JP3800181B2 - PROPYLENE COMPOSITION AND PROCESS FOR PRODUCING THE SAME, POLYPROPYLENE COMPOSITION AND MOLDED ARTICLE - Google Patents

Description

【０１３３】
【表２】

【０１３４】
【表３】

【０１３５】
【表４】

【０１３６】
Ｂ．射出成形用ポリプロピレン系組成物(Ｃi)および射出成型品
１）ポリプロピレン系組成物
本発明のプロピレン系組成物Ａ−１〜６および比較組成物ｃＡ−１〜７の各パウダーに、各種添加成分を加え高速撹拌式混合機(ヘンシェルミキサー)を用いて、室温下に５〜１０分間混合し、混合物をスクリュー口径４０mmの押出造粒機を用い、シリンダー設定温度２３０℃で造粒してペレットを調製した。
【０１３７】
表３および表４に本発明射出成形用ポリプロピレン系組成物Ｃi−１〜１２およびＣi−１３〜１８を、表５および表６に比較組成物ｃＣｉ−１〜７およびｃＣｉ−１３の各添加成分およびそれらの添加量を示す。
使用した添加成分およびその表中の略号を下記に示す。
【０１３８】
プロピレンホモポリマー
ＰＨＰ１：チタン含有固体触媒成分：ａ−１を用い、Ａｌ／Ｓｉモル比２、水素／プロピレンモル比０.０３、重合圧力２.５ＭＰaおよび重合温度７０℃の条件でプロピレンを単独重合して得たメルトフローレートＭＦＲ_PHP１および融点１６３℃の結晶性プロピレンホモポリマー。
ＰＨＰ２：チタン含有固体触媒成分：ａ−１を用い、Ａｌ／Ｓｉモル比２、水素／プロピレンモル比０.０１、重合圧力２.５ＭＰaおよび重合温度７０℃の条件でプロピレンを単独重合して得たメルトフローレートＭＦＲ_PHP１.９および融点１６４℃の結晶性プロピレンホモポリマー。
ＰＨＰ３：チタン含有固体触媒成分：ａ−１を用い、Ａｌ／Ｓｉモル比２、水素／プロピレンモル比０.０５５、重合圧力２.５ＭＰaおよび重合温度７０℃の条件でプロピレンを単独重合して得たメルトフローレートＭＦＲ_PHP６および融点１６４℃の結晶性プロピレンホモポリマー(比較用)。
【０１３９】
酸化防止剤
Ｐｈ−１：フェノール系熱安定剤
Ｐｈ−２：テトラキス(メチレン−３−(３',５'−ジ−ｔ−ブチル−４'−ヒドロキシフェニル)プロピオネート)メタン。
【０１４０】
α晶造核剤
α−１：アルミニウムヒドロキシ−ビス(４−ｔ−ブチルベンゾエート)
α−２：１・３,２・４−ビス(ｐ−メチルベンジリデン)ソルビトール
α−３：ナトリウム−２,２'−メチレン−ビス(４,６−ジ−ｔ−ブチルフェニル)フォスフェート。
ラジカル発生剤：１,３−ビス(ｔ−ブチルパーオキシイソプロピル)ベンゼン
中和剤：ステアリン酸カルシウム
【０１４１】
【表５】

【０１４２】
【表６】

【０１４３】
【表７】

【０１４４】
【表８】

【０１４５】
２）射出成形
上記調製した各ペレットを射出成形機で溶融樹脂温度２３０℃、金型温度５０℃に設定し、ＪＩＳ形のテストピースおよび諸物性測定用テストピースを作成した。
テストピースを湿度５０％、室温２３℃の室内で７２時間状態調整した後、下記方法により諸物性値を測定した。
【０１４６】
ａ）成形収縮率：成形機の金型の全長から調製した引張試験片(ＪＩＳ Ｋ ７１１３ １号引張り試験片)の全長の長さを減じた長さと金型の長さの比を100倍する下記式により算出。
【数５】
成形収縮率＝(金型の全長−試験片の全長)×100／金型の全長
ｂ）曲げ弾性率(ＭＰa)：ＪＩＳ Ｋ ７２０３に準拠して測定。
ｃ）耐衝撃性(Ｊ／ｍ)：ＪＩＳ Ｋ ７１１０に準拠して−２０℃または２３℃で測定。
ｄ）アイゾット衝撃強度(Ｊ／m²)：ＪＩＳ Ｋ ７１１０に準拠して−３０℃で測定。
ｅ）ヘイズ：２５×５０×１mmの平板状テストピースによりＡＳＴＭ Ｄ１００３に準拠して測定。
ｆ）光沢：ＡＳＴＭ Ｄ ５２３ 鏡面光沢度法に準拠して指示角６０度で測定。
ｇ）難白化性：ヒンジ構造を有するテストピースを用い、ヒンジ部分で折り曲げ白化の程度を目視観察し、下記の３段階で評価した。
○：ヒンジ部分の色が他の部分と同等。
△：ヒンジ部分の色が他の部分に比較してわずかに白い。
×：ヒンジ部分の色が他の部分に比較して著しく白い。
測定結果を表３〜表６中に示す。なお、表中の衝撃試験データでＮＢは、設定条件で試験片が破壊しなかったことを意味する。
【０１４７】
また、本発明試料Ｃi−１〜６および比較試料ｃＣi−１〜６のプロピレンホモポリマーとプロピレン−エチレンコポリマーの極限粘度比と重量比の積対成形収縮率の関係を図１に、曲げ弾性率の関係を図２に示す。
【０１４８】
Ｃ．シート成形用ポリプロピレン系組成物(Ｃs)およびシートの製造
１）ポリプロピレン系組成物
本発明のプロピレン系組成物Ａ−１〜Ａ−６および比較組成物ｃＡ−１、３、５および７の各パウダーに、各種添加成分を加え高速撹拌式混合機(ヘンシェルミキサー)を用いて、室温下に５〜１０分間混合し、混合物をスクリュー口径
４０mmの押出造粒機を用い、シリンダー設定温度２３０℃で造粒してペレットを調製した。
【０１４９】
本発明のポリプロピレン系組成物Ｃs−１〜６および比較組成物ｃＣs−１〜４の各添加成分およびそれらの添加量を表７および表８に示す。
使用した添加成分およびその表中の略号を下記に示す。
酸化防止剤
Ｐ−１：リン系熱安定剤
Ｐ−２：トリス(２,４−ジ−ｔ−ブチルフェニル)フォスファイト
中和剤：前記に同じ。
【０１５０】
【表９】

【０１５１】
【表１０】

【０１５２】
２）シート成形
上記調製した各組成物をＴダイおよびポリッシングロールを有するシート成形機を用い、表９および１０中に示す、シリンダー設定温度、冷却ロール温度および成形速度で厚さ５ｍｍのシートを成形した。
成形したシートを、湿度５０％、室温２３℃の室内で７２時間状態調整し、下記の物性を測定した。成形条件および物性測定結果を表７および表８に示す。
【０１５３】
ａ）引張降伏点強度(ＭＰa)：５０℃の恒温槽中に３０分以上放置後、ＡＳＴＭ Ｄ ８８２に準拠して測定。
ｂ）ヤング率(ＭＰa)：２３℃の室内に４８時間以上放置後、ＡＳＴＭ Ｄ ８８２に準拠して測定。
ｃ）打抜衝撃強度(Ｊ)：ＡＳＴＭ Ｄ ７８１に準拠して測定。
ｄ）折曲げ白化性(ｍｍφ)：幅１０ｍｍ、長さ１２０ｍｍのシートを打ち抜き試験片とした。この試験片の両端を徐々に近づけながら折り曲げ、湾曲部に白化が生起した時点での曲率を測定し、この曲率に対応する円の直径を算出して折り曲げ白化性とし、難白化性の指標とした。
ｅ）印刷性：グラビア印刷機を用いて、乾燥温度５０℃、印刷速度５ｍ／分で３色刷り印刷を行い、印刷ズレを目視観察した。
○：印刷ズレなし
×：明白な印刷ズレあり
表７および表８に成形条件および物性測定結果を示す。
【０１５４】
Ｄ．フィルム用ポリプロピレン系組成物(Ｃf)およびフィルムの製造
１）ポリプロピレン系組成物
本発明のプロピレン系組成物Ａ−７〜１４、２、４および５、ならびにプロピレン系比較組成物cＡ８〜１４、５および６に、各添加成分を配合し、ヘンシェルミキサー(商品名)で混合後、単軸押出機（口径４０mmφ）を用いて溶融混練してペレット化し、フィルム用ポリプロピレン系組成物Ｃf−１〜１２および比較組成物cＣf−１〜９を調製した。
ポリプロピレン系組成物および比較組成物を表９および表１０に示す。
【０１５５】
使用した添加成分およびその表中の略号を下記に示す。
【０１５６】
酸化防止剤
Ｐｈ−２：テトラキス[メチレン（３,５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート]メタン
Ｐ−２：トリス（２,４−ジ−ｔ−ブチルフェニル)フォスファイト
中和剤：ステアリン酸カルシウム
ブロッキング防止剤：シリカ
滑 剤：オレイン酸アマイド
【０１５７】
【表１１】

【０１５８】
【表１２】

【０１５９】
２）単層フィルムの成形
ａ）無延伸フィルム
Ｔダイを備えた単層押出機(口径６５mmφ)を用いＣf−１〜８およびｃＣf−１〜７を押出温度２３０℃で押出し、エアーチャンバーおよび表面温度３０℃の冷却ロールで急冷して厚み２５μmの無延伸フィルムを得た。
ｂ）二軸延伸フィルム
Ｔダイを備えた単層押出機(口径４０mmφ)を用いＣf−９〜１１、ｃＣf８−８および９を押出温度２３０℃で押出し、エアーナイフおよび表面温度３０℃の冷却ロールで冷却固化して厚み２.０mmの未延伸シートを成形した。次いで、得られた未延伸シートをバッチ式二軸延伸機を用いて延伸温度１５７℃で二軸延伸（押出方向に５.０倍、横方向に８.０倍）して厚み５０μｍの二軸延伸フィルムを得た。
ｃ）一軸延伸フィルム
Ｔダイを備えた単層押出機(口径４０mmφ)を用いＣf−９〜１１、ｃＣf８−８および９を押出温度２３０℃で押出し、エアーナイフおよび表面温度６０℃の冷却ロールで冷却固化して厚み０.２５mmの未延伸シートを成形した。次いで、得られた未延伸シートをバッチ式二軸延伸機を用いて延伸温度１２０℃で押出方向に５.０倍一軸延伸して厚み５０μｍの一軸延伸フィルムを得た。
【０１６０】
３）積層フィルムの成形
ａ）無延伸フィルム
本発明のポリプロピレン系組成物Ｃf−２および４ならびに比較組成物ｃＣf−１および６と、下記のポリオレフィン系組成物との２種３層または３種３層無延伸フィルムを調製する。
【０１６１】
ポリオレフィン系組成物
ＰＯ−１：密度０.９０g/cm³、結晶融点１６３℃、メルトフーレート(ＭＦＲ)７.０g/10分であるプロピレンホモポリマー９９．４９重量％に、テトラキス[メチレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート]メタン０.０３重量％、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト０.０８重量％、ステアリン酸カルシウム０.１重量％、シリカ（ブロッキング防止剤）０.２重量％およびオレイン酸アマイド（滑剤）０.１重量％を配合し、ヘンシェルミキサー（商品名）で混合後、単軸押出機（口径４０mmφ）を用いて溶融混練し、ペレット化した組成物。
【０１６２】
ＰＯ−２：密度０.９０g/cm³、結晶融点が１３２℃、メルトフーレート(ＭＦＲ)６.０g/10分であるプロピレン−エチレン−ブテン−１コポリマー９９．４９重量％に、テトラキス［メチレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン０.０３重量％、トリス（２,４−ジ−ｔ−ブチルフェニル）フォスファイト０.０８重量％、ステアリン酸カルシウム０.１重量％、シリカ（ブロッキング防止剤）０.２重量％およびオレイン酸アマイド（滑剤）０.１重量％を配合し、ヘンシェルミキサー（商品名）で混合後、単軸押出機（口径４０mmφ）を用いて溶融混練し、ペレット化した組成物。
【０１６３】
多層Ｔダイを備えた３種３層押出機(口径６５mmφの中間層用単軸押出機が１台、口径５０mmφの表層用単軸押出機が２台)を用い、前記ポリプロピレン系組成物を中間層用単軸押出機に、前記ポリオレフィン系組成物を表層用単軸押出機に供給し、２３０℃で溶融させ、２種３層または３種３層多層共押出を行い、エアーチャンバーおよび表面温度３０℃の冷却ロールで冷却固化して厚み３０μm(厚み構成比＝１：４：１)からなる２種３層または３種３層無延伸フィルムを得た。
表１１および表１２に層構成を示す。
【０１６４】
ｂ）二軸延伸フィルム
多層Ｔダイを備えた３種３層押出機(口径６５mmφの中間層用単軸押出機が１台、口径５０mmφの表層用単軸押出機が２台)を用い、ポリプロピレン系組成物Ｃf−１２またはｃＣf−８を中間層用単軸押出機に、前記ポリオレフィン系組成物を表層用単軸押出機に供給し、２３０℃で溶融させ、２種３層多層共押出を行い、エアーナイフおよび表面温度３０℃の冷却ロールで冷却固化して厚み２.０mm(厚み構成比＝１／１８／１)からなる２種３層未延伸シートを成形した。次いで、得られた２種３層未延伸シートをバッチ式二軸延伸機を用いて延伸温度１５７℃で二軸延伸(押出方向に５.０倍、横方向に８.０倍)して厚み５０μｍの二軸延伸フィルムを得た。
表１１および表１２に層構成を示す。
【０１６５】
【表１３】

【０１６６】
【表１４】

【０１６７】
４）フィルム物性
上記調製した単層フィルムおよび積層フィルムについて下記物性を評価した。
ａ）透明性(％)：ＡＳＴＭ Ｄ １００３に準じ、フィルムのヘイズを測定して透明性の基準とした。
ｂ）光沢(％)：ＡＳＴＭ Ｄ ５２３に準じ、フィルムの光沢度を指示角を２０度で測定。
ｃ）引裂強度(N/mm)：ＡＳＴＭ Ｄ １９２２に準じ、フィルムのエレメンドルフ引裂強度を測定。
ｄ）引張破断強度(ＭＰａ)：ＡＳＴＭ Ｄ ８８２に準じ、フィルムの引張り破断強度を測定。
ｅ）引張破断伸度(ＭＰａ)：ＡＳＴＭ Ｄ ８８２に準じ、フィルムの引張り破断伸度を測定。
ｆ）耐寒温度(℃)：恒温槽中で１５分間フィルムを保持した後、ＡＳＴＭＤ ７８１に準じてフィルムのインパクト強度を測定し、０.５Ｊ以上のインパクト強度が得られるフィルムの保持温度。
ｇ）耐熱性(℃)：フィルムから１０×１００mmの短冊状に切り抜いたサンプルを所定温度に設定したシリコンオイル槽に１０分間保持した後、長手方向の長さを測定し、収縮した長さの初期長さに対する百分率で表した値が２％を越える時の温度。
ｈ）ヒートシール温度(℃)：二軸延伸ポリプロピレンフィルム(２０μ)と接着剤を用いてドライラミネートし、ラミネートを行ったフィルムをシール温度１３０℃〜１９０℃の範囲で５℃間隔(計８温度条件)に、シール圧力２ＭＰa、シール時間０.５秒で幅１０mmのヒートシールをした後、１５mm幅の短冊状に切り抜いたサンプルを用いて各シール温度でのシール部の９０℃の剥離試験を、引張り速度３００mm／分で引張り試験機により測定し、０.５N／15mm以上の剥離強度を示す最低シール温度。
単層フィルムの評価結果を表９および表１０中に、積層フィルムの評価結果を表１１および表１２中に示す。
【０１６８】
Ｅ． 中空成型品用ポリプロピレン系組成物(Ｃb)および中空成型品
１）ポリプロピレン系組成物
本発明のプロピレン系組成物Ａ−１、２および比較組成物ｃＡ−３に各種添加成分を配合し、ヘンシェルミキサーを用いて混合して２５０℃に設定された押出機によって溶融混練および押出を行い、ペレット状のポリプロピレン系組成物Ｃb−１〜７および比較組成物ｃＣb−１〜４を調製した。
【０１６９】
ポリプロピレン系組成物および比較組成物を表１３および表１４に示す。
【０１７０】
使用した添加成分およびその表中の略号を下記に示す。
【０１７１】
可塑化成分
ＬＰＤＥ：メルトフーレート(ＭＦＲ)０.４g/10分、結晶融点１１０℃、密度０.９２０g/cm³である低密度ポリエチレン。
ＥＶＡＣ：メルトフーレート(ＭＦＲ)０.５g/10分、結晶融点１０４℃、密度０.９２５g/cm³、酢酸ブチル含有量３重量％であるエチレン酢酸ビニール共重合体。
酸化防止剤および中和剤：前記のとおり。
【０１７２】
【表１５】

【表１６】

【０１７３】
２）中空成型品の成形
ａ）中空成型品(単品)
上記調製したペレット状のポリプロピレン系組成物Ｃb−１〜６またはｃＣb−１〜３を中空成形機(SN−50(プラコー社製))の押出機に供給して２００℃でパリソンを押出し、このパリソンを３０℃に調整した金型内でブローして側面部に蛇腹構造部を持つ円柱状の中空成型品(６０φ×３００×１.６mmｔ/中央部に蛇腹構造７ピッチ、ピッチ間１０mm、溝の深さ１０mm、蛇腹部の平均肉厚０.９mmｔ)を成形した。上面および底面を切断して中空成型品を得た。
ｂ）中空成型品(複合品)
ペレット状のポリプロピレン系組成物Ｃb−１、２または７、もしくは比較組成物ｃＣb−１、２または４を押出機を２機持つ中空成形機の１方の押出機に供給し、他方の押出機に下記のポリマー組成物のいずれかを供給し、はじめに前記押出機より２００℃でパリソンを押出し、続いて後記押出機より２００℃でパリソンを押出し、２つの組成物が連結したパリソンを作り、このパリソンを３０℃に調整した金型内でブローして側面部に蛇腹構造部を持つ円柱状の中空成型品(６０φ×３００×１.６mmｔ/中央部に蛇腹構造７ピッチ、ピッチ間１０mm、溝の深さ１０mm、蛇腹部の平均肉厚０.９mmｔ)を成形した。この際、前記押出機より押し出されたパリソンが蛇腹部へ来るよう調節を行った。上面および底面を切断して中空成型品(複合品)を得た。
【０１７４】
ＥＰ−１：結晶融点１６５℃、曲げ弾性率１,１００Ｍｐa、ＭＦＲ０.６５g／10分である、エチレン含有量５９重量％のエチレン−プロピレンコポリマー１２.７重量％およびプロピレンホモポリマー８７.３重量％よりなるプロピレン系組成物１００重量部に対してトリス(２,４−ジ−ｔ−ブチルフェニル)フォスファイト０.０５重量部、テトラキス[メチレン(３,５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナメート)]メタン０.１５重量部、ステアリン酸カルシウム０.１重量部を配合したポリマー組成物。
【０１７５】
ＥＰ−２：ＥＰ−１１００重量部に平均粒径が１.６μｍのタルクを１０重量部配合した曲げ弾性率２,１００Ｍｐa、ＭＦＲ０.７２g/10分であるポリマー組成物。
【０１７６】
ポリプロピレン系組成物とポリマー組成物の組み合わせを表１３および表１４中に示す。
【０１７７】
３）中空成型品の評価
上記調製した中空成型品について、下記の特性および評価基準で評価した。
【０１７８】
ａ）成形性：成形温度２００℃、スクリュウ径５０φ、スクリュウ回転数４０rpm、にて溶融パリソンを押し出し(ダイス径２１mm、コアー径１９mm)パリソンが１２cmおよび５０cmまで垂れ下がる速度を測定し、両者の垂れ下がり速度の差(５０cmまでの速度−１２cmまでの速度)で判定。
Ａ：ドローダウンが小さく速度差が５％未満
Ｂ：ドローダウンの速度差が５〜２０％
Ｃ：ドローダウンの速度差が２０％を超える。
【０１７９】
ｂ）柔軟性：２３±２℃の室内にて中空成形品の一端を固定し、一方に１Kgの荷重を乗せた時の変形量を角度で判定。
Ａ：３０度以上の変形量
Ｂ：２０度以上、３０度未満の変形量
Ｃ：１０度以上、２０度未満の変形量
Ｄ：１０度未満の変形量。
【０１８０】
ｃ）耐衝撃白化性：２０〜２５℃の環境下にて中空成形品を水平に寝かせ成形品(ポリプロピレン系組成物使用部位)に先端半径が６.３５mmの撃芯(１９０ｇ)をあて、５００gの荷重を高さ５０cmから撃芯上に落とし撃芯周辺に発生する白化面の直径を測定。
Ａ：撃芯部に傷が見られるが白化が見られない
Ｂ：撃芯部の白化が８mmφ未満
Ｃ：撃芯部の白化が８〜１５mmφ
Ｄ：撃芯部の白化が１５mmφを超える。
【０１８１】
ｄ）耐熱性：成形品を１５０℃のオーブン中に５００時間放置したときの変形、外観を目視観察。
Ａ：変形、外観異常なし
Ｂ：寸法変化が２％以下で外観変化が殆どなし
Ｃ：寸法変化が２％以上で外観変化(劣化)あり。
【０１８２】
ｅ）ウェルド強度：成形品のウェルド部を圧縮し(５０mm)パリソンの押し出し方向に沿ったの白化および亀裂を目視観察。
Ａ：白化および亀裂の発生なし
Ｃ：白化または亀裂が発生。
【０１８３】
ｆ）接合強度：筒状成形品より重合体組成物及びそれ以外の組成物との接合部より試験片を切り出し引張強度を測定し、その値を下記標準品の値と比較。
標準品：中空成型品よりポリプロピレン系組成物よりなる部位より切り出した試験片。
Ａ：標準品の８５％を超える強度
Ｂ：標準品の８５〜７０％の強度
Ｃ：標準品の７０％未満の強度。
【０１８４】
表１３および表１４中に、各物性の評価結果を示す。
【０１８５】
【発明の効果】
本発明のプロピレン系組成物は、成形性、成形収縮率、剛性、柔軟性、耐衝撃性、特に低温での耐衝撃性、透明性、光沢、難白化性に優れ、かつそれらのバランスの優れた各種の成型品を得るためのポリプロピレン系組成物のベース樹脂として好適に使用される。
【０１８６】
本発明のプロピレン系組成物をベース樹脂とするポリプロピレン系組成物を使用した射出成型品においては、図１および図２に示すように、プロピレン系組成物を構成するプロピレンホモポリマー(ＰＰ)とプロピレン−エチレンコポリマー(ＲＣ)の極限粘度比と重量比との積([η]_RC／[η]_PP)×(Ｗ_PP／Ｗ_RC)が、１.０〜３.０の範囲にある場合に成形収縮率はほぼ１にあり、高い曲げ弾性率(剛性)を示し、さらに表３および表５に示すように優れた低温耐衝撃性、透明性、光沢および難白化性を示す。さらにα晶造核剤を配合したポリプロピレン系組成物Ｃi−７〜１２においては、さらに低温耐衝撃性が改善され、また表４および表６に示すようにラジカル発生剤および／または高結晶性プロピレンホモポリマーを配合したポリプロピレン系組成物Ｃi−１３〜１８においては、難白化性がさらに改善される。
【０１８７】
また、これらのポリプロピレン系組成物を使用して、各種のシート状成型品はもとより、容器およびその栓(キャップ)、ヒンジ構造を有する成型品など複雑な構造を有する成型品を射出成形により製造することができる。
【０１８８】
本発明のプロピレン系組成物をベース樹脂とするポリプロピレン系組成物を使用したシートにおいては、その成形方法との組み合わせによって表７および表８に示すように打ち抜き衝撃強度、折曲げ難白化性および印刷性に優れ、かつ引張降伏点強度およびヤング率のバランスの優れたシートが得られる。
【０１８９】
本発明のプロピレン系組成物をベース樹脂とするポリプロピレン系組成物を使用して成形した単層フィルムは、表９および表１０に示すように透明性および耐熱性に優れ、引裂強度、引張破断強度、破断伸度および低温耐衝撃性などの機械的特性のバランスに優れた無延伸、二軸延伸および一軸延伸フィルムを提供する。また、このポリプロピレン系組成物とポリオレフィン系組成物との積層フィルムは、表１１および１２に示すように上記の単層フィルムの特性を維持した上で、優れたヒートシール性を有する。
【０１９０】
これらのフィルムは、食品包装用をはじめとする各種の包装用フィルムとして好適である。
【０１９１】
本発明のプロピレン系組成物をベース樹脂とするポリプロピレン系組成物を使用して成形した中空成型品、特に蛇腹構造を有する中空成型品は、表１３および表１４に示したように成形性、柔軟性、衝撃難白化性、耐熱性、ウェルド特性に優れ、特に可塑化成分を添加したポリプロピレン系組成物Ｃb−２、３、５および７においては、柔軟性がさらに改善される。また他のポリマー組成物と接合させた複合品においては高い接合強度を有する。
【０１９２】
これらの蛇腹構造を有する中空成型品およびその複合品は、エアーダクトなどとして好適である。
【０１９３】
本発明は、各種の成型品の成形に使用されるポリプロピレン系組成物およびそのベース樹脂として好適なプロピレン系組成物を提供するものであり、当該分野における意義は極めて大きい。
【図面の簡単な説明】
【図１】プロピレンホモポリマー(ＰＰ)とプロピレン−エチレンコポリマー(ＲＣ)の極限粘度比と重量比との積([η]_RC／[η]_PP)×(Ｗ_PP／Ｗ_RC)に対する成形収縮率を表す曲線。
【図２】プロピレンホモポリマー(ＰＰ)とプロピレン−エチレンコポリマー(ＲＣ)の極限粘度比と重量比との積([η]_RC／[η]_PP)×(Ｗ_PP／Ｗ_RC)に対する曲げ弾性率を表す曲線。
【図３】実施例で用いたプロピレン系組成物の連続重合装置のフローシート。
【符号の説明】
１、１０：重合器
２：水素配管
３：原料プロピレン配管
４、８：未反応ガス配管
５、９：重合体抜き出し配管
６：原料混合ガス配管[0001]
[Industrial application fields]
The present invention relates to a propylene-based composition, and more specifically, a composition comprising a propylene homopolymer and a propylene-ethylene copolymer, a method for producing the same, a polypropylene-based composition based on this composition, and these compositions In particular, the present invention relates to an injection molded product, an extruded sheet, a film, and a hollow molded product.
[0002]
BACKGROUND OF THE INVENTION
Polypropylene resin is relatively inexpensive and has excellent properties, so it is today a variety of molded products such as sheets, containers, caps, etc., and injection molded products having their hinge structure, films, and air ducts. It is used in various fields such as hollow molding products. Films are also widely used for packaging materials such as foods and textiles by utilizing their mechanical, optical and thermal properties.
[0003]
In accordance with the properties required for each molding application, a composition comprising a propylene homopolymer, a copolymer of propylene and an α-olefin, particularly enalene, and a propylene polymer and a propylene-α-olefin copolymer is mainly used. A polypropylene composition as a component is used.
[0004]
In general, propylene homopolymer has high rigidity and excellent heat resistance, but lacks flexibility, and is inferior in impact resistance, particularly low temperature impact resistance, and tear strength when used as a film. The propylene-α-olefin copolymer is excellent in transparency and flexibility, but is inferior in heat resistance and impact resistance at low temperatures. Conventionally known compositions are widely used in various industrial fields including automobiles and home appliances because they are excellent in heat resistance and impact resistance at low temperatures, but are more transparent than homopolymers. In addition, the gloss is inferior and the molding shrinkage ratio is large like the homopolymer, while the tear strength and flexibility are inferior to the copolymer. In any case, the phenomenon of whitening due to impact or bending is observed, and the whitening resistance is insufficient.
[0005]
Methods for improving these insufficient properties include changing the properties of the polymer, copolymer or composition and using additives.
[0006]
For example, as a general method, a method of improving the molding shrinkage ratio of the composition by filling with an inorganic substance such as talc is adopted, but a large amount of inorganic substance such as talc is added to improve the molding shrinkage ratio. Is necessary, and the weight increase of the molded product is large and the appearance is remarkably deteriorated. On the other hand, a method of improving the transparency and gloss by reducing the ethylene content of the copolymer in the composition is also adopted, but the decrease in the ethylene content in the copolymer contributes to the improvement of the gloss, but impact resistance at low temperature At the same time, the rigidity generally decreases.
[0007]
Japanese Patent Application Laid-Open No. 60-28411 discloses a method for producing a high-rigidity ethylene / propylene copolymer, that is, a propylene composition, in which an ethylene-propylene copolymer is divided into three stages, and each of the ethylene contents is sequentially copolymerized. is doing. The composition obtained by this method not only has high rigidity, but also has excellent whitening resistance, impact resistance, heat resistance, etc., but the transparency, gloss, appearance, and molding shrinkage ratio during molding. There are still points to be improved.
[0008]
Japanese Examined Patent Publication No. 7-30145 is composed of a crystalline polypropylene part and an ethylene propylene random copolymer block, the content of the crystalline polypropylene component is 55 to 95% by weight, and the intrinsic viscosity ratio of both components ([η]_EP/ [Η]_PP) Is 0.5 to 2.0, and a propylene block copolymer having a glass transition temperature of −30 ° C. or lower of an ethylene-propylene random copolymer block, that is, a propylene-based composition is disclosed. This composition has an ethylene-propylene copolymer component content ratio and an intrinsic viscosity ratio of the propylene homopolymer and copolymer component in substantially the same range, and has excellent mechanical properties such as impact resistance and rigidity. Such as transparency, gloss, appearance, etc., in particular, have a point to be improved in the whitening property of the molded product and the molding shrinkage ratio at the time of molding.
[0009]
Japanese Patent Application Laid-Open No. 6-93061 polymerizes a propylene-based polymer in an amount of 60 to 80% by weight of the total polymerization amount, and then polymerizes an ethylene-propylene copolymer part having an ethylene content of 20 to 50% by weight. A block copolymer having an intrinsic viscosity ([η]) of an ethylene-propylene copolymer part_B) Is 2.0 dl / g or more and the intrinsic viscosity ratio of both components ([η]_B/ [Η]_A) Is a polypropylene block copolymer obtained by melt-kneading a block copolymer having a molecular weight of 1.8 or less. This composition also has the ethylene-propylene copolymer component content and the intrinsic viscosity ratio of the propylene homopolymer and copolymer component in substantially the same range, and has excellent low temperature impact resistance, blocking resistance, appearance, etc. In addition, there are points that should be improved in terms of mechanical properties such as rigidity and molding shrinkage during molding.
[0010]
Japanese Laid-Open Patent Publication No. 6-328640 proposes a multilayer film having a greatly improved tear strength in which a polypropylene resin layer is laminated on both sides of a linear low density polyethylene layer. In this multilayer film, the compatibility between the low-density polyethylene and the polypropylene resin to be laminated is not so good, and fish eyes are likely to occur when remelted and reusable as a film.
[0011]
JP 52-126450 discloses a three-component blend of ethylene-α-olefin copolymer rubber, polypropylene or high density polyethylene, and paraffin oil or naphthenic oil. This blend is excellent in flexibility, but heat resistance is reduced.
[0012]
Japanese Patent Laid-Open No. 4-282232 proposes a resinous tubular body in which a rigid portion formed of a hard polyolefin resin and a flexible portion formed of a thermoplastic elastomer are connected. This tubular body lacks the bonding strength between the rigid portion and the flexible portion.
[0013]
[Problems to be solved by the invention]
The present invention is excellent in impact resistance of various molded products, in particular, low temperature impact resistance, rigidity, tear strength, heat resistance, transparency, gloss, whitening resistance, and molding shrinkage ratio during molding. Another object of the present invention is to provide a propylene composition suitable as a base resin for a polypropylene composition having an excellent balance between them, and a method for producing the same.
[0014]
Another object of the present invention is to provide a polypropylene composition having the above propylene composition as a base resin.
[0015]
Furthermore, an object of the present invention is to provide various molded products using the above polypropylene-based composition and methods for producing them.
[0016]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that propylene alone, and then propylene and ethylene, in the presence of a stereoregular catalyst using a titanium-containing solid catalyst component having a large particle size. A propylene composition comprising a propylene homopolymer and a propylene-ethylene copolymer obtained by continuously subjecting a mixture to gas phase polymerization has the intrinsic viscosity of propylene-ethylene copolymer, the intrinsic viscosity ratio of both components, and the intrinsic viscosity ratio and both. When the product of the weight ratio of the components is within a certain range, impact resistance, especially impact resistance at low temperature, rigidity, transparency, gloss, whitening resistance, molding shrinkage during molding, etc. It was found that the balance between them was excellent, and the present invention was completed.
[0017]
The present invention comprises a propylene homopolymer (PP) and a propylene-ethylene copolymer (RC), and the intrinsic viscosity ([η]) of the propylene-ethylene copolymer (RC)_RC) Is 1.7 to 2.8 dl / g; intrinsic viscosity ratio ([η]) of propylene homopolymer (PP) and propylene-ethylene copolymer (RC)_RC/ [Η]_PP) Is 0.7 to 1.2; and the weight ratio of propylene homopolymer (PP) to propylene-ethylene copolymer (RC) (W_PP/ W_RC) And their intrinsic viscosity ratio ([η]_RC/ [Η]_PP) Product ([η]_RC/ [Η]_PP) × (W_PP/ W_RC) Is in the range of 1.0 to 3.0; the propylene-based composition (A).
[0018]
Another invention provides a titanium-containing solid catalyst component (a) having an average particle size of 25 to 300 μm;
General formula AlR¹mX_3-m(Where R¹Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, m is a positive number of 3 ≧ m> 1.5), and the general formula R² _XR^Three _YSi (OR^Four)_Z(Where R²And R^FourIs a hydrocarbon group, R^ThreeRepresents a hydrocarbon group or a hydrocarbon group containing a hetero atom, and X, Y, and Z are 0 ≦ X ≦ 2, 1 ≦ Y ≦ 3, 1 ≦ Z ≦ 3, and X + Y + Z = 4) First polymerization in which propylene is homopolymerized in the gas phase in the presence of a stereoregular catalyst in combination with an organosilicon compound (c) to produce propylene homopolymer (PP) of 78 to 60% by weight of the total weight A second polymerization step in which ethylene and propylene are then copolymerized to produce a propylene-ethylene copolymer (RC) having an ethylene unit content of 25 to 55 wt% in the polymer of 22 to 40 wt% of the total weight; Is a method for producing the propylene-based composition (A).
[0019]
Another invention is a polypropylene-based composition (C) containing the propylene-based composition (A) as a main component and optionally added additives.
[0020]
Still another invention is a molded article (D) using this polypropylene composition, particularly an injection molded article, a sheet, a film and a hollow molded article.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
In the propylene-based composition (A) of the present invention, the propylene homopolymer (PP) has a high crystallinity with an isotactic pentad fraction (P) of 0.95 or more, preferably 0.955 or more, that is, stereoregulation. It is a polypropylene with properties. The isotactic pentad fraction (P) of the propylene homopolymer (PP) affects mechanical properties such as rigidity and heat resistance of the molded product (D), and the rigidity and heat resistance increase as the value increases. .
[0022]
On the other hand, the propylene-ethylene copolymer (RC) is an ethylene-propylene random copolymer containing 25 to 55 wt%, preferably 30 to 55 wt% of ethylene polymerized units based on the weight of the propylene-ethylene copolymer (RC). is there.
[0023]
The ethylene polymer unit in the propylene-ethylene copolymer (RC) affects the rigidity, flexibility and impact resistance of the molded article (D), particularly impact resistance and whitening resistance at low temperatures. However, if it is too large, the dispersibility of the propylene-ethylene copolymer (RC) in the propylene homopolymer (PP) will be affected, and the transparency, gloss, whitening resistance, etc. of the molded product (D) will decrease.
[0024]
In addition, propylene-ethylene copolymer (RC) has an intrinsic viscosity ([η]) measured in 135 ° C. tetralin._RC) In the range of 1.7 to 2.8 dl / g, and the intrinsic viscosity ([η]) measured under the same conditions of the propylene homopolymer (PP)_PP) To the intrinsic viscosity ratio ([η]_RC/ [Η]_PP) Is in the range of 0.7 to 1.2, preferably 0.8 to 1.2.
[0025]
Intrinsic viscosity of propylene-ethylene copolymer (RC) ([η]_RC) Cannot be measured directly, so the intrinsic viscosity of propylene homopolymer (PP) ([η]_PP) And the intrinsic viscosity of the entire propylene composition (A) ([η]_WHOLE) As well as weight percent of propylene-ethylene copolymer (RC) (W_RC) From the following formula.
[0026]
[Expression 1]
[η]_RC= [[Η]_WHOLE-(1-W_RC/ 100) [η]_PP] / (W_RC/ 100)
Intrinsic viscosity of propylene-ethylene copolymer (RC) ([η]_RC) Affects the mechanical properties such as the molding cycle property of the polypropylene-based composition (C), the film-forming property in the production of a film, the rigidity and heat resistance of the molded product (D), and the propylene-ethylene copolymer (RC ) And propylene homopolymer (PP) intrinsic viscosity ratio ([η]_RC/ [Η]_PP) Affects the dispersibility of the propylene-ethylene copolymer (RC) into the propylene homopolymer (PP). Intrinsic viscosity of propylene-ethylene copolymer (RC) ([η]_RC) Is larger, the mechanical properties of the molded product (D) are improved, but the molding cycle property of the polypropylene-based composition (C) is lowered, and the intrinsic viscosity ratio ([η]) with the propylene homopolymer (PP) is decreased._RC/ [Η]_PP) Is too large or too small, the molded article (D) has insufficient impact resistance at low temperatures and whitening resistance. Further, if it is too small, the flexibility of the molded product (D) is insufficient, and if it is excessive, the effect of improving the molding shrinkage of the polypropylene composition (C) and the transparency of the molded product (D) is reduced. The desired properties cannot be achieved.
[0027]
The propylene-ethylene copolymer (RC) contains at least 80% by weight, preferably 85% by weight, of a 20 ° C. xylene soluble component based on the weight of the propylene-ethylene copolymer (RC). Propylene-ethylene copolymer (RC) 20 ° C xylene soluble component weight% (CXS_RC) Cannot be measured directly, so propylene homopolymer (PP) 20 ° C. xylene soluble component weight% (CXS_PP) And 20% by weight of the total composition (A) xylene soluble component (CXS)_WHOLE) As well as weight percent of propylene-ethylene copolymer (RC) (W_RC) From the following formula.
[0028]
[Expression 2]
CXS_RC= [CXS_WHOLE-(1-W_RC/ 100) CXS_PP] / (W_RC/ 100)
In the propylene-based composition (A) of the present invention, the weight ratio of propylene homopolymer (PP) to propylene-ethylene copolymer (RC) (W_PP/ W_RC) Is the intrinsic viscosity ratio of both components ([η]_RC/ [Η]_PP) As the product of ([η]_RC/ [Η]_PP) × (W_PP/ W_RC) Is in the range of 1.0 to 3.0.
[0029]
The product of the weight ratio of both components and the intrinsic viscosity ratio is an index representing the molding shrinkage of the polypropylene composition (C). When the value is decreased, the molding shrinkage ratio and the tear strength and weld strength of the molded product (D) are improved. However, the heat resistance and rigidity of the molded product (D) are greatly decreased. In addition, the desired mold shrinkage ratio and the improvement effect of tear strength and weld strength cannot be obtained.
[0030]
The specific composition of the propylene-based composition (A) is 22 to 40% by weight, preferably 25 to 40% by weight of the propylene-ethylene copolymer (RC) based on the weight of the composition (A).
[0031]
The propylene composition (A) has a narrow dispersive molecular weight distribution with a Q value (Mw / Mn) of 5 or less, more preferably 4.5 or less. When the molecular weight distribution width increases, the gloss and weld strength of the molded product (D) decrease.
[0032]
The propylene-based composition (A) of the present invention satisfies the above-mentioned various properties, so that the molding shrinkage rate at the time of molding, the film-forming property, and the transparency, gloss, rigidity, flexibility, and impact resistance of the molded product. In particular, it is suitably used as a base resin of a polypropylene-based composition (C) for producing a molded article having excellent mechanical properties such as impact resistance at low temperatures, tear strength, weld strength and the balance between them.
[0033]
The propylene composition (A) of the present invention may be produced by any method as long as the above properties are satisfied. For example, propylene homopolymer (PP) and propylene-ethylene copolymer (RC) produced separately can be produced by mixing using a mixing device, but preferably produced by employing the production method of the present invention. can do.
[0034]
The process for producing the propylene-based composition (A) of the present invention is carried out in the presence of a stereoregular catalyst comprising a titanium-containing solid catalyst component (a) having a large particle size, an organoaluminum compound (b) and an organosilicon compound (c). In the gas phase, a propylene homopolymer is produced in the first stage (first polymerization step), and then a propylene-ethylene copolymer is produced in the second stage (second polymerization step).
[0035]
In the production method of the present invention, the titanium-containing solid catalyst component (a) is obtained by supporting a titanium compound on an inorganic carrier such as a magnesium compound, a silica compound, or alumina, or an organic carrier such as polystyrene, and if necessary on such a carrier. Any known compounds obtained by reacting an electron donating compound such as an ether or an ester can be used.
[0036]
For example, an alcohol solution of a magnesium compound is sprayed, the solid component is partially dried, and then the dried solid component is treated with a titanium halide and an electron donating compound (Japanese Patent Laid-Open No. 3-119003), Magnesium compound dissolved in tetrahydrofuran / alcohol / electron donor and TiCl_FourExamples thereof include a titanium-containing solid catalyst component obtained by treating magnesium alone or a combination of electron donors with titanium halide and an electron donating compound (JP-A-4-103604).
[0037]
As the titanium-containing solid catalyst component (a), one having an average particle diameter of 25 to 300 μm, preferably 30 to 150 μm is used. When the average particle diameter of the titanium-containing catalyst component is 25 μm or less, the fluidity of the powder of the propylene-based composition (A) to be produced is remarkably impaired, and the inside of the polymerization system due to adhesion to the wall of the polymerization vessel, the stirring blade, etc. This hinders stable operation, such as contamination and difficulty in conveying powder discharged from the polymerization vessel.
[0038]
The titanium-containing catalyst component (a) preferably has a normal distribution with a uniformity of 2.0 or less. If the degree of uniformity exceeds 2, the powder fluidity of the propylene-based composition (A) is deteriorated, and stable operation in which the first polymerization step and the second polymerization step are continued becomes difficult.
[0039]
As the organoaluminum compound (b), the general formula R¹ _mX_3-m(Where R¹Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and m is a positive number of 3 ≧ m> 1.5).
[0040]
Specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum sesquichloride, di-n- Examples thereof include propylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum iodide, ethoxydiethylaluminum, and preferably triethylaluminum is used.
[0041]
These organoaluminum compounds can be used alone or as a mixture of two or more.
[0042]
As the organosilicon compound (c), the general formula R² _XR^Three _YSi (OR_Four)_Z(Where R²And R^FourIs a hydrocarbon group, R^ThreeRepresents a hydrocarbon group or a hydrocarbon group containing a hetero atom, and X, Y, and Z are 0 ≦ X ≦ 2, 1 ≦ Y ≦ 3, 1 ≦ Z ≦ 3, and X + Y + Z = 4) Organosilicon compounds are used.
[0043]
Specifically, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, phenylmethyldimethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, methylethyldimethoxysilane , Methylphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, cyclohexylmethyldimethoxysilane, trimethylethoxysilane, etc. Preferably, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane Cyclohexylmethyl dimethoxysilane and diphenyl dimethoxysilane is used.
[0044]
These organosilicon compounds can be used alone or as a mixture of two or more.
[0045]
In the method for producing the propylene-based composition (A) of the present invention, prior to the homopolymerization of propylene in the first polymerization step, the titanium-containing solid catalyst component (a) is added to the organoaluminum compound (b ′) and, if necessary, In the presence of the organosilicon compound (c ′), the α-olefin is preferably reacted in advance to be pre-activated and used. In the preactivation treatment of the titanium-containing solid catalyst component (a), the amount of the organoaluminum compound (b ′) used is not particularly limited, but is usually 1 mol of titanium atom in the titanium-containing solid catalyst component. 0.1 to 40 mol, preferably 0.3 to 20 mol, and α-olefin is used at 10 to 80 ° C. for 10 minutes to 48 hours, and 0.1 to 100 per gram of the titanium-containing solid catalyst component. React grams, preferably 0.5 to 50 grams.
[0046]
In the preactivation treatment, the organosilane compound (c ′) may be used in the range of 0.01 to 10 mol, preferably 0.05 to 5 mol, per mol of the organoaluminum compound.
[0047]
Examples of the organoaluminum (b ′) used in the preactivation treatment include the exemplified organoaluminum (b) used in the main polymerization. The (B ′) organoaluminum compound (b ′) may be the same as or different from the organoaluminum compound (b) used in the main polymerization, but preferably triethylaluminum is used.
[0048]
Examples of the organosilicon compound (c ′) used as necessary for the preactivation treatment include the same type as the above-mentioned exemplified organosilicon compound (c). As this organosilicon compound (c ′), the same type as the organosilicon compound (c) used in the main polymerization or a different type can be used. Preferably, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane are used.
[0049]
The olefin used for the preactivation treatment of the titanium-containing solid catalyst component (a) is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene. 1-hexadecene, 1-octadecene, 1-eicocene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like. These olefins may contain not only a single olefin but also one or a mixture of two or more other olefins. In addition, a molecular weight regulator such as hydrogen can be used in combination in order to regulate the molecular weight of the polymer during the polymerization.
[0050]
The inert solvent used for the preactivation treatment of the titanium-containing solid catalyst component (a) is a liquid oil such as hexane, heptane, octane, decane, dodecane and liquid paraffin, and a silicone oil having a structure of dimethylpolysiloxane. It is an inert solvent that does not significantly affect the isopolymerization reaction. These inert solvents may be either one kind of single solvent or two or more kinds of mixed solvents.
[0051]
When these inert solvents are used, it is preferable to use them after removing impurities such as moisture and sulfur compounds which adversely affect the polymerization.
[0052]
In the method for producing the propylene-based composition (A) of the present invention, propylene is polymerized in the gas phase in the presence of the pre-activated titanium-containing solid catalyst component (a) to produce a propylene homopolymer (PP). Then, a first polymerization step for producing a polymer, and then a second polymerization step for copolymerizing ethylene and propylene to produce a propylene-ethylene copolymer (RC) are continuously performed. The first polymerization step is not limited to gas phase polymerization, and slurry polymerization or bulk polymerization may be adopted. However, since the second polymerization step continuous thereto is preferably gas phase polymerization, the first polymerization step is also important. It is preferable to employ phase polymerization. When slurry polymerization or bulk polymerization is employed as the second polymerization step, the propylene-ethylene copolymer (RC) is eluted into the solution, making it difficult to continue stable operation.
[0053]
The polymerization conditions of the propylene homopolymer (PP) differ depending on the polymerization type, but in the case of the gas phase polymerization method, the titanium-containing solid catalyst component (a) and the organoaluminum component pretreated by mixing and stirring a certain amount of powder. In the presence of a stereoregular catalyst comprising (b) and an organosilicon compound (c), a polymerization temperature of 20 to 120 ° C., preferably 40 to 100 ° C., a polymerization pressure of atmospheric pressure to 9.9 MPa, preferably 0.59 to 5 Propylene is supplied and polymerized under the condition of 0.0 MPa to produce a propylene homopolymer (A). The usage rate of the organoaluminum compound (b) and the titanium-containing solid catalyst component (a) is Al / Ti = 1 to 500 (molar ratio), preferably 10 to 300. In this case, the number of moles of the titanium-containing solid catalyst component (a) substantially means the number of Ti gram atoms in the titanium-containing solid catalyst component (a).
[0054]
The usage rate of the organosilicon compound (c) and the organoaluminum component (b) is b / c = 1 to 10 (molar ratio), preferably 1.5 to 8.
[0055]
When the molar ratio of b / c is excessive, the crystallinity of the propylene homopolymer (PP) is lowered and the rigidity of the molded product (D) becomes insufficient. On the other hand, when the b / c molar ratio is too small, the polymerization activity is remarkably lowered and the productivity is lowered.
[0056]
The molecular weight of the propylene homopolymer (PP) can be adjusted by using a molecular weight regulator such as hydrogen during the polymerization, and the intrinsic viscosity of the propylene homopolymer (PP) is performed so as to satisfy the requirements of the present invention. . After polymerizing the propylene homopolymer (PP), a part of the produced powder is extracted and the intrinsic viscosity ([η]_PP), Melt flow rate (MFR)_PP), 20 ° C. xylene soluble component amount and isotactic fraction (P), and polymerization yield per unit weight of catalyst.
[0057]
Subsequent to propylene homopolymerization in the first polymerization step, ethylene and ethylene under conditions of a polymerization temperature of 20 to 120 ° C., preferably 40 to 100 ° C., a polymerization pressure of atmospheric pressure to 9.9 MPa, preferably 0.59 to 5.0 MPa. A second polymerization step is carried out in which a mixed monomer of propylene is copolymerized to form a propylene-ethylene copolymer (RC). The ethylene unit content in the propylene-ethylene copolymer (RC) is controlled by controlling the gas molar ratio of the ethylene monomer to the propylene monomer in the comonomer gas so that the ethylene unit content in the propylene-ethylene copolymer (RC) is 25 to 55% by weight. Adjust so that
[0058]
On the other hand, the weight of the propylene-ethylene copolymer (RC) relative to the weight of the propylene homopolymer (PP) is determined by adjusting the polymerization time and using a polymerization activity regulator of a catalyst such as carbon monoxide or hydrogen sulfide. The weight of (RC) is adjusted to 22 to 40% by weight. Furthermore, the molecular weight of the propylene-ethylene copolymer (RC) is polymerized with a molecular weight regulator such as hydrogen so that the intrinsic viscosity of the propylene-ethylene copolymer (RC) meets the requirements of the propylene-based composition (A). Sometimes adjusted in addition. The hydrogen is supplied in such a way that the Q value (Mw / Mn) of the propylene composition (A) satisfies the requirements of the propylene composition (A).
[0059]
As the polymerization method, any of batch type, anti-continuous type or continuous type can be adopted, but industrially preferable is continuous polymerization.
[0060]
After completion of the second polymerization step, the monomer can be removed from the polymerization system to obtain a particulate polymer. The obtained polymer was treated with intrinsic viscosity ([η]_WHOLEE), 20 ° C. xylene soluble component amount, Q value (M_w/ M_n) And ethylene content and polymerization yield per unit weight of catalyst.
[0061]
The polypropylene-based composition (C) of the present invention is a composition comprising the propylene-based composition (A) as a base resin and blended with desired additive components corresponding to the required characteristics of the molded product and the molding method.
[0062]
The polypropylene composition (C) of the present invention usually has various additives generally used as polyolefin additives, for example, antioxidants such as phenol-based, thioether-based, and phosphorus-based antioxidants; Dispersants or neutralizers such as higher fatty acid salts (metal soaps) such as calcium stearate; light stabilizers; heavy metal deactivators (copper damage inhibitors); clearing agents; β crystal nucleating agents; lubricants such as steric acid Amides, etc .; Antistatic agents such as fatty acid esters such as glycerin monostearate, etc .; Cloud proofing agents; Dropless agents; Flame retardants; Flame retardant aids; Pigments; Halogen scavengers; Organic and inorganic antibacterial agents; Agents and antiblocking agents such as talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, Calcium acid, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, hydrotalcite, basic aluminum, lithium, hydroxy, carbonate, hydrate, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, calcium oxide, zinc oxide, sulfuric acid Barium, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber, etc., coupling agents such as silane, titanate, boron, aluminate, Zircoaluminate and the like, as well as inorganic fillers or organic fillers surface-treated with them, such as wood flour, pulp, waste paper, synthetic fibers, natural fibers and the like are usually contained within a range not impairing the object of the invention.
[0063]
In general, the polypropylene-based composition (C) is blended with a phenol-based antioxidant and / or a phosphorus-based antioxidant and calcium stearate as a neutralizing agent (dispersing agent).
[0064]
The polypropylene composition (C) in which a general additive is blended with the polyolefin of the present invention is a polypropylene composition for injection molding (Ci), a polypropylene composition for sheet molding (Cs), and a film molding. It can be suitably used as a polypropylene composition (Cf).
[0065]
In the polypropylene composition (Ci), the α crystal nucleating agent is 0.0001 to 1 part by weight, preferably 0.001 to 0.8 part by weight with respect to 100 parts by weight of the propylene composition (A). By blending the part, the rigidity of the injection molded product can be increased and the impact resistance at low temperature can be further improved.
[0066]
α crystal nucleating agents include inorganic compounds such as talc, alum, silica, titanium oxide, calcium oxide, magnesium oxide, carbon black, clay minerals; malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid , Dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 1 -Methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexanecarboxylic acid, 4-cyclohexene Aliphatic monocarboxylic acids such as N-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylyl acid, ethyl benzoic acid, 4-t-butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc. Carboxylic acid to be removed; normal salt or basic salt of the non-aliphatic monocarboxylic acid such as lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, aluminum, etc .; 1,2,3,4-dibenzylidenesorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1. 3-p-ethylbenzylidene-2 • 4-benzylidenesorbitol, 1 • 3- p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (pn-propylbenzylidene) sorbitol, 1,3,2,4-bis (pi -Propylbenzylidene) sorbitol, 1,3,2,4-bis (pn-butylbenzylidene) sorbitol, 1,3,2,4-bis (ps-butylbenzylidene) sorbitol, 1,3,2, 4-bis (pt-butylbenzylidene) sorbitol, 1,3- (2 ′ · 4′-dimethylbenzylidene) -2 · 4-benzylidenesorbitol, 1,3-benzylidene-2 · 4- (2 ′・ 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (3 ′, 4′-dimethylbenzylidene) sorbitol 1,3,2,4-bis (p-methoxybenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidenesorbitol 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p -Ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-ethylbenzyl Dibenzylidene sorbitol compounds such as den-2 · 4-p-chlorobenzylidene sorbitol and 1,3,2,4-bis (p-chlorobenzylidene) sorbitol; lithium-bis (4-t-butylphenyl) phosphate Sodium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-cumylphenyl) phosphate, sodium-bis (4-cumylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate Calcium-mono (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-mono (4-t-butylphenyl) phosphate, magnesium-bis (4-t -Butylphenyl) phosphate, zinc-mono (4-t-butyl) Phenyl) phosphate, zinc-bis (4-t-butylphenyl) phosphate, aluminum dihydroxy- (4-t-butylphenyl) phosphate, aluminum hydroxy-bis (4-t-butylphenyl) phosphate, aluminum Tris (4-t-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4,4 6-di-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-cumyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4, 6-di-t-butylphenyl) phosphate, lithium-2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Lithium-2,2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis (4-i-propyl-6-tert-butylphenyl) phosphate Fete, lithium-2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, lithium-2,2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate Fate, sodium-2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-butylidene-bis (4,6-di-t-butylphenyl) phosphate, Sodium-2,2′-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2′-t-octylmethylene-bis (4,6-di-t-butylphenyl) ) Sulfate, sodium-2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate Fate, sodium (4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl) phosphate, sodium-2,2′-ethylidene-bis (4-s-butyl-6) -T-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethyl) Phenyl) phosphate, potassium-2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2′-methylene-bis (4,6-di-t) -Butylphenyl) phosphor , Magnesium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], zinc-bis [2,2′-methylene-bis (4,6-di-) t-butylphenyl) phosphate], aluminum-tris [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], calcium-bis [2,2′-methylene-bis ( 4-methyl-6-tert-butylphenyl) phosphate], calcium-bis [2,2′-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate], calcium-bis [2,2 '-Thiobis (4-methyl-6-tert-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6-tert-butylphenyl) phosphate], calcium-bis [2 , 2'-thiobis (4,6-di-t-butylphenol ) Phosphate], magnesium-bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis (4-t-octylphenyl) Phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], calcium-bis [(4,4′-dimethyl-6,6′-di) -T-butyl-2,2'-biphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2, 2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], Aluminum dihydroxy-2,2'-methylene-bis (4, 6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4-cumyl-6-t-butylphenyl) phosphate, aluminum hydroxy-bis [2,2'- Methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum hydrodoxy-bis [2,2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate], Titanium dihydroxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], tindihydroxy-bis [2,2′-methylene-bis (4,6-di-t) -Butylphenyl) phosphate], zirconium oxy-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum dihydroxy-2,2'-methylene-bi (4-Methyl-6-tert-butylphenyl) phosphate, aluminum hydroxy-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], aluminum dihydroxy-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, aluminum hydroxy-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], etc. Aryl phosphate compounds; among the above-mentioned aryl phosphate compounds, cyclic polyvalent metal aryl phosphate compounds and acetic acid, lactic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, Myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, 12-hydroxystearate Of fatty acid group monocarboxylic acids such as acid, ricinoleic acid, behenic acid, erucic acid, montanic acid, melicic acid, stearoyl lactic acid, β-N-laurylaminopropionic acid, β-N-methyl-N-lauroylaminopropionic acid Fatty acid monocarboxylic acid alkali metal salts such as lithium, sodium or potassium salts, or mixtures with basic aluminum, lithium, hydroxy, carbonate, hydrate; poly-3-methyl-1-butene, poly-3-methyl-1-pentene, Poly-3-ethyl-1-pentene, poly-4-methyl-1-pentene, poly-4-methyl-1-hexene, poly-4,4-dimethyl-1-pentene, poly-4,4-dimethyl-1-hexene, poly 4-ethyl-1-hexene, poly-3-ethyl-1-hexene, polyallylnaphthalene, polya High in rilnorbornane, atactic polystyrene, syndiotactic polystyrene, polydimethylstyrene, polyvinylnaphthalene, polyallylbenzene, polyallyltoluene, polyvinylcyclopentane, polyvinylcyclohexane, polyvinylcyclopeptane, polyvinyltrimethylsilane, polyallyltrimethylsilane, etc. Molecular compounds; and the like.
[0067]
Among them, talc, aluminum hydroxy-bis (4-t-butylbenzoate), 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol, 1. 3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (3', 4 '-Dimethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-bis (p-chlorobenzylidene) sorbitol, sodium-bis (4-t -Butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-2,2'-methylene-bis (4, -Di-t-butylphenyl) phosphate, aluminum-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, aluminum dihydroxy-2,2'-methylene-bis (4, 6-di-t-butylphenyl) phosphate or cyclic polyvalent metal aryl phosphates such as aluminum hydroxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate] Preference is given to mixtures of compounds with fatty acid monocarboxylic acid alkali metal salts, poly-3-methyl-1-butene, polyvinylcyclohexane or polyallyltrimethylsilane.
[0068]
Of course, these α crystal nucleating agents can be used alone, or two or more α crystal nucleating agents can be used in combination.
[0069]
The polypropylene composition (Ci) of the present invention can be further blended with a radical generator and / or crystalline propylene homopolymer (PHP) to further improve the whitening of the injection-molded product.
[0070]
The blended crystalline propylene homopolymer (PHP) has a density of 0.91 to 0.89 g / cm.^ThreeAnd the melt flow rate ratio (MFR) of the propylene-based composition (A) and the crystalline propylene homopolymer (PHP)_WHOLE/ MFR_Ph) Propylene homopolymer having 0.5-2, preferably 0.8-1.2.
[0071]
In this composition, the MFR ratio between the propylene-based composition (A) and the crystalline propylene homopolymer (Ph) affects the whitening property of the molded product, and the whitening property is too large or too small. Run short.
[0072]
The blending amount of crystalline propylene homopolymer (PHP) is 10 to 95% by weight based on the resin, and the content of the propylene-based composition (A) is based on the resin based on the balance between the rigidity and impact resistance of the molded product. It is in the range of 5 to 90% by weight.
[0073]
That is, in this composition, since the propylene-based composition (A) acts as a whitening agent for preventing whitening of the molded product, this composition is used for molding a molded product having a bent portion such as a hinge or a container cap (cap). Suitable for use.
[0074]
On the other hand, the radical generator makes the compound highly fluid and significantly improves the moldability.
[0075]
As the radical generator, the decomposition temperature is desirably not too low in order to obtain a uniform composition, and the temperature for obtaining a half-life of 10 hours is 70 ° C. or higher, preferably 100 ° C. or higher. For example, benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (t-benzoylperoxy) hexane, , 5-di-methyl-2,5-di- (t-benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, Methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane, 2, 5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl) benzene, t Butylcumyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxybutane), p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1,3,3 -Organic peroxides such as tetra-methylbutyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy) hexane. In particular 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3 and 1 3-bis- (t-butylperoxyisopropyl) benzene is preferred. These radical generators can be used alone or in combination of two or more. The polypropylene composition (C) in which a general additive is blended with the aforementioned polyolefin of the present invention can also be used as a polypropylene composition (Cb) for molding a hollow molded product.
[0076]
The polypropylene composition (Cb) can be blended with 5 to 20 parts by weight of a plasticizing component with respect to 100 parts by weight of the propylene composition (A) to impart flexibility to the molded product.
[0077]
As a plasticizing component (Ps), a density of 0.910 to 0.930 g / cm, generally referred to as low density polyethylene.^ThreeAn ethylene homopolymer and an ethylene-α- of a crystalline melting point (Tm) of 100 to 115 ° C., a melt flow rate (MFR: 190 ° C .; 21.18 N) of 0.1 to 5 g / 10 min, preferably 0.1 to 1 g / 10 min. Olefin copolymer and density from 0.92 to 0.935 g / cm^ThreeAn ethylene-vinyl acetate copolymer having a crystal melting point (Tm) of 90 to 108 ° C. and a melt flow rate (MFR: 190 ° C .: 21.18 N) of 0.1 to 5 g / 10 min, preferably 0.1 to 1 g / 10 min. .
[0078]
Since the compounding of the plasticizing component imparts flexibility to the molded product, the polypropylene composition (Cb) is suitable for molding hollow molded products and films having a bellows structure.
[0079]
Each polypropylene composition of the present invention described above is prepared by mixing the propylene composition (A) and each additive component as desired using a high-speed mixing device such as a Henschel mixer (trade name), a ribbon blender, a tumbler mixer, or the like. Using a single screw extruder, a twin screw extruder, a kneader, etc., the mixture is melt-kneaded at 150 to 300 ° C., preferably 200 to 250 ° C., and pelletized, and used for molding various molded products.
[0080]
The molded product of the present invention is a molded product molded by various molding methods using each of the polypropylene-based compositions.
[0081]
The molded product of the first aspect is an injection molded product. More specifically, it is a molded product obtained by injection molding pellets of the above-mentioned polypropylene-based compositions such as a sheet-shaped molded product, a container and a container stopper (cap), and a molded product with a hinge.
[0082]
Any of the above-described polypropylene-based compositions for injection molding may be used, but the polypropylene-based composition for injection molding (Ci) is preferably used.
[0083]
A composition in which an α crystal nucleating agent, a radical generator and / or a crystalline propylene homopolymer, etc. are blended depending on the molded article to be molded and the properties required for it.
[0084]
By using these polypropylene-based compositions (Ci), the whitening resistance, transparency, gloss, rigidity, impact resistance, especially low temperature impact resistance of the bent part (hinge structure part, etc.), molding shrinkage during molding It is possible to produce an injection-molded article having an excellent rate and a balance between them.
[0085]
The molded product of the second aspect of the present invention is a sheet, and from the viewpoint of printability and flexibility of the sheet, the sheet has a Young's modulus in the longitudinal direction at 23 ° C of 200 to 450 MPa, preferably 300 to 400 MPa, and at 50 ° C. It has a tensile yield point strength in the longitudinal direction of 15 MPa or more, preferably 17 MPa or more.
[0086]
The sheet of the present invention can be produced by any known sheet molding method, but extrusion molding or calender molding is preferred because of good productivity. Specifically, an apparatus (T die sheet molding machine) having processes such as an extruder, a T die, a polishing roll (cooling roll), a guide roll, a take-up roll, a trimming cutter, masking, a regular cutting cutter, and a stacker is used. Sheet forming by T die method and equipment (calendar molding machine) with processes such as Banbury mixer, mixing roll, warming roll, extruder, calender roll, cooling roll, trimming cutter, masking, regular cutting cutter, winder To do.
[0087]
More preferably, the polypropylene-based composition (C), preferably the same polypropylene-based composition (Cs) as described in the injection molding, is produced by the method for producing the sheet of the present invention, that is, the T-die method, at a resin temperature of 180 to 300. Extrusion is performed at a temperature of 5 ° C. to 80 ° C., and the difference from the resin temperature is set to 120 ° C. or more, and molding is performed at a sheet speed of 0.1 to 100 m / min.
[0088]
If the resin temperature is in the range of 180 to 300 ° C., the polypropylene composition (Cs) is in a range where the polypropylene composition (Cs) is sufficiently melted and is not thermally deteriorated, so that good moldability can be obtained while maintaining the melt tension of the sheet, And the surface of a sheet | seat does not become a skin shape, but the sheet | seat excellent in the external appearance is obtained.
[0089]
If the temperature of the cooling roll is 5 ° C. or higher, the cooling roll will not condense so that no spotted pattern is generated on the surface of the sheet. If the temperature is 80 ° C. or lower, the sheet can be sufficiently cooled, and the roll-shaped sheet is unwound. Sometimes a linear pattern does not occur and a sheet with a good appearance is obtained.
[0090]
The sheet has a weak molecular orientation, so that there is little difference in thermal shrinkage between the machine direction and the transverse direction.
[0091]
[Equation 3]
Resin temperature−cooling roll temperature ≧ 120
By maintaining the relationship expressed by the above, a sheet having excellent formability can be obtained.
[0092]
If the sheet forming speed is 0.1 m / min or more, a sheet having a uniform thickness and a low defect rate can be obtained at a sufficient production rate. On the other hand, if the sheet forming speed is 100 m / min or less, the sheet can be cooled sufficiently. Since the generation of the linear pattern when the sheet is unwound can be prevented, a sheet having a good appearance can be obtained.
[0093]
The molded product of the third aspect of the present invention uses the polypropylene composition (C), preferably a polypropylene composition (Cf) in which a general polyolefin additive is blended with the propylene composition (A). It is a film formed by This film includes unstretched, uniaxially stretched and biaxially stretched films.
[0094]
The unstretched film is obtained by the T-die method or the inflation method used for the production of a normal polyolefin film, and the uniaxially stretched film or the biaxially stretched film is obtained by uniaxially stretching the unstretched film obtained by the above method by the tenter method. It can manufacture by extending | stretching by the simultaneous biaxial stretching method by a sequential biaxial stretching method or a tubular system.
[0095]
These films are excellent in impact resistance, heat resistance and tear strength at low temperatures by using the polypropylene composition (C) based on the propylene composition of the present invention.
[0096]
Another aspect of the film of the present invention is a laminated film in which a functional polymer layer is laminated on one side or both sides of the film.
[0097]
The laminated film of the present invention is not particularly limited as long as a polymer layer capable of imparting a specific function is laminated on the film made of the polypropylene composition (C), but has at least a heat-sealable layer.
[0098]
As the heat-sealable layer, the density is from 0.89 to 0.91 g / cm.^ThreeA propylene homopolymer having a crystalline melting point of 165 to 160 ° C. and / or a density of 0.89 to 0.91 g / cm^ThreeA propylene-α-olefin copolymer having a crystalline melting point of 159 to 110 ° C. is preferably used.
[0099]
The melt flow rate (230 ° C .; 21.18N) of the polymer used for these heat-sealable layers is 0.1 to 50 g / 10 min, preferably 1 in terms of moldability during film forming and the appearance of the resulting film. ~ 20 g / 10 min. Examples of the α-olefin copolymerized with propylene include ethylene, butene-1, and pentene-1.
[0100]
As a propylene-α-olefin copolymer, an ethylene-propylene copolymer having an ethylene component content of 0.2 to 10% by weight, an ethylene component content of 0.2 to 10% by weight, and a butene-1 component content of 0.4 to Examples thereof include 5% by weight of ethylene-propylene-butene-1-copolymer.
[0101]
The crystal melting point of the propylene homopolymer is 165 to 160 ° C. in that a multilayer film having excellent surface gloss, surface hardness and rigidity can be obtained.
[0102]
The crystal melting point of the propylene-α-olefin copolymer is 159 ° C to 110 ° C, preferably 140 ° C to 110 ° C, in that a laminated film having excellent heat sealability can be obtained.
[0103]
These propylene homopolymers and propylene-α-olefin copolymers are formed from composites containing at least magnesium, titanium, and halogen, organometallic compounds of Group 1 to 3 metals of the periodic table, and electron donors. Propylene can be homopolymerized by a known publicly known polymerization method using a catalyst, or can be produced by a method of copolymerizing propylene and an α-olefin.
[0104]
The multilayer film of the present invention is an unstretched, uniaxially stretched or biaxially stretched multilayer film having a layer using a polypropylene composition and the functional polymer layer.
[0105]
As the layer structure of the multilayer film, functional polymer layer / polypropylene-based composition layer, two types / two layers, functional polymer layer / polypropylene-based composition layer / functional polymer layer, two types / three layers or three types / three layers A layer can be illustrated. Among these, a laminated film composed of a propylene homopolymer layer / polypropylene composition layer / propylene-α-olefin copolymer layer is preferable in terms of heat resistance and heat sealability of the obtained laminated film.
[0106]
Although the thickness of a laminated | multilayer film is not specifically limited, 10-100micro is preferable at the point of the moldability of a film, More preferably, it is 15-70micro. Further, the thickness of each layer of the laminated film is not particularly limited, but the ratio of the thickness of the propylene-based composition layer to the total thickness of the film is 30 to 30 in terms of impact resistance at low temperatures, heat resistance, and tear strength. 90%, preferably 50 to 90%.
[0107]
Examples of the method for producing a laminated film include a multilayer extrusion molding method, a dry lamination method, and an extrusion lamination method. Examples of the multilayer extrusion molding method include a T-die method and an inflation method that are usually used for the production of polyolefin films. Examples of the stretching method include a sequential biaxial stretching method using a tenter method and a simultaneous biaxial stretching method using a tubular method.
[0108]
In the case of producing a laminated film by the above-mentioned publicly known methods, there is no particular limitation on the melt flow rate (MFR) of the polypropylene composition and functional polymer constituting each layer, but the film moldability and the appearance of the product film The ratio of MFR of the polypropylene composition to the functional polymer is 0.1 to 10, preferably 0.5 to 2.
[0109]
The laminated film of the present invention can also be produced by laminating with a transparent base film such as BOPP film, PET film, nylon film, and eval film via an adhesive by a method such as dry lamination.
[0110]
The film and laminated film of the present invention can be further subjected to surface treatments such as corona discharge treatment, flame treatment, plasma treatment, etc. by the methods generally employed in the industry for the purpose of imparting printability, laminate suitability, and metal deposition characteristics. It is.
[0111]
The molded product of the fourth aspect of the present invention is a hollow molded product made of the above-described polypropylene composition (C), particularly a composition (Cb) in which a plasticizing component is blended with a propylene composition.
This hollow molded article preferably has a bellows structure.
[0112]
The hollow molded article of the present invention can be easily produced by a blow molding method in which a pellet of the polypropylene composition (C) is supplied to an extruder of a blow molding machine and extruded into a hollow cylindrical shape. Further, by using a mold having an uneven surface (bellows surface) as a mold for the molding machine, a hollow molded product having a bellows structure can be easily manufactured.
[0113]
Another aspect of the hollow molded article of the present invention is a composite hollow molded article in which a hollow molded article portion having a bellows structure and a hollow molded article portion made of a polyolefin-based composition (PO) having excellent rigidity and impact resistance are connected. It is.
[0114]
The polyolefin-based composition (PO) used for the hollow molded part connected to the bellows structure is an ethylene-propylene copolymer containing 1 to 20% by weight containing 25 to 55% by weight, preferably 35 to 55% by weight of ethylene polymerized units. Preferably, an inorganic filler such as talc, calcium carbonate, calcium silicate and the like added for the purpose of imparting rigidity to a composition comprising 10 to 20% by weight and a propylene homopolymer 99 to 80% by weight is provided for the purpose of the present invention. It is the composition mix | blended in the range which is not impaired. The blending ratio of the inorganic filler is preferably 20% by weight or less based on the weight of the composition.
[0115]
This hollow molded article uses an accumulator blow molding machine equipped with a set of mold clamping devices, one ram cylinder and at least two extruders, and the polypropylene composition (C ), Supplying the polyolefin-based composition (PO) to another extruder, first storing the composition melted from one extruder in the ram cylinder, and then storing the composition melted from the other extruder in the ram cylinder .
[0116]
Next, the melted polypropylene composition (C) was set so that the parison of the melted polypropylene composition (C) was introduced into a mold part having an uneven surface (bellows surface), and the parison was extruded from the ram cylinder. It can be manufactured by blowing pressurized air of 1 MPa.
[0117]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
A. Synthesis of propylene-based composition (A) 1) Measurement of various physical properties
In the process of synthesizing the propylene-based composition, various physical properties of the intermediate product and the final product were measured by the following methods.
The synthesis conditions and measurement results are shown in Tables 1 and 2.
a) Average particle diameter (μm) of the titanium-containing solid catalyst component (a): calculated from a particle size distribution measured using a master sizer (manufactured by MALVERN).
b) Uniformity of the titanium-containing solid catalyst component (a): the particle size under 60% obtained from the particle size distribution measured using Mastersizer (manufactured by MALVERN) is divided by the particle size under 10%. Calculated.
c) Polymer production per catalyst unit weight: measured by inductively coupled plasma emission analysis (IPC method) of Mg in the sample.
d) Isotactic pentad fraction in polypropylene molecular chain P: in accordance with macromolecules 8687 (1975),¹³Measured using C-NMR.
e) Ethylene unit content (% by weight): Measured by infrared absorption spectrum method.
f) Intrinsic viscosity (dl / g): Measured using a viscometer (AVS2 type, manufactured by Mitsui Toatsu Co., Ltd.) in a tetralin (tetrachloronaphthalene) solvent at a temperature of 135 ° C.
g) Melt flow rate (g / 10 min): Measured according to JIS K 6760.
h) Average molecular weight Q value (Mn / Mw): Using a GPC apparatus (Gel Permination Chromatograph, Model 150C, Waters, column used: TSK GEL GMH6-HT) for a sample dissolved in orthodichlorobenzene at 135 ° C. Measurement.
i) 20 ° C. xylene-soluble component amount (% by weight): Measured according to ISO / DIS 1873-1.
j) Powder flowability: The compressibility of the powder is calculated by the following formula.
[Expression 4]
Compressibility = (hard apparent density-loose apparent density) x 100 / hard apparent density
The higher the degree of compression, the worse the powder flowability.
[0118]
2) Preparation of titanium-containing solid catalyst component (a)
a) Titanium-containing solid catalyst component: a-1
SUS autoclave purged with nitrogen was added to anhydrous MgCl₂95.3 g and dry EtOH 352 ml were added, and the mixture was heated to 105 ° C. with stirring to dissolve. After stirring for 1 hour, the solution was fed into a two-fluid spray nozzle with pressurized nitrogen (1.1 MPa) heated to 105 ° C. The flow rate of nitrogen gas was 381 / min. Liquid nitrogen was introduced into the spray tower for cooling, and the temperature in the tower was maintained at -15 ° C. The product was collected in cold hexane introduced at the bottom of the column to obtain 256 g. From the analysis results of the product, the composition of this support is the same MgCl as the starting solution.₂-It was 6 EtOH. For use as a carrier, 205 g of a spherical carrier having a particle size of 45 to 212 μm was obtained by sieving. The resulting support was dried by aeration with nitrogen at a flow rate of 31 / min for 181 hours at room temperature to give a MgCl composition.₂-A dry carrier of 1.7 EtOH was obtained.
[0119]
In a glass flask, 20 g of dry carrier, 160 ml of titanium tetrachloride and 240 ml of purified 1,2-dichloroethane were mixed and heated to 100 ° C. with stirring. Next, 6.8 ml of diisobutyl phthalate was added, and the mixture was further heated at 100 ° C. for 2 hours, and then the liquid phase part was removed by decantation. Again, 160 ml of titanium tetrachloride and 320 ml of purified 1,2-dichloroethane were added and heated to 100 ° C. for 1 hour. The liquid phase part was removed by decantation, washed with purified hexane, and dried to obtain a titanium-containing solid catalyst component: a-1. The obtained titanium-containing solid catalyst component: a-1 had an average particle size of 115 μm, and analyzed values thereof were Mg: 19.5 wt%, Ti: 1.6 wt%, Cl: 59.0 wt%, Diisobutyl phthalate; 4.5% by weight.
[0120]
b) Titanium-containing solid catalyst component: a-2
SUS autoclave purged with nitrogen, 1,050 ml of refined kerosene, anhydrous MgCl₂15 g, 36.3 g of dry ethanol and 4.5 g of a surfactant (trade name Emazole 320, manufactured by Kao Atlas Co., Ltd.) were added, and the mixture was heated with stirring at 800 rpm and maintained at 120 ° C. for 30 minutes. did. Teflon with an inner diameter of 5 mm while stirring the molten mixture at high speed^{( R )}Using a tube made, it was transferred to a 3,000 ml stirred flask filled with 1,500 ml of purified kerosene cooled to -10 ° C. The product was filtered and washed thoroughly with hexane to obtain a carrier.
[0121]
After 15 g of the carrier was suspended in 300 ml of titanium tetrachloride at room temperature, 2.6 ml of diisobutyl phthalate was added, and the solution of the mixture was heated to 120 ° C. After stirring and mixing for 2 hours at a temperature of 120 ° C., the solid was filtered and suspended again in 300 ml of titanium tetrachloride. The suspension was stirred and mixed at 130 ° C. for 2 hours, and then the solid was filtered and thoroughly washed with purified hexane to obtain a titanium-containing solid catalyst component: a-2.
The obtained titanium-containing solid catalyst component: a-2 had an average particle size of 72 μm, and the analytical values thereof were Mg; 21.1 wt%, Ti; 2.4 wt%, Cl; 64.15 wt%, Diisobutyl phthalate: 5.3% by weight.
[0122]
c) Titanium-containing solid catalyst component: a-3
A mixture of 300 g of magnesium ethoxide, 550 ml of 2-ethylhexanol and 600 ml of toluene was stirred at 93 ° C. for 3 hours in a 0.20 MPa carbon dioxide atmosphere. Further, 800 ml of toluene and 800 ml of n-decane were added to obtain a magnesium carbonate solution.
Preparation was made while stirring 800 ml of toluene, 60 ml of chlorobenzene, 18 ml of tetraethoxysilane, 17 ml of titanium tetrachloride and 200 ml of Isopar G (an isoparaffin hydrocarbon having an average carbon number of 10 and a boiling point of 156-176 ° C.) at 30 ° C. for 5 minutes. 100 ml of magnesium carbonate solution was added.
[0123]
After further stirring for 5 minutes, 44 ml of tetrahydrofuran was added and stirred at 60 ° C. for 1 hour. Stirring was stopped and the supernatant was removed, and the resulting solid was washed with 100 ml of toluene, 200 ml of chlorobenzene and 200 ml of titanium tetrachloride were added to the obtained solid, and the mixture was stirred at 135 ° C. for 1 hour. After stirring was stopped and the supernatant was removed, 500 ml of chlorobenzene, 200 ml of titanium tetrachloride and 4.2 ml of di-n-butyl phthalate were added and stirred at 135 ° C. for 1.5 hours. After removing the supernatant, the solid was sequentially washed with 1,200 ml of toluene, 1,600 ml of Isopar G, and 800 ml of hexane to collect a comparative titanium-containing solid catalyst component: a-3.
The obtained titanium-containing solid catalyst component: a-3 had an average particle diameter of 18.5 μm, and analyzed values thereof were Mg: 17.0 wt%, Ti: 2.3 wt%, Cl: 55.0 wt %, Di-n-butyl phthalate; 7.5% by weight.
[0124]
3) Preactivation treatment of titanium-containing solid catalyst component (a)
Saturated hydrocarbon solvent (CRYSTOL-52, manufactured by Esso Oil Co., Ltd.) with a kinematic viscosity at 40 ° C of 7.3 centistokes after replacing a stainless steel reactor with inclined blades with an internal volume of 15 liters with nitrogen gas After adding 8.3 liters, 525 mmol of triethylaluminum, 80 mmol of diisopropyldimethoxysilane and 700 g of the titanium-containing solid catalyst component prepared in the previous section at room temperature, the mixture was heated to 40 ° C., and propylene was reacted at a partial pressure of 0.15 MPa for 7 hours. Pre-activation treatment was performed. As a result of the analysis, 3.0 g of propylene was reacted per 1 g of the titanium-containing solid catalyst component.
[0125]
4) Synthesis of propylene homopolymer (PP): first polymerization step
In the flow sheet shown in FIG. 3, a horizontal polymerization vessel having a stirring blade; 0.5 g / hr of a titanium-containing solid catalyst component preliminarily treated in 1 (L / D = 6, internal volume 100 liters), organoaluminum Triethylaluminum as the compound (b) and diisopropyldimethoxysilane as the organosilicon compound (c) were continuously supplied so as to have the Al / Si molar ratios shown in Tables 1 and 2. Propylene is continuously supplied so as to maintain the conditions of a reaction temperature of 70 ° C., a reaction pressure of 2.5 MPa, and a stirring speed of 40 rpm, and hydrogen gas is continuously circulated to adjust the molecular weight of the produced propylene homopolymer; The intrinsic viscosity of the produced propylene homopolymer was controlled by the hydrogen concentration in the gas phase of the reactor.
The reaction heat was removed by the vaporization heat of the raw material propylene supplied from the pipe;
[0126]
The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through a pipe; 4 and refluxed to the polymerization reactor;
Polymerizer; Propylene homopolymer obtained in 1 is piped so that the polymer retention level is 50% by volume of the reaction volume; Polymerizer through 5; Polymerizer in the second polymerization step continuously extracted from 1; 10 was supplied. At this time, a part of the propylene homopolymer was intermittently withdrawn from the pipe; 5 to obtain isotactic pentad fraction (P), 20 ° C. xylene-soluble component amount, intrinsic viscosity ([η]_PP) And the polymer yield per unit weight of the catalyst.
[0127]
5) Synthesis of propylene-ethylene copolymer (RC): second polymerization step
Propylene homopolymer and ethylene-propylene mixed gas from the first polymerization step are continuously supplied to a horizontal polymerization vessel having stirring blades; 10 (L / D = 6, internal volume 100 liters), and copolymerization of ethylene and propylene Went. The reaction conditions were a stirring speed of 40 rpm, a temperature of 60 ° C., a pressure of 2.1 MPa, and the gas composition of the gas phase was adjusted as shown in Tables 1 and 2 with respect to the ethylene / propylene molar ratio and the hydrogen / ethylene molar ratio. Carbon monoxide was supplied as a polymerization activity inhibitor to adjust the polymerization amount of the produced propylene-ethylene copolymer, and hydrogen gas was supplied from a pipe; 7 to regulate the molecular weight of the produced propylene-ethylene copolymer.
The reaction heat was removed by vaporization heat of the raw material liquid propylene supplied from the pipe;
[0128]
The unreacted gas discharged from the polymerization vessel was cooled and condensed outside the reactor system through a pipe; 8 and refluxed to the copolymerization step. The propylene-based composition (A) produced in the copolymerization step was extracted from the polymerization vessel; 10 with the pipe; 9 so that the retained level of the polymer was 50% by volume of the reaction volume.
The production rate of the propylene-based composition (A) was 8 to 12 kg / hr.
[0129]
Monomers are removed from the extracted propylene-based composition (A), and some of the intrinsic viscosity ([η]_WHOLE), Q value (Mw / Mn), 20 ° C. xylene soluble component amount and infrared measurement of ethylene in propylene-ethylene copolymer, and measurement of propylene-ethylene copolymer polymerization ratio. Furthermore, the fluidity of the powder of the propylene composition (A) was evaluated.
[0130]
By changing the kind of titanium-containing solid catalyst component (a) to be used, Al / Si molar ratio and hydrogen / propylene molar ratio in the first polymerization step, ethylene / propylene molar ratio and hydrogen / ethylene molar ratio in the second polymerization step Samples A-1 to A-14 and comparative samples cA-1 to cA-14 were obtained.
[0131]
Table 1 shows the reaction conditions and measurement results of physical properties, Table 1 shows the production conditions and characteristics of the propylene composition of the present invention, and Table 2 shows the production conditions and characteristics of the propylene-based comparative composition.
[0132]
[Table 1]

[0133]
[Table 2]

[0134]
[Table 3]

[0135]
[Table 4]

[0136]
B. Polypropylene composition for injection molding (Ci) and injection molded product
1) Polypropylene composition
Various additives are added to each powder of the propylene-based compositions A-1 to 6 and comparative compositions cA-1 to 7 of the present invention, and a high-speed stirring mixer (Henschel mixer) is used. The mixture was mixed for a minute, and the mixture was granulated at a cylinder set temperature of 230 ° C. using an extrusion granulator having a screw diameter of 40 mm to prepare pellets.
[0137]
Tables 3 and 4 show the polypropylene-based compositions Ci-1 to 12 and Ci-13 to 18 of the present invention, and Tables 5 and 6 show each additive component of the comparative compositions cCi-1 to 7 and cCi-13. And the amount of addition thereof.
The additive components used and the abbreviations in the table are shown below.
[0138]
Propylene homopolymer
PHP1: Titanium-containing solid catalyst component: obtained by homopolymerizing propylene under the conditions of Al / Si molar ratio 2, hydrogen / propylene molar ratio 0.03, polymerization pressure 2.5 MPa and polymerization temperature 70 ° C. Melt flow rate MFR_PHP1 and a crystalline propylene homopolymer having a melting point of 163 ° C.
PHP2: obtained by homopolymerizing propylene under the conditions of Al / Si molar ratio 2, hydrogen / propylene molar ratio 0.01, polymerization pressure 2.5 MPa and polymerization temperature 70 ° C. using a solid catalyst component containing titanium: a-1. Melt flow rate MFR_PHPA crystalline propylene homopolymer with a 1.9 and a melting point of 164 ° C.
PHP3: obtained by homopolymerizing propylene with a titanium-containing solid catalyst component: a-1 and using an Al / Si molar ratio of 2, a hydrogen / propylene molar ratio of 0.055, a polymerization pressure of 2.5 MPa, and a polymerization temperature of 70 ° C. Melt flow rate MFR_PHP6 and a crystalline propylene homopolymer having a melting point of 164 ° C. (for comparison).
[0139]
Antioxidant
Ph-1: Phenolic heat stabilizer
Ph-2: Tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane.
[0140]
α crystal nucleating agent
α-1: Aluminum hydroxy-bis (4-t-butylbenzoate)
α-2: 1,3,2,4-bis (p-methylbenzylidene) sorbitol
α-3: Sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate.
Radical generator: 1,3-bis (t-butylperoxyisopropyl) benzene
Neutralizer: calcium stearate
[0141]
[Table 5]

[0142]
[Table 6]

[0143]
[Table 7]

[0144]
[Table 8]

[0145]
2) Injection molding
Each of the prepared pellets was set to a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine to prepare JIS type test pieces and various physical property measurement test pieces.
The test piece was conditioned for 72 hours in a room with a humidity of 50% and a room temperature of 23 ° C., and various physical properties were measured by the following methods.
[0146]
a) Molding shrinkage ratio: The ratio of the length obtained by subtracting the total length of the tensile test piece (JIS K 7113 No. 1 tensile test piece) prepared from the full length of the mold of the molding machine to the mold length is multiplied by 100. Calculated by the following formula.
[Equation 5]
Mold shrinkage = (full length of mold-full length of test piece) x 100 / full length of mold
b) Flexural modulus (MPa): Measured according to JIS K 7203.
c) Impact resistance (J / m): Measured at −20 ° C. or 23 ° C. according to JIS K 7110.
d) Izod impact strength (J / m²): Measured at −30 ° C. in accordance with JIS K 7110.
e) Haze: Measured according to ASTM D1003 using a flat test piece of 25 × 50 × 1 mm.
f) Gloss: Measured at an indicated angle of 60 degrees in accordance with ASTM D 523 specular gloss method.
g) Whitening resistance: Using a test piece having a hinge structure, the degree of whitening by bending at the hinge portion was visually observed and evaluated in the following three stages.
○: The color of the hinge part is the same as the other parts.
(Triangle | delta): The color of a hinge part is slightly white compared with another part.
X: The color of a hinge part is remarkably white compared with another part.
The measurement results are shown in Tables 3 to 6. In the impact test data in the table, NB means that the test piece did not break under the set conditions.
[0147]
FIG. 1 shows the relationship between the product of the intrinsic viscosity ratio and the weight ratio of the propylene homopolymer and propylene-ethylene copolymer of the present invention samples Ci-1 to 6 and comparative samples cCi-1 to 6 and the molding shrinkage, and FIG. The relationship is shown in FIG.
[0148]
C. Production of polypropylene composition (Cs) and sheet for sheet molding
1) Polypropylene composition
To each powder of the propylene-based compositions A-1 to A-6 and comparative compositions cA-1, 3, 5 and 7 of the present invention, various additive components were added and a high-speed stirring mixer (Henschel mixer) was used. Mix for 5-10 minutes at room temperature and mix the screw diameter
Using a 40 mm extrusion granulator, granulation was carried out at a cylinder setting temperature of 230 ° C. to prepare pellets.
[0149]
Tables 7 and 8 show the respective additive components and their addition amounts of the polypropylene-based compositions Cs-1 to 6 and comparative compositions cCs-1 to 4 of the present invention.
The additive components used and the abbreviations in the table are shown below.
Antioxidant
P-1: Phosphorus heat stabilizer
P-2: Tris (2,4-di-t-butylphenyl) phosphite
Neutralizer: Same as above.
[0150]
[Table 9]

[0151]
[Table 10]

[0152]
2) Sheet molding
Each of the prepared compositions was formed into a sheet having a thickness of 5 mm at a cylinder setting temperature, a cooling roll temperature and a forming speed shown in Tables 9 and 10 using a sheet forming machine having a T die and a polishing roll.
The molded sheet was conditioned for 72 hours in a room with a humidity of 50% and a room temperature of 23 ° C., and the following physical properties were measured. Tables 7 and 8 show the molding conditions and physical property measurement results.
[0153]
a) Tensile yield strength (MPa): Measured in accordance with ASTM D882 after standing in a thermostatic bath at 50 ° C for 30 minutes or more.
b) Young's modulus (MPa): Measured according to ASTM D882 after leaving it in a room at 23 ° C. for 48 hours or more.
c) Punching impact strength (J): Measured according to ASTM D 781.
d) Bending whitening property (mmφ): A sheet having a width of 10 mm and a length of 120 mm was used as a punched specimen. The test piece is bent while gradually approaching both ends, and the curvature at the time when whitening occurs in the curved portion is measured. did.
e) Printability: Using a gravure printing machine, three-color printing was performed at a drying temperature of 50 ° C. and a printing speed of 5 m / min, and printing displacement was visually observed.
○: No printing misalignment
×: Clear printing misalignment
Tables 7 and 8 show the molding conditions and physical property measurement results.
[0154]
D. Production of polypropylene composition for film (Cf) and film
1) Polypropylene composition
Each additive component is blended with the propylene-based compositions A-7 to 14, 2, 4 and 5 of the present invention and the propylene-based comparative compositions cA8 to 14, 5 and 6 and mixed with a Henschel mixer (trade name). Then, it was melt-kneaded and pelletized using a single screw extruder (caliber 40 mmφ) to prepare polypropylene-based compositions Cf-1-12 for films and comparative compositions cCf-1-9.
Tables 9 and 10 show the polypropylene-based composition and the comparative composition.
[0155]
The additive components used and the abbreviations in the table are shown below.
[0156]
Antioxidant
Ph-2: Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane
P-2: Tris (2,4-di-t-butylphenyl) phosphite
Neutralizer: calcium stearate
Antiblocking agent: Silica
Lubricant: Oleic acid amide
[0157]
[Table 11]

[0158]
[Table 12]

[0159]
2) Molding of single layer film
a) Unstretched film
Cf-1 to 8 and cCf-1 to 7 were extruded at an extrusion temperature of 230 ° C. using a single layer extruder (caliber 65 mmφ) equipped with a T die, and rapidly cooled with a cooling roll having an air chamber and a surface temperature of 30 ° C. to a thickness of 25 μm. An unstretched film was obtained.
b) Biaxially stretched film
Cf-9-11, cCf8-8 and 9 were extruded at an extrusion temperature of 230 ° C. using a single layer extruder (40 mmφ diameter) equipped with a T die, and then cooled and solidified with an air knife and a cooling roll with a surface temperature of 30 ° C. A 2.0 mm unstretched sheet was formed. Next, the obtained unstretched sheet was biaxially stretched at a stretching temperature of 157 ° C. using a batch type biaxial stretching machine (5.0 times in the extrusion direction and 8.0 times in the transverse direction), and biaxial with a thickness of 50 μm. A stretched film was obtained.
c) Uniaxially stretched film
Cf-9-11, cCf8-8 and 9 were extruded at an extrusion temperature of 230 ° C. using a single layer extruder (40 mmφ diameter) equipped with a T die, and then cooled and solidified with an air knife and a cooling roll having a surface temperature of 60 ° C. A 0.25 mm unstretched sheet was formed. Subsequently, the obtained unstretched sheet was uniaxially stretched 5.0 times in the extrusion direction at a stretching temperature of 120 ° C. using a batch type biaxial stretching machine to obtain a uniaxially stretched film having a thickness of 50 μm.
[0160]
3) Molding of laminated film
a) Unstretched film
A two-type three-layer or three-type three-layer unstretched film of the polypropylene-based compositions Cf-2 and 4 and the comparative compositions cCf-1 and 6 of the present invention and the following polyolefin-based composition is prepared.
[0161]
Polyolefin composition
PO-1: Density 0.90 g / cm^Three, 99.49% by weight of a propylene homopolymer having a crystalline melting point of 163 ° C. and a melt foulate (MFR) of 7.0 g / 10 min, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] 0.03% by weight of methane, 0.08% by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.1% by weight of calcium stearate, 0.2% by weight of silica (antiblocking agent) and olein A composition in which 0.1% by weight of acid amide (lubricant) is blended, mixed with a Henschel mixer (trade name), melt-kneaded using a single screw extruder (40 mm diameter), and pelletized.
[0162]
PO-2: Density 0.90 g / cm^Three, 99.49% by weight of a propylene-ethylene-butene-1 copolymer having a crystalline melting point of 132 ° C. and a melt furate (MFR) of 6.0 g / 10 min was added to tetrakis [methylene (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] methane 0.03% by weight, tris (2,4-di-t-butylphenyl) phosphite 0.08% by weight, calcium stearate 0.1% by weight, silica (antiblocking agent) 0 2% by weight and 0.1% by weight of oleic acid amide (lubricant), mixed with a Henschel mixer (trade name), melt-kneaded using a single screw extruder (caliber 40 mmφ), and pelletized .
[0163]
Using a three-layer three-layer extruder equipped with a multi-layer T die (one single-axis extruder for an intermediate layer with a diameter of 65 mmφ and two single-screw extruders for a surface layer with a diameter of 50 mmφ) The polyolefin composition is supplied to a single screw extruder for a layer and supplied to a single screw extruder for a surface layer, melted at 230 ° C., subjected to two-type three-layer or three-type three-layer multi-coextrusion, and an air chamber and a surface temperature. It cooled and solidified with a 30 degreeC cooling roll, and obtained the 2 type 3 layer or 3 type 3 layer unstretched film which consists of thickness 30micrometer (thickness composition ratio = 1: 4: 1).
Tables 11 and 12 show the layer structure.
[0164]
b) Biaxially stretched film
A polypropylene composition Cf-12 using a three-layer three-layer extruder (one single-axis extruder for 65 mmφ intermediate layer and two single-axis extruders for 50 mmφ surface layer) equipped with a multilayer T die Alternatively, cCf-8 is supplied to a single screw extruder for intermediate layer, and the polyolefin composition is supplied to a single screw extruder for surface layer, melted at 230 ° C., and subjected to two-kind three-layer multi-coextrusion. Two kinds of three-layer unstretched sheets having a thickness of 2.0 mm (thickness ratio = 1/18/1) were formed by cooling and solidifying with a cooling roll having a temperature of 30 ° C. Next, the obtained two types of three-layer unstretched sheets were biaxially stretched at a stretching temperature of 157 ° C. using a batch-type biaxial stretching machine (5.0 times in the extrusion direction and 8.0 times in the transverse direction) to obtain a thickness. A 50 μm biaxially stretched film was obtained.
Tables 11 and 12 show the layer structure.
[0165]
[Table 13]

[0166]
[Table 14]

[0167]
4) Film properties
The following physical properties of the prepared single layer film and laminated film were evaluated.
a) Transparency (%): According to ASTM D 1003, the haze of the film was measured and used as a standard for transparency.
b) Gloss (%): According to ASTM D 523, the gloss of the film is measured at an indicated angle of 20 degrees.
c) Tear strength (N / mm): Measures the Elmendorf tear strength of the film according to ASTM D 1922.
d) Tensile breaking strength (MPa): The tensile breaking strength of the film was measured according to ASTM D882.
e) Tensile elongation at break (MPa): The tensile elongation at break of the film was measured according to ASTM D882.
f) Cold resistance temperature (° C.): A film holding temperature at which an impact strength of 0.5 J or more is obtained by measuring the impact strength of the film according to ASTM D 781 after holding the film in a thermostatic bath for 15 minutes.
g) Heat resistance (° C.): A sample cut out in a strip of 10 × 100 mm from a film is held in a silicon oil bath set at a predetermined temperature for 10 minutes, then the length in the longitudinal direction is measured, and the length of the contracted length is measured. Temperature at which the value expressed as a percentage of the initial length exceeds 2%.
h) Heat-sealing temperature (° C.): A biaxially stretched polypropylene film (20 μm) and an adhesive are dry-laminated, and the laminated film is spaced at a temperature of 130 ° C. to 190 ° C. at intervals of 5 ° C. (8 temperatures in total). Condition), a 90 mm peel test was performed at each seal temperature using a sample cut into a 15 mm wide strip after heat sealing with a seal pressure of 2 MPa and a seal time of 0.5 seconds and a width of 10 mm. Minimum sealing temperature measured with a tensile tester at a pulling speed of 300 mm / min and showing a peel strength of 0.5 N / 15 mm or more.
The evaluation results of the single layer film are shown in Table 9 and Table 10, and the evaluation results of the laminated film are shown in Table 11 and Table 12.
[0168]
E. Polypropylene composition for hollow molded article (Cb) and hollow molded article
1) Polypropylene composition
Various additive components are blended in the propylene-based compositions A-1 and A2 and comparative composition cA-3 of the present invention, mixed using a Henschel mixer, and melt kneaded and extruded by an extruder set at 250 ° C. A pellet-shaped polypropylene-based composition Cb-1 to 7 and a comparative composition cCb-1 to 4 were prepared.
[0169]
Tables 13 and 14 show the polypropylene-based composition and the comparative composition.
[0170]
The additive components used and the abbreviations in the table are shown below.
[0171]
Plasticizing component
LPDE: Melt Folate (MFR) 0.4 g / 10 min, crystal melting point 110 ° C., density 0.920 g / cm^ThreeLow density polyethylene.
EVAC: Melt folate (MFR) 0.5 g / 10 min, crystal melting point 104 ° C., density 0.925 g / cm^ThreeAn ethylene vinyl acetate copolymer having a butyl acetate content of 3% by weight.
Antioxidants and neutralizers: as described above.
[0172]
[Table 15]

[Table 16]

[0173]
2) Molding of hollow molded products
a) Hollow molded product (single product)
The above prepared pellet-shaped polypropylene-based composition Cb-1 to 6 or cCb-1 to 3 was supplied to an extruder of a hollow molding machine (SN-50 (Placo)), and a parison was extruded at 200 ° C. A cylindrical hollow molded product with a bellows structure on the side by blowing in a mold adjusted to 30 ° C (60φ × 300 × 1.6mmt / 7 pitch bellows in the center, 10mm pitch, groove And an average thickness of 0.9 mm of the bellows part). The top and bottom surfaces were cut to obtain a hollow molded product.
b) Hollow molded products (composite products)
The pellet-shaped polypropylene-based composition Cb-1, 2 or 7 or the comparative composition cCb-1, 2 or 4 is supplied to one extruder of a hollow molding machine having two extruders, and the other extruder Is supplied with one of the following polymer compositions, first the parison is extruded from the extruder at 200 ° C., and then the parison is extruded from the extruder at 200 ° C. to make a parison in which the two compositions are connected, A cylindrical hollow molded product with a bellows structure on the side by blowing in a mold adjusted to 30 ° C (60φ × 300 × 1.6mmt / 7 pitch bellows in the center, 10mm pitch, groove And an average thickness of 0.9 mm of the bellows part). At this time, the parison extruded from the extruder was adjusted to come to the bellows. The top and bottom surfaces were cut to obtain a hollow molded product (composite product).
[0174]
EP-1: crystalline melting point 165 ° C., flexural modulus 1,100 Mpa, MFR 0.65 g / 10 min, ethylene content 59 wt% ethylene-propylene copolymer 12.7 wt% and propylene homopolymer 87.3% wt Tris (2,4-di-t-butylphenyl) phosphite 0.05 parts by weight, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) Hydrocinnamate)] A polymer composition containing 0.15 part by weight of methane and 0.1 part by weight of calcium stearate.
[0175]
EP-2: A polymer composition having a flexural modulus of 2,100 Mpa and MFR of 0.72 g / 10 min in which 10 parts by weight of talc having an average particle diameter of 1.6 μm is blended with 100 parts by weight of EP-1.
[0176]
Tables 13 and 14 show combinations of the polypropylene composition and the polymer composition.
[0177]
3) Evaluation of hollow molded products
The hollow molded article prepared above was evaluated according to the following characteristics and evaluation criteria.
[0178]
a) Formability: Melting parison is extruded at a molding temperature of 200 ° C., a screw diameter of 50φ and a screw rotation speed of 40 rpm (die diameter: 21 mm, core diameter: 19 mm), and the speed at which the parison hangs down to 12 cm and 50 cm is measured. Judged by the difference (speed up to 50 cm-speed up to 12 cm).
A: The drawdown is small and the speed difference is less than 5%.
B: 5 to 20% difference in drawdown speed
C: The drawdown speed difference exceeds 20%.
[0179]
b) Flexibility: One end of a hollow molded product is fixed in a room of 23 ± 2 ° C., and the amount of deformation when a load of 1 kg is placed on one is determined by angle.
A: Deformation amount of 30 degrees or more
B: Deformation amount of 20 degrees or more and less than 30 degrees
C: Deformation amount of 10 degrees or more and less than 20 degrees
D: Deformation amount less than 10 degrees.
[0180]
c) Impact whitening resistance: A hollow molded product is laid down horizontally in an environment of 20 to 25 ° C., and a hitting core (190 g) having a tip radius of 6.35 mm is applied to the molded product (use of the polypropylene composition) to give 500 g The diameter of the whitening surface generated around the strike core is measured by dropping the load of 50cm onto the strike core.
A: Scratches are seen in the hitting core, but no whitening is seen
B: Whitening of the hitting core is less than 8mmφ
C: Whitening of the hitting core is 8-15mmφ
D: Whitening of the hitting core part exceeds 15 mmφ.
[0181]
d) Heat resistance: Visual observation of deformation and appearance when the molded product is left in an oven at 150 ° C. for 500 hours.
A: No deformation or abnormal appearance
B: Dimensional change is 2% or less, almost no change in appearance
C: Appearance change (deterioration) when dimensional change is 2% or more.
[0182]
e) Weld strength: The weld part of the molded product was compressed (50 mm), and whitening and cracks along the direction of extrusion of the parison were visually observed.
A: No whitening or cracking
C: Whitening or cracking occurs.
[0183]
f) Joining strength: A test piece was cut out from a joint part with the polymer composition and the other composition from the cylindrical molded product, the tensile strength was measured, and the value was compared with the value of the following standard product.
Standard product: A test piece cut out from a part made of a polypropylene composition from a hollow molded product.
A: Strength exceeding 85% of standard products
B: 85-70% strength of standard product
C: Strength less than 70% of the standard product.
[0184]
In Table 13 and Table 14, the evaluation result of each physical property is shown.
[0185]
【The invention's effect】
The propylene-based composition of the present invention is excellent in moldability, molding shrinkage, rigidity, flexibility, impact resistance, particularly impact resistance at low temperatures, transparency, gloss, whitening resistance, and an excellent balance thereof. In addition, it is preferably used as a base resin of a polypropylene composition for obtaining various molded products.
[0186]
As shown in FIGS. 1 and 2, in the injection-molded article using the polypropylene-based composition based on the propylene-based composition of the present invention, propylene homopolymer (PP) and propylene constituting the propylene-based composition are used. -Product of intrinsic viscosity ratio and weight ratio of ethylene copolymer (RC) ([η]_RC/ [Η]_PP) × (W_PP/ W_RC) Is in the range of 1.0 to 3.0, the molding shrinkage is almost 1, showing a high flexural modulus (rigidity), and excellent low temperature impact resistance as shown in Table 3 and Table 5. , Transparency, gloss and whitening resistance. Further, in the polypropylene-based compositions Ci-7 to 12 containing an α crystal nucleating agent, the low-temperature impact resistance is further improved, and as shown in Tables 4 and 6, a radical generator and / or highly crystalline propylene is used. In the polypropylene-based compositions Ci-13-18 blended with the homopolymer, the whitening resistance is further improved.
[0187]
Also, using these polypropylene-based compositions, not only various sheet-shaped molded products, but also molded products having complicated structures such as containers and their stoppers (caps), molded products having a hinge structure are manufactured by injection molding. be able to.
[0188]
In a sheet using a polypropylene composition based on the propylene composition of the present invention as a base resin, punching impact strength, bending whitening resistance and printing are shown in Tables 7 and 8 depending on the combination with the molding method. And a sheet with an excellent balance of tensile yield strength and Young's modulus.
[0189]
The single-layer film formed using a polypropylene composition based on the propylene composition of the present invention is excellent in transparency and heat resistance, as shown in Table 9 and Table 10, and has a tear strength and a tensile strength at break. An unstretched, biaxially stretched and uniaxially stretched film having an excellent balance of mechanical properties such as elongation at break and low temperature impact resistance. In addition, the laminated film of the polypropylene composition and the polyolefin composition has excellent heat seal properties while maintaining the characteristics of the above single layer film as shown in Tables 11 and 12.
[0190]
These films are suitable as various packaging films including food packaging.
[0191]
As shown in Table 13 and Table 14, the hollow molded product molded using the polypropylene composition based on the propylene composition of the present invention as a base resin, particularly the hollow molded product having the bellows structure, has moldability and flexibility. In the polypropylene compositions Cb-2, 3, 5 and 7 to which the plasticizing component is added, the flexibility is further improved. In addition, a composite article bonded with another polymer composition has high bonding strength.
[0192]
A hollow molded article having these bellows structures and a composite article thereof are suitable as an air duct or the like.
[0193]
The present invention provides a polypropylene-based composition used for molding various molded products and a propylene-based composition suitable as a base resin thereof, and is extremely significant in this field.
[Brief description of the drawings]
FIG. 1 is a product of intrinsic viscosity ratio and weight ratio of propylene homopolymer (PP) and propylene-ethylene copolymer (RC) ([η]_RC/ [Η]_PP) × (W_PP/ W_RC) Represents the molding shrinkage ratio.
FIG. 2 is a product of intrinsic viscosity ratio and weight ratio of propylene homopolymer (PP) and propylene-ethylene copolymer (RC) ([η]_RC/ [Η]_PP) × (W_PP/ W_RC) Is a curve representing the flexural modulus.
FIG. 3 is a flow sheet of a continuous polymerization apparatus for a propylene-based composition used in Examples.
[Explanation of symbols]
1, 10: Polymerizer
2: Hydrogen piping
3: Raw material propylene piping
4, 8: Unreacted gas piping
5, 9: Polymer extraction piping
6: Raw material mixed gas piping

Claims (18)

A propylene-based composition comprising 60 to 78% by weight of a propylene homopolymer and 22 to 40% by weight of a propylene-ethylene copolymer containing 25 to 55% by weight of ethylene polymerized units, wherein the isotactic pendant of the propylene homopolymer The fraction (P) is 0.95 or more; the intrinsic viscosity ([η] _RC ) of the propylene-ethylene copolymer is in the range of 1.7 to 2.8 dl / g; the intrinsic viscosity ratio of the propylene homopolymer to the propylene-ethylene copolymer ([η] _RC / [η] _PP ) is in the range of 0.7 to 1.2; and the weight ratio of propylene homopolymer to propylene-ethylene copolymer (W _PP / W _RC ) and their intrinsic viscosity ratio ([η ] _RC / [η] _PP ) (W _PP / W _RC ) × ([η] _RC / [η] _PP ) is in the range of 1.0 to 3.0, and the propylene-ethylene copolymer is Xylene soluble composition at 20 ° C A propylene-based composition comprising 85% by weight or more based on the weight of a propylene-ethylene copolymer.   The propylene-based composition according to claim 1, wherein the propylene-based composition has a Q value (Mw / Mn) of 5 or less.   The propylene composition according to claim 1 or 2, wherein the propylene composition further contains an antioxidant and a neutralizing agent.   The propylene-based composition according to claim 3, wherein the antioxidant is a phenol-based heat stabilizer and / or a phosphorus-based heat stabilizer, and the neutralizing agent is calcium stearate.   The propylene-based composition according to any one of claims 1 to 4, further comprising 0.0001 to 1% by weight of an α crystal nucleating agent.   α crystal nucleating agent is talc, aromatic carboxylic acid metal salt, dibenzylidene sorbitol compound, aromatic phosphoric acid metal salt, poly-3-methyl-1-butene, polyvinylcyclohexane, polyallyltrimethylsilane, or a mixture thereof. The propylene-based composition according to claim 5.   Furthermore, the propylene-type composition of any one of Claims 1-6 containing a radical generator.   The propylene-based composition according to claim 7, wherein the radical generator is an organic peroxide.   The molded article which consists of a propylene-type composition of any one of Claims 1-8.   The manufacturing method of the molded article of Claim 9 which injection-molds the pellet which consists of a propylene-type composition of any one of Claims 1-8.   The sheet | seat which consists of a propylene-type composition of any one of Claims 1-8.   A pellet comprising the propylene-based composition according to any one of claims 1 to 8, a resin temperature of 180 to 300 ° C, a cooling roll temperature of 5 to 80 ° C, and a resin temperature-cooling roll temperature ≧ 120, and a molding speed. The manufacturing method of the sheet | seat of Claim 11 which extrudes by the T-die method on the conditions of 0.1-100 m / min.   The film which consists of a propylene-type composition of any one of Claims 1-8.   The multilayer film which laminated | stacked the functional polymer layer on the film layer of Claim 13. A functional polymer layer comprising a propylene homopolymer having a density of 0.89 to 0.91 g / cm ³ , a crystalline melting point (Tm) of 165 to 160 ° C. and an optional additive, and / or a density of 0.89 to 15. A multilayer film according to claim 14 which is a heat-sealable layer comprising a propylene- [alpha] -olefin copolymer having 0.91 g / cm < ³ >, a crystalline melting point (Tm) of 159-110 [deg.] C. and optionally additives.   A hollow molded article comprising the propylene-based composition according to any one of claims 1 to 8.   The hollow molded article according to claim 16, which has a bellows structure. A part comprising a hollow molded article having a bellows structure according to claim 17; and 1 to 20% by weight of an ethylene-propylene copolymer containing 25 to 55% by weight of ethylene units and 99 to 80% by weight of a propylene homopolymer, Other parts consisting of hollow molded articles of polyolefin-based compositions containing optional additives;
A hollow molded product consisting of both parts joined together.

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