JP3993011B2 - Polypropylene composition - Google Patents

Description

【００３１】
【表２】

【００３２】
【表３】

【００３３】
［Ｂ］ポリプロピレン成分（Ｂ）の調製
重合に用いた固体触媒は、上記ポリプロピレン成分（Ａ）と同様に、高立体規則性のZiegler-Natta触媒である。これはMgCl₂上に2.5質量%のTiと内部ドナーとしてジイソブチルフタレートをヨーロッパ特許第674991号に記載の方法で、担持させたものである。
触媒系及び予備重合
該固体触媒成分をトリエチルアルミニウム（TEAL）とジシクロペンチルメトキシシラン（DCPMS）との混合物に-5℃において5分間接触させた。ここで、TEAL/DCMPS=15 wt/wt、TEAL/Ti=65 mol/molである。第一重合反応容器で反応させる前に、ここで得られた触媒系を液化プロピレン中に懸濁させ２０℃で２０分間保持した。
重合
重合は、重合したポリマー成分を直ちに次のリアクターに送ることができる装置を有した３段の気相リアクターを用いて実施した。ポリプロピレンホモポリマーは第１段目のリアクターで、プロピレンガスを先に作製した予重合した触媒、及び水素（分子量調整の目的で使用）とともに連続・定速で供給することによって行なった。この結果、Ｂ^I成分が得られた。水素、及びプロピレンモノマーはリアクター内の濃度が一定になるように連続的に分析・供給した。
Ｂ^II成分を得るために、第１リアクターで得られたポリプロピレンホモポリマーを一定流量で未反応モノマーをパージした後に放出し、一定流量のエチレンガスとともに第２リアクターに導入した。
Ｂ^III成分を得るために、第２リアクターで生成したポリマー成分を一定流量で未反応モノマーをパージした後に放出し、一定流量のガス状のエチレン、１−ブテン及び水素とともに第３リアクターに導入した。
第３リアクターに存在するポリマー粒子は、反応性モノマー、及び揮発分を取り除くために、スチームで処理した。
こうしてポリプロピレン成分Ｂ−１を調製した。
表４にポリプロピレン成分Ｂ−１の重合条件を示す。得られたＢ−１のポリマー分析結果を表５に示す。
ポリプロピレン成分Ｂ−１と同様にして、各条件を制御することによって、表６に示すＢ−２、Ｂ−３、Ｂ−４、Ｂ−５を製造した。但し、ポリプロピレン成分Ｂ−５は第３リアクターでブテン−１の代わりにプロピレンを使用した。
併せて、ゴム量を調整するために、MFR=0.5 dg/minのエチレン−プロピレン共重合体のゴム（EPR：ＣＳＤ＝１.１）を適宜使用した。
【００３４】
【表４】

【００３５】
【表５】

【００３６】
【表６】

【００３７】
［Ｃ］ポリプロピレン成分（Ｃ）の調製
触媒の調製
（１）９,９−ビス（ヒドロキシメチル）フルオレンの合成
５００mlフラスコに、無水雰囲気中で、順に、ＣａＨ上で蒸留したジメチルスルホキシド（ＤＭＳＯ）１００ml、パラホルムアルデヒド（常温および圧力２torrで８時間脱水）８ｇ、およびエタノール６ml中に溶解させたナトリウムエチラート１.４ｇを入れた。懸濁液を氷浴で冷却した後（ＤＭＳＯ／ＥｔＯＨ混合物の融解温度は１３℃である）、懸濁液を攪拌しながら、フルオレン１６ｇのＤＭＳＯ溶液１００mlを３０秒間で加えた。フルオレンのＤＭＳＯ溶液を加え始めてから３分後、１.５mlの３７％ＨＣｌで反応を停止させ、次いで水４００mlで希釈した。混合物をＮａＣｌで飽和させ、９,９−ビス（ヒドロキシメチル）フルオレンを酢酸エチルで抽出した。次いで、有機相を無水Ｎａ₂ＳＯ₄ で除湿し、溶剤を留別した。トルエンで結晶化させた後、生成物１５.２ｇ（収率７０％）が得られた。
（２）９,９−ビス（メトキシメチル）フルオレンの合成
１００mlフラスコに、窒素雰囲気中で、順に、テトラヒドロフラン（ＴＨＦ）３０ml、上記で調整した９,９−ビス（ヒドロキシメチル）フルオレン１１.３ｇ、およびＣＨ₃Ｉ ３１.１mlを入れた。攪拌し、常温で操作しながら、鉱油中６０質量％ＮａＨ ４ｇを２時間３０分かけて加え、次いで内容物を１時間３０分反応させた。蒸留により、未反応ＣＨ₃Ｉを回収し、残りの内容物を水１００mlで希釈し、得られた浮揚固体を濾過し、４０℃で減圧乾燥させた。エタノールで結晶化させることにより、生成物１１.３ｇ（収率９０％）が得られた。
重合
特開平09-020803号公報における実施例１記載の方法で調製された固体触媒成分とトリエチルアルミニウムからなる触媒成分およびプロピレンモノマー、およびＭＦＲを調整するための水素を、容積290Ｌのループ型重合槽に連続的に供給した。具体的には次のようにした。
濾過バリヤーを備えた５００ml円筒形ガラス製反応器に０℃で、TiCl₄ を２２５ml、および攪拌しながら１５分間の間に、下記のようにして得た微小長球形ＭｇＣｌ₂ .２．１Ｃ₂Ｈ₅ＯＨ １０.１ｇ（５４mmol）を入れた。次いで温度を７０℃に上げ、９,９−ビス（メトキシメチル）フルオレン９mmolを入れた。温度を１００℃に増加し、２時間後、ＴｉＣｌ₄ を濾過により除去した。ＴｉＣｌ₄ ２００mlおよび９,９−ビス（メトキシメチル）フルオレン９mmolを加え、１２０℃で１時間後、内容物を再度濾過し、さらに２００mlのＴｉＣｌ₄ を加え、１２０℃でさらに１時間処理を続行し、最後に、内容物を濾過し、濾液から塩素イオンが完全に消失するまで６０℃のｎ−ヘプタンで洗浄した。
このようにして得た触媒成分は、Ｔｉ＝３.５質量％、９,９−ビス（メトキシメチル）フルオレン＝１６.２質量％を含む。微小長球形ＭｇＣｌ₂ ．２．１Ｃ₂Ｈ₅ＯＨは、次のように製造した。タービン攪拌機および吸引パイプを備えた２リットルオートクレーブ中に、不活性ガス中、常温で、無水ＭｇＣｌ₂ ４８ｇ、無水Ｃ₂Ｈ₅ＯＨ７７ｇ、および灯油８３０mlを入れた。攪拌しながら内容物を１２０℃に加熱することにより、ＭｇＣｌ₂ とアルコールの間の付加物が生じるが、この付加物は融解し、分散剤と混合される。オートクレーブ内の窒素圧を１５気圧に維持する。オートクレーブの吸引パイプを加熱ジャケットで外部から１２０℃に加熱した。吸引パイプは内径が１mmで、加熱ジャケットの一端から他端までの長さが３メートルである。このパイプを通して混合物を７m/sec の速度で流した。パイプの出口で、灯油２.５リットルを含み、初期温度を−４０℃に維持したジャケットで外部から冷却されている５リットルフラスコ中に、分散液を攪拌しながら採取した。分散液の最終温度は０℃である。エマルションの分散相を構成する球状固体生成物を沈降させ、濾過して分離し、ヘプタンで洗浄して乾燥させた。これらの操作はすべて不活性ガス雰囲気中で行なった。最大直径が５０ミクロン以下の、固体球状粒子形のＭｇＣｌ₂ ．３Ｃ₂Ｈ₅ ＯＨが１３０ｇ得られた。こうして得られた生成物から、ＭｇＣｌ₂ １モルあたりアルコール含有量が２.１モルに減少するまで、窒素気流中で温度を５０℃から１００℃に徐々に高めてアルコールを除去した。予め気体状プロピレンで７０℃で１時間掃気した４リットルオートクレーブ中に、常温、プロピレン気流中で、アルミニウムトリエチル７mmolおよび上記のようにして製造した固体触媒成分４mgを含む無水ｎ−ヘキサン７０mlを入れた。オートクレーブを閉じ、水素１.７Ｎリットルおよび液体プロピレン１.２kgを導入し、攪拌機を作動させ、温度を５分間で７０℃に上げた。７０℃で２時間後、攪拌を停止し、未重合モノマーを除去し、内容物を常温に冷却した。ポリプロピレン３８０ｇがオートクレーブから放出されるが、該ポリプロピレンは、２５℃におけるキシレン不溶画分（Ｘ.Ｉ.）＝９７.７％、メルトインデックスＭＦＲ／Ｌ＝４.５ｇ／１０分であった。重合体収率は、固体触媒成分１ｇあたりポリプロピレン９５,０００ｇであった。
トリエチルアルミニウムはプロピレンモノマー当たりのモル分率で６０molppmとなるように供給され、重合圧力４.５ＭＰａ、重合温度７０℃に保ち、２０ｋｇ／時間の生産速度で連続的に重合を実施した。得られたホモプロピレン重合体は、重合槽を出てフラッシュドラムにて未反応モノマーが除去されたのち、スチームによる触媒不活性化、乾燥工程を経て、サンプルとして採取した。
重合時、系内の水素濃度が未反応プロピレンモノマーに対し８０００から１５０００molppmになるように水素を導入し、ＭＦＲが１０００g/10minのホモプロピレン重合体を得た（Ｃ−２）。
同様にして表７に示す各結晶性ポリプロピレンＣ−１、Ｃ−３を得た。
【００３８】
【表７】

【００３９】
［Ｄ］無機充填剤成分
無機充填剤として表８に示すタルクを用いた。
【００４０】
【表８】

【００４１】
［Ｅ］その他の成分
その他の追添ゴムとして、ＥＯＲ−１（デュポン・ダウエラストマー製「ＥＧ８１３０」）、ＥＯＲ−２（デュポン・ダウエラストマー製「ＥＧ８２００」）、ＥＰＲ−１（ＪＳＲ製「ＥＰ０２Ｐ」）、ＥＰＲ−２（サンアロマー製「ＳＴ１５０Ｔ」）を用いた。
【００４２】
［２］ポリプロピレン組成物の製造
表９に示す処方で、各種のポリプロピレン組成物を製造した。この際、ＫＴＸ−３０ニ軸押出し機（神戸製鋼製）を用いて、下記条件にて樹脂組成物を製造した。
<混練条件>
シリンダー温度；１８０℃
回転数；３５０ｒｐｍ
吐出量；２０ｋｇ／時間
なお、全ての処方に共通して、以下の添加剤を該樹脂組成物１００質量部あたり、添加した。
イルガノックス1076（チバガイギー社）: 0.1 質量部
イルガフォス168（チバガイギー社）：0.1質量部
LA502XP（旭電化工業社）：0.4質量部
チヌビン120（チバガイギー社）：0.2質量部
ステアリン酸カルシウム（耕正社）：0.1質量部
黒色顔料（大日精化社）：3質量部
【００４３】
【表９】

【００４４】
得られた各組成物について、機械的強度（剛性、耐衝撃強度）、成形性（ＭＦＲ、スパイラルフロー）、外観性（タイガーマーク、ボイド、デフォーム）、収縮率を評価した。評価方法は次の通りである。評価結果は表１０に示した。
【００４５】
〔１〕物性測定用試験片作製
射出成形機（Fanuc α１００Ｃ（株）ファナック製）を用い、試験片金型により測定用試験片を作製した。成形条件を下記に示す。
<成形条件>
シリンダー温度；２００℃
金型温度；４０℃
射出圧力；９０ＭＰａ
冷却時間；２０秒
〔２〕メルトフローレート
ＪＩＳ Ｋ６９２１−２に準拠
＜試料＞ ペレット
＜試験条件＞ 温度；２３０℃
荷重値；２.１６ｋｇ
〔３〕曲げ弾性率
ＪＩＳ Ｋ７２０３に準拠
<試験片> １２.７（幅）×４.０（厚み）×１２７ｍｍ（長さ）
<試験条件> 温度；２３℃
スパン間；６０ｍｍ
曲げ速度；２.０ｍｍ／分
〔４〕アイゾッド衝撃試験
機械切削にてノッチ加工した試験片を用いて、ＪＩＳ Ｋ７１１０に準拠して測定を行った。試験は、２３℃、−３０℃の両雰囲気下でそれぞれ行った。
＜試験片＞ １２.７（幅）×４.０（厚み）×６４ｍｍ（長さ）
【００４６】
〔５〕スパイラルフロー
射出成形機（Ｊ１００Ｅ−Ｐ（日本製鋼製））を用いて、スパイラルフロー金型（流路断面：幅１０ｍｍ×高さ３ｍｍの長方形）を用いて、下記成形条件によって成形し、スパイラル流動長を測定した。
<成形条件>
シリンダー温度；１７０℃
金型温度；４０℃
射出圧力；４４ＭＰａ
射出時間；１０秒（定圧力制御）
冷却時間；２０秒
〔６〕タイガーマーク評価
フィルムゲートを有する成形金型に対して射出成形機（「ＩＳ１５０ＥＮ」東芝機械製）を用いて、前面フィルムゲートを有する金型を用いて図１に示すような平板（１４０ｍｍ×３００ｍｍ×３ｍｍ）を射出成形し、タイガーマークの評価を行った。
<成形条件>
シリンダー温度；２１０℃
金型温度；４０℃
射出時間；１１秒
冷却時間；２０秒
評価はゲートからのタイガーマークが発生し始めるまでの距離を計測した。
また、目視でその目立ち易さを評価した。目立ち易さは下記４段階で評価した。
４；タイガーマーク発生無し、或いは極めて目立ちにくい。
３；タイガーマーク目立ちにくい。
２；タイガーマークやや目立つ。
１；タイガーマーク目立つ。
〔７〕ボイド・デフォーム評価
上記同様に、射出成形機（「ＩＳ１５０ＥＮ」東芝機械製）を用いて図１に示すような平板（１４０ｍｍ×３００ｍｍ×３ｍｍ）を射出成形した。
<成形条件>
シリンダー温度；２１０℃
金型温度；４０℃
射出時間；１.５秒
保圧時間；４.０秒
保圧力；５０ＭＰａ
冷却時間；２０秒
目視でボイド・デフォームを下記のように４段階で評価した。
４；ボイド・デフォームなし或いは極めて目立ちにくい。
３；ボイド・デフォーム目立ちにくい。
２；ボイド・デフォームやや目立つ。
１；ボイド・デフォーム目立つ。
〔８〕収縮率
上記〔６〕タイガーマークの評価と同様にして長さ（樹脂の流動方向）が３００ｍｍの平板を成形し、試料とした。これを２３℃、相対湿度５０％の恒温・恒湿室内で４８時間静置した後に、その長さＬを計測し、次式により収縮率を求めた。
収縮率＝（３００−Ｌ）／３００
【００４７】
【表１０】

【００４８】
［３］ポリプロピレン組成物の評価結果
実施例−１と比較例−１の比較から、Ａ成分におけるＡ^IのＭＦＲが低すぎると、スパイラルフローの急激な低下を招き、ボイド・デフォーム性が悪化する。一方、比較例−２の結果から、Ａ^IのＭＦＲが高すぎると、成形品の外観（タイガーマーク）の著しい悪化を招く。また、比較例−６のように、Ａ成分を、分割して供給すると、成形品の外観（タイガーマーク）の著しい悪化を招くことが明らかになった。
比較例−３の結果から、Ｂ成分中にエチレン−ブテンのゴム成分が無いと、力学的物性（曲げ弾性率とＩＺＯＤのバランス）が悪化する。同様に比較例−７からＢ成分中にエチレン−プロピレンのゴム成分が無いと、力学的物性（曲げ弾性率とＩＺＯＤのバランス）が悪化することが明らかである。
比較例−４の結果から、Ａ成分が無いと成形品の外観（タイガーマーク）の著しい悪化を招く。
比較例−５の結果は、粒子径の粗い充填剤を用いると、衝撃強度が著しく低下することが明らかである。
比較例−８の結果から、ＣＳＤの小さいゴムを追添加すると、たとえそれが比較的分子量の高い物であっても（ＭＦＲ：０.５ｄｇ／ｍｉｎ）ボイド・デフォーム性の著しい悪化が生じることがわかる。
比較例−９の結果はコポリマー成分がC2C3で１種類からなる物（B-6）を用いた場合、収縮率が著しく大きくなるため、成形品の変形が大きく好ましくないことを示す。
従って表１０の結果から、本発明によるポリプロピレン組成物を使用することによって、力学物性、成形性、外観品質に優れた成形品を提供できることが明らかになった。
【００４９】
【発明の効果】
本発明のポリプロピレン組成物は、後からゴム成分の多量な添加を要することなく、諸物性、成形性、成形外観性に優れ、安価なものである。特に、剛性と耐衝撃強度を高次元でバランスされているので、多くの成形品、特に、自動車用部品、例えば、バンパや、インスツルメントパネル、ドアライナやピラー等の内装部品等に好適である。
【図面の簡単な説明】
【図１】 成形外観性の評価に用いた成形板を示すもので、図１（ａ）は平面図、図１（ｂ）は側面図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an inexpensive polypropylene composition that is excellent in various physical properties, moldability, and molded appearance, and particularly relates to a material that is suitable for automobile bumpers, interior parts, and the like.
[0002]
[Prior art]
Polypropylene compositions are widely used in many resin molded products because they exhibit excellent lightness, mechanical strength, moldability and the like while being inexpensive. In particular, in automobiles, it is used for interior parts such as bumpers, instrument panels, glove boxes, door liners and pillars. In such automobile parts and the like, since high impact resistance is required, hydrogenated products of polypropylene, ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR), and styrene-butadiene block copolymer are used. Blend polymers added with rubber components such as (SBR), polystyrene-ethylene / butene-polystyrene triblock copolymer (SEBS), and ethylene-octene rubber (EOR) are used. (Reference: JP-A-9-59451, JP-A-9-124636, JP-A-9-137035, JP-A-9-176406, JP-A-9-183876, JP-A-9-194646, JP-A-9-216975 No. publications).
[0003]
[Problems to be solved by the invention]
However, since a large amount of rubber component is added to exhibit sufficient impact resistance performance, this has resulted in an increase in cost.
[0004]
The present invention has been made to solve the above-mentioned problems, and aims at an inexpensive polypropylene composition excellent in various physical properties, moldability and molding appearance without requiring a large amount of addition of a rubber component later. It is.
[0005]
[Means for Solving the Problems]
The polypropylene composition of the present invention contains a polypropylene component (A), a polypropylene component (B), a polypropylene component (C), and an inorganic filler.
Here, the polypropylene component (A) is a crystalline polypropylene (A) having a melt flow rate of 0.5 g / 10 min or more and less than 10 g / 10 min.^I) And a crystalline polypropylene having a melt flow rate of 30 g / 10 min or more and less than 2000 g / 10 min (A^II) And an ethylene-propylene copolymer (A) having an ethylene amount of 10% by mass or more and less than 70% by mass and an intrinsic viscosity of 4 dl / g or more and less than 9 dl / g^III) And continuous multi-stage polymerization,
The polypropylene component (B) is a crystalline polypropylene (B) having a melt flow rate of 30 g / 10 min or more and less than 200 g / 10 min.^I) And an ethylene-propylene copolymer (B) having an ethylene content of 30% by mass or more and less than 70% by mass and an intrinsic viscosity of 2 dl / g or more and less than 4 dl / g.^II) And an ethylene-butene copolymer (B) having an ethylene amount of 70% by weight to less than 80% by weight and an intrinsic viscosity of 2 dl / g or more and less than 3 dl / g.^III) And continuous multi-stage polymerization,
The polypropylene component (C) is a crystalline polypropylene having a melt flow rate of 500 g / 10 min or more and less than 3000 g / 10 min.
The inorganic filler has a mean particle size of 4 μm or less.
Furthermore, the polypropylene component (A) is 3% by mass or more and less than 25% by mass, the polypropylene component (B) is 30% by mass or more and less than 60% by mass, the polypropylene component (C) is 5% by mass or more and less than 50% by mass, an inorganic filler. Is preferably 10% by mass or more and less than 25% by mass.
Further, in the polypropylene component (A), crystalline polypropylene (A^I) And crystalline polypropylene (A^II) Is 20% by mass or more and less than 90% by mass, an ethylene-propylene copolymer (A^III) Is less than 80% by mass and 10% by mass or more,
Crystalline polypropylene (A^I) And crystalline polypropylene (A^II) In the total amount of crystalline polypropylene (A^I) Is 25 mass% or more and less than 75 mass%, crystalline polypropylene (A^II) Is preferably less than 75% by mass and 25% by mass or more.
Furthermore, the polypropylene component (B) is made of crystalline polypropylene (B^I) Is 20 mass% or more and less than 60 mass%,
Ethylene-propylene copolymer (B^II) And ethylene-butene copolymer (B^III) In the total amount of ethylene-propylene copolymer (B^II) Is 25 mass% or more and less than 75 mass%, ethylene-butene copolymer (B^III) Is preferably less than 75% by mass and 25% by mass or more.
[0006]
In the polypropylene composition of the present invention, other rubber components may be contained within a range of 5% by mass or less.
[0007]
In the polypropylene composition of the present invention, the ratio of the spiral flow to the melt flow rate can be 1.70 or more and less than 3.00.
Further, the CSD of the xylene-soluble component can be 1.5 or more and less than 4.5.
Furthermore, the weight average molecular weight of the xylene-insoluble matter can be 60,000 or more and less than 100,000.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The polypropylene composition of the present invention essentially contains a polypropylene component (A), a polypropylene component (B), a polypropylene component (C), and an inorganic filler. The details are described below.
[0009]
Polypropylene component (A)
The polypropylene component (A) is a crystalline polypropylene having a melt flow rate of 0.5 g / 10 min or more and less than 10 g / 10 min (A^I) And a crystalline polypropylene having a melt flow rate of 30 g / 10 min or more and less than 2000 g / 10 min (A^II) And an ethylene-propylene copolymer (A) having an ethylene amount of 10% by mass or more and less than 70% by mass and an intrinsic viscosity of 4 dl / g or more and less than 9 dl / g^III) And continuous multistage polymerization.
In the present invention, the melt flow rate is measured according to JIS K6921-2, and is measured at 230 ° C. and a 2.16 kg load.
Crystalline polypropylene (A^I) Contributes to improvement of the flow balance during molding, and is a random copolymer containing homopolypropylene or ethylene in an amount of 8% by mass or less.
If the melt flow rate is less than 0.5 g / 10 min, the moldability is lowered, and voids and deforms are generated to deteriorate the mold appearance. In addition, dispersibility deteriorates and A^IIIThe component gel remains. On the other hand, when it is 10 g / 10 min or more, the appearance when molded is deteriorated, and in particular, a striped pattern, so-called tiger mark, tends to be generated on the surface.
[0010]
Crystalline polypropylene (A^II) Is a random copolymer containing homopolypropylene or ethylene in an amount of 8% by mass or less.
This crystalline polypropylene (A^II) Is characterized by a high melt flow rate. When the melt flow rate is 30 g / 10 min or more, the fluidity is increased, the moldability is improved, and the occurrence of weld marks can be suppressed. By being less than 10 minutes, it is possible to prevent a decrease in mechanical properties.
Crystalline polypropylene (A^I) And crystalline polypropylene (A^II) In the total amount of crystalline polypropylene (A^I) Is 25 mass% or more and less than 75 mass%, crystalline polypropylene (A^II) Is preferably less than 75% by mass and 25% by mass or more. Crystalline polypropylene (A^IThis is because a good flow balance can be maintained by the above) being within this range.
[0011]
Ethylene-propylene copolymer (A^III) Is an ethylene-propylene copolymer having an ethylene content of 10% by mass or more and less than 70% by mass, and contributes to improvement of moldability and molding appearance. When the ethylene content is less than 10% by mass, the moldability is lowered, and when it is 70% by mass or more, the rigidity is lowered.
Further, this ethylene-propylene copolymer (A^III) Is characterized by a high intrinsic viscosity, which is 4 dl / g or more and less than 9 dl / g. When this intrinsic viscosity is 4 dl / g or more, generation of tiger marks is suppressed and molding appearance is improved, and when it is less than 9 dl / g, gelation is suppressed.
In the present invention, the intrinsic viscosity is also called intrinsic viscosity or IV value. This is a value obtained by measuring at 135 ° C. in tetralin.
[0012]
In polypropylene component (A), crystalline polypropylene (A^I) And crystalline polypropylene (A^II) Is 20% by mass or more and less than 90% by mass, an ethylene-propylene copolymer (A^III) Is preferably less than 80% by mass and 10% by mass or more. More preferably, an ethylene-propylene copolymer (A^III) Is less than 40% by mass and 30% by mass or more. Ethylene-propylene copolymer (A^III) Is in the above ratio, good fluidity is exhibited and the molded appearance can be further improved.
[0013]
The polypropylene component (A) is composed of the crystalline polypropylene (A^I) And crystalline polypropylene (A^II) And ethylene-propylene copolymer (A^IIIHowever, it is not a mixture of these. That is, in order to exert the effects of the present invention, these must be constituted by a series of continuous multistage polymerizations.
If this polypropylene component (A) can be prepared so that the said requirements may be satisfied, the manufacturing method will not be specifically limited. For example, it can be produced by polymerization of propylene using a Ziegler-Natta catalyst. In particular, it can be obtained by adjusting the polymerization conditions using a catalyst that gives isotactic polypropylene.
Although the catalyst used for manufacture of this polypropylene component (A) is not specifically limited, For example, what combined the organometallic component with the catalyst component for olefin polymerization obtained by the following preparation methods can be used. Olefin-based polymerization catalyst components are: (1) Magnesium chloride / alkoxysilene adduct, titanium tetrachloride / electron-donating compound complex, method of co-grinding titanium compound and electron-donating compound, (2) Magnesium chloride / alkoxysilane addition It can be prepared by, for example, a method in which a titanium tetrachloride / electron-donating compound complex is contacted with a titanium compound and an electron-donating compound in succession. The olefin-based polymerization catalyst component thus obtained may be used as it is for the production of an olefin-based polymer, but may also be used after removing unreacted products and by-products by operations such as filtration and washing. it can.
The titanium compound is preferably a titanium halide such as titanium tetrachloride, titanium trichloride, or titanium tetrabromide, more preferably a tetravalent titanium compound containing halogen, and particularly preferably titanium tetrachloride.
As the electron donating compound, it is preferable to use at least one compound selected from an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound. Of these, it is particularly preferable to use an organosilicon compound having an alkoxy group. The amount of the electron-donating compound used is such that the molar ratio to the organoaluminum compound is 0.001 or more and less than 5, preferably 0.01 or more and less than 1.
[0014]
An example of a specific production method in the case of producing this polypropylene component (A) by continuous multi-stage polymerization is illustrated by using a three-stage gas phase reactor having an apparatus capable of immediately sending the polymer component polymerized to the next reactor. The first stage is a slurry polymerization or gas phase process, a Ziegler-Natta catalyst, using hydrogen as a molecular weight control agent, and supplying propylene gas at a continuous and constant speed together with the prepolymerized catalyst prepared earlier and hydrogen. By doing. As a result, A^IIngredients are obtained. Hydrogen and propylene monomer are continuously analyzed and supplied so that the concentration in the reactor is constant.
And A^IIIIn order to obtain the components, the polypropylene homopolymer obtained in the first reactor is discharged after purging the unreacted monomer at a constant flow rate and introduced into the second reactor together with a constant flow rate of propylene and ethylene gas.
And A^IIIn order to obtain a component (homopolymer), the polymer component produced in the second reactor is discharged after purging the unreacted monomer at a constant flow rate, and introduced into the third reactor together with gaseous propylene and hydrogen at a constant flow rate.
Then, the polymer particles present in the third reactor are treated with steam in order to remove reactive monomers and volatile components, whereby a polypropylene component (A) is obtained.
Various objective polypropylene components (A) can be obtained by appropriately changing the conditions such as the polymerization temperature and molecular weight control agent in the continuous multistage polymerization.
[0015]
Polypropylene component (B)
The polypropylene component (B) is a crystalline polypropylene (B) having a melt flow rate of 30 g / 10 min or more and less than 200 g / 10 min.^I) And an ethylene-propylene copolymer (B) having an ethylene content of 30% by mass or more and less than 70% by mass and an intrinsic viscosity of 2 dl / g or more and less than 4 dl / g.^II) And an ethylene-butene copolymer (B) having an ethylene amount of 70% by weight to less than 80% by weight and an intrinsic viscosity of 2 dl / g or more and less than 3 dl / g.^III) And continuous multistage polymerization.
Crystalline polypropylene (B^I) Has a melt flow rate of 30 g / 10 min or more and less than 200 g / 10 min. When the melt flow rate is less than 30 g / 10 minutes, the dispersibility is deteriorated, and as a result, the impact strength is lowered. When it is 200 g / 10 min or more, the impact strength is lowered.
[0016]
Ethylene-propylene copolymer (B^II) Is an ethylene-propylene copolymer having an ethylene content of 30% by mass or more and less than 70% by mass, and contributes to improvement of various physical properties, particularly rigidity and impact strength. When the amount of ethylene is less than 30% by mass, the shrinkage rate is increased, and the deformation of the molded product is increased. When it is 70% by mass or more, the impact strength is lowered.
Moreover, intrinsic viscosity is 2 dl / g or more and less than 4 dl / g. When the intrinsic viscosity is less than 2 dl / g, the impact strength is lowered. When it is 4 dl / g or more, the shrinkage ratio increases, dispersion is likely to occur, and impact resistance strength decreases.
Ethylene-butene copolymer (B^III) Is an ethylene-butene copolymer having an ethylene amount of 70% by mass or more and less than 80% by mass, and contributes to improvement of various physical properties, particularly rigidity and impact strength.
If the amount of ethylene is less than 70% by mass, the productivity will deteriorate. When it is 80% by mass or more, the impact strength is lowered.
The intrinsic viscosity is 2 dl / g or more and less than 3 dl / g. When the intrinsic viscosity is less than 2 dl / g, the impact strength is lowered. This is because if it is 3 dl / g or more, the shrinkage rate increases.
These ethylene-propylene copolymers (B^II) And ethylene-butene copolymer (B^III) In the total amount of ethylene-propylene copolymer (B^II) Is 25 mass% or more and less than 75 mass%, ethylene-butene copolymer (B^III) Is preferably less than 75% by mass and 25% by mass or more. Ethylene-propylene copolymer (B^II) Is less than 25% by mass, the impact strength is reduced. Ethylene-propylene copolymer (B^IIThis is because the shrinkage rate becomes large when the amount of) is 75% by mass or more.
[0017]
Further, in the polypropylene component (B), crystalline polypropylene (B^I) Is 20 mass% or more and less than 60 mass%, ethylene-propylene copolymer (B^II) And ethylene-butene copolymer (B^III) Is preferably less than 80% by mass and 40% by mass or more. Crystalline polypropylene (B^I) Is less than 20% by mass, the balance between rigidity and impact strength deteriorates. When it is 60% by mass or more, the shrinkage rate is increased, and the molded product is easily deformed.
The polypropylene component (B) is composed of the crystalline polypropylene (B^I) And ethylene-propylene copolymer (B^II) And ethylene-butene copolymer (B^IIIHowever, it is not a mixture of these. That is, in order to exert the effects of the present invention, these must be constituted by a series of continuous multistage polymerizations.
If this polypropylene component (B) can be prepared so that the said requirements may be satisfied, the manufacturing method will not be specifically limited. For example, it can be produced by polymerization of propylene using a Ziegler-Natta catalyst. In particular, it can be obtained by adjusting the polymerization conditions using a catalyst that gives isotactic polypropylene.
Although the catalyst used for manufacture of this polypropylene component (B) is not specifically limited, For example, what combined the organometallic component with the catalyst component for olefin polymerization obtained by the following preparation methods can be used. Olefin-based polymerization catalyst components are: (1) Magnesium chloride / alkoxysilene adduct, titanium tetrachloride / electron-donating compound complex, method of co-grinding titanium compound and electron-donating compound, (2) Magnesium chloride / alkoxysilane addition It can be prepared by, for example, a method in which a titanium tetrachloride / electron-donating compound complex is contacted with a titanium compound and an electron-donating compound in succession. The olefin-based polymerization catalyst component thus obtained may be used as it is for the production of an olefin-based polymer, but may also be used after removing unreacted products and by-products by operations such as filtration and washing. it can.
The titanium compound is preferably a titanium halide such as titanium tetrachloride, titanium trichloride, or titanium tetrabromide, more preferably a tetravalent titanium compound containing halogen, and particularly preferably titanium tetrachloride.
As the electron donating compound, it is preferable to use at least one compound selected from an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound. Of these, it is particularly preferable to use an organosilicon compound having an alkoxy group. The amount of the electron-donating compound used is such that the molar ratio to the organoaluminum compound is 0.001 or more and less than 5, preferably 0.01 or more and less than 1.
[0018]
An example of a specific production method in the case of producing this polypropylene component (B) by continuous multi-stage polymerization is illustrated by using a three-stage gas phase reactor having an apparatus capable of immediately sending the polymer component polymerized to the next reactor. In a slurry polymerization or gas phase process, the polypropylene homopolymer is continuously and constant in the first stage reactor, along with the prepolymerized catalyst previously prepared with propylene gas, and hydrogen (used for molecular weight adjustment). This is done by supplying at high speed. As a result, B^IIngredients are obtained. Hydrogen and propylene monomer are continuously analyzed and supplied so that the concentration in the reactor is constant.
And B^IIIn order to obtain the components, the polypropylene homopolymer obtained in the first reactor is discharged after purging the unreacted monomer at a constant flow rate and introduced into the second reactor together with a constant flow rate of ethylene gas.
In addition, B^IIIIn order to obtain the components, the polymer component produced in the second reactor is discharged after purging the unreacted monomer at a constant flow rate and introduced into the third reactor together with the gaseous ethylene, 1-butene and hydrogen at a constant flow rate.
The polymer particles present in the third reactor are treated with steam to remove reactive monomers and volatiles.
Thus, the polypropylene component (B) is produced.
Various polypropylene components (B) for various purposes can be obtained by appropriately changing the conditions such as polymerization temperature and molecular weight control agent in the continuous multistage polymerization.
[0019]
Polypropylene component (C)
The polypropylene component (C) is a crystalline polypropylene having a melt flow rate (MFR) of 500 g / 10 min or more and less than 3000 g / 10 min. The melt flow rate is more preferably 800 g / 10 min or more and less than 2500 g / 10 min, and still more preferably 1000 g / 10 min or more and less than 2000 g / 10 min. Since the melt flow rate is 500 g / 10 min or more, the fluidity is improved and appearance defects such as weld marks and flow marks can be suppressed. On the other hand, since it is less than 3000 g / 10 minutes, impact resistance can be enhanced.
Further, the boiling p-xylene soluble content is preferably 6.0% by mass or less. More preferably, it is 3.0 mass% or less.
The boiling p-xylene soluble content is determined as follows.
5 g of crystalline polypropylene is soxhlet extracted with boiling p-xylene, and the filtrate is allowed to stand overnight at 20 ° C., and then acetone is added to the filtrate to precipitate it. The precipitate is filtered and dried, and the mass of the obtained product is measured (W₁(G)) and calculated by the following equation.
((W₁) / 5) × 100 (%)
Methods for adjusting the MFR of this crystalline homopolypropylene include a method of adjusting the polymerization conditions such as the amount of molecular weight regulator such as hydrogen, polymerization temperature, pressure and the like during polymerization, and disclosed in JP-A-8-302105. As described above, there is a method of adjusting with an organic peroxide such as diacyl peroxide or dialkyl peroxide after polymerization. For the adjustment of MFR, the former method at the time of polymerization is preferable from the viewpoint of the appearance of the molded product.
As the catalyst used in this polymerization method, almost all catalysts that give crystalline isotactic polypropylene can be used, and among them, JP-A-3-706, JP-A-8-170984, and JP-A-9- The most preferred method is to use a catalyst comprising an electron donor containing a plurality of ether bonds in the titanium catalyst component disclosed in Japanese Patent No. 20803.
Two or more kinds of these crystalline polypropylenes may be used in combination.
[0020]
Inorganic filler
Examples of inorganic fillers used in the present invention include natural silicic acid or silicates such as talc, kaolinite, calcined clay, virophilite, sericite, and wollastonite, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Carbonates, hydroxides such as aluminum hydroxide, magnesium hydroxide, oxides such as zinc oxide, zinc white, magnesium oxide, hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, anhydrous silicic acid, synthetic silicic acid or silicates Fibrous filler such as mica, flake filler such as mica, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Filler), zonotlite, potassium titanate, elestite Glass bar Emissions, such as balloon-shaped fillers such as fly ash balloon may be employed.
Of these, talc is preferably used in the present invention. In particular, talc having an average particle size of 0.10 μm or more and less than 4.0 μm, and more preferably 0.20 μm or more and less than 3.0 μm is preferably used. If the average particle size is less than 0.10 μm, secondary aggregation occurs during kneading and mechanical properties are lowered. Further, even when the thickness is 4.0 μm or more, the mechanical properties, particularly the impact resistance is lowered.
Such talc has a content of particles having an average particle diameter of 5.0 μm or more of 10% by mass or less, preferably 8.0% by mass or less.
In the present invention, the average particle size of the inorganic filler means a particle size at which the cumulative value of the particle size distribution measurement curve measured by the liquid phase precipitation method based on JIS Z8820 is 50%.
Furthermore, among these talcs, those having an average aspect ratio (indicating a ratio of length to thickness of either length or width) of 3.0 or more, particularly 4.0 or more are preferable from the viewpoint of improving mechanical properties. Used.
The inorganic filler, particularly talc, may be untreated or may be surface-treated in advance. Examples of the surface treatment include a chemical or physical method using a surface treatment agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, or polyethylene glycol.
The above inorganic fillers may be used alone or in combination of two or more.
[0021]
In the above-described polypropylene composition of the present invention, the polypropylene component (A) is 3% by mass or more and less than 25% by mass, the polypropylene component (B) is 30% by mass or more and less than 60% by mass, and the polypropylene component (C) is 5% by mass. It is desirable that the amount is not less than 50% by mass and the inorganic filler is not less than 10% by mass and less than 25% by mass.
When the polypropylene component (A) is less than the above ratio, a tiger mark or the like is generated, and the molded appearance is deteriorated. When the polypropylene component (B) is less than the above ratio, various physical properties such as impact resistance are lowered. This is because if the polypropylene component (C) is less than the above ratio, the moldability is lowered, and if the inorganic filler is less than the above ratio, the rigidity is lowered.
[0022]
Although it is possible to add a rubber component to the present invention, it is preferably 5% by mass or less so as not to increase the cost, and is sufficient for exhibiting various characteristics. .
Examples of such rubber components include ethylene-propylene rubber (EPR), ethylene-butene rubber (EBR), EDR, EPDM, hydrogenated styrene-butadiene block copolymer (SBR), polystyrene-ethylene / butene- Polystyrene triblock copolymer (SEBS), ethylene-octene rubber (EOR), etc. are mentioned.
[0023]
Furthermore, the polypropylene composition of the present invention includes a nucleating agent, an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, in addition to the components shown so far, within a range not to impair the purpose of the present invention. Ultraviolet absorbers, internal lubricants, external lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizers, plasticizers, foaming agents, antifoaming agents, crosslinking agents, peroxides, etc. The additive may be included.
As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like can be used.
Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-hydroxy-3, 5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert-butyl-4 '-Hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis (4-methyl-6-tert- Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis [4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl) -m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy- 3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxy Phenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4,4'-thiobis ( 6-tert-butyl-m -Cresol) and other phenolic carbonic acid oligoesters such as 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) carbonic acid oligoesters (for example, polymerization degree 2-10) It is done.
Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (for example, glycerin, And esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralaurylthiopropionate).
Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite. Phyto, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4 -Hydroxyphenyl) butanediphosphite, tetra (mixed alkyl of C12 or more and C15 or less) -4,4'-isopropylidenediphenyldiphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6- tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, Lis (mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-tert -Butylphenol)], 1,6-hexanediol diphosphite, phenyl, 4,4'-isopropylidenediphenol, pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phyto, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-tert-butylphenol)] phosphite, phenyl diisodecylphos Phyto, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-stearoyloxyisopropyl) phosphite 4,4'-isopropylidenebis (2-tert-butylphenol) di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene- Examples thereof include 10-oxide and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite.
Further, as other antioxidants, 6-hydroxychroman derivatives such as various tocopherols of α, β, γ, δ or mixtures thereof, 2,5 of 2- (4-methyl-pent-3-enyl) -6-hydroxychroman -Dimethyl substituted, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2,2 , 5-Trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert-butyl-6-hydroxy Chroman and the like can also be used.
In addition, the general formula M_xAl_y(OH)_{2x + 3y-2z}(A)_z・ AH₂A compound represented by O (M is Mg, Ca or Zn, A is an anion other than a hydroxyl group, x, y and z are positive numbers, and a is 0 or a positive number), for example, Mg₆Al₂(OH)₁₆CO_Three・ 4H₂O, Mg₆Al₂(OH)₂₀CO_Three・ 5H₂O, Mg_FiveAl₂(OH)₁₄CO_Three・ 4H₂O, Mg_TenAl₂(OH)_{twenty two}(CO_Three)₂・ 4H₂O, Mg₆Al₂(OH)₁₆HPO_Four・ 4H₂O, Ca₆Al₂(OH)₁₆CO_Three・ 4H₂O, Zn₆Al₂(OH)₁₆CO_Three・ 4H₂O, Zn₆Al₂(OH)₁₆SO_Four・ 4H₂O, Mg₆Al₂(OH)₁₆SO_Three・ 4H₂O, Mg₆Al₂(OH)₁₂CO_Three・ 3H₂For example, O can be used as a hydrochloric acid absorbent.
Examples of the light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2′-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Hydroxybenzophenones, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert- Butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole Benzotriazoles such as phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di -tert-Butyl-4-hydroxybenzoate Which benzoates, 2,2'-thiobis (4-tert-octylphenol) Ni salt, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine Ni, (3,5-di- tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester nickel compounds such as Ni salt, substituted acrylonitriles such as methyl α-cyano-β-methyl-β- (p-methoxyphenyl) acrylate and N′- Oxalic dianilides such as 2-ethylphenyl-N-ethoxy-5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide, bis (2,2,6 , 6-Tetramethyl-4-piperidine) sebacate, poly [{(6- (1,1,3,3-tetramethylbutyl) imino} -1,3,5-triazine-2,4-diyl {4- (2,2,6,6-tetramethylpiperidyl) imino} hexamethylene], 2- (4-hydroxy-2,2,6,6 And hindered amine compounds such as a condensate of -tetramethyl-1-piperidyl) ethanol and dimethyl succinate.
Examples of the lubricant include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, capric acids, higher fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid, or These metal salts (for example, lithium salt, calcium salt, sodium salt, magnesium salt, potassium salt), aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, capron amide, caprylic amide, capric amide, Aliphatic amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, esters of aliphatic and alcohol, fluoroalkylcarboxylic acid or metal salt thereof, fluoroalkyl Fluorine compounds such as sulfonic acid metal salts.
The above additives can be used in an amount of 0.0001 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the propylene-based resin composition.
The polypropylene composition according to the present invention comprises a molded article having further improved physical property balance, durability, paintability, printability, scratch resistance, molding processability, and the like by containing the additives as described above. Can be formed.
Moreover, the polypropylene composition according to the present invention may contain a nucleating agent as described above. As the nucleating agent, conventionally known various nucleating agents are used without particular limitation, and among them, the nucleating agents such as aromatic phosphate ester salts and dibenzylidene sorbitol described below are preferable.
Specific examples of aromatic phosphate salts include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6 -Di-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, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis ( 4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis ( 4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate], potassium Cium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate Fate], magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], 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) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t- Butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-me Ren-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium -Bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl- 6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di- Ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-) t-Butylphenyl ) 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'-methylene-bis (4,6-di-t-butylfell) phosphate], aluminum-tris [2,2'-ethylidene-bis ( 4,6-di-t-butylphenyl) phosphate], sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) ) Phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis ( 4-t-Butyl Fe ) Phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and combinations thereof Can be illustrated. Of these, sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.
Specific examples of sorbitol nucleating agents include 1,3,2,4-dibenzylidene sorbitol, 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-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4- p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4- Di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4 -Di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbi 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (P-methoxybenzylidene) sorbitol, 1,3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene- 2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p -Methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and These combinations can be exemplified. Among these, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and combinations thereof are preferred
.
Furthermore, as the nucleating agent, a metal salt of an aromatic carboxylic acid or a metal salt of an aliphatic carboxylic acid can be used. Specifically, an aluminum benzoate, an aluminum pt-butylbenzoate, a sodium adipate, thio Examples thereof include sodium phenecarboxylate and sodium pyrolecarboxylate.
An inorganic compound such as talc can also be used as a nucleating agent. The nucleating agent as described above is 0.001 part by weight or more and less than 10 parts by weight, preferably 0.01 part by weight or more and less than 5 parts by weight, particularly preferably 0.1 part by weight or more, per 100 parts by weight of the propylene resin composition. You may contain in the composition in the quantity of less than 3 mass parts.
When the nucleating agent as described above is contained, the crystallization speed of the propylene polymer composition is improved, the crystal particles can be refined during crystallization, and molding can be performed at a higher speed.
[0024]
The polypropylene composition of the present invention is produced by uniformly blending the above essential components and, if necessary, additives and the like. The blending method (mixing method) is not particularly limited, and a method generally used in the field of synthetic resins may be applied. The mixing method includes dry blending using a general mixer such as a Henschel mixer, tumbler and ribbon mixer, and melting using an open roll, extrusion mixer, kneader and Banbury mixer. The method of mixing is mentioned. Of these methods, two or more of these mixing methods may be used in combination to obtain a more uniform resin composition. For example, after dry blending in advance, the mixture is melt-mixed. Even when a dry blend is used in combination or when one or more melt mixing methods are used in combination, it is particularly preferable to use a pelletizer to produce a molded product by using a pelletizer. .
When mixing, it must be carried out at a temperature at which the resin used melts. However, since the resin undergoes thermal decomposition and deterioration when carried out at a high temperature, it is generally carried out at 160 ° C. or more and less than 350 ° C. (preferably 170 ° C. or more and less than 260 ° C.).
[0025]
In the polypropylene composition of the present invention, the ratio of spiral flow (SPF) to melt flow rate (MFR) can be 1.70 or more and less than 3.00.
This SPF (cm) / MFR (g / 10 min) is an index of moldability, and if it is small, the moldability tends to decrease, and if it is high, it tends to cause burrs. If it is 1.70 or more and less than 3.00 like this invention, it means that the moldability excellent in the balance of a high shaping | molding precision and a burr | flash prevention is exhibited.
In the present invention, the spiral flow length is determined by using an injection molding machine (J100E-P (manufactured by Nippon Steel)), a spiral flow mold in which an Archimedes spiral is formed (channel cross section: rectangle having a width of 10 mm and a height of 3 mm). ) And measured values under the following molding conditions.
Cylinder temperature: 170 ° C
Mold temperature: 40 ° C
Injection pressure: 44 MPa
Injection time: 10 seconds (constant pressure control)
Cooling time: 20 seconds
[0026]
In the polypropylene composition of the present invention, the comonomer sequence distribution (CSD) of the xylene-soluble component can be 1.5 or more and less than 4.5.
The CSD value is 0 when the ethylene-α-olefin copolymer composition is a completely alternating copolymer, infinite when it is a complete block copolymer, and 1.0 when it is a random copolymer.
CSD in the boiling p-xylene soluble part of a polypropylene composition was calculated | required as follows.
Polypropylene composition (5 g) was soxhlet extracted with boiling p-xylene and filtered hot to separate inorganic fillers, pigments and the like. The filtrate was allowed to stand at 20 ° C. for a whole day and night, and then the solution was separated and acetone was added. The precipitate was filtered and dried, and CSD was measured for the obtained product.
CSD is a parameter indicating the randomness of the copolymer composition,¹³Ethylene content (molar fraction; P) by dyad chain determined from C-NMR_E) And α-olefin content (molar fraction; P_α) Is the mole fraction of alternating ethylene-α-olefin chains (P_{E α}) Divided by the square of, and is obtained by the following formula.
CSD = ((2P_E・ P_α) / (P_{E α})²)
This P_{E α}, P_EAnd P_αSpecifically, the value is measured as follows.
200 mg of ethylene-α-olefin copolymer rubber was uniformly dissolved in 2 ml of a mixed solvent of 1,2,4-trichlorobenzene and deuterated benzene (volume ratio 9: 1) in a 10 mmφ sample tube,¹³C-NMR spectrum was measured under the following conditions.
Device: JNM-EX270 (manufactured by JEOL Ltd.)
Measurement temperature: 120 ° C
Measurement frequency: 100.50 MHz
Pulse interval: 3.8 sec
Integration count: 5,000 times
P_{E α}, P_EAnd P_αValues were measured as above¹³From the C-NMR spectrum, GJRay et al, Macromolecules, 10, 773 (1977), JCRandall et al, Macromolecules, 15, 353 (1982), J. Polym. Sci., Polym. Phy. Ed., 11, 275 (1973), K. Kimura et al, Polymer, 25, 441 (1984) et al.
[0027]
In the polypropylene composition of the present invention, the weight average molecular weight of the xylene insoluble matter can be 60,000 or more and less than 100,000.
The weight average molecular weight of the xylene insoluble portion of the polypropylene composition was determined as follows.
The polypropylene composition was dissolved and filtered hot with boiling xylene, and the inorganic filler, pigment, and the like were filtered out. The filtrate was allowed to stand at 20 ° C. for a whole day and night, and the precipitate was collected. About what was obtained, the molecular weight distribution was measured using the gel permeation chromatograph. The weight average molecular weight of the peak top was calculated from the molecular weight distribution curve.
[0028]
The molding method using the polypropylene composition of the present invention is not particularly limited, and various known methods can be applied depending on the application. For example, an injection molding method, an extrusion molding method, a compression molding method and a hollow molding method can be applied. Further, after forming into a sheet using an extruder, the sheet may be formed into a desired shape by a secondary processing method such as vacuum forming or pressure forming.
The polypropylene composition of the present invention can be molded into a wide variety of molded products, but is particularly suitable for automotive parts such as interior parts such as bumpers, instrument panels, door liners, pillars, and the like.
[0029]
【Example】
Hereinafter, the present invention will be described in detail using examples.
[1] Preparation of each component
[A] Preparation of polypropylene component (A)
The solid catalyst used for the polymerization is a highly stereoregular Ziegler-Natta catalyst. This is MgCl₂On top of this, 2.5% by mass of Ti and diisobutyl phthalate as an internal donor were supported by the method described in European Patent No. 674991.
Catalyst system and prepolymerization
The solid catalyst component was contacted with a mixture of triethylaluminum (TEAL) and dicyclopentylmethoxysilane (DCPMS) at −5 ° C. for 5 minutes. Here, TEAL / DCMPS = 15 wt / wt and TEAL / Ti = 65 mol / mol. Prior to the reaction in the first polymerization reaction vessel, the catalyst system obtained here was suspended in liquefied propylene and kept at 20 ° C. for 20 minutes.
polymerization
The polymerization was carried out using a three-stage gas phase reactor with equipment that allowed the polymerized polymer components to be immediately sent to the next reactor. The polypropylene homopolymer was a first-stage reactor by supplying propylene gas at a continuous and constant speed together with the prepolymerized catalyst prepared earlier and hydrogen (used for molecular weight adjustment). As a result, A^IIngredients were obtained. Hydrogen and propylene monomer were continuously analyzed and supplied so that the concentration in the reactor was constant.
A^IIIIn order to obtain the components, the polypropylene homopolymer obtained in the first reactor was discharged after purging unreacted monomers at a constant flow rate and introduced into the second reactor together with a constant flow rate of propylene and ethylene gas.
A^IIIn order to obtain a component (homopolymer), the polymer component produced in the second reactor was discharged after purging the unreacted monomer at a constant flow rate, and introduced into the third reactor together with gaseous propylene and hydrogen at a constant flow rate.
The polymer particles present in the third reactor were treated with steam to remove reactive monomers and volatiles.
In this way, polypropylene component A-1 was prepared.
Table 1 shows the polymerization conditions for A-1. Table 2 shows the polymer analysis results of the obtained A-1.
Each polypropylene component A-2, A-3, A-4, A-5, A-6 shown in Table 3 was produced by controlling each condition in the same manner as in the polypropylene component A-1.
In addition, a polymer obtained by continuously polymerizing a polypropylene homopolymer of MFR = 1.5 g / 10 min and a polypropylene homopolymer of MFR = 800 g / 10 min at a ratio of 1: 1 was prepared (referred to as HOMO).
[0030]
[Table 1]

[0031]
[Table 2]

[0032]
[Table 3]

[0033]
[B] Preparation of polypropylene component (B)
The solid catalyst used for the polymerization is a highly stereoregular Ziegler-Natta catalyst, like the polypropylene component (A). This is MgCl₂On top of this, 2.5% by mass of Ti and diisobutyl phthalate as an internal donor were supported by the method described in European Patent No. 674991.
Catalyst system and prepolymerization
The solid catalyst component was contacted with a mixture of triethylaluminum (TEAL) and dicyclopentylmethoxysilane (DCPMS) at −5 ° C. for 5 minutes. Here, TEAL / DCMPS = 15 wt / wt and TEAL / Ti = 65 mol / mol. Prior to the reaction in the first polymerization reaction vessel, the catalyst system obtained here was suspended in liquefied propylene and kept at 20 ° C. for 20 minutes.
polymerization
The polymerization was carried out using a three-stage gas phase reactor with equipment that allowed the polymerized polymer components to be immediately sent to the next reactor. The polypropylene homopolymer was a first-stage reactor by supplying propylene gas at a continuous and constant speed together with the prepolymerized catalyst prepared earlier and hydrogen (used for molecular weight adjustment). As a result, B^IIngredients were obtained. Hydrogen and propylene monomer were continuously analyzed and supplied so that the concentration in the reactor was constant.
B^IITo obtain the components, the polypropylene homopolymer obtained in the first reactor was discharged after purging the unreacted monomer at a constant flow rate, and introduced into the second reactor together with a constant flow rate of ethylene gas.
B^IIIIn order to obtain the components, the polymer component produced in the second reactor was discharged after purging the unreacted monomer at a constant flow rate and introduced into the third reactor together with a constant flow rate of gaseous ethylene, 1-butene and hydrogen.
The polymer particles present in the third reactor were treated with steam to remove reactive monomers and volatiles.
Thus, polypropylene component B-1 was prepared.
Table 4 shows the polymerization conditions for the polypropylene component B-1. Table 5 shows the polymer analysis results of the obtained B-1.
B-2, B-3, B-4, and B-5 shown in Table 6 were produced by controlling each condition in the same manner as in the polypropylene component B-1. However, as the polypropylene component B-5, propylene was used in place of butene-1 in the third reactor.
In addition, in order to adjust the amount of rubber, an ethylene-propylene copolymer rubber (EPR: CSD = 1.1) with MFR = 0.5 dg / min was appropriately used.
[0034]
[Table 4]

[0035]
[Table 5]

[0036]
[Table 6]

[0037]
[C] Preparation of polypropylene component (C)
Catalyst preparation
(1) Synthesis of 9,9-bis (hydroxymethyl) fluorene
1. In a 500 ml flask, sodium ethylate dissolved in 100 ml of dimethyl sulfoxide (DMSO) distilled over CaH, 8 g of paraformaldehyde (dehydrated at room temperature and pressure of 2 torr for 8 hours) and 6 ml of ethanol in order in an anhydrous atmosphere. 4 g was added. After cooling the suspension in an ice bath (the melting temperature of the DMSO / EtOH mixture is 13 ° C.), 100 ml of a DMSO solution of 16 g of fluorene was added over 30 seconds while stirring the suspension. Three minutes after the start of the addition of fluorene in DMSO, the reaction was quenched with 1.5 ml of 37% HCl and then diluted with 400 ml of water. The mixture was saturated with NaCl and 9,9-bis (hydroxymethyl) fluorene was extracted with ethyl acetate. The organic phase is then dried over anhydrous Na₂SO_Four And the solvent was distilled off. After crystallization with toluene, 15.2 g (70% yield) of product was obtained.
(2) Synthesis of 9,9-bis (methoxymethyl) fluorene
In a nitrogen atmosphere, in a nitrogen atmosphere, 30 ml of tetrahydrofuran (THF), 11.3 g of 9,9-bis (hydroxymethyl) fluorene prepared above, and CH_ThreeI 31.1 ml was added. While stirring and operating at room temperature, 4 g of 60% NaH in mineral oil was added over 2 hours and 30 minutes, and then the contents were reacted for 1 hour and 30 minutes. Unreacted CH by distillation_ThreeI was recovered, the remaining contents were diluted with 100 ml of water, and the resulting floating solid was filtered and dried at 40 ° C. under reduced pressure. Crystallization with ethanol yielded 11.3 g (90% yield) of product.
polymerization
A solid catalyst component prepared by the method described in Example 1 of JP-A-09-020803, a catalyst component composed of triethylaluminum, propylene monomer, and hydrogen for adjusting MFR were placed in a loop type polymerization tank having a volume of 290 L. Continuously fed. Specifically:
In a 500 ml cylindrical glass reactor equipped with a filtration barrier at 0 ° C., TiCl_Four 225 ml, and for 15 minutes with stirring, the microelongated MgCl obtained as follows₂ 2.1C₂H_Five10.1 g (54 mmol) of OH was added. The temperature was then raised to 70 ° C. and 9 mmol of 9,9-bis (methoxymethyl) fluorene was added. The temperature was increased to 100 ° C. and after 2 hours TiCl_Four Was removed by filtration. TiCl_Four 200 ml and 9,9-bis (methoxymethyl) fluorene 9 mmol are added and after 1 hour at 120 ° C., the contents are filtered again and another 200 ml of TiCl 2 is added._Four And the treatment was continued for an additional hour at 120 ° C., and finally the contents were filtered and washed with n-heptane at 60 ° C. until the chlorine ions disappeared completely from the filtrate.
The catalyst component thus obtained contains Ti = 3.5% by mass and 9,9-bis (methoxymethyl) fluorene = 16.2% by mass. Micro long spherical MgCl₂ . 2.1C₂H_FiveOH was produced as follows. In a 2 liter autoclave equipped with a turbine stirrer and suction pipe, anhydrous MgCl in inert gas at room temperature₂ 48g, anhydrous C₂H_FiveOH 77g and kerosene 830ml were added. By heating the contents to 120 ° C. with stirring, MgCl₂ An adduct is formed between the alcohol and the alcohol, which melts and is mixed with the dispersant. The nitrogen pressure in the autoclave is maintained at 15 atmospheres. The suction pipe of the autoclave was heated to 120 ° C. from the outside with a heating jacket. The suction pipe has an inner diameter of 1 mm and a length from one end of the heating jacket to the other end of 3 meters. The mixture was allowed to flow through this pipe at a speed of 7 m / sec. At the outlet of the pipe, the dispersion was collected with stirring in a 5 liter flask containing 2.5 liters of kerosene and cooled from the outside with a jacket maintained at an initial temperature of −40 ° C. The final temperature of the dispersion is 0 ° C. The spherical solid product constituting the dispersed phase of the emulsion was allowed to settle, separated by filtration, washed with heptane and dried. All of these operations were performed in an inert gas atmosphere. MgCl in the form of solid spherical particles with a maximum diameter of 50 microns or less₂ . 3C₂H_Five130 g of OH was obtained. From the product thus obtained, MgCl₂ The alcohol was removed by gradually increasing the temperature from 50 ° C. to 100 ° C. in a nitrogen stream until the alcohol content per mole decreased to 2.1 mol. In a 4 liter autoclave previously purged with gaseous propylene at 70 ° C. for 1 hour, 70 ml of anhydrous n-hexane containing 7 mmol of aluminum triethyl and 4 mg of the solid catalyst component prepared as described above was placed in a propylene stream at room temperature. . The autoclave was closed, 1.7 N liters of hydrogen and 1.2 kg of liquid propylene were introduced, the stirrer was activated and the temperature was raised to 70 ° C. in 5 minutes. After 2 hours at 70 ° C., stirring was stopped, unpolymerized monomers were removed, and the contents were cooled to room temperature. Although 380 g of polypropylene was released from the autoclave, the polypropylene had a xylene-insoluble fraction (XI) at 25 ° C. = 97.7% and a melt index MFR / L = 4.5 g / 10 min. The polymer yield was 95,000 g of polypropylene per 1 g of the solid catalyst component.
Triethylaluminum was supplied at a molar fraction of 60 molppm per propylene monomer, and was continuously polymerized at a production rate of 20 kg / hour while maintaining a polymerization pressure of 4.5 MPa and a polymerization temperature of 70 ° C. The obtained homopropylene polymer was taken out as a sample after leaving the polymerization tank and removing unreacted monomers with a flash drum, followed by catalyst deactivation with steam and a drying process.
During the polymerization, hydrogen was introduced so that the hydrogen concentration in the system was 8000 to 15000 molppm with respect to the unreacted propylene monomer to obtain a homopropylene polymer having an MFR of 1000 g / 10 min (C-2).
Similarly, crystalline polypropylenes C-1 and C-3 shown in Table 7 were obtained.
[0038]
[Table 7]

[0039]
[D] Inorganic filler component
Talc shown in Table 8 was used as an inorganic filler.
[0040]
[Table 8]

[0041]
[E] Other ingredients
Other additional rubbers include EOR-1 ("EG8130" made by DuPont Dow Elastomer), EOR-2 ("EG8200" made by DuPont Dow Elastomer), EPR-1 ("EP02P" made by JSR), EPR-2 ( Sun Allomer “ST150T”) was used.
[0042]
[2] Production of polypropylene composition
Various polypropylene compositions were produced according to the formulations shown in Table 9. Under the present circumstances, the resin composition was manufactured on the following conditions using the KTX-30 biaxial extruder (made by Kobe Steel).
<Kneading conditions>
Cylinder temperature: 180 ° C
Rotation speed: 350rpm
Discharge rate: 20 kg / hour
In addition, common to all prescriptions, the following additives were added per 100 parts by mass of the resin composition.
Irganox 1076 (Ciba Geigy): 0.1 parts by mass
Irgafos 168 (Ciba Geigy): 0.1 parts by mass
LA502XP (Asahi Denka Kogyo Co., Ltd.): 0.4 parts by mass
Tinuvin 120 (Ciba Geigy): 0.2 parts by mass
Calcium stearate (Kohshosha): 0.1 parts by mass
Black pigment (Daiichi Seika): 3 parts by mass
[0043]
[Table 9]

[0044]
Each composition obtained was evaluated for mechanical strength (rigidity, impact strength), moldability (MFR, spiral flow), appearance (tiger mark, void, deform), and shrinkage. The evaluation method is as follows. The evaluation results are shown in Table 10.
[0045]
[1] Preparation of test specimens for measuring physical properties
Using an injection molding machine (Fanuc α100C manufactured by Fanuc Co., Ltd.), a test specimen for measurement was produced using a test specimen mold. The molding conditions are shown below.
<Molding conditions>
Cylinder temperature: 200 ° C
Mold temperature: 40 ° C
Injection pressure: 90 MPa
Cooling time: 20 seconds
[2] Melt flow rate
Conforms to JIS K6921-2
<Sample> Pellets
<Test conditions> Temperature: 230 ° C
Load value: 2.16 kg
[3] Flexural modulus
Conforms to JIS K7203
<Test piece> 12.7 (width) x 4.0 (thickness) x 127 mm (length)
<Test conditions> Temperature: 23 ° C
Between spans: 60mm
Bending speed: 2.0 mm / min
[4] Izod impact test
Using a test piece notched by mechanical cutting, measurement was performed in accordance with JIS K7110. The test was performed in both atmospheres of 23 ° C. and −30 ° C., respectively.
<Test piece> 12.7 (width) x 4.0 (thickness) x 64 mm (length)
[0046]
[5] Spiral flow
Using an injection molding machine (J100E-P (manufactured by Nippon Steel)), using a spiral flow mold (channel cross section: rectangle with a width of 10 mm and a height of 3 mm), molding is performed under the following molding conditions, and the spiral flow length is determined. It was measured.
<Molding conditions>
Cylinder temperature: 170 ° C
Mold temperature: 40 ° C
Injection pressure: 44 MPa
Injection time: 10 seconds (constant pressure control)
Cooling time: 20 seconds
[6] Tiger mark evaluation
An injection molding machine ("IS150EN" manufactured by Toshiba Machine) is used for a mold having a film gate, and a flat plate (140 mm x 300 mm x 3 mm) as shown in Fig. 1 is used using a mold having a front film gate. The tiger mark was evaluated by injection molding.
<Molding conditions>
Cylinder temperature: 210 ° C
Mold temperature: 40 ° C
Injection time: 11 seconds
Cooling time: 20 seconds
In the evaluation, the distance from the gate until the tiger mark began to occur was measured.
Moreover, the conspicuousness was visually evaluated. The conspicuousness was evaluated according to the following four levels.
4: No generation of tiger marks or extremely inconspicuous.
3; Tiger mark is inconspicuous.
2; Tiger mark is slightly conspicuous.
1: Tiger mark is conspicuous.
[7] Evaluation of void deformation
In the same manner as described above, a flat plate (140 mm × 300 mm × 3 mm) as shown in FIG. 1 was injection molded using an injection molding machine (“IS150EN” manufactured by Toshiba Machine).
<Molding conditions>
Cylinder temperature: 210 ° C
Mold temperature: 40 ° C
Injection time: 1.5 seconds
Holding time: 4.0 seconds
Holding pressure: 50 MPa
Cooling time: 20 seconds
The void deformation was visually evaluated in four stages as follows.
4: No void deformation or extremely inconspicuous
3; Void deformation is not noticeable.
2; Slightly noticeable void deformation.
1; Void deformation is conspicuous.
[8] Shrinkage rate
A flat plate having a length (resin flow direction) of 300 mm was molded in the same manner as in the evaluation of [6] Tiger Mark, and used as a sample. This was left to stand in a constant temperature / humidity chamber at 23 ° C. and a relative humidity of 50% for 48 hours, and then its length L was measured, and the shrinkage rate was determined by the following equation.
Shrinkage rate = (300-L) / 300
[0047]
[Table 10]

[0048]
[3] Evaluation result of polypropylene composition
From the comparison between Example-1 and Comparative Example-1, A in the A component^IIf the MFR is too low, the spiral flow is drastically reduced and the void deformability is deteriorated. On the other hand, from the result of Comparative Example-2, A^IWhen the MFR is too high, the appearance (tiger mark) of the molded product is significantly deteriorated. In addition, as in Comparative Example-6, when the component A was supplied in a divided manner, it became clear that the appearance (tiger mark) of the molded product was significantly deteriorated.
From the result of Comparative Example-3, when there is no ethylene-butene rubber component in the B component, the mechanical properties (the balance between flexural modulus and IZOD) are deteriorated. Similarly, from Comparative Example-7, it is clear that the mechanical properties (the balance between flexural modulus and IZOD) deteriorate if the ethylene / propylene rubber component is absent in the B component.
From the result of Comparative Example-4, when there is no A component, the appearance (tiger mark) of the molded product is significantly deteriorated.
From the results of Comparative Example-5, it is clear that the impact strength is remarkably lowered when a filler having a coarse particle diameter is used.
From the results of Comparative Example-8, when a rubber having a small CSD is additionally added, even if it has a relatively high molecular weight (MFR: 0.5 dg / min), the void / deformability is significantly deteriorated. I understand.
The result of Comparative Example-9 shows that when a copolymer component of C2C3 and one type (B-6) is used, the shrinkage rate is remarkably increased, so that the deformation of the molded product is large and undesirable.
Therefore, from the results of Table 10, it became clear that by using the polypropylene composition according to the present invention, it is possible to provide a molded product having excellent mechanical properties, moldability and appearance quality.
[0049]
【The invention's effect】
The polypropylene composition of the present invention is excellent in various physical properties, moldability, and molding appearance without requiring a large amount of addition of a rubber component later, and is inexpensive. In particular, since rigidity and impact strength are balanced at a high level, it is suitable for many molded products, especially automotive parts such as interior parts such as bumpers, instrument panels, door liners and pillars. .
[Brief description of the drawings]
FIG. 1 shows a molded plate used for evaluation of molded appearance, FIG. 1 (a) is a plan view, and FIG. 1 (b) is a side view.

Claims (5)

Containing a polypropylene component (A), a polypropylene component (B), a polypropylene component (C) and an inorganic filler;
The polypropylene component (A) is 3 to 25% by mass, the polypropylene component (B) is 30 to 60% by mass, the polypropylene component (C) is 5 to 50% by mass, and an inorganic filler. 10 mass% or more and less than 25 mass%,
The polypropylene component (A) is a crystalline polypropylene (A ^I ) having a melt flow rate of 0.5 g / 10 min or more and less than 10 g / 10 min, an ethylene content of 10 mass% or more and less than 70 mass%, and an intrinsic viscosity of 4 dl. / G or more and less than 9 dl / g ethylene-propylene copolymer (A ^III ) and crystalline polypropylene (A ^II ) having a melt flow rate of 30 g / 10 min or more and less than 2000 g / 10 min in this order. And
In the polypropylene component (A), the total amount of the crystalline polypropylene (A ^I ) and the crystalline polypropylene (A ^II ) is 20% by mass or more and less than 90% by mass, and the ethylene-propylene copolymer (A ^III ) is 80% by mass. Less than 10% by mass, and in the total amount of crystalline polypropylene (A ^I ) and crystalline polypropylene (A ^II ), crystalline polypropylene (A ^I ) is 25% by mass or more and less than 75% by mass, crystalline polypropylene (A ^II ) is less than 75% by mass and 25% by mass or more,
The polypropylene component (B) includes crystalline polypropylene (B ^I ) having a melt flow rate of 30 g / 10 min or more and less than 200 g / 10 min, an ethylene content of 30 mass% or more and less than 70 mass%, and an intrinsic viscosity of 2 dl / g. An ethylene-propylene copolymer (B ^II ) having an ethylene content of less than 4 dl / g and an ethylene-butene copolymer having an ethylene content of 70 mass% to less than 80 mass% and an intrinsic viscosity of 2 dl / g to less than 3 dl / g (B ^III ) and continuous multistage polymerization,
The polypropylene component (B) contains 20% by mass or more and less than 60% by mass of crystalline polypropylene (B ^I ), and is a total of ethylene-propylene copolymer (B ^II ) and ethylene-butene copolymer (B ^III ). In the amount, the ethylene-propylene copolymer (B ^II ) is 25% by mass or more and less than 75% by mass, the ethylene-butene copolymer (B ^III ) is less than 75% by mass and 25% by mass or more,
The polypropylene component (C) is a crystalline polypropylene having a melt flow rate of 500 g / 10 minutes or more and less than 3000 g / 10 minutes,
The inorganic filler has an average particle size of 4 μm or less, and is a polypropylene composition.  2. The polypropylene composition according to claim 1, further comprising another rubber component within a range of 5% by mass or less. The ratio of the spiral flow with respect to a melt flow rate is 1.70 or more and less than 3.00, The polypropylene composition in any one of Claims 1-2 characterized by the above-mentioned. The polypropylene composition according to any one of claims 1 to 3 , wherein the CSD of the xylene-soluble component is 1.5 or more and less than 4.5. The polypropylene composition according to any one of claims 1 to 4 , wherein the xylene-insoluble component has a weight average molecular weight of 60,000 or more and less than 100,000.

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