JP3648803B2 - Manufacturing method of resin composite material - Google Patents

Description

【００５９】
また、表１において、ＬＣ３０００−ＱＢ５４０とＬＣ３０００−Ｐ４２０１とを比較すると、後者の方が、より少ない量で、成形品強度がより高い複合材が得られることが分かる。一方、このＬＣ３０００−Ｐ４２０１とＬＣ３０００−９０００Ｍとを比較すると、後者の方が、最適添加量が少ないにもかかわらず、成形品強度は低かった。これは、上述の混合比の最適化が十分でなかったことに起因していると推察することができる。
従って、相溶化剤の性能としては、次の順であると考えられる。
ＬＣ３０００-９０００Ｍ>ＬＣ３０００-Ｐ４２０１>ＬＣ３０００-ＱＢ５４０
ここで、ＬＣ３０００−９０００Ｍは、上記３種類の相溶化剤のうちで、最もＰＰとの相溶性に劣る相溶化剤である。上記の試験結果と併せて考えると、３種類ともにＰＰとの相溶性は十分であり、この３種類の相溶化剤の性能を最も大きく左右するのは、ＬＣＰとの相溶性（相溶化剤分子中のＬＣ３０００の量）であると考えられる。
【００６０】
尚、一般に、長繊維で補強された複合材を射出成形すると、相間の接着力が十分な場合であっても、繊維状補強相の配向の乱れや該補強相の短繊維化などの影響により、強度が低下することが知られている。
そして、相間の接着が十分であると仮定した場合、成形品の強度は、次の式で表すことができるとされている。
射出成形品＝（配向の影響）＊（短繊維化による影響）
＊長繊維で補強された複合材
この（配向の影響）＊（短繊維化による影響）の値は、種々バラツキはあるが、一般に、０.３〜０.５の範囲である。
今回調査したＬＣＰ複合材の場合、成形品強度が最大のときで７４［ＭＰａ］、成形前のストランドの強度は１４４［ＭＰａ］であった。従って、成形によって強度は約半分（０.５１）に低下したことになる。この０.５１という係数は、「相間が十分に接着している」という仮定に基づく値の上限値と同等であるので、上記相溶化剤は、この材料系に対して、十分な接着力を与えていると考えることができる。
【００６１】
低融点の液晶ポリマーと無水マレイン酸変性ＰＰとを反応させ生成された相溶化剤を用いて複合材を製造する場合、相溶化剤と複合材とで調製温度が異なるため、通常であれば工程を分ける必要がある。
ところが、押出機は一般に上流側と下流側とで設定温度を変えることができ、この機能を利用することにより、相溶化剤の調製と複合材の調製とを一つの工程で行うようにすることができる。
以下、この相溶化剤と複合材とを一工程で調製するようにした、本発明の他の実施の形態に係る製造方法について説明する。 図１６に示すように、この製造方法に適用される押出機３０は、前述の製造方法で用いられたものと同一の構造を備えている。
【００６２】
すなわち、上記押出機３は、中空円筒状の本体３１内に２本の回転スクリュー３２を収納して成り、上記本体３１には各々二つのホッパ３３Ａ，３３Ｂが設けられている。また、具体的には図示しなかったが、本体３１には、その内部を所望の温度に加熱する加熱手段が付設されている。尚、この加熱手段は、上流側と下流側とを別々に温度設定できるように構成されている。
そして、この加熱手段によって本体３１（バレル）内を所定温度に保った状態で、上記ホッパ３３Ａ，３３Ｂから本体３１内へそれぞれ調製材料を投入して回転スクリュー３２，３２を所定の回転数で回転させることにより、投入された材料が、可塑化溶融して混練されながら、本体３１の下流側端末に設けられた押出ノズル３４から、例えばフィルム状あるいはストランド状に押し出される。そして、この押し出された押出物は、ローラ３５の回転によって引き取られ、所定の延伸比で延伸された上で、カッタ３６により所定長さに切り揃えられるようになっている。
【００６３】
本実施の形態では、上流側（上流側ホッパ３３Ａと下流側ホッパ３３Ｂの間の領域：相溶化剤調製領域）のバレル温度を相溶化剤の調製温度に設定する一方、下流側（下流側ホッパ３３Ｂと押出ノズル３４の間の領域：複合材調製領域）のバレル温度をＬＣＰ複合材の調製温度に設定した上で、上流側ホッパ３３Ａ（メインフィーダ）から相溶化剤の原料を投入し、下流側ホッパ３３Ｂ（サイドフィーダ）からＬＣＰ複合材の原料を投入するようにしている。
【００６４】
上記の製造方法を適用する場合、相溶化剤調製工程においては、相溶化剤原料間の反応を良好に進行させるためには、相溶化剤調製領域の長さを一定とした場合、材料供給速度Ｖａをある上限値以下に抑制する必要がある。
また、複合材調製工程においては、複合材の強度を高めるためには、一定量以上の剪断および延伸を加える必要がある。この剪断および延伸は、押出機３０のダイ出口径ｄ，ペレタイザー（ローラ３５）の引き取り速度ｋ，材料供給速度Ｖａ，Ｖｂを用いて、以下の式で表される。
剪断＝（３２／π）・（１／ｄ^３）・（Ｖａ＋Ｖｂ） …＜式１＞
延伸＝（π／４）・ｄ^２・ｋ・１／（Ｖａ＋Ｖｂ） …＜式２＞
ここで、押出機３０のダイ出口径ｄおよびペレタイザーの引き取り速度ｋが、装置３０によって定まると、複合材に必要な剪断から（Ｖａ＋Ｖｂ）の下限値が、また、複合材に必要な延伸から（Ｖａ＋Ｖｂ）の上限値が、それぞれ決まることになる。
【００６５】
更に、相溶化剤調製工程および複合材調製工程の両方に関係する制約として、複合材に対する相溶化剤の添加割合があり、それに応じて、Ｖａ／Ｖｂの値が定まる。なお、一般には、Ｖａ／Ｖｂは０.１以下の値が用いられる。
また、更に、上述の材料特性による制約とは別に、装置１０に起因する制約として、ブローアップ及びフィーダの供給能力がある。ブローアップとは、フィーダから落下した材料がスクリューに噛み込まず、材料供給孔に堆積する現象を言い、スクリュー形状と材料供給速度Ｖａ，Ｖｂによって回避することが可能である。フィーダの供給能力のうち、材料供給速度Ｖａ，Ｖｂの上限を規制するものに、モータ回転数による供給能力の限界があり、一方、下限を規制するものに、モータ低回転域に見られる材料の安定供給限界がある。
【００６６】
材料供給速度Ｖａ，Ｖｂに対する以上の制約条件をまとめると、下記のようになる。
＜１＞ 上流側（相溶化剤調製工程）での材料供給速度Ｖａ
・上限：延伸／ブローアップ／フィーダ供給能力
・下限：剪断／フィーダ安定供給限界
＜２＞ 下流側（複合材調製工程）での材料供給速度Ｖｂ
・上限：反応時間／ブローアップ／フィーダ供給能力
・下限：フィーダ安定供給限界
従って、本実施の形態に係る製造方法を適用する場合には、この材料供給速度Ｖａ，Ｖｂを適正に定めて行う必要がある。
【００６７】
以上の検討結果を、実機（押出機３０）を用いて次のようにして検証した。
この検証の条件は以下のように設定した。
＜１＞ 材料
・ 補強相（ＬＣＰ）：ベクトラＡ９５０
・ 連続相（ＰＰ） ：住友ノーブレンＨ５０１
・ 相溶化剤原料
：無水マレイン酸変性ＰＰ(日石ＮポリマーＰ４２０１)
：低融点の液晶ポリマー（ロッドランＬＣ３０００）
＜２＞ 配合比
上記材料の配合比は、射出成形品の強度が最大値を示す配合比（図１５参照）に設定した。
・ 相溶化剤：低融点の液晶ポリマー／無水マレイン酸変性ＰＰ＝１／１
・ 複合材：ＰＰ／ＬＣＰ／相溶化剤＝７０／３０／１０
【００６８】
上記の配合比で調製を行う場合、複合材調製工程での材料供給速度Ｖｂは、相溶化剤調製工程での材料供給速度Ｖａに対して１０倍必要であるので、Ｖｂの値は高い方が好ましい。従って、まず、Ｖｂの上限値を求めた。
Ｖｂの上限値の制約条件のうち、材料特性に起因する制約である「延伸」は、引き取り速度（Ｄｒａｗ ｒａｔｉｏ）ｋを装置の最大値に設定した場合、上記＜式１＞及び＜式２＞に基づいて、剪断およびダイ径ｄと図１８に示すような関係にある。また、Ｖｂは、ダイ径ｄが大きいほど、高く設定できる。そして、複合材が強度を発現できる条件として、剪断＞１８００／ｓ，延伸＞１２を仮定して設定し、複合材の調製条件を、ダイ径＝２ｍｍ，剪断＝１８００／ｓ，延伸＝１２に仮設定した。
【００６９】
続いて、この仮設定条件が残りの条件を満たすか否かを検証した。
複合材調製工程における装置に起因する制約は、実際に材料を投入し、その条件で材料投入が可能であることを確認した。
相溶化剤調製工程における下限である「フィーダ安定供給限界」は、押出機に、着色粒状の所謂カラーマスタと無色のＰＰペレットとを混ぜ合わせたものを投入し、仮設定条件から導いた材料供給速度Ｖａで流すという手法で確認した。相溶化剤調製工程後の材料の色が均一であったことから、設定したＶａで材料が安定して供給されていることが分かった。
【００７０】
また、相溶化剤調製工程における上限である「相溶化剤反応時間」については、材料が相溶化剤調製領域を通過する時間を、カラーマスタを用いて測定することによって確認した。その結果、上記仮設定から導いた材料供給速度Ｖａでの通過時間は、射出成形品の強度が最大値を示す試験条件における場合よりも長いことが分かった。従って、仮設定の条件で、相溶化剤の反応は十分に進行すると言える。
以上より、上記の仮設定条件は、Ｖａ，Ｖｂの制約条件を全て満たしていると考えられる。従って、押出機の上流側で相溶化剤を調製し、下流側で複合材を調製するプロセスの検証条件としては、上記仮設定条件を用いる。
【００７１】
次に、上記プロセスにより製造した複合材の強度を評価する試験を行った。
試験条件を以下に示す。
・ 押出機
：同方向回転２軸混練機（ＢＴ-３０-Ｓ２：プラスチック工業研究所製）
− 径３０ｍｍ，Ｌ／Ｄ＝３６
・ 押出機運転条件
− バレル温度：２００℃（相溶化剤調製領域）
：２９０℃（複合材調製領域）
− 剪断速度：１８００／ｓｅｃ.
− スクリュー回転数：１５０ｒｐｍ
− ダイ径：２ｍｍ
− 延伸比：１２
− 以上の条件で、押出機先端に取り付けたダイを用いてストランド状の押
出物を押し出し、ダイ出口から５０〜１００ｍｍに位置した水浴で冷却し
た。
【００７２】
また、上記プロセスと比較する試験を併せて行った。この場合の比較試験としては、図１７に示すように、２台の押出機４０，５０を用意し、一方の押出機４０で相溶化剤を調製し、他方の押出機５０で複合材を調製した。この場合、相溶化剤調製工程では材料をメインフィーダ４３Ａから投入し、複合材調製工程では材料をサイドフィーダ５３Ｂから投入するようにした。
試験条件を以下に示す。
＜１＞ 相溶化剤の調製条件
・材料配合
：低融点の液晶ポリマー／無水マレイン酸変性ＰＰ＝１／１
・ 押出機
：同方向回転２軸混練機（ＢＴ-３０-Ｓ２：プラスチック工業研究所製）
− 径３０ｍｍ，Ｌ／Ｄ＝３６
・ 押出機運転条件
− バレル温度：２００℃
− 剪断速度：７００／ｓｅｃ.
− スクリュー回転数：１５０ｒｐｍ
− ダイ径：２ｍｍ
− 以上の条件で、押出機先端に取り付けたダイを用いてストランド状の押
出物を押し出し、ダイ出口から５０〜１００ｍｍに位置した水浴で冷却し
た。
＜３＞ 複合材の調製条件
・材料配合：ＰＰ／ＬＣＰ／相溶化剤＝７０／３０／１０
尚、押出機およびその運転条件は、上述の試験と同様とした。
【００７３】
そして、得られた複合材を用いて射出成形を行い、成形品の強度を比較した。射出成形の条件および強度測定条件は、以下の通りであった。
＜４＞ 成形条件（射出成形）
・ 成形機
：射出成形機（ＩＳ−２２０ＥＮ−５Ｙ：東芝機械株式会社製）
・ 成形機運転条件
− バレル温度：１８０℃
− スクリュー形状：ＤＢＹ
− スクリュー回転数：１０〜１２ｒｐｍ
− 背圧：２ｋｇｆ／ｃｍ^２
− 射出圧：９９％
− 射出速度：３０％
− 型温：５０℃
＜５＞ 強度測定条件
・測定装置
万能試験機（オートグラフＤＳＳ−５０００：株式会社島津製作所製）
・測定条件
引張速度：２０ｍｍ／ｍｉｎ.（ストランド）
【００７４】
その結果、本実施の形態に係るプロセスで製造した成形品の強度は６８［ＭＰａ］、比較例に係るプロセスで製造した成形品の強度は６９［ＭＰａ］であり、ほとんど同等の結果が得られた。
従って、押出機の上流側で相溶化剤を調製し、下流側で複合材を調製するという、本実施の形態に係るプロセスが、工程短縮の手段として、有効であることが確認された。
【００７５】
尚、押出条件の選定を迅速に行えるように、各Ｖｂにおける、制約条件に対応する値を表計算ソフトを用いて計算し、それぞれの上限値／下限値と比べる手法を試みた。各制約の上限値／下限値を明確にするために、相溶化剤調製工程における制約条件である「フィーダ安定供給限界」および「相溶化剤反応時間」を、上述の方法と同様にして数値化した。また、材料供給速度Ｖｂは、より運転時間に近いパラメータである「サイドフィーダ回転数」に置き換えた。
図１９および図２０は、上記試験で使用した押出機のウィンドウを制限している条件とサイドフィーダ回転数との関係を示したもので、これらの図で斜線を施した領域が、制約条件を満足しない領域である。
尚、上記図１９は相溶化剤の添加割合を１０［ｐｈｒ］（複合材１００に対して相溶化剤１０）に設定し、また、図２０は相溶化剤の添加割合を５［ｐｈｒ］に設定して、それぞれ試算を行ったものである。この図２０の場合には、メインフィーダに関して、制約条件を満たす領域がなく、押出機の運転が不可能であることが分かる。
【００７６】
押出機のウィンドウを広げる手段としては、装置自体の仕様を変更することが考えられるが、ここでは、材料供給手順に工夫を加えることにより、その改善を図った。
例えば、メインフィーダの安定供給限界条件を満たすためには、Ｖｂ／Ｖａを小さくすれば良いのであるが、相溶化剤の添加量を一定にしたままで、このＶｂ／Ｖａを下げる方法の一つとしては、サイドフィーダから供給していた複合材原料の一部をメインフィーダから供給することが考えられる。
この場合、ＬＣＰは溶融温度が高い（２８０℃）ので、メインフィーダから供給することはできないが、連続相が、２００℃で溶融する樹脂（例えば、ＰＰ：１８０℃）であれば、その一部をメインフィーダに振り分けて供給することは可能である。
図２１に、ＰＰをメインフィーダ／サイドフィーダ＝０.１５／０.８５の割合で供給した場合の試算結果を示す。図２０と図２１とを比較して分かるように、メインフィーダの運転条件に関して、制約条件を満たす領域を確保することができ、押出機の運転が可能となることが分かる。
【００７７】
以上、説明したように、本発明によれば、基本的には、ＬＣＰ複合材の各素材（ＰＰ，ＬＣＰ）にそれぞれ相溶する相溶化素材である低融点の液晶ポリマーと無水マレイン酸変性ＰＰを互いに反応させて相溶化剤を調製するようにしたので、上記ＬＣＰ複合材に適した相溶化剤を調製することが可能になる。そして、この調製された相溶化剤と上記複合材の各素材とを溶融混練せしめて樹脂複合材を調製するようにしたので、複合材の各素材（ＰＰ，ＬＣＰ）間の接着性の向上を図ることができる。
【００７８】
また、単一の押出機３０の上流側で相溶化剤を調製し、上記押出機３０の下流側でこの調製された相溶化剤と上記ＬＣＰ複合材の各素材とを溶融混練せしめて樹脂複合材を調製するようにしたので、相溶化剤の調製と樹脂複合材の調製とを一つの押出機３０で（つまり一つの工程で）行うことができ、複合材の製造工程を短縮することができるのである。
尚、本発明は、以上の実施態様に限定されるものではなく、その要旨を逸脱しない範囲において、種々の改良あるいは設計上の変更が可能であることは言うまでもない。
【図面の簡単な説明】
【図１】 市販の相溶化剤の熱的安定性の確認試験の試験結果を示すグラフである。
【図２】 低融点の液晶ポリマーと無水マレイン酸変性ＰＰの相溶化剤生成反応を示す説明図である。
【図３】 低融点の液晶ポリマーと無水マレイン酸変性ＰＰの反応で生成した相溶化剤の作用を模式的に示す説明図である。
【図４】 本発明の実施の形態に係るＬＣＰ複合材の強度評価試験のための押出機を示す説明図である。
【図５】 上記ＬＣＰ複合材の強度評価試験の結果を示すグラフである。
【図６】 無水マレイン酸変性ＰＰとＰＰ樹脂の分子骨格の類似性を示す説明図である。
【図７】 低融点の液晶ポリマーとＬＣＰの分子骨格の類似性を示す説明図である。
【図８】 低融点の液晶ポリマーと無水マレイン酸変性ＰＰとを混練したサンプルの動的粘弾性の測定結果を示すグラフである。
【図９】 低融点の液晶ポリマーとＰＰ樹脂とを混練したサンプルの動的粘弾性の測定結果を示すグラフである。
【図１０】 低融点の液晶ポリマーと無水マレイン酸変性ＰＰの反応を示す説明図である。
【図１１】 変性量の異なる３種類の無水マレイン酸変性ＰＰのＩＲスペクトルを示す説明図である。
【図１２】 変性量の異なる３種類の無水マレイン酸変性ＰＰの構造を模式的に示す説明図である。
【図１３】 分子中のＬＣ３０００／ＰＰ鎖の比率の異なる３種類の相溶化剤の構造を模式的に示す説明図である。
【図１４】 低融点の液晶ポリマーと無水マレイン酸変性ＰＰの最適混合比を求める試験の試験結果を示すグラフである。
【図１５】 相溶化剤の最適添加量を決定する試験の試験結果を示すグラフである。
【図１６】 相溶化剤の調製と複合材の調製を一工程で行う製造方法に用いる押出機の断面説明図である。
【図１７】 上記製造方法に対する比較試験に用いた押出機を示す説明図である。
【図１８】 引き取り速度と剪断およびダイ径との関係を示すグラフである。
【図１９】 押出機の運転条件設定の試算結果を示すグラフである。
【図２０】 押出機の運転条件設定の他の試算結果を示すグラフである。
【図２１】 押出機の運転条件設定の更に他の試算結果を示すグラフである。
【符号の説明】
１０,２０,３０,４０,５０…押出機
３３Ａ…上流側ホッパ
３３Ｂ…下流側ホッパ[0001]
BACKGROUND OF THE INVENTION
  This invention, CompatibleResin composite containing chemical agentMaterialIt relates to a manufacturing method.
[0002]
[Prior art]
  Conventionally, when manufacturing a resin composite by combining a reinforcing material with a matrix resin, bothCompatibleDoCompatibleIt is generally well known that by adding an agent, the adhesion between the two is improved, the composite effect is increased, and a resin composite material with improved physical properties can be obtained.
  For example, in JP-A-6-41444, a thermoplastic resin having a matrix resin composed of a thermoplastic resin and a liquid crystal transition temperature higher than the minimum moldable temperature (melting point in the case of a crystalline resin) of the matrix resin. When compounding the resin, both the resinCompatibleHave sexCompatibleIt is disclosed that an agent is added and then melted and extruded.
[0003]
[Problems to be solved by the invention]
  By the way, when manufacturing a thermoplastic liquid crystal resin (LCP) composite material as described above, if a polypropylene (PP) resin that is versatile at a relatively low cost is adopted as the matrix resin (continuous phase), this PP Is poor in reactivity, and LCP is not compatible with resins other than LCP.CompatibleBecause it is scarce,CompatibleOnly a limited number of agents can be applied.
[0004]
  As a material applicable to such a material system, PP andCompatibleIt is considered promising that both the PP chain and the functional group capable of reacting with LCP exist, but according to the present inventors' research,CompatibleIt has been found that all of the agents that can be applied as the agent have low thermal stability and cause thermal decomposition in the preparation temperature range of the LCP composite.
  In other words, PP and LCP and commercialCompatibleIf you try to prepare the material by putting the agent into the extruder at the same time,CompatibleReaction of the agent with LCP and commercialCompatibleIt is considered that the thermal decomposition of the agent proceeds at the same time.
[0005]
  As a result of further research on the problem, the present inventor has found thatCompatibleWhat is obtained by combining an agent (for example, maleic anhydride-modified PP) and a low melting point liquid crystal polymer and reacting both in advance is newlyCompatibleIt was found that the adhesiveness between PP and LCP was improved by adding it to the PP-LCP system as an agent.
[0006]
  Therefore, the present invention is commercially available.CompatibleBy reacting a liquid crystal polymer with a low melting point in combination with an agent, the product produced by this reaction is renewed.CompatibleIt was made by paying attention to the fact that it can be applied at the time of preparation of resin composites as an agent, and improves the adhesion between the materials of resin composites.CompatibleIt aims at shortening the process at the time of manufacturing a resin composite material using an agent.
[0007]
[Means for Solving the Problems]
  Therefore, the invention according to claim 1 of the present application (hereinafter referred to as the first invention) is applied to each material of the composite material.CompatibleDoCompatibleA resin composite manufacturing method for preparing a resin composite by adding an agent, wherein each material of the composite is respectivelyCompatibleConsisting of multiple materialsCompatibleChemical materialOn the upstream side of a single extruderReact with each otherCompatiblePreparing the agent,On the downstream side of the extruderThis preparedCompatibleThe resin composite material is prepared by melt-kneading the agent and each material of the composite material.
[0008]
  Also, Claims of the present application2Inventions related to2Said invention)1In the invention, the preparation temperature is different between the upstream side and the downstream side of the extruder.
[0009]
FurtherAnd claims of the present application3Inventions related to3Said invention)2In the invention of the above,CompatibleThe pyrolysis temperature of the chemical material is lower than the melting temperature of each material of the composite material, and the preparation temperature on the upstream side of the extruder is set lower than the preparation temperature on the downstream side It is.
[0010]
  Furthermore, the claims of this application4Inventions related to4Said invention)1~3In any one of the inventions, to the upstream side,CompatibleIt is characterized in that at least one of the composite materials is supplied simultaneously with the agent material.
[0011]
  Furthermore, the claims of this application5Inventions related to5Said invention)4In this invention, the preparation temperature on the upstream side of the extruder is set lower than the preparation temperature on the downstream side, and the composite material simultaneously supplied to the upstream side is melted at the temperature in the upstream region. It is characterized by that.
[0012]
  Furthermore, the claims of this application6Inventions related to6Of the first to the second)5In any one of the inventions described above,CompatibleChemical material,Maleic anhydride modified PP andThan thermoplastic liquid crystal resinA low melting point liquid crystal polymer, and the composite material comprises a PP resin and a high melting point thermoplastic liquid crystal resin that can be oriented in a fiberized state in the PP resin. It is a thing.
[0013]
Operation and effect of the invention
  According to the first invention of the present application, each material of the composite materialCompatibleConsisting of multiple materialsCompatibleReacting chemicals with each otherCompatibleSince the preparation of the agentCompatibleSuitable for the above composite materials by appropriately selecting chemical materialsCompatibleIt becomes possible to prepare the agent. And this preparedCompatibleSince the resin composite material is prepared by melt-kneading the agent and each material of the composite material, it is possible to improve the adhesion between the materials of the composite material.
In this case, the compatibilizing materials are reacted with each other on the upstream side of a single extruder to prepare a compatibilizing agent, and the prepared compatibilizing agent and each material of the composite material on the downstream side of the extruder. Is prepared by melting and kneading the resin, so that the compatibilizing agent and the resin composite can be prepared in one extruder (that is, in one step). The manufacturing process can be shortened.
[0014]
  AlsoNo. of this application2Basically, according to the invention of the above,1The same effects as those of the invention can be obtained. Moreover, since the preparation temperature is different between the upstream side and the downstream side of the extruder,CompatibleEven when the preparation temperature of the agent is different from the preparation temperature of the resin composite, it can be effectively applied.
[0015]
FurtherIn the present application3Basically, according to the invention of the above,2The same effects as those of the invention can be obtained. In particular, the aboveCompatibleEven when the pyrolysis temperature of the chemical material is lower than the melting temperature of each material of the composite material, it can be effectively applied.
[0016]
  In addition, the4Basically, according to the invention of the above,1~3The same effect as any one of the inventions of (1) can be achieved. Moreover, to the upstream side,CompatibleSince at least one of the composite materials is supplied simultaneously with the agent material, the material supply amount to the upstream side can be easily adjusted,CompatibleEven when the addition ratio of the agent is reduced, the stable supply limit of the material on the upstream side can be easily lowered. As a result, it is possible to increase the degree of freedom in setting the operating conditions of the extruder.
[0017]
  In addition, the5Basically, according to the invention of the above,4The same effects as those of the invention can be obtained. Moreover, the preparation temperature on the upstream side of the extruder is set lower than the preparation temperature on the downstream side, and the composite material supplied simultaneously to the upstream side is melted at the temperature in the upstream region. As a result, the mechanical resistance accompanying the rotation of the screw on the upstream side can be reduced.
[0018]
  In addition, the6According to the invention, basically, the first to the above-mentioned5The same effect as any one of the inventions of (1) can be achieved. In particular, the aboveCompatibleChemical material,Maleic anhydride modified PP andThan thermoplastic liquid crystal resinA low melting point liquid crystal polymer, and the composite material contains a PP resin and a high melting point thermoplastic liquid crystal resin that can be oriented in a fiberized state in the PP resin. Can be effectively applied to the production of a resin composite material using as a matrix resin and a thermoplastic liquid crystal resin as a reinforcing material.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, an embodiment of the present invention will be described with reference to a matrix resin made of a thermoplastic resin and a thermoplastic liquid crystal resin having a liquid crystal transition temperature higher than the minimum moldable temperature (melting point in the case of a crystalline resin) ( The case where the present invention is applied to the production of a resin composite material that is combined with (LCP) will be described in detail with reference to the accompanying drawings.
  First,CompatibleThe selection of the raw material for the agent will be described.
  When a general-purpose and relatively low-cost polypropylene (PP) resin is used as the matrix resin, this PP resin has low reactivity, and the LCP resin is different from resins other than LCP.CompatibleLowCompatibleAs the agent, PP resin andCompatibleAnd the type that can react with LCP is the most promising. For this purpose, PP resin andCompatibleIt is required that both the PP chain and the functional group capable of reacting with LCP exist.
[0020]
  Examples of the functional group capable of reacting with LCP include an epoxy group, a maleic anhydride group, an oxazonyl group, and a hydroxyl group.CompatibleAmong the agents that satisfy the above requirements, the following may be considered.
  -Maleic anhydride modified PP
    : Nisseki N polymer P4201 (manufactured by Nippon Petrochemical Co., Ltd.)
  ・ Oxazoline-modified PP
    : Oxazoline-based reactive polymer RAS1005 (manufactured by Nippon Shokubai Co., Ltd.)
  ・ Hydroxyl-modified PP
    : Umex 1201 (manufactured by Sanyo Chemical Co., Ltd.)
[0021]
  These commercially availableCompatibleThe agent is usually added for the purpose of imparting reactivity to the PP resin and is reactive. In other words, since it is thermally unstable, it is added when preparing the LCP composite according to the present embodiment.CompatibleIt is necessary to confirm whether it is suitable as a raw material for the agent from the viewpoint of thermal stability.
  Therefore, the above three types of commercially availableCompatibleThe agent was tested for thermal stability. Each testCompatibleThis was performed by raising the temperature of the agent in a nitrogen atmosphere and measuring the increase or decrease in its weight. The apparatus and measurement conditions used for the thermogravimetry were as follows.
  ・ Thermogravimetry equipment
      : TG / DTA30 (Seiko Electronics Industry Co., Ltd.)
  · Measurement condition
      -Temperature increase rate: 5 ° C / min.
      -N₂Gas supply condition: 100 ml / min.
[0022]
  The test results were as shown in FIG. In FIG. 1, the curves indicated by (a), (b), and (c) respectively indicate the following samples.
  (A): Maleic anhydride modified PP
  (B): Oxazolic acid-modified PP
  (C): Hydroxyl-modified PP
  As can be seen from FIG.CompatibleAlso for the agent, weight loss was observed at a temperature lower than the LCP composite preparation temperature (temperature above the LCP melting temperature). In addition, among the three types, it was found that maleic anhydride-modified PP had the highest temperature at which weight loss was greatest and was thermally most stable.
[0023]
  Therefore, theseCompatibleAs it is when preparing the LCP composite according to the present embodiment.CompatibleWhen added as an agent,CompatibleReaction of the agent with LCP;CompatibleIt is conceivable that the thermal decomposition of the agent proceeds simultaneously.
  Therefore, in order to avoid such a phenomenon,CompatibleA method in which the reaction of the agent is allowed to proceed in advance at a temperature below the composite material preparation temperature is conceivable. The partner material for this prior reaction isCompatibleIt has a molecular structure capable of reacting with an agent and has a melting temperature on the marketCompatibleLower than the decomposition temperature of the agent, and LCPCompatibleIt is necessary to satisfy the following three conditions.
[0024]
  In this embodiment, the LCP resin is different from other types of resins.CompatibleWith this LCPCompatibleFrom the viewpoint of the properties, LCP resin was mainly studied, and LC3000 (melting temperature: 195 ° C / manufactured by Unitika Co., Ltd.), which is one of the lowest melting point liquid crystal polymers, was taken up as one having the lowest melting temperature. Since LC3000 is a polyester compound, it is considered to have a functional group capable of reacting with maleic anhydride-modified PP.
  This low-melting liquid crystal polymer and commercially availableCompatibleThe agent is described in the claims of this application.CompatibleCorresponds to chemical materials.
[0025]
  Accordingly, this maleic anhydride-modified PP and LC3000 are reacted in advance at about 200 ° C.CompatibleBy adding it during the preparation of the LCP composite (PP-LCP system) as an agent, this newCompatibleWith both PP and LCPCompatibleIt is conceivable to improve the adhesion between PP and LCP.
  That is, as schematically shown in FIG. 2 and FIG.CompatibleAmong the agents, LC3000 in the molecule enters the LCP phase, and PP chain in the molecule enters the PP phase.CompatibleIt is thought that sex develops.
  Therefore, commercially availableCompatibleAgent (maleic anhydride modified PP) and low melting pointofA liquid crystal polymer (LC3000) is used as a raw material, and both are reacted in advance.CompatibleAn experiment was conducted to prepare an LCP composite as an agent.
[0026]
  FIG. 4 is an explanatory view schematically showing a manufacturing apparatus for manufacturing the LCP composite material according to the present embodiment. As shown in this figure, the manufacturing apparatus is used in the composite material preparation step.CompatibleThe first extruder 10 for preparing the agent, and obtained by the first extruder 10CompatibleAnd a second extruder 20 for preparing an LCP composite by adding an agent.
  Both of these extruders 10 and 20 are of a biaxial type, and basically have the same structure. That is, two rotary screws 12 and 22 are accommodated in hollow cylindrical main bodies 11 and 21, and the main bodies 11 and 21 are provided with two hoppers 13 and 23, respectively. Although not specifically shown, the main bodies 11 and 21 are provided with heating means for heating the inside thereof to a desired temperature.
[0027]
  The main bodies 11 and 21 (from the upstream hoppers 13 and 23 in the case of the present embodiment) are kept in a state where the inside of the main bodies 11 and 21 (barrel) is kept at a predetermined temperature by the heating means. The prepared material is introduced into the rotary screw 12 and 22 and the rotary screws 12 and 22 are rotated at a predetermined rotational speed, so that the charged material is plasticized and melted and kneaded while being provided at the downstream end of the main body 11 and 21. From the extrusion nozzles 14 and 24, for example, it is extruded in the form of a film or a strand. Then, the extruded extrudate is taken up by the rotation of the rollers 15 and 25, and the composite material is stretched at a predetermined stretch ratio after extrusion and then cut into a predetermined length by the cutters 16 and 26. It is like that.
[0028]
  In the present embodiment, as described above, the first extruder 10CompatibleThe agent is prepared, and the second extruder 20CompatibleA liquid crystal resin composite material is prepared by adding an agent, and a test for evaluating the strength of the composite material thus obtained was conducted. Hereinafter, this strength evaluation test will be described.
  The materials and preparation conditions used in this test are shown below. In addition, in this test, the material compounding ratio at the time of preparing the composite material was changed variously (five kinds), and the tensile strength of the obtained film-like composite material was measured.
[0029]
<1> Material
  ・ Reinforcing phase (thermoplastic liquid crystal resin: LCP)
    : Vectra A950 (manufactured by Polyplastics Co., Ltd.)
  ・ Continuous phase (thermoplastic matrix resin: PP)
    : Sumitomo Noblen H501 (manufactured by Sumitomo Chemical Co., Ltd.)
  ・CompatibleRaw material
    : Maleic anhydride modified PP (Nisseki N polymer P4201: Nippon Petrochemical)
    : Low melting point liquid crystal polymer (Rod Run LC3000: manufactured by Unitika)
[0030]
<2>CompatiblePreparation conditions
  ・ Mixing ratio of materials
    : Maleic anhydride-modified PP / low melting point liquid crystal polymer = 1/1
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 200 ° C
    -Shear rate: 700 / sec.
    -Screw speed: 150rpm
    -Die diameter: 2mm
    − Under the above conditions, using a die attached to the tip of the extruder,
      Extrude the product and cool it in a water bath located 50-100mm from the die exit.
      It was.
[0031]
<3> Preparation conditions of composite material (film)
  ・ Mixing ratio of materials
    : PP / LCP /CompatibleAgent = 70/30/0
                              70/30/5
                              70/30/10
                              70/30/20
                              70/30/40
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 290 ° C
    -Shear rate: 4000 / sec.
    -Screw speed: 150rpm
    -Stretch ratio: 10-13
    -Die: 100mm x 0.3mm film die
    -Film-like extrusion using a die attached to the tip of the extruder under the above conditions.
      Extrude the product and cool it in a water bath located 50-100mm from the die exit
        It was.
[0032]
  When preparing a composite material under the above test conditionsCompatibleThe tensile strength of the obtained film-shaped composite material was measured in the fiber direction and the direction perpendicular to the fiber while changing the amount of the agent added.
  The measurement apparatus and measurement conditions were as follows. The measurement results are shown in FIG.
  ·measuring device
      Universal testing machine (Autograph DSS-5000: manufactured by Shimadzu Corporation)
  ·Measurement condition
      Tensile speed: 5 mm / min.
[0033]
  In general, in the case of a composite material reinforced with long fibers, the strength in the direction perpendicular to the fiber depends only on the adhesive strength between the reinforcing phase and the continuous phase, and the strength in the fiber direction also shows the effect of adhesion, but mainly the reinforcement phase. It is known to depend on strength.
  From the figure,CompatibleAs the amount of the agent added increases, strength in the direction perpendicular to the fiber, that is, improvement in adhesive strength is recognized,CompatibleIt was confirmed that the agent contributed to the improvement of the adhesive force between the reinforcing phase and the continuous phase.
[0034]
  On the other hand, from the test results for strength in the fiber direction,CompatibleA unique phenomenon was observed when the agent was added. That is, for LCP composites:CompatibleIt is known that the agent promotes dispersion particle formation of the reinforcing phase.CompatibleAs the amount of the agent added increases, the aspect ratio of the reinforcing phase decreases due to dispersion of particles, and the strength of the composite material in the fiber direction decreases. In addition, it has also confirmed from the visual observation of a film-form composite material that the dispersion | distribution particle-izing phenomenon of this reinforcement phase has arisen.
  From the above, for the preparation of LCP compositesCompatibleWhen the agent is added, there are two effects of improving the adhesion and dispersing particles of the reinforcing phase, and it can be said that the strength of the composite material is maximized at a point where both these effects are balanced.
[0035]
  In the preparation of the above LCP composite,CompatibleThe mechanism for improving the adhesion between PP and LCP by the agent is to connect the respective substances in the following relationship.
PP <Compatible >Maleic anhydride modified PP << Reaction >> Low melting pointofLiquid crystal polymerCompatible >LCP
  Of these linking relationships, the following relationships are shown in FIG. 6 and FIG.ofSince the molecular skeletons of the liquid crystal polymer and LCP are similar to each other,CompatibleIt is thought that there is sex.
  ・ PP <Compatible> Maleic anhydride modified PP
  ・ Low melting pointofLiquid crystal polymer <Compatible> LCP
  However, the remaining maleic anhydride modified PP << reaction >> low melting pointofIt is necessary to confirm the reactivity of the liquid crystal polymer.
[0036]
  Therefore, maleic anhydride modified PP (Nisseki N polymer P4201) and low melting pointofA test was conducted to confirm the reactivity with the liquid crystal polymer (Rodlan LC3000).
  Next, this test will be described. Test is low melting pointofA mixture of liquid crystal polymer and maleic anhydride-modified PP is used as sample A, and has a low melting point.ofA sample obtained by kneading a PP resin (Sumitomo Noblene H501) having no reactive activity with a liquid crystal polymer was used as sample B, and these two types of film materials were prepared, and their dynamic viscoelasticity was measured and compared.
[0037]
  Sample preparation conditions were as follows.
  ・ Mixing ratio of materials
    -Sample A: PP modified with maleic anhydride / liquid crystal polymer with low melting point = 1/1
    Sample B: PP resin / low melting point liquid crystal polymer = 1/1
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 200 ° C
    -Shear rate: 4000 / sec.
    -Screw speed: 150rpm
    -Stretch ratio: 7-8
[0038]
  The measurement apparatus and measurement conditions were as follows.
  ・ Measuring device: Dynamic viscoelasticity measuring device (DMS2000 tension module)
                        MASS700 Material Analysis Station
                        : Seiko Electronics Co., Ltd.
  · Measurement condition
      -Temperature increase rate: 5 ° C / min.
      -Applied frequency: 2Hz
[0039]
  The measurement result of the dynamic viscoelasticity about each sample is shown in FIG. 8 and FIG. In FIG. 8, the curves indicated by (a), (b), and (c) respectively indicate the following samples.
  (A): Low melting point liquid crystal polymer
  (B): Sample A
  (C): Maleic anhydride modified PP
  In FIG. 9, the curves indicated by (a), (b), and (c) indicate the following samples, respectively.
  (A): Low melting point liquid crystal polymer
  (B): Sample B
  (C): PP
[0040]
  As can be seen from FIG. 8, with respect to Sample A, a temperature shift of the peak position of tan δ (loss factor) was observed. This shift is partly between the low melting point liquid crystal polymer and the maleic anhydride modified PP.CompatibleHowever, due to the difference in their molecular skeletons,CompatibleIt's hard to think.
  A reaction occurs between the low melting point liquid crystal polymer and the maleic anhydride-modified PP, and as shown in FIG. 10, a compound having both structures in one molecule is produced.CompatibleIt is reasonable to think that it acted as an agent.
  On the other hand, for sample B, the shift of the peak position of tan δ as described above was not recognized.
[0041]
  Therefore, the difference in shift between samples A and B is considered to be due to the difference in reactivity between maleic anhydride-modified PP and PP. That is, the peak position shift observed in Sample A suggests a reaction between the low melting point liquid crystal polymer and the maleic anhydride-modified PP.
  From the above, it can be considered that the improvement in adhesiveness between PP and LCP is manifested as a result of the aforementioned mechanism acting.
[0042]
  A product obtained by reacting maleic anhydride-modified PP with a low melting point liquid crystal polymer (LC3000)CompatibleIt was confirmed that the adhesion between LCP and PP in the LCP composite was improved by adding as an agent, but here, between PP / LCPCompatibleSex is, CompatibleIt is thought that it depends on the molecular structure of the agent molecule,CompatibleThere appears to be an optimal value for the ratio of LC3000 / PP chains in the agent molecule.
  Different ratio of LC3000 / PP chainCompatibleIn order to obtain an agent, the following three types of maleic anhydride-modified PPs having different amounts of maleic anhydride modification were selected.
  ・ QB540 (Admer QB540: Mitsui Petrochemical Co., Ltd.)
  ・ P4201 (Nisseki N polymer P4201: Nippon Petrochemical Co., Ltd.)
  ・ 9000M (Nisseki N polymer P9000M: Nippon Petrochemical Co., Ltd.)
[0043]
  FIG. 11 shows IR spectra of the three maleic anhydride-modified PPs. In addition, in this FIG. 11, the diagram respectively shown by (a), (b), (c), (d) has shown the following samples, respectively.
  (A): 9000M
  (B): P4201
  (C): QB540
  (D): H501
[0044]
  In FIG. 11, the amount of modification can be estimated from the ratio of the signal attributed to the PP chain and the signal attributed to the carbonyl group of maleic anhydride. Arranging these in ascending order of the amount of denaturation results in the following.
    QB540 <P4201 <9000M
  This infrared absorption spectrum was measured by a microscopic transmission method using an infrared absorbance measuring apparatus (FTS-60) manufactured by BIO-RAD.
  In addition, maleic anhydride-modified PP is generally said to decrease in molecular weight as the amount of modification increases. Accordingly, the structure of the above three types of maleic anhydride-modified PP is schematically depicted as shown in FIG.
[0045]
  By reacting the above three kinds of maleic anhydride-modified PP with a low melting point liquid crystal polymer (LC3000), three kinds of different ratios of LC3000 / PP chains in the molecule are obtained.CompatibleAn agent is obtained. theseCompatibleA schematic drawing of the structure of the agent is shown in FIG.
  theseCompatibleAmong the agents, the shorter the PP chain, the more PP andCompatibleAnd the higher the ratio of LC3000 in the molecule,CompatibleIt is thought that the sex will improve.
  Therefore, with PPCompatibleRegarding the sex, (LC3000 / QB540)> (LC3000 / P4201)> (LC3000 / 9000M), and with LCPCompatibleRegarding the sex, it is considered that (LC3000 / QB540) <(LC3000 / P4201) <(LC3000 / 9000M).
[0046]
  As described above, by melting and kneading the maleic anhydride-modified PP and the low melting point liquid crystal polymer (LC3000) and reacting them.CompatibleIt is considered that there is an optimum material mixing ratio depending on the amount of modification of the maleic anhydride-modified PP during the melt-kneading.
  That is, when LC3000 is insufficient, unreacted maleic anhydride-modified PP remains, and when LC3000 is excessive,CompatibleSince the concentration of the agent will be diluted,CompatibleThe effect of the agent is reduced. And it can be considered that the optimum mixing ratio becomes higher as the amount of modification of maleic anhydride-modified PP increases, because it can react with a larger amount of LC3000.
[0047]
  Then, the test which calculates | requires the optimal mixing ratio of maleic anhydride modified PP and a low melting-point liquid crystal polymer (LC3000) was done. This test was conducted by examining the relationship between the strength of the injection molded product and the mixing ratio when QB540 and P4201 were used as maleic anhydride-modified PP. Test conditions are shown below.
<1>CompatiblePreparation conditions
  ・ Mixing ratio of materials
    : LC3000 / QB540 = 1/9, 3/7, 5/5, 7/3
    : LC3000 / P4201 = 1/9, 3/7, 5/5, 7/3, 9/1
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 200 ° C
    -Shear rate: 600 / sec.
    -Screw speed: 150rpm
[0048]
<2> Preparation conditions for composite materials
  ・ Mixing ratio of materials
    : H501 / A950 /CompatibleAgent = 70/30/10
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 300 ° C
    -Shear rate: 2800 / sec.
    -Screw speed: 150rpm
    -Stretch ratio: 4-6
[0049]
<3> Molding conditions (injection molding)
  · Molding machine
    : Injection molding machine (IS-220EN-5Y: manufactured by Toshiba Machine Co., Ltd.)
  ・ Molding machine operating conditions
    -Barrel temperature: 180 ° C
    -Screw shape: DBY
    -Screw rotation speed: 10-12 rpm
    -Back pressure: 2kgf / cm²
    -Injection pressure: 99%
    -Injection speed: 30%
    -Mold temperature: 50 ° C
[0050]
  The test results are shown in FIG. In this graph, black circles (●) and white circles (◯) indicate the following data, respectively.
    ●: LC3000 / (LC3000 + QB540)
    ○: LC3000 / (LC3000 + P4201)
  Both data draw a gentle curve that is convex upward.The mixing fraction of LC3000 in the compatibilizer isThey were at 0.3 (QB540) and 0.5 (P4201), respectively.
  Therefore, the optimum mixing ratio was determined as follows.
    LC3000 / QB540 = 3/7
    LC3000 / P4201 = 5/5
  In addition, about 9000M, since the material shape is powdery and accurate control of the mixing ratio is difficult, the above-mentioned test was not performed. It is considered to be slightly higher than the case. In the following, LC3000 / 9000M = 3/1CompatibleIt was made to use as an agent.
[0051]
  For LCP compositesCompatibleWhen the agent is added, the strength of the injection-molded product once increases as the amount added increases, and then gradually decreases after the maximum value is reached. As described above, this phenomenon isCompatibleThis is due to a balance between two effects of the agent on the composite material (adhesion improvement and dispersion particle formation). AndCompatibleIn the relationship between the additive amount of the agent and the strength of the molded product,CompatibleIt is considered that the better the performance of the agent, the smaller (or less) the optimum amount added.
  Also,CompatibleAgent performance with PPCompatibleBetween sex and LCPCompatibleBecause it is determined by the balance with sex,CompatibleGender is differentCompatibleWhen an agent is added, the optimum addition amount is considered to vary depending on the degree.
[0052]
  next,CompatibleA test for examining the optimum addition amount of the agent will be described. This test isCompatibleThis was carried out by measuring the tensile strength of the injection-molded product when each additive amount was changed using an agent.
  ・ LC3000 / QB540 = 3/7
  ・ LC3000 / P4201 = 5/5
  LC3000 / 9000M = 3/1
  Test conditions are shown below.
<1> Material
  ・ Reinforcement phase (LCP): Vectra A950
  ・ Continuous phase (PP): H501
  ・CompatibleRaw material
    : Low melting point liquid crystal polymer (LC3000)
    : Maleic anhydride modified PP (P4201) / (9000M) / (QB540)
[0053]
<2>CompatiblePreparation conditions
  ・ Material composition
    : LC3000 / QB540 = 3/7
      LC3000 / P4201 = 5/5
      LC3000 / 9000M = 3/1
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 200 ° C
    -Shear rate: 600 / sec.
    -Screw speed: 150rpm
    -Die diameter: 2mm
    − Under the above conditions, using a die attached to the tip of the extruder,
      Extrude the product and cool it in a water bath located 50-100mm from the die exit.
      It was.
[0054]
<3> Preparation conditions of composite material (strand)
  ・ Material composition
    : H501 / A950 /CompatibleAgent = 70/30/0
                                    70/30 / 2.5
                                    70/30/5
                                    70/30/10
                                    70/30/20
                                    70/30/40
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 290 ° C
    -Shear rate: 2800 / sec.
    -Screw speed: 150rpm
    -Stretch ratio: 4-6
    -Die diameter: 2mm
    − Under the above conditions, using a die attached to the tip of the extruder,
      Extrude the product and cool it in a water bath located 50-100mm from the die exit.
      It was.
[0055]
<4> Molding conditions (injection molding)
  · Molding machine
    : Injection molding machine (IS-220EN-5Y: Toshiba Machine Co., Ltd.)
  ・ Molding machine operating conditions
    -Barrel temperature: 180 ° C
    -Screw shape: DBY
    -Screw rotation speed: 10-12 rpm
    -Back pressure: 2kgf / cm²
    -Injection pressure: 99%
    -Injection speed: 30%
    -Mold temperature: 50 ° C
[0056]
  When preparing a composite material under the above test conditionsCompatibleThe tensile strength of the obtained strand composite was measured by changing the amount of the agent added. The measurement apparatus and measurement conditions were as follows. The measurement results are shown in FIG.
  ·measuring device
      Universal testing machine (Autograph DSS-5000: manufactured by Shimadzu Corporation)
  ·Measurement condition
      Tensile speed: 5 mm / min. (Strand),
                20mm / min. (Molded product)
[0057]
  WhichCompatibleEven when an agent is used, the strength of the injection-molded product once increases with the increase in the amount added, and gradually decreases after the maximum value. As intendedCompatibleIt is thought that it functions as an agent. Table 1 shows eachCompatibleThe optimum addition amount of the agent and the strength of the injection molded product at that time were shown.
  The maximum value of the strength of the injection-molded product was obtained under the condition that 10 [phr] was added to a composite material using P4201 as maleic anhydride-modified PP mixed with a low melting point liquid crystal polymer at a ratio of 1/1. , 76 [MPa]CompatibleThe strength of the molded article was improved by about 1.6 times by adding the agent.
[0058]
[Table 1]

[0059]
  In Table 1, when LC3000-QB540 and LC3000-P4201 are compared, it can be seen that a composite material with higher strength of the molded product can be obtained with a smaller amount of the latter. On the other hand, when LC3000-P4201 and LC3000-9000M were compared, the strength of the molded product was lower in the latter, although the optimum addition amount was smaller. It can be inferred that this is due to the fact that the above-mentioned optimization of the mixing ratio was not sufficient.
  Therefore,CompatibleThe performance of the agent is considered to be in the following order.
LC3000-9000M> LC3000-P4201> LC3000-QB540
  Here, LC3000-9000M has the above three types.CompatibleOf the agents, most with PPCompatibleInferiorCompatibleAgent. When combined with the above test results, all three typesCompatibleSex is enough, these three kindsCompatibleThe biggest influence on the performance of the agent is with LCPCompatiblesex(CompatibleThe amount of LC3000 in the agent molecule).
[0060]
  In general, when a composite material reinforced with long fibers is injection-molded, even if the adhesive strength between the phases is sufficient, the orientation of the fibrous reinforcing phase may be disturbed or the reinforcing phase may be shortened. It is known that the strength decreases.
  And when it assumes that the adhesion | attachment between phases is enough, it is supposed that the intensity | strength of a molded article can be represented with the following formula | equation.
            Injection molded product = (Influence of orientation) * (Influence of shortening fiber)
                                      * Composite material reinforced with long fibers
  The value of (the influence of orientation) * (the influence of shortening the fiber) is generally in the range of 0.3 to 0.5, although there are various variations.
  In the case of the LCP composite material investigated this time, the strength of the molded product was 74 [MPa] at the maximum, and the strength of the strand before molding was 144 [MPa]. Therefore, the strength is reduced to about half (0.51) by molding. This coefficient of 0.51 is equivalent to the upper limit of the value based on the assumption that “the phase is sufficiently bonded”.CompatibleIt can be considered that the agent provides sufficient adhesion to this material system.
[0061]
  Produced by reacting low melting point liquid crystal polymer with maleic anhydride modified PPCompatibleWhen manufacturing a composite material using an agent,CompatibleSince the preparation temperature differs between the agent and the composite material, it is usually necessary to divide the process.
  However, the extruder can generally change the set temperature between the upstream side and the downstream side, and by using this function,CompatibleThe preparation of the agent and the preparation of the composite material can be performed in one step.
  Hereafter, thisCompatibleA manufacturing method according to another embodiment of the present invention in which the agent and the composite material are prepared in one step will be described. As shown in FIG. 16, the extruder 30 applied to this manufacturing method has the same structure as that used in the above-described manufacturing method.
[0062]
  That is, the extruder 3 is configured by housing two rotary screws 32 in a hollow cylindrical main body 31, and the main body 31 is provided with two hoppers 33A and 33B. Although not specifically shown, the main body 31 is provided with a heating means for heating the inside to a desired temperature. The heating means is configured so that the temperature can be set separately for the upstream side and the downstream side.
  Then, in a state where the inside of the main body 31 (barrel) is maintained at a predetermined temperature by this heating means, the prepared materials are put into the main body 31 from the hoppers 33A and 33B, and the rotary screws 32 and 32 are rotated at a predetermined rotation speed. Thus, the charged material is extruded, for example, in the form of a film or a strand from the extrusion nozzle 34 provided at the downstream end of the main body 31 while being plasticized and melted and kneaded. Then, the extruded extrudate is taken up by the rotation of the roller 35, stretched at a predetermined stretching ratio, and then trimmed to a predetermined length by the cutter 36.
[0063]
  In the present embodiment, the upstream side (region between the upstream hopper 33A and the downstream hopper 33B:CompatibleThe barrel temperature of the preparation agent)CompatibleOn the other hand, the barrel temperature on the downstream side (region between the downstream hopper 33B and the extrusion nozzle 34: composite material preparation region) is set to the preparation temperature of the LCP composite material, and then the upstream hopper is set. From 33A (main feeder)CompatibleThe raw materials for the LCP composite material are fed from the downstream hopper 33B (side feeder).ChargeI am trying to throw it in.
[0064]
  When applying the above manufacturing method,CompatibleIn the agent preparation step,CompatibleIn order for the reaction between the agent raw materials to proceed well,CompatibleWhen the length of the agent preparation region is constant, it is necessary to suppress the material supply rate Va to a certain upper limit value or less.
  Further, in the composite material preparation step, it is necessary to apply a certain amount or more of shearing and stretching in order to increase the strength of the composite material. This shearing and stretching are expressed by the following equations using the die exit diameter d of the extruder 30, the take-up speed k of the pelletizer (roller 35), and the material supply speeds Va and Vb.
    Shear = (32 / π) · (1 / d³) · (Va + Vb) (Formula 1)
    Stretch = (π / 4) · d²* K * 1 / (Va + Vb) ... <Formula 2>
  Here, when the die exit diameter d of the extruder 30 and the take-up speed k of the pelletizer are determined by the apparatus 30, the lower limit of (Va + Vb) from the shear required for the composite material, and the stretching required for the composite material ( The upper limit value of Va + Vb) is determined.
[0065]
  Furthermore,CompatibleAs a constraint relating to both the agent preparation process and the composite preparation processCompatibleThere is an addition ratio of the agent, and the value of Va / Vb is determined accordingly. In general, Va / Vb is a value of 0.1 or less.
  Furthermore, apart from the restrictions due to the material properties described above, the restrictions resulting from the apparatus 10 include blow-up and feeder supply capabilities. Blow-up refers to a phenomenon in which the material dropped from the feeder does not bite into the screw and accumulates in the material supply hole, and can be avoided by the screw shape and the material supply speeds Va and Vb. Among the feeder supply capacities, the upper limit of the material supply speeds Va and Vb is limited to the limit of the supply capacity depending on the motor rotation speed. On the other hand, the lower limit is controlled by the material that can be found in the motor low speed range. There is a stable supply limit.
[0066]
  The above constraint conditions for the material supply speeds Va and Vb are summarized as follows.
<1> Upstream (CompatibleMaterial supply rate Va in the agent preparation step)
    ・ Upper limit: Stretch / Blow-up / Feeder supply capacity
    ・ Lower limit: Shear / feeder stable supply limit
<2> Material supply speed Vb on the downstream side (composite preparation step)
    ・ Upper limit: Reaction time / Blow-up / Feeder supply capacity
    ・ Lower limit: Feeder stable supply limit
  Therefore, when applying the manufacturing method according to the present embodiment, it is necessary to appropriately determine the material supply rates Va and Vb.
[0067]
  The above examination results were verified as follows using an actual machine (extruder 30).
The conditions for this verification were set as follows.
<1> Material
  ・ Reinforcement phase (LCP): Vectra A950
  ・ Continuous phase (PP): Sumitomo Noblen H501
  ・CompatibleRaw material
    : Maleic anhydride modified PP (Nisseki N polymer P4201)
    : Low melting point liquid crystal polymer (Rod Run LC3000)
<2> Mixing ratio
  The blending ratio of the above materials was set to a blending ratio (see FIG. 15) at which the strength of the injection molded product showed the maximum value.
  ・CompatibleAgent: Low melting point liquid crystal polymer / maleic anhydride modified PP = 1/1
  ・ Composite: PP / LCP /CompatibleAgent = 70/30/10
[0068]
  When the preparation is performed at the above blending ratio, the material supply rate Vb in the composite material preparation step isCompatibleSince 10 times the material supply rate Va in the agent preparation step is necessary, a higher value of Vb is preferable. Therefore, first, an upper limit value of Vb was obtained.
  Among the constraint conditions for the upper limit value of Vb, “stretching”, which is a constraint due to material properties, is the above-mentioned <formula 1> and <formula 2> when the drawing rate (Draw ratio) k is set to the maximum value of the apparatus. Is based on the relationship between the shear and die diameter d as shown in FIG. Vb can be set higher as the die diameter d is larger. The conditions under which the composite material can develop strength are set assuming shear> 1800 / s, stretching> 12, and the composite material preparation conditions are set to die diameter = 2 mm, shear = 1800 / s, stretching = 12. Temporarily set.
[0069]
  Subsequently, it was verified whether or not this temporary setting condition satisfies the remaining conditions.
  It was confirmed that the constraints caused by the apparatus in the composite material preparation process were that materials were actually input and that materials could be input under the conditions.
  Compatible“Feeder stable supply limit”, which is the lower limit in the agent preparation process, is a material feed rate derived from temporary setting conditions by introducing a mixture of colored granular so-called color master and colorless PP pellets into an extruder. It confirmed by the method of flowing with Va.CompatibleSince the color of the material after the agent preparation step was uniform, it was found that the material was stably supplied with the set Va.
[0070]
  Also,CompatibleWhich is the upper limit in the agent preparation processCompatibleFor `` agent reaction time '', the materialCompatibleThe time to pass through the agent preparation area was confirmed by measuring with a color master. As a result, it has been found that the passage time at the material supply speed Va derived from the temporary setting is longer than that in the test conditions in which the strength of the injection molded product shows the maximum value. Therefore, with provisional conditions,CompatibleIt can be said that the reaction of the agent proceeds sufficiently.
  From the above, it is considered that the above temporary setting conditions satisfy all of the constraints of Va and Vb. Therefore, on the upstream side of the extruderCompatibleAs the verification conditions for the process of preparing the agent and preparing the composite material on the downstream side, the above temporarily set conditions are used.
[0071]
  Next, a test for evaluating the strength of the composite material produced by the above process was conducted.
  Test conditions are shown below.
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 200 ° C (CompatibleAgent preparation area)
                 : 290 ° C (composite material preparation region)
    -Shear rate: 1800 / sec.
    -Screw speed: 150rpm
    -Die diameter: 2mm
    -Stretch ratio: 12
    − Under the above conditions, using a die attached to the tip of the extruder,
      Extrude the product and cool it in a water bath located 50-100mm from the die exit.
      It was.
[0072]
  Moreover, the test compared with the said process was done together. As a comparative test in this case, two extruders 40 and 50 are prepared as shown in FIG.CompatibleAn agent was prepared, and a composite material was prepared using the other extruder 50. in this case,CompatibleIn the agent preparation step, the material is supplied from the main feeder 43A, and in the composite material preparation step, the material is supplied from the side feeder 53B.
  Test conditions are shown below.
<1>CompatiblePreparation conditions
  ・ Material composition
    : Low-melting-point liquid crystal polymer / maleic anhydride-modified PP = 1/1
  ・ Extruder
    : Two-axis kneading machine rotating in the same direction (BT-30-S2: manufactured by Plastic Industry Laboratory)
    -Diameter 30mm, L / D = 36
  ・ Extruder operating conditions
    -Barrel temperature: 200 ° C
    -Shear rate: 700 / sec.
    -Screw speed: 150rpm
    -Die diameter: 2mm
    − Under the above conditions, using a die attached to the tip of the extruder,
      Extrude the product and cool it in a water bath located 50-100mm from the die exit.
      It was.
<3> Preparation conditions of composite material
  ・ Material composition: PP / LCP /CompatibleAgent = 70/30/10
  The extruder and its operating conditions were the same as in the above test.
[0073]
  And the injection molding was performed using the obtained composite material, and the strength of the molded product was compared. The injection molding conditions and strength measurement conditions were as follows.
<4> Molding conditions (injection molding)
  · Molding machine
    : Injection molding machine (IS-220EN-5Y: Toshiba Machine Co., Ltd.)
  ・ Molding machine operating conditions
    -Barrel temperature: 180 ° C
    -Screw shape: DBY
    -Screw rotation speed: 10-12 rpm
    -Back pressure: 2kgf / cm²
    -Injection pressure: 99%
    -Injection speed: 30%
    -Mold temperature: 50 ° C
<5> Strength measurement conditions
  ·measuring device
      Universal testing machine (Autograph DSS-5000: manufactured by Shimadzu Corporation)
  ·Measurement condition
      Tensile speed: 20 mm / min. (Strand)
[0074]
  As a result, the strength of the molded product manufactured by the process according to the present embodiment is 68 [MPa], and the strength of the molded product manufactured by the process according to the comparative example is 69 [MPa]. It was.
  Therefore, on the upstream side of the extruderCompatibleIt was confirmed that the process according to the present embodiment in which the agent is prepared and the composite material is prepared on the downstream side is effective as a means for shortening the process.
[0075]
  In order to select the extrusion conditions quickly, a value corresponding to the constraint condition in each Vb was calculated using spreadsheet software, and a method of comparing with the respective upper limit value / lower limit value was tried. To clarify the upper and lower limits of each constraint,Compatible“Feeder stable supply limit” and “CompatibleThe “agent reaction time” was quantified in the same manner as described above. Further, the material supply speed Vb was replaced with “side feeder rotation speed” which is a parameter closer to the operation time.
  19 and 20 show the relationship between the conditions for limiting the window of the extruder used in the above test and the rotation speed of the side feeder, and the hatched areas in these figures show the constraint conditions. This is an unsatisfactory area.
  Note that FIG.CompatibleThe addition ratio of the agent is 10 [phr] (based on the composite material 100CompatibleAgent 20), and FIG.CompatibleThe addition ratio of the agent is set to 5 [phr], and each calculation is performed. In the case of FIG. 20, it can be seen that there is no region that satisfies the constraint conditions for the main feeder, and the operation of the extruder is impossible.
[0076]
  As means for expanding the window of the extruder, it is conceivable to change the specifications of the apparatus itself, but here, the improvement was made by adding a device to the material supply procedure.
  For example, in order to satisfy the stable supply limit condition of the main feeder, Vb / Va may be reduced.CompatibleOne method for lowering the Vb / Va while keeping the addition amount of the agent constant is to supply a part of the composite material material supplied from the side feeder from the main feeder.
  In this case, since LCP has a high melting temperature (280 ° C.), it cannot be supplied from the main feeder. However, if the continuous phase is a resin that melts at 200 ° C. (for example, PP: 180 ° C.), a part thereof Can be distributed and supplied to the main feeder.
  FIG. 21 shows a trial calculation result when PP is supplied at a ratio of main feeder / side feeder = 0.15 / 0.85. As can be seen from a comparison between FIG. 20 and FIG. 21, it can be seen that a region satisfying the constraint condition can be secured with respect to the operating condition of the main feeder, and the operation of the extruder can be performed.
[0077]
  As described above, according to the present invention, basically, each material (PP, LCP) of the LCP composite material is respectively provided.CompatibleDoCompatibleA low melting point liquid crystal polymer and maleic anhydride-modified PPCompatibleSince the agent is prepared, it is suitable for the LCP composite material.CompatibleIt becomes possible to prepare the agent. And this preparedCompatibleSince the resin composite material is prepared by melt-kneading the agent and each material of the composite material, it is possible to improve the adhesion between the composite materials (PP, LCP).
[0078]
  Also on the upstream side of a single extruder 30CompatibleThe agent was prepared and prepared on the downstream side of the extruder 30.CompatibleSince the resin composite material was prepared by melt-kneading the agent and each material of the LCP composite material,CompatibleThe preparation of the agent and the preparation of the resin composite can be performed by one extruder 30 (that is, in one step), and the manufacturing process of the composite can be shortened.
  In addition, this invention is not limited to the above embodiment, It cannot be overemphasized that a various improvement or a design change is possible in the range which does not deviate from the summary.
[Brief description of the drawings]
[Figure 1] Commercially availableCompatibleIt is a graph which shows the test result of the confirmation test of the thermal stability of an agent.
FIG. 2 shows a low melting point liquid crystal polymer and maleic anhydride-modified PP.CompatibleIt is explanatory drawing which shows an agent production | generation reaction.
FIG. 3 produced by reaction of low melting point liquid crystal polymer and maleic anhydride modified PP.CompatibleIt is explanatory drawing which shows typically the effect | action of an agent.
FIG. 4 is an explanatory view showing an extruder for a strength evaluation test of an LCP composite material according to an embodiment of the present invention.
FIG. 5 is a graph showing the results of a strength evaluation test of the LCP composite material.
FIG. 6 is an explanatory diagram showing the similarity of the molecular skeleton of maleic anhydride-modified PP and PP resin.
FIG. 7 is an explanatory diagram showing the similarity between the low melting point liquid crystal polymer and the molecular skeleton of LCP.
[Figure 8] Low melting pointofIt is a graph which shows the measurement result of the dynamic viscoelasticity of the sample which knead | mixed liquid crystal polymer and maleic anhydride modified PP.
[Figure 9] Low melting pointofIt is a graph which shows the measurement result of the dynamic viscoelasticity of the sample which knead | mixed liquid crystal polymer and PP resin.
FIG. 10 Low melting pointofIt is explanatory drawing which shows reaction of a liquid crystal polymer and maleic anhydride modified PP.
FIG. 11 is an explanatory diagram showing IR spectra of three types of maleic anhydride-modified PP having different modification amounts.
FIG. 12 is an explanatory view schematically showing the structures of three types of maleic anhydride-modified PP having different modification amounts.
FIG. 13 shows three types with different LC3000 / PP chain ratios in the molecule.CompatibleIt is explanatory drawing which shows the structure of an agent typically.
FIG. 14 Low melting pointofIt is a graph which shows the test result of the test which calculates | requires the optimal mixing ratio of liquid crystal polymer and maleic anhydride modified PP.
FIG. 15CompatibleIt is a graph which shows the test result of the test which determines the optimal addition amount of an agent.
FIG. 16CompatibleIt is sectional explanatory drawing of the extruder used for the manufacturing method which performs preparation of an agent, and preparation of a composite material in one process.
FIG. 17 is an explanatory view showing an extruder used in a comparative test for the manufacturing method.
FIG. 18 is a graph showing the relationship between take-up speed, shear and die diameter.
FIG. 19 is a graph showing a result of a trial calculation for setting operating conditions of an extruder.
FIG. 20 is a graph showing another calculation result of setting operating conditions of the extruder.
FIG. 21 is a graph showing still another calculation result of setting operating conditions of the extruder.
[Explanation of symbols]
  10, 20, 30, 40, 50 ... Extruder
  33A: Upstream hopper
  33B: Downstream hopper

Claims (6)

A method for producing a resin composite material by adding a compatible agent which is compatible to the respective materials of the composite to prepare a resin composite material,
Said the compatibility of materials consisting of multiple materials that each compatible with the material of the composite material, to prepare the compatible agent are reacted with each other at the upstream side of the single extruder, the downstream side of the extruder method for producing a resin composite material, characterized in that the prepared compatible agent and the respective materials of the composite material caused to melt-kneading to prepare a resin composite material. The process according to claim 1, wherein the resin composite material characterized by preparing a temperature between the upstream side and the downstream side of the extruder is different. Characterized in that the thermal decomposition temperature of the compatible of material is lower than the melting temperature of each material of the composite material, preparation temperature of the upstream side of the extruder is set lower than the preparation temperature of the downstream side The method for producing a resin composite material according to claim 2 . To the upstream side, method for producing a resin composite according to any one of claims 1 to 3 in which at least one of the composite material, characterized in that it is provided simultaneously with compatible agent material. The preparation temperature on the upstream side of the extruder is set lower than the preparation temperature on the downstream side, and the composite material supplied simultaneously to the upstream side is melted at the temperature of the upstream region. The manufacturing method of the resin composite material of Claim 4 . The compatibility of materials, maleic anhydride-modified PP, than the thermoplastic liquid crystal resin and also contains a liquid crystal polymer having a low melting point, the composite material material PP resin, a fiber state in said PP resin The method for producing a resin composite according to any one of claims 1 to 5, comprising a high-melting-point thermoplastic liquid crystal resin that can be aligned.

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