JPH0533269B2 - - Google Patents
Info
- Publication number
- JPH0533269B2 JPH0533269B2 JP60032738A JP3273885A JPH0533269B2 JP H0533269 B2 JPH0533269 B2 JP H0533269B2 JP 60032738 A JP60032738 A JP 60032738A JP 3273885 A JP3273885 A JP 3273885A JP H0533269 B2 JPH0533269 B2 JP H0533269B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- propylene
- component
- resin composition
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 17
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 8
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
〔発明の技術分野〕
本発明はポリプロピレン共重合樹脂組成物に関
し、更に詳しくは、通常の改質処理を施して得ら
れた、優れた耐低温衝撃強度と高い剛性とを兼備
したポリプロピレン共重合樹脂組成物に関する。
〔発明の技術的背景とその問題点〕
ポリプロピレン樹脂は高い剛性を備えているも
のの、その反面、耐衝撃強度とりわけ耐低温衝撃
強度が低いという欠点をもつ。
この点を改良したものとして、プロピレンに
エチレンなどの他のα−オレフインを共重合させ
たもの、ポリプロピレンに、ポリブタジエン、
エチレン−プロピレンゴムなどのゴム状物質を配
合したもの、などが提案されかつ製造されてい
る。これらのものは、いずれもゴム成分を含有す
るため、耐衝撃強度はある程度改善されるが、逆
に、ポリプロピレンが本来有する剛性を低下させ
るという不都合が生ずる。
そのため、更に改良策として、上記又はの
樹脂組成物に対し、有機過酸化物、架橋助剤を配
合して改質処理を施すことが提案されている。
しかしながら、かかる改質処理によつても、ポ
リプロピレン樹脂の剛性を低下させることなく、
耐低温衝撃強度を充分高めることは容易ではない
という問題があつた。
〔発明の目的〕
本発明は、従来のかかる問題を解消し、上記し
た改質処理を施すことによつて、高い剛性を低下
させることなく、耐衝撃強度、特に耐低温衝撃強
度が著しく改善されたポリプロピレン共重合樹脂
組成物を提供することを目的とする。
〔発明の概要〕
本発明者らは、改質処理を施すことによつて耐
低温衝撃強度が飛躍的に向上するポリプロピレン
共重合樹脂組成物を見出すべく鋭意研究を重ねた
結果、所定の極限粘度を有するポリプロピレン共
重合樹脂及びゴム状物質を所定量配合して得られ
る樹脂組成物が上記目的を達することを見出し、
本発明を完成するに至つた。
すなわち、本発明は、
成分Ａ：極限粘度が0.8〜3.0dl／ｇのプロピレン
−エチレン共重合体キシレン不溶部ポリマー50
〜90重量％、並びに
成分Ｂ：（ｂ−１）エチレンプロピレンゴム及
び／又は（ｂ−２）プロピレン−エチレン共重
合体キシレン可溶部ポリマーからなり、かつ、
成分Ａの極限粘度の0.6〜1.5倍の極限粘度を有
するものを成分Ｂ中60重量％以上含有するゴム
状物質50〜10重量％
からなる樹脂組成物100重量部に、有機過酸化物
0.01〜1.0重量部及び架橋助剤0.01〜5.0重量部を
加え、溶融混練して改質処理したポリプロピレン
共重合樹脂組成物である。
まず、成分Ａはプロピレン−エチレン共重合体
のキシレン不溶部ポリマーで、極限粘度が0.8〜
3.0dl／ｇ、好ましくは1.0〜2.8dl／ｇのものを使
用する。極限粘度が0.8dl／ｇ未満の場合は後述
する改質処理を施しても得られるポリプロピレン
共重合樹脂組成物はその耐衝撃性の飛躍的な向上
は望めず、また、極限粘度が3.0dl／ｇを超える
と組成物の流動性が低下して成形性に難点が生ず
る。
極限粘度0.8〜3.0dl／ｇのプロピレン−エチレ
ン共重合体キシレン不溶部ポリマーＡはプロピレ
ン−エチレン共重合体を140℃の熱キシレンで２
時間抽出し、50℃に冷却して更に２時間抽出する
ことにより、キシレンに不溶のポリマーとして容
易に得ることができる。なお、原料となるプロピ
レン−エチレン共重合体はチーグラー・ナツタ触
媒を用い、２段又は３段以上の多段重合法で製造
することができる。例えば１段目でプロピレンホ
モポリマーの重合を行い、次いでプロピレンモノ
マーを除去し若しくは除去せずに、２段目以降で
エチレンの存在下又はエチレンとプロピレンとの
共存下で重合反応を進めることにより製造するこ
とができる。各段の反応における圧力は数気圧〜
40気圧、温度は室温〜80℃でよい。また、重合反
応としては溶液重合、スラリー重合、気相重合又
はこれらの併用法などが適用できる。なお、必要
に応じて各段に水素を供給してもよい。
次いで、成分Ｂはゴム状物質であり、エチレン
プロピレンゴム（ｂ−１）及び／又はプロピレン
−エチレン共重合体キシレン可溶部ポリマー（ｂ
−２）からなる。成分Ｂは、成分Ａの極限粘度の
0.6〜1.5倍の極限粘度を有する上記ポリマーが成
分Ｂ中60重量％以上含有されていることは必要で
ある。極限粘度が上記範囲に入らないもの、又
は、極限粘度が上記範囲内であつても含有量が60
重量％未満の場合には、得られたポリプロピレン
共重合樹脂組成物における耐衝撃性の改良が充分
ではない。
また、成分Ｂとしての、エチレンプロピレンゴ
ム（ｂ−１）は、例えば、日本合成ゴム(株)製、
E07P，E02P，EP11P（以上、いずれも商品名）
などの市販品を用いればよく、これらの１種若し
くは２種以上を使用することができる。一方、プ
ロピレン−エチレン共重合体キシレン可溶部ポリ
マー（ｂ−２）は、上記したように、プロピレン
−エチレン共重合体を140℃の熱キシレンで２時
間抽出し、50℃に冷却して更に２時間抽出した可
溶部分のポリマーである。すなわち、プロピレン
−エチレン共重合体はキシレン不溶部を成分Ａと
して、キシレン可溶部を成分Ｂとして使用するこ
とができる。
本発明のポリプロピレン共重合樹脂組成物は、
上記成分Ａと成分Ｂとからなる樹脂組成物を原料
とする。成分Ａの配合量は50〜90重量％、好まし
くは、60〜80重量％であり、したがつて、成分Ｂ
の配合量は50〜10重量％、好ましくは40〜20重量
％である。成分Ａの配合量が50重量％未満の場合
（成分Ｂの配合量が50重量％を超える場合）、樹脂
組成物中のゴム分が増加して剛性の低下を招来
し、一方、成分Ａの配合量が90重量％を超える場
合（成分Ｂの配合量が10重量％未満の場合）、改
質処理を施しても耐衝撃性の改良が充分ではな
い。
上記樹脂組成物は、成分Ａと成分Ｂとを上記の
割合で配合したのち、例えば、一軸混練機、バン
バリミキサー、スーパーミキサーなどを使用して
溶融混練することにより容易に製造することがで
きる。この樹脂組成物は、以下に述べる改質処理
を施すことによつて、その耐低温衝撃強度が飛躍
的に向上するという特長を有する。
すなわち、改質処理は、上記樹脂組成物に有機
過酸化物及び架橋助剤を配合したのち溶融混練す
ることによつて行われる。この改質処理工程に使
用される有機過酸化物及び架橋助剤としては、公
知のものを使用することができる。具体的には、
有機過酸化物として、例えば、１，３−ビス（ｔ
−ブチルパーオキシイソプロピル）ベンゼン、ジ
クミルパーオキシド、ジ−ｔ−ブチルパーオキシ
ド、２，５−ジメチル−２，５−ジ（ｔ−ブチル
パーオキシ）ヘキシン−３，２，５−ジメチル−
２，５−ジ（ｔ−ブチルパーオキシ）ヘキサンな
どが好ましく、架橋助剤としては、例えば、イオ
ウ；ジビニルベンゼンのようなジビニル化合物；
ジアリルフタレートのようなジアリル化合物；ｐ
−キノンジオキシム、ｐ，p′−ジベンゾイルキノ
ンジオキシムのようなオキシム化合物；フエニル
マレイミドのようなマレイミド化合物などが好ま
しいものとして挙げられる。
なお、これらの配合量は、上記樹脂組成物100
重量部に対し、有機過酸化物が0.01〜1.0重量部、
架橋助剤が0.01〜5.0重量部である。また、前者
と後者の間の配合比は１：１〜１：10となるよう
に設定することが好ましい。
実際の改質処理の操作としては、先ず、上記樹
脂組成物に前記した有機過酸化物及び架橋助剤を
それぞれ所定量配合し、全体を例えば一軸押出機
で溶融混練してペレツト化する。この溶融混練時
に適用する温度は180〜270℃、好ましくは190〜
250℃である。
かかる改質処理によつて本発明のポリプロピレ
ン共重合樹脂の耐衝撃強度は飛躍的に向上し、一
方、該ポリプロピレン共重合樹脂が本来的に具備
している高い剛性はこの改質処理によつても損わ
れることがないので、結果として、優れた耐低温
衝撃強度と高い剛性とを兼備したポリプロピレン
共重合樹脂組成物が得られるのである。
〔実施例〕
実施例１〜２及び比較例１〜３
プロピレン−エチレン共重合体及びエチレンプ
ロピレンゴムとして、それぞれ下記に示すものを
用意した。
プロピレン−エチレン共重合体
本実施例においては以下に述べる製造例により
調製した５種類のプロピレン−エチレン共重合体
(イ)〜(ホ)を使用した。
(1) プロピレン−エチレン共重合体(イ)の製造
三塩化チタン5.0g、ジエチルアルミニウムクロ
ライド50.0g，ｎ−ヘプタン40を充分乾燥した
内容積100の撹拌器付オートクレーブに仕込ん
だ後、水素ガスを1.1Kg／cm2Ｇ（一段目水素圧）と
なるまで張込み、ついで、プロピレンガスを圧力
9.0Kg／cm2Ｇとなるまで供給し、65℃において90
分間重合反応を行つた。重合終了後、大半の残留
プロピレンを脱気しつつ57℃まで降温した。その
後、再び水素ガスを1.0Kg／cm2Ｇ（二段目水素圧）
となるまで供給し、エチレンを流量12N／分、
プロピレンを流量25N／分で同時に供給して30
分間重合させた。
重合反応終了後、ただちにｎ−ブタノール70ml
を加え未反応ガスをパージした。次いで、ｎ−ヘ
プタンにより洗浄し、乾燥した。得られた重合体
のうち10gを沸騰キシレン1500mlに溶解させたの
ち、20℃に降温し４時間放置した。その後、この
ものを別乾燥し、キシレン不溶部ポリマー8.3g
（85重量％）を得た。一方、液にメタノールを
加えて再沈し、これを別乾燥することによりキ
シレン可溶部ポリマーとしてゴム状物質1.5g（15
重量％）を得た。このポリマー及びゴム状物質の
極限粘度はそれぞれ1.4dl／ｇ及び4.0dl／ｇであ
つた。
(2) プロピレン−エチレン共重合体(ロ)〜(ホ)の製造
製造例(1)において、一段目及び二段目水素圧、
並びに、エチレン及びプロピレンの流量を下記第
１表の如く設定した点を除いては、上記製造例(1)
と全く同様にしてプロピレン−エチレン共重合体
(ロ)〜(ホ)を得たのち、そのキシレン不溶部ポリマー
とキシレン可溶部ポリマーであるゴム状物質との
分離を行つた。
[Technical Field of the Invention] The present invention relates to a polypropylene copolymer resin composition, and more specifically to a polypropylene copolymer resin that has both excellent low-temperature impact strength and high rigidity and is obtained through a conventional modification treatment. Regarding the composition. [Technical background of the invention and its problems] Although polypropylene resin has high rigidity, it has the disadvantage of low impact strength, particularly low-temperature impact strength. To improve this point, propylene is copolymerized with other α-olefins such as ethylene, polypropylene is copolymerized with polybutadiene,
Products containing rubber-like substances such as ethylene-propylene rubber have been proposed and manufactured. Since these materials all contain a rubber component, the impact resistance strength is improved to some extent, but on the contrary, the inherent rigidity of polypropylene is reduced, which is a disadvantage. Therefore, as a further improvement measure, it has been proposed that the above resin composition or the above resin composition be subjected to a modification treatment by blending an organic peroxide and a crosslinking aid. However, even with such modification treatment, the rigidity of polypropylene resin is not reduced.
There was a problem in that it was not easy to sufficiently increase the low-temperature impact strength. [Object of the Invention] The present invention solves the conventional problems, and by performing the above-mentioned modification treatment, the impact strength, especially the low temperature impact strength, is significantly improved without reducing the high rigidity. The object of the present invention is to provide a polypropylene copolymer resin composition. [Summary of the Invention] The present inventors have conducted intensive research to find a polypropylene copolymer resin composition whose low-temperature impact strength can be dramatically improved by performing a modification treatment. It has been discovered that a resin composition obtained by blending a predetermined amount of a polypropylene copolymer resin having the following and a rubber-like substance achieves the above object,
The present invention has now been completed. That is, the present invention comprises: Component A: propylene-ethylene copolymer with an intrinsic viscosity of 0.8 to 3.0 dl/g xylene-insoluble part polymer 50
~90% by weight, and component B: consisting of (b-1) ethylene propylene rubber and/or (b-2) propylene-ethylene copolymer xylene-soluble portion polymer, and
An organic peroxide is added to 100 parts by weight of a resin composition consisting of 50 to 10% by weight of a rubbery substance containing 60% by weight or more of a rubber-like substance in component B that has an intrinsic viscosity of 0.6 to 1.5 times that of component A.
This is a polypropylene copolymer resin composition obtained by adding 0.01 to 1.0 parts by weight and 0.01 to 5.0 parts by weight of a crosslinking aid, and then melt-kneading and modifying the composition. First, component A is a xylene-insoluble polymer of propylene-ethylene copolymer with an intrinsic viscosity of 0.8 to
3.0 dl/g, preferably 1.0 to 2.8 dl/g. If the intrinsic viscosity is less than 0.8 dl/g, the resulting polypropylene copolymer resin composition cannot be expected to dramatically improve its impact resistance even if it is subjected to the modification treatment described below, and the intrinsic viscosity is less than 3.0 dl/g. If it exceeds g, the fluidity of the composition decreases, causing difficulties in moldability. Polymer A is a propylene-ethylene copolymer with an intrinsic viscosity of 0.8 to 3.0 dl/g.
It can be easily obtained as a xylene-insoluble polymer by extracting for 1 hour, cooling to 50°C, and further extracting for 2 hours. The propylene-ethylene copolymer used as a raw material can be produced by a two-stage, three-stage or more multistage polymerization method using a Ziegler-Natsuta catalyst. For example, production is carried out by polymerizing a propylene homopolymer in the first stage, then proceeding with the polymerization reaction in the presence of ethylene or in the coexistence of ethylene and propylene in the second and subsequent stages, with or without removing the propylene monomer. can do. The pressure in each stage of reaction is several atmospheres ~
The pressure may be 40 atm and the temperature may be between room temperature and 80°C. Further, as the polymerization reaction, solution polymerization, slurry polymerization, gas phase polymerization, or a combination thereof can be applied. Note that hydrogen may be supplied to each stage as necessary. Next, component B is a rubber-like substance, and includes ethylene propylene rubber (b-1) and/or propylene-ethylene copolymer xylene soluble portion polymer (b-1).
-2). Component B has the intrinsic viscosity of component A.
It is necessary that component B contains at least 60% by weight of the above-mentioned polymer having an intrinsic viscosity of 0.6 to 1.5 times. Items whose intrinsic viscosity does not fall within the above range, or whose content is 60% even if the intrinsic viscosity is within the above range.
If the amount is less than % by weight, the impact resistance of the obtained polypropylene copolymer resin composition will not be sufficiently improved. In addition, the ethylene propylene rubber (b-1) as component B is, for example, manufactured by Japan Synthetic Rubber Co., Ltd.
E07P, E02P, EP11P (all of the above are product names)
Commercially available products such as these may be used, and one or more of these may be used. On the other hand, the propylene-ethylene copolymer xylene-soluble polymer (b-2) is obtained by extracting the propylene-ethylene copolymer with hot xylene at 140°C for 2 hours, cooling it to 50°C, and further producing the xylene-soluble polymer (b-2). This is the soluble portion of the polymer extracted for 2 hours. That is, in the propylene-ethylene copolymer, the xylene-insoluble part can be used as component A, and the xylene-soluble part can be used as component B. The polypropylene copolymer resin composition of the present invention is
A resin composition consisting of the above component A and component B is used as a raw material. The amount of component A is 50 to 90% by weight, preferably 60 to 80% by weight, and therefore component B
The blending amount is 50 to 10% by weight, preferably 40 to 20% by weight. When the amount of component A is less than 50% by weight (when the amount of component B is more than 50% by weight), the rubber content in the resin composition increases, resulting in a decrease in rigidity. When the blending amount exceeds 90% by weight (when the blending amount of component B is less than 10% by weight), impact resistance is not sufficiently improved even if the modification treatment is performed. The above resin composition can be easily produced by blending component A and component B in the above ratio and then melt-kneading the mixture using, for example, a single-screw kneader, a Banbury mixer, a super mixer, or the like. This resin composition has the feature that its low-temperature impact strength is dramatically improved by subjecting it to the modification treatment described below. That is, the modification treatment is performed by blending an organic peroxide and a crosslinking aid into the resin composition and then melt-kneading the resin composition. As the organic peroxide and crosslinking aid used in this modification process, known ones can be used. in particular,
As the organic peroxide, for example, 1,3-bis(t
-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-
2,5-di(t-butylperoxy)hexane and the like are preferred, and examples of crosslinking aids include sulfur; divinyl compounds such as divinylbenzene;
diallyl compounds such as diallyl phthalate; p
Preferred examples include oxime compounds such as -quinone dioxime and p,p'-dibenzoylquinone dioxime; and maleimide compounds such as phenylmaleimide. In addition, these compounding amounts are 100% of the above resin composition.
Organic peroxide is 0.01 to 1.0 parts by weight,
The crosslinking aid is 0.01 to 5.0 parts by weight. Moreover, it is preferable to set the blending ratio between the former and the latter to be 1:1 to 1:10. In the actual modification process, first, the above-described organic peroxide and crosslinking aid are added to the resin composition in predetermined amounts, and the whole is melt-kneaded using, for example, a single-screw extruder to form pellets. The temperature applied during this melt-kneading is 180-270℃, preferably 190-270℃.
The temperature is 250℃. Through this modification treatment, the impact strength of the polypropylene copolymer resin of the present invention is dramatically improved, and on the other hand, the high rigidity that the polypropylene copolymer resin inherently has is improved by this modification treatment. As a result, a polypropylene copolymer resin composition having both excellent low-temperature impact strength and high rigidity can be obtained. [Example] Examples 1 to 2 and Comparative Examples 1 to 3 The propylene-ethylene copolymer and ethylene propylene rubber shown below were prepared. Propylene-ethylene copolymer In this example, five types of propylene-ethylene copolymers prepared according to the production examples described below were used.
(a) to (e) were used. (1) Production of propylene-ethylene copolymer (a) After charging 5.0 g of titanium trichloride, 50.0 g of diethylaluminum chloride, and 40 g of n-heptane into a sufficiently dried autoclave with an internal volume of 100 and equipped with a stirrer, hydrogen gas was added. Fill the tank until it reaches 1.1Kg/cm 2 G (first stage hydrogen pressure), then pressurize propylene gas.
9.0Kg/cm 2 G at 65℃.
The polymerization reaction was carried out for minutes. After the polymerization was completed, the temperature was lowered to 57°C while degassing most of the remaining propylene. After that, hydrogen gas is added again to 1.0Kg/cm 2 G (second stage hydrogen pressure)
Supply ethylene at a flow rate of 12N/min until
30 by simultaneously supplying propylene at a flow rate of 25 N/min.
Polymerization was carried out for minutes. Immediately after the polymerization reaction, add 70 ml of n-butanol.
was added to purge unreacted gas. Then, it was washed with n-heptane and dried. After dissolving 10 g of the obtained polymer in 1500 ml of boiling xylene, the temperature was lowered to 20°C and left for 4 hours. After that, this material was dried separately, and 8.3g of xylene-insoluble polymer was added.
(85% by weight) was obtained. On the other hand, by adding methanol to the liquid and reprecipitating it, and drying this separately, 1.5 g (15
% by weight) was obtained. The intrinsic viscosities of the polymer and rubbery material were 1.4 dl/g and 4.0 dl/g, respectively. (2) Production of propylene-ethylene copolymers (b) to (e) In production example (1), the first and second stage hydrogen pressure,
Also, the above production example (1) except that the flow rates of ethylene and propylene were set as shown in Table 1 below.
Propylene-ethylene copolymer in exactly the same manner as
After obtaining (b) to (e), the xylene-insoluble part of the polymer and the rubber-like substance which is the xylene-soluble part of the polymer were separated.
以上の説明から明らかなように、本発明のポリ
プロピレン共重合樹脂組成物は、改質処理を施し
たことによつてその耐低温衝撃強度は飛躍的に向
上すると同時に、高い剛性を維持することができ
たものであるため、優れた耐低温衝撃強度と高い
剛性とを兼備したポリプロピレン共重合樹脂組成
物であり、自動車、或いは弱電分野における工業
用素材として極めて有用である。
As is clear from the above explanation, the polypropylene copolymer resin composition of the present invention can dramatically improve its low-temperature impact strength and maintain high rigidity by undergoing the modification treatment. Because of this, it is a polypropylene copolymer resin composition that has both excellent low-temperature impact strength and high rigidity, and is extremely useful as an industrial material in the automobile and light electrical fields.
【表】【table】
Claims (1)
ピレン−エチレン共重合体キシレン不溶部ポリ
マー50〜90重量％、並びに 成分Ｂ：（ｂ−１）エチレンプロピレンゴム及
び／又は（ｂ−２）プロピレン−エチレン共重
合体キシレン可溶部ポリマーからなり、かつ、
成分Ａの極限粘度の0.6〜1.5倍の極限粘度を有
するものを成分Ｂ中60重量％以上含有するゴム
状物質50〜10重量％ からなる樹脂組成物100重量部に、有機過酸化物
0.01〜1.0重量部及び架橋助剤0.01〜5.0重量部を
加え、溶融混練して改質処理したポリプロピレン
共重合樹脂組成物。[Scope of Claims] 1 Component A: 50 to 90% by weight of a propylene-ethylene copolymer with an intrinsic viscosity of 0.8 to 3.0 dll/g, xylene-insoluble polymer, and Component B: (b-1) ethylene propylene rubber and/or or (b-2) consisting of a propylene-ethylene copolymer xylene soluble portion polymer, and
An organic peroxide is added to 100 parts by weight of a resin composition consisting of 50 to 10% by weight of a rubbery substance containing 60% by weight or more of a rubber-like substance in component B that has an intrinsic viscosity of 0.6 to 1.5 times that of component A.
A polypropylene copolymer resin composition obtained by adding 0.01 to 1.0 parts by weight and 0.01 to 5.0 parts by weight of a crosslinking aid, and then melt-kneading and modifying the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3273885A JPS61192752A (en) | 1985-02-22 | 1985-02-22 | Polypropylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3273885A JPS61192752A (en) | 1985-02-22 | 1985-02-22 | Polypropylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61192752A JPS61192752A (en) | 1986-08-27 |
| JPH0533269B2 true JPH0533269B2 (en) | 1993-05-19 |
Family
ID=12367171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3273885A Granted JPS61192752A (en) | 1985-02-22 | 1985-02-22 | Polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61192752A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2598407B2 (en) * | 1987-05-11 | 1997-04-09 | 三井東圧化学株式会社 | Propylene-ethylene copolymer composition and method for producing the same |
| US5623013A (en) * | 1994-12-16 | 1997-04-22 | Ube Industries, Ltd. | Xonotlite-reinforced organic polymer composition |
| CN110753726B (en) * | 2017-06-26 | 2022-05-03 | 博里利斯股份公司 | Polypropylene composition with excellent surface appearance |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5439453A (en) * | 1977-09-05 | 1979-03-26 | Hitachi Ltd | Polypropylene resin composition |
| JPS5827731A (en) * | 1981-08-12 | 1983-02-18 | Mitsubishi Chem Ind Ltd | Polyolefin composition and its preparation |
| JPS5852313A (en) * | 1981-09-22 | 1983-03-28 | Mitsui Toatsu Chem Inc | Polypropylene resin composition having excellent surface property |
| JPS59223740A (en) * | 1983-06-02 | 1984-12-15 | Mitsui Petrochem Ind Ltd | Production of polypropylene composition |
| JPS6015254A (en) * | 1983-07-04 | 1985-01-25 | 株式会社日立製作所 | Double spindle electric truck for railway rolling stock |
-
1985
- 1985-02-22 JP JP3273885A patent/JPS61192752A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5439453A (en) * | 1977-09-05 | 1979-03-26 | Hitachi Ltd | Polypropylene resin composition |
| JPS5827731A (en) * | 1981-08-12 | 1983-02-18 | Mitsubishi Chem Ind Ltd | Polyolefin composition and its preparation |
| JPS5852313A (en) * | 1981-09-22 | 1983-03-28 | Mitsui Toatsu Chem Inc | Polypropylene resin composition having excellent surface property |
| JPS59223740A (en) * | 1983-06-02 | 1984-12-15 | Mitsui Petrochem Ind Ltd | Production of polypropylene composition |
| JPS6015254A (en) * | 1983-07-04 | 1985-01-25 | 株式会社日立製作所 | Double spindle electric truck for railway rolling stock |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61192752A (en) | 1986-08-27 |
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