上記１に記載の高濃度植物セルロース組成物の製造方法。
３．高濃度植物セルロース組成物を撹拌して、加熱した後に、冷却し混合することを特徴とする上記１または２に記載の高濃度植物セルロース組成物の製造方法。
【０００９】
４．高濃度植物セルロース組成物を撹拌して、加熱した高濃度植物セルロース組成物１００重量部に対して、熱可塑性樹脂１〜２００重量部添加し、冷却し混合することを特徴とする上記１〜３のいずれかに記載の植物セルロース組成物の製造方法。
５．高濃度植物セルロース組成物を撹拌して、加熱した後に冷却し混合する過程で、高濃度植物セルロース組成物１００重量部に対して、熱可塑性樹脂１〜２００重量部添加し、冷却することを特徴とする上記１〜３のいずれかに記載の植物セルロース組成物の製造方法。
【００１０】
６．熱可塑性樹脂が、ポリエチレンおよび／またはポリプロピレンであることを特徴とする上記１〜５のいずれかに記載の高濃度植物セルロース組成物および植物セルロース組成物の製造方法。
７．ポリエチレンのメルトインデックスが、０．０１〜２５．０であることを特徴とする上記１〜６のいずれかに記載の植物セルロース組成物の製造方法。
８．上記１〜７のいずれかに記載の方法から得られる成形品。
【００１１】
【発明の実施の形態】
本発明について、以下具体的に説明する。
本発明の高濃度植物セルロース組成物の製造方法は、植物セルロース８０〜９８重量％および熱可塑性樹脂２０〜２重量％よりなる高濃度植物セルロース組成物を製造する際に、熱可塑性樹脂の融点以上２２０℃以下の温度の範囲になるよう混合物を撹拌することを特徴とする高濃度植物セルロース組成物の製造方法である。
【００１２】
本発明に用いる熱可塑性樹脂は、非塩素系の熱可塑性樹脂であり、ポリオレフィン系樹脂であることが好ましい。
ポリオレフィン系樹脂は、疎水性が強い樹脂であるため、効果的に植物セルロース熱可塑性樹組成物を乾燥するため、好ましく使用できる。
ポリオレフィン系樹脂としては、ポリプロピレン、エチレン−プロピレン共重合体およびポリエチレンなどが使用できる。
【００１３】
なかでも、ポリエチレンは、ゲル状の組成物の発生を抑制する点で特に好ましい。ポリエチレンとしては、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、エチレンと炭素数３〜１２のα−オレフィンとの共重合体、最近開発されている種々のメタロセン触媒などの新触媒を用いて重合したエチレン系重合体及びそれらの混合物が使用できる。またポリエチレンとポリプロピレンおよび／またはポリスチレンなどの他の樹脂との混合物が使用できる。また、各種ポリエチレン系樹脂製品のリサイクルによって得られたポリエチレン系樹脂もコスト・性能バランスの良い材料として使用できる。
【００１４】
また、ポリエチレンのメルトインデックスは、好ましくは０．０１〜２５．０の範囲、最も好ましくは０．０５〜３．０の範囲である。メルトインデックスの値は、植物セルロース熱可塑性樹脂組成物の成形性の点で０．０１以上が好ましく、植物セルロース熱可塑性樹脂組成物の機械的強度および成形時の形状安定性の点で２５．０以下が好ましい。また、ポリエチレンのメルトインデックスを好ましい範囲にするために、分子量の異なるポリエチレンをブレンドする方法も用いることができる。また、ポリエチレンのメルトインデックスを好ましい範囲にするために、分子量の異なるポリエチレンをブレンドする方法も用いることができる。
【００１５】
本発明に使用する植物セルロース系粉体としてはいかなるものであってもよく、例えば木粉、パルプ、バカス、ケナフ、おが屑、木質繊維、籾殻、破砕チップ材、果実殻粉、古紙、竹の粉末、ビールの絞り粕、コーヒーの絞り粕等があげられ、これらを単独又は２種類以上組み合わせて用いることができる。
植物セルロース系粉体は、目的とする用途によって適当に選択することができるが、機械的強度及び釘打ち、ネジ止めなどの加工性の点で木粉が好ましい。これらの植物セルロース系粉体は、おが屑、廃木材等を必要であれば乾式又は湿式粉砕または篩い分けにより粒径が０．１ｍｍ〜１０ｍｍの粉粒としたものを用いることが好ましい。植物セルロース系粉体の粒径は、粉立ちなどの問題や、粉砕や篩い分けの手間によるコストを考慮すると、１ｍｍ以上が好ましい。また、得られた成形体の機械的強度の点を考慮すると、１０ｍｍ以下であることが好ましい。植物セルロース系粉体の形状は、粒子状だけでなく、扁平な形状、異型形状およびそれらの混合物でも良い。
【００１６】
本発明の高濃度植物セルロース組成物の比率は、植物セルロース８０〜９８重量％であり且つ熱可塑性樹脂２０〜２重量％よりなり、好ましくは、植物セルロースが８５〜９５重量％であり且つ熱可塑性樹脂１５〜５重量％である。最も好ましい高濃度植物セルロース組成物の比率は、植物セルロース８７〜９２重量％であり且つ熱可塑性樹脂１３〜８重量％である。
高濃度植物セルロース組成物がゲル状の溶融体を形成し、撹拌時に高速撹拌機に負荷を与えてしまうことを考慮すると、植物セルロースが８０重量％以上であり、熱可塑性樹脂が２０重量％未満であることが好ましい。
撹拌中、植物セルロースが嵩高くなり効率的に処理できなくなることや、得られる高濃度植物セルロース組成物の流動性および成形性を考慮すると、植物セルロースが９８重量％以下且つ熱可塑性樹脂が２重量％以上であることが好ましい。
【００１７】
本発明で、高濃度植物セルロース組成物を高速で撹拌する手段として、高速撹拌機を用いる。本発明で用いる高速撹拌機は、高濃度植物セルロース組成物を高速で撹拌して混合でき且つこれを乾燥する際に発生する水蒸気等の揮発成分および揮発分が凝集した液体を系外に排出できるベント口などの排出機構を備えた装置である。
本発明で用いる高速撹拌機としては、ベント口などの排出機構を備えたヘンシェルミキサー、バンバリーミキサー、シユーラー、リボンブレンダー、パドルドライヤーなどが好ましく使用でき、その中でも、ヘンシェルミキサー、バンバリーミキサーが特に好ましく使用できる。
本発明では、高速撹拌機中で撹拌する際に発生するせん断力により高濃度植物セルロース組成物を加熱して乾燥する。
【００１８】
本発明では、熱水、スチーム、高温のオイルなどの熱媒を用いて高速撹拌機を加熱し、内部の高濃度植物セルロース組成物を加熱して乾燥することもできる。また、必要に応じて、高速撹拌機内を常圧、減圧または加圧にして、高濃度植物セルロース組成物を加熱して乾燥することができる。
本発明で、高濃度植物セルロース組成物を加熱する時の温度は、熱可塑性樹脂の融点以上で且つ２２０℃以下である。
【００１９】
本発明で、高濃度植物セルロース組成物を加熱する時の温度は、熱可塑性樹脂の融点＋１０℃以上で且つ２１０℃以下の温度までとすることが好ましい。
本発明では、高濃度植物セルロース組成物がゲル状の溶融物を形成しないため、加熱する時の温度が高いほど効率的に組成物を乾燥することができる。
本発明では、効率的に組成物を乾燥することを考慮すると、高濃度植物セルロース組成物を加熱する時の温度は、熱可塑性樹脂の融点以上であることが好ましい。また、植物性セルロースが熱分解することを考慮すると高濃度植物セルロース組成物を加熱する時の温度は、２２０℃以下であることが好ましい。
【００２０】
本発明の方法では、粉状の乾燥した高濃度植物セルロース組成物が得られ、そのまま、押出成形加工、射出成形加工の原料として使用することが可能である。
本発明では、高濃度植物セルロース組成物を撹拌して、加熱した後に、冷却し混合して成形材料として用いることが好ましい。
本発明では、高濃度植物セルロース組成物を撹拌して、加熱した高濃度植物セルロース組成物１００重量部に対して、熱可塑性樹脂１〜２００重量部添加することにより、効率的に冷却および混合でき且つゲル状の溶融物を形成しないため、好ましい方法として採用することができる。
【００２１】
本発明では、高濃度植物セルロース組成物を撹拌して、加熱した後に、冷却し混合する過程で、高濃度植物セルロース組成物１００重量部に対して、熱可塑性樹脂１〜２００重量部添加することにより、更に効率的に冷却できかつゲル状の溶融物を形成しないため、極めて好ましい方法として採用することができる。
本発明の高濃度植物セルロース組成物には、製造する際に、充填材を添加してもよく、充填材としてはタルク、炭酸カルシウムなどの粒子状無機充填材、ガラス繊維などの無機繊維状充填材、ポリエステル繊維などの有機繊維状充填材などを用いることができる。充填材の配合により、植物セルロース系粉体の分散性、成形体表面状態の変化などの効果も期待できる。充填材の配合量は、成形性及び機械的強度を考慮して決めることが好ましい。
【００２２】
本発明においては、前記各成分の他に必要に応じて、熱可塑性樹脂と植物セルロース系粉体との親和性を向上させるための変性剤、例えば不飽和カルボン酸あるいはその誘導体または不飽和カルボン酸あるいはその誘導体で変性したポリオレフィン系樹脂を好ましく使用することができる。
その他、着色剤、滑剤、安定剤、紫外線吸収剤、酸化防止剤、帯電防止剤などの各種添加剤を加えることができる。
本発明の高濃度植物セルロース組成物の成形方法としては、押出成形、射出成形、プレス成形等の従来公知の各種成形方法を用いることができる。
【００２３】
【実施例】
本発明を実施例に基づいて説明する。
以下、本発明を実施例に基づいてさらに詳細に説明する。尚、実施例中における「部」は、「重量部」を表す。
＜原料＞
実施例で用いた原料は以下の通りである。
尚、使用した熱可塑性樹脂の融点はＤＳＣ法で測定されたものである。
（Ａ）熱可塑性樹脂
熱可塑性樹脂ａ：旭化成（株）製、サンテックＨＤ（登録商標）
Ｊ３４０、融点１３０℃
熱可塑性樹脂ｂ：サンアロマー（株）製、サンアロマー（登録商標）
ＰＭ６００Ａ、融点１６７℃
（Ｂ）植物セルロース
植物セルロースａ：Ｊ．ＲＥＴＴＥＮＭＡＩＥＲ ＆ ＳＯＨＮＥ ＧｍｂＨ＆ Ｃｏ製、ＬＩＧＮＯＣＥＬ（登録商標） Ｐ ＳＵＰＥＲ
【００２４】
【実施例１】
（Ａ）成分として熱可塑性樹脂ａ１０ｋｇ、（Ｂ）成分として植物セルロースａ９０ｋｇを、冷却水を流通できるジャケットおよび揮発分を系外に排出するベント口を備えた５００Ｌヘンシェルミキサー（三井鉱山製）へ入れ、高速度で撹拌して内部温度を上昇した。内部温度が１００℃を越えるとベント口から揮発分が系外に排出され、内部温度が１７０℃に達すると揮発分の系外への排出が止まった。内部温度が２００℃に達した後、撹拌速度を低速にし且つジャケットに冷却水を流して高濃度植物セルロース熱可塑性樹脂組成物を冷却した。この時、ヘンシェルミキサー内部の高濃度植物セルロース組成物の形状を確認すると粉末状であった。この高濃度植物セルロース組成物を室温まで冷却し、排出口から排出した。高濃度植物セルロース組成物は円滑に排出できた。排出後に確認したところ、ヘンシェルミキサー内部に高濃度植物セルロース組成物の付着はなかった。
【００２５】
【実施例２】
実施例１と同様、（Ａ）成分として熱可塑性樹脂ａ１０ｋｇ、（Ｂ）成分として植物セルロースａ９０ｋｇを、５００Ｌヘンシェルミキサーへ入れ、高速度で撹拌して内部温度を加熱した。内部温度が２００℃までに達した後、撹拌速度を低速にし、冷却水を流して高濃度植物セルロース熱可塑性樹脂組成物を冷却した。内部温度が１８０℃になった時、撹拌速度を高速にし、ヘンシェルミキサー内に熱可塑性樹脂ａ２８．５７ｋｇを追加投入した。内部温度は１２０℃まで急激に低下した。撹拌速度を低速にし、内部温度が室温になるまで冷却を継続し、撹拌を停止した。ヘンシェルミキサー内部の植物セルロース組成物の形状を確認すると粉末状であった。この植物セルロース組成物を室温まで冷却し、排出口から排出した。植物セルロース組成物は円滑に排出できた。排出後に確認したところ、ヘンシェルミキサー内部に植物セルロース組成物の付着はなかった。
【００２６】
この植物セルロース組成物を１７５℃に設定したＰＣＭ３０型二軸押出機（池貝鉄鋼社製、３０ｍｍφ）により溶融混練した。問題なく溶融混練でき、良好なペレットが得られた。このペレットを射出成形（東芝機械社製、成形温度１９０℃、金型温度６０℃）し、ＩＳＯ規格準拠物性試験サンプルを作成した。得られた試験サンプルを用いて曲げ弾性率、シャルピー衝撃強さを測定すると、曲げ弾性率は、５，３００ＭＰａ、シャルピー衝撃強度は、２００Ｊ／ｍであった。
【００２７】
【比較例１】
実施例１で（Ａ）成分３０部、（Ｂ）成分７０部を、実施例１のヘンシェルミキサーにいれ、高速度で撹拌して内部を加熱した。内部温度が１００℃を超えるとベント口から揮発分の揮発が始まり、約１７０℃で揮発が停止した。また、内部温度が約１４０℃になると異音が発生した。内部を観察すると溶融した植物セルロース組成物の塊がゲル状態を形成していた。この時、電流計が規定値付近まで上昇したため、ヘンシェルミキサー回転速度を低速に変更し、電流計の値が許容値に入っていることを確認しながら撹拌を継続した。内部温度が２００℃に達した時点で内部を確認したところ、溶融した植物セルロース組成物の塊がゲル状態を形成して且つヘンシェルミキサーの内部部品に付着いている状態が確認できた。ジャケットに冷却水を流し、この植物セルロース組成物を冷却した。内部温度が約１２０℃に達した時に異音が発生し、その直後に電流計が規定値を超えたため、安全装置が作動してヘンシェルミキサーが停止した。内部を観察すると固化した植物セルロース組成物の塊が確認できた。撹拌を継続することは困難であると判断し、撹拌せずに、ジャケットに冷却水を２時間流し続け、内部温度を室温まで下げた。
【００２８】
排出口を開放したところ、一部の植物セルロース組成物が排出されたが、大部分の植物セルロース組成物はヘンシェルミキサーの内部部品に固着し、排出できなかった。固着したものをハンマー等用いて排出し、粉砕機を用いて１０ｍｍ以下に粉砕した。
この高濃度植物セルロース組成物を実施例２と同様の方法で溶融混練した。問題なく溶融混練でき、良好なペレットが得られた。次に実施例２同様に物性試験サンプルを作成し、曲げ弾性率、シャルピー衝撃強さをそれぞれ評価した。得られた試験サンプルを用いて曲げ弾性率、シャルピー衝撃強さを測定すると、曲げ弾性率は、５，１００ＭＰａ、シャルピー衝撃強度は、１９０Ｊ／ｍであった。
【００２９】
【実施例３】
実施例１と同様の方法で、（Ａ）成分として熱可塑性樹脂ｂ１５ｋｇ、（Ｂ）成分として植物セルロースａ８５ｋｇを、５００Ｌヘンシェルミキサーへ入れ、高速度で撹拌して内部温度を加熱した。内部温度が２００℃までに達した後、撹拌速度を低速にし、冷却水を流して高濃度植物セルロース熱可塑性樹脂組成物を冷却した。内部温度が室温になるまで冷却を継続し、撹拌を停止した。ヘンシェルミキサー内部の高濃度植物セルロース組成物の形状を確認すると粉末状であった。この高濃度植物セルロース組成物を室温まで冷却し、排出口から排出した。高濃度植物セルロース組成物は円滑に排出できた。排出後に確認したところ、ヘンシェルミキサー内部に高濃度植物セルロース組成物の付着はなかった。
【００３０】
【発明の効果】
本発明により、効果的に高濃度植物セルロース組成物を乾燥でき、かつ、ゲル状の組成物の発生を抑制できる。また、本発明で得られる高濃度植物セルロース組成物は冷却後に粉砕せずに、そのまま押出成形加工、射出成形加工の原料として用いることができ、得られた成形体は従来法で得たものと同等の物性を示す。即ち、本発明は、混合機に大きな付加を及ぼさず、かつ、冷却後に組成物を粉砕する必要のない、合理的な高濃度植物セルロース組成物の製法である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing and adjusting a high-concentration plant cellulose composition.
[0002]
[Prior art]
BACKGROUND ART Conventionally, various developments of a plant cellulose thermoplastic resin composition and a molded article composed of a vegetable cellulose thermoplastic resin composition have been carried out, and many vegetable cellulose thermoplastic resin compositions and molded articles composed of the composition are known. . (For example, refer to Patent Documents 1 to 11.)
It also discloses a method for preparing and manufacturing a vegetable cellulose thermoplastic resin composition. (For example, refer to Patent Documents 11 to 17.)
The adjusting method and the manufacturing method disclosed above use a high-speed mixer such as a Banbury mixer or a Henschel mixer, and stir the raw material at high speed.The shear force generated at this time causes the raw material to reach a temperature higher than the melting point of the thermoplastic resin. This is a method for producing a vegetable cellulose thermoplastic resin composition by heating the mixture to remove volatile components such as water in the composition, particularly in the vegetable cellulose, and melting the raw materials.
[0003]
According to the above-mentioned preparation method and production method, the molten vegetable cellulose thermoplastic resin composition becomes a very high-viscosity gel-like substance, and when it is cooled, it becomes a lump. Since the gelled vegetable cellulose thermoplastic tree composition produced at the time of melting is a very high-viscosity melt, a large stress is generated during stirring, and exerts a large addition to the mixer. In addition, in order to use the plant cellulose thermoplastic tree composition obtained by the above-mentioned adjustment method and manufacturing method for extrusion molding and injection molding, it is necessary to pulverize a lump composition formed after cooling, and There were problems with the properties and production facilities.
Therefore, the disclosed technology related to the conventional preparation method and the production method has a problem in the effect on the durability of the production equipment and productivity, and has not yet been widely deployed as a production method and a preparation method of the plant cellulose thermoplastic tree composition. .
[0004]
[Patent Document 1]
JP-A-55-131031 [Patent Document 2]
Japanese Patent Application Laid-Open No. 57-11537 [Patent Document 3]
JP-A-62-39642 [Patent Document 4]
JP 2000-316352 A [Patent Document 5]
JP-A-57-185351 [Patent Document 6]
JP-A-11-269316 [Patent Document 7]
JP-A-11-43562 [Patent Document 8]
Japanese Patent Application Laid-Open No. 9-286880 [Patent Document 9]
Japanese Patent Application Laid-Open No. 2000-38467 [Patent Document 10]
Japanese Patent Application Laid-Open No. 2000-271909 [Patent Document 11]
Japanese Patent Application Laid-Open No. 2002-11816 [Patent Document 12]
JP-A-60-30304 [Patent Document 13]
Japanese Patent Publication No. 4-48606 [Patent Document 14]
JP-A-8-216122 [Patent Document 15]
JP-A-8-310147 [Patent Document 16]
JP-A-8-323710 [Patent Document 17]
JP 2000-109566 A
[Problems to be solved by the invention]
In view of the above conventional problems, an object of the present invention is to provide a method for efficiently producing a vegetable cellulose composition without giving a large addition to a mixer and without having to grind the composition after cooling. .
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, when producing a high-concentration plant cellulose composition comprising a specific ratio of plant cellulose and a thermoplastic resin, the melting point of the thermoplastic resin or more 220 ℃ It has been found that by stirring the mixture so as to be in the following temperature range, generation of a gel-like composition can be suppressed, and the high-concentration plant cellulose composition can be dried efficiently.
[0007]
Furthermore, they have found that the high-concentration plant cellulose composition obtained by this method can be used as it is as a raw material for extrusion molding and injection molding without pulverization after cooling, and the present invention has been accomplished.
That is, the present invention is as follows.
1. When producing a high-concentration vegetable cellulose composition consisting of 80 to 98% by weight of vegetable cellulose and 20 to 2% by weight of thermoplastic resin, the mixture is stirred so as to be in a temperature range from the melting point of the thermoplastic resin to 220 ° C or less. A method for producing a high-concentration plant cellulose composition, comprising:
[0008]
2. When producing a high-concentration vegetable cellulose composition comprising 85 to 95% by weight of vegetable cellulose and 15 to 5% by weight of a thermoplastic resin, the temperature range is from 10 ° C higher than the melting point of the thermoplastic resin to 210 ° C or less. 2. The method for producing a high-concentration vegetable cellulose composition according to the above item 1, wherein the mixture is stirred.
3. 3. The method for producing a high-concentration plant cellulose composition according to 1 or 2, wherein the high-concentration plant cellulose composition is stirred, heated, cooled and mixed.
[0009]
4. The high-concentration plant cellulose composition is agitated, and the thermoplastic resin is added in an amount of 1 to 200 parts by weight based on 100 parts by weight of the heated high-concentration plant cellulose composition, and the mixture is cooled and mixed. The method for producing a plant cellulose composition according to any one of the above.
5. In the process of stirring and heating, then cooling and mixing the high-concentration plant cellulose composition, 100 to 100 parts by weight of the high-concentration plant cellulose composition is added with 1 to 200 parts by weight of a thermoplastic resin and cooled. The method for producing a plant cellulose composition according to any one of the above 1 to 3.
[0010]
6. The method for producing a high-concentration plant cellulose composition and the plant cellulose composition according to any one of the above 1 to 5, wherein the thermoplastic resin is polyethylene and / or polypropylene.
7. 7. The method for producing a plant cellulose composition according to any one of the above items 1 to 6, wherein the polyethylene has a melt index of 0.01 to 25.0.
8. A molded article obtained by the method according to any one of the above 1 to 7.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be specifically described below.
The method for producing a high-concentration plant cellulose composition of the present invention comprises the steps of: producing a high-concentration plant cellulose composition comprising 80 to 98% by weight of plant cellulose and 20 to 2% by weight of a thermoplastic resin; A method for producing a high-concentration plant cellulose composition, which comprises stirring the mixture to a temperature within a range of 220 ° C. or lower.
[0012]
The thermoplastic resin used in the present invention is a chlorine-free thermoplastic resin, and is preferably a polyolefin resin.
Since the polyolefin resin is a resin having strong hydrophobicity, it can be preferably used because it effectively dries the plant cellulose thermoplastic tree composition.
As the polyolefin-based resin, polypropylene, ethylene-propylene copolymer, polyethylene and the like can be used.
[0013]
Among them, polyethylene is particularly preferable from the viewpoint of suppressing the generation of a gel composition. Polyethylene is polymerized using new catalysts such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and α-olefins having 3 to 12 carbon atoms, and various metallocene catalysts recently developed. Ethylene polymers and mixtures thereof can be used. Also, mixtures of polyethylene and other resins such as polypropylene and / or polystyrene can be used. In addition, polyethylene resins obtained by recycling various polyethylene resin products can also be used as a material having a good cost / performance balance.
[0014]
Further, the melt index of polyethylene is preferably in the range of 0.01 to 25.0, and most preferably in the range of 0.05 to 3.0. The value of the melt index is preferably 0.01 or more from the viewpoint of moldability of the vegetable cellulose thermoplastic resin composition, and 25.0 from the viewpoint of mechanical strength and shape stability during molding of the vegetable cellulose thermoplastic resin composition. The following is preferred. Further, a method of blending polyethylene having different molecular weights can be used in order to keep the melt index of polyethylene within a preferable range. Further, a method of blending polyethylene having different molecular weights can be used in order to keep the melt index of polyethylene within a preferable range.
[0015]
The plant cellulosic powder used in the present invention may be any, for example, wood flour, pulp, bacas, kenaf, sawdust, wood fiber, chaff, crushed chip material, fruit husk powder, waste paper, bamboo powder And beer pomace and coffee pomace, and these can be used alone or in combination of two or more.
The vegetable cellulosic powder can be appropriately selected depending on the intended use, but wood flour is preferred in view of mechanical strength and workability such as nailing and screwing. These plant cellulosic powders are preferably used in the form of sawdust, waste wood or the like, if necessary, obtained by dry or wet pulverization or sieving to obtain particles having a particle size of 0.1 mm to 10 mm. The particle size of the plant cellulosic powder is preferably 1 mm or more in view of problems such as powdering and the cost of labor for grinding and sieving. Further, in consideration of the mechanical strength of the obtained molded body, it is preferably 10 mm or less. The shape of the plant cellulosic powder may be not only a particle shape but also a flat shape, an irregular shape and a mixture thereof.
[0016]
The proportion of the high-concentration vegetable cellulose composition of the present invention is 80 to 98% by weight of vegetable cellulose and 20 to 2% by weight of thermoplastic resin, preferably 85 to 95% by weight of vegetable cellulose and thermoplastic. Resin is 15 to 5% by weight. The most preferred high-concentration vegetable cellulose composition ratio is 87-92% by weight of vegetable cellulose and 13-8% by weight of thermoplastic resin.
Considering that the high-concentration vegetable cellulose composition forms a gel-like melt and gives a load to the high-speed stirrer during stirring, the vegetable cellulose is at least 80% by weight and the thermoplastic resin is less than 20% by weight. It is preferable that
In consideration of the fact that the vegetable cellulose becomes bulky and cannot be efficiently treated during the stirring, and that the fluidity and moldability of the resulting high-concentration vegetable cellulose composition are taken into account, the vegetable cellulose is 98% by weight or less and the thermoplastic resin is 2% by weight. % Is preferable.
[0017]
In the present invention, a high-speed stirrer is used as means for stirring the high-concentration plant cellulose composition at high speed. The high-speed stirrer used in the present invention can stir and mix a high-concentration plant cellulose composition at high speed, and can discharge a volatile component such as water vapor generated when drying the same and a liquid in which volatile components are aggregated out of the system. It is a device provided with a discharge mechanism such as a vent port.
As the high-speed stirrer used in the present invention, a Henschel mixer, a Banbury mixer, a Schuller, a ribbon blender, a paddle dryer and the like having a discharge mechanism such as a vent port can be preferably used, and among them, a Henschel mixer and a Banbury mixer are particularly preferably used. it can.
In the present invention, the high-concentration plant cellulose composition is heated and dried by the shear force generated when stirring in a high-speed stirrer.
[0018]
In the present invention, the high-speed stirrer can be heated using a heat medium such as hot water, steam, or high-temperature oil to heat and dry the internal high-concentration plant cellulose composition. Further, if necessary, the high-concentration plant cellulose composition can be dried by heating the high-speed stirrer to normal pressure, reduced pressure or increased pressure.
In the present invention, the temperature at which the high-concentration plant cellulose composition is heated is not lower than the melting point of the thermoplastic resin and not higher than 220 ° C.
[0019]
In the present invention, the temperature at which the high-concentration plant cellulose composition is heated is preferably set to a temperature not lower than the melting point of the thermoplastic resin plus 10 ° C. and not higher than 210 ° C.
In the present invention, since the high-concentration plant cellulose composition does not form a gelled melt, the higher the heating temperature, the more efficiently the composition can be dried.
In the present invention, in consideration of efficient drying of the composition, the temperature at which the high-concentration plant cellulose composition is heated is preferably equal to or higher than the melting point of the thermoplastic resin. In consideration of the fact that the vegetable cellulose is thermally decomposed, the temperature at which the high-concentration vegetable cellulose composition is heated is preferably 220 ° C. or lower.
[0020]
According to the method of the present invention, a powdery dried high-concentration plant cellulose composition is obtained, and can be used as it is as a raw material for extrusion molding and injection molding.
In the present invention, it is preferable that the high-concentration plant cellulose composition is stirred, heated, cooled, mixed, and used as a molding material.
In the present invention, the high-concentration plant cellulose composition is agitated, and can be efficiently cooled and mixed by adding 1 to 200 parts by weight of the thermoplastic resin to 100 parts by weight of the heated high-concentration plant cellulose composition. Further, since a gel-like melt is not formed, it can be adopted as a preferable method.
[0021]
In the present invention, the high-concentration plant cellulose composition is stirred, heated, then cooled and mixed, and the thermoplastic resin is added in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the high-concentration plant cellulose composition. Thereby, it is possible to employ a highly preferable method since cooling can be performed more efficiently and a gel-like melt is not formed.
In the high-concentration plant cellulose composition of the present invention, a filler may be added at the time of production, and as the filler, talc, a particulate inorganic filler such as calcium carbonate, and an inorganic fibrous filler such as glass fiber. Materials, organic fibrous fillers such as polyester fibers and the like can be used. By blending the filler, effects such as dispersibility of the plant cellulosic powder and changes in the surface state of the molded product can be expected. The amount of the filler is preferably determined in consideration of moldability and mechanical strength.
[0022]
In the present invention, in addition to the above components, if necessary, a modifier for improving the affinity between the thermoplastic resin and the plant cellulosic powder, for example, an unsaturated carboxylic acid or a derivative thereof or an unsaturated carboxylic acid Alternatively, a polyolefin resin modified with a derivative thereof can be preferably used.
In addition, various additives such as a coloring agent, a lubricant, a stabilizer, an ultraviolet absorber, an antioxidant, and an antistatic agent can be added.
As a molding method of the high-concentration plant cellulose composition of the present invention, various conventionally known molding methods such as extrusion molding, injection molding, and press molding can be used.
[0023]
【Example】
The present invention will be described based on examples.
Hereinafter, the present invention will be described in more detail based on examples. In the examples, “parts” means “parts by weight”.
<Raw materials>
The raw materials used in the examples are as follows.
The melting point of the used thermoplastic resin was measured by a DSC method.
(A) Thermoplastic resin Thermoplastic resin a: Suntech HD (registered trademark) manufactured by Asahi Kasei Corporation
J340, melting point 130 ° C
Thermoplastic resin b: manufactured by Sun Allomer Co., Ltd., Sun Allomer (registered trademark)
PM600A, melting point 167 ° C
(B) Plant cellulose Plant cellulose a: LIGHTNOCEL (registered trademark) P SUPER made by RETTENMAER & SOHNE GmbH & Co
[0024]
Embodiment 1
10 kg of thermoplastic resin a as the component (A) and 90 kg of vegetable cellulose a as the component (B) are put into a 500 L Henschel mixer (manufactured by Mitsui Mining) equipped with a jacket through which cooling water can flow and a vent port for discharging volatiles out of the system. The internal temperature was increased by stirring at high speed. When the internal temperature exceeded 100 ° C., volatiles were discharged from the vent port to the outside of the system, and when the internal temperature reached 170 ° C., the discharge of volatiles to the system stopped. After the internal temperature reached 200 ° C., the stirring speed was reduced and cooling water was flowed through the jacket to cool the high-concentration vegetable cellulose thermoplastic resin composition. At this time, the shape of the high-concentration plant cellulose composition inside the Henschel mixer was confirmed to be powder. The high-concentration plant cellulose composition was cooled to room temperature and discharged from the outlet. The high-concentration plant cellulose composition could be discharged smoothly. When confirmed after discharge, there was no adhesion of the high-concentration plant cellulose composition inside the Henschel mixer.
[0025]
Embodiment 2
As in Example 1, 10 kg of the thermoplastic resin a as the component (A) and 90 kg of vegetable cellulose a as the component (B) were placed in a 500 L Henschel mixer and stirred at a high speed to heat the internal temperature. After the internal temperature reached 200 ° C., the stirring speed was reduced and cooling water was flown to cool the high-concentration vegetable cellulose thermoplastic resin composition. When the internal temperature reached 180 ° C., the stirring speed was increased, and 28.57 kg of the thermoplastic resin a was additionally charged into the Henschel mixer. The internal temperature dropped sharply to 120 ° C. The stirring speed was reduced, the cooling was continued until the internal temperature reached room temperature, and the stirring was stopped. The shape of the plant cellulose composition inside the Henschel mixer was confirmed to be powder. The plant cellulose composition was cooled to room temperature and discharged from the outlet. The plant cellulose composition could be discharged smoothly. When confirmed after discharge, there was no adhesion of the vegetable cellulose composition inside the Henschel mixer.
[0026]
This plant cellulose composition was melt-kneaded with a PCM30 type twin screw extruder (30 mmφ, manufactured by Ikegai Iron & Steel) set at 175 ° C. Melt kneading was possible without any problem, and good pellets were obtained. The pellets were injection-molded (manufactured by Toshiba Machine Co., molding temperature 190 ° C., mold temperature 60 ° C.) to prepare a sample of a physical property test conforming to the ISO standard. When the flexural modulus and the Charpy impact strength were measured using the obtained test sample, the flexural modulus was 5,300 MPa and the Charpy impact strength was 200 J / m.
[0027]
[Comparative Example 1]
In Example 1, 30 parts of the component (A) and 70 parts of the component (B) were placed in the Henschel mixer of Example 1, and stirred at a high speed to heat the inside. When the internal temperature exceeded 100 ° C., volatilization of volatile components started from the vent port, and stopped at about 170 ° C. Further, when the internal temperature reached about 140 ° C., abnormal noise occurred. When the inside was observed, the lump of the melted vegetable cellulose composition formed a gel state. At this time, the rotation of the Henschel mixer was changed to a low speed because the ammeter rose to near the specified value, and stirring was continued while confirming that the value of the ammeter was within the allowable value. When the inside temperature reached 200 ° C., the inside was confirmed. As a result, a state was confirmed in which the mass of the melted vegetable cellulose composition formed a gel state and adhered to the internal parts of the Henschel mixer. Cooling water was flowed through the jacket to cool the plant cellulose composition. When the internal temperature reached about 120 ° C., an abnormal noise was generated. Immediately after that, the ammeter exceeded the specified value, and the safety device was activated to stop the Henschel mixer. When the inside was observed, a lump of the solidified plant cellulose composition was confirmed. It was judged that it was difficult to continue stirring, and without stirring, cooling water was continuously flowed through the jacket for 2 hours to lower the internal temperature to room temperature.
[0028]
When the outlet was opened, a part of the plant cellulose composition was discharged, but most of the plant cellulose composition adhered to the internal parts of the Henschel mixer and could not be discharged. The adhered matter was discharged using a hammer or the like, and crushed to 10 mm or less using a crusher.
This high-concentration plant cellulose composition was melt-kneaded in the same manner as in Example 2. Melt kneading was possible without any problem, and good pellets were obtained. Next, a physical property test sample was prepared in the same manner as in Example 2, and the flexural modulus and the Charpy impact strength were evaluated. When the flexural modulus and the Charpy impact strength were measured using the obtained test sample, the flexural modulus was 5,100 MPa and the Charpy impact strength was 190 J / m.
[0029]
Embodiment 3
In the same manner as in Example 1, 15 kg of the thermoplastic resin b as the component (A) and 85 kg of vegetable cellulose a as the component (B) were charged into a 500 L Henschel mixer, and stirred at a high speed to heat the internal temperature. After the internal temperature reached 200 ° C., the stirring speed was reduced and cooling water was flown to cool the high-concentration vegetable cellulose thermoplastic resin composition. Cooling was continued until the internal temperature reached room temperature, and stirring was stopped. The shape of the high-concentration plant cellulose composition inside the Henschel mixer was confirmed to be powder. The high-concentration plant cellulose composition was cooled to room temperature and discharged from the outlet. The high-concentration plant cellulose composition could be discharged smoothly. When confirmed after discharge, there was no adhesion of the high-concentration plant cellulose composition inside the Henschel mixer.
[0030]
【The invention's effect】
According to the present invention, a high-concentration plant cellulose composition can be effectively dried, and generation of a gel composition can be suppressed. In addition, the high-concentration plant cellulose composition obtained in the present invention can be used as it is as a raw material for extrusion molding and injection molding without pulverization after cooling, and the obtained molded article is the same as that obtained by the conventional method. Shows equivalent physical properties. That is, the present invention is a method for producing a reasonable high-concentration plant cellulose composition that does not significantly add to the mixer and does not require grinding the composition after cooling.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003073048A JP2004277622A (en) | 2003-03-18 | 2003-03-18 | Method for producing high-concentration vegetable cellulose composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003073048A JP2004277622A (en) | 2003-03-18 | 2003-03-18 | Method for producing high-concentration vegetable cellulose composition |
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| JP2004277622A true JP2004277622A (en) | 2004-10-07 |
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| JP2003073048A Withdrawn JP2004277622A (en) | 2003-03-18 | 2003-03-18 | Method for producing high-concentration vegetable cellulose composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008110956A (en) * | 2006-10-05 | 2008-05-15 | M & F Technology Co Ltd | Method for producing molded article containing medicinal component, medicinal component-containing molded article, molded article, method for producing thermoplastic resin and the thermoplastic resin |
| WO2009054262A1 (en) * | 2007-10-26 | 2009-04-30 | Toyota Boshoku Kabushiki Kaisha | Process for producing thermoplastic resin composition and process for producing molded thermoplastic resin |
-
2003
- 2003-03-18 JP JP2003073048A patent/JP2004277622A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008110956A (en) * | 2006-10-05 | 2008-05-15 | M & F Technology Co Ltd | Method for producing molded article containing medicinal component, medicinal component-containing molded article, molded article, method for producing thermoplastic resin and the thermoplastic resin |
| WO2009054262A1 (en) * | 2007-10-26 | 2009-04-30 | Toyota Boshoku Kabushiki Kaisha | Process for producing thermoplastic resin composition and process for producing molded thermoplastic resin |
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