JP3234070B2 - Propylene resin composition for injection molding - Google Patents
Propylene resin composition for injection moldingInfo
- Publication number
- JP3234070B2 JP3234070B2 JP24715293A JP24715293A JP3234070B2 JP 3234070 B2 JP3234070 B2 JP 3234070B2 JP 24715293 A JP24715293 A JP 24715293A JP 24715293 A JP24715293 A JP 24715293A JP 3234070 B2 JP3234070 B2 JP 3234070B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- propylene
- olefin
- weight
- 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 - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、常温耐衝撃性及び低温
耐衝撃性が改良され、また、剛性と耐衝撃性の物性バラ
ンスの良好な、自動車内外装部品、電気機器外装部品等
に有用な射出成形用プロピレン系樹脂組成物に関するも
のである。The present invention is useful for interior and exterior parts of automobiles, exterior parts of electric equipment, etc., which have improved impact resistance at normal temperature and low temperature and have a good balance of physical properties of rigidity and impact resistance. The present invention relates to a propylene-based resin composition for injection molding.
【0002】[0002]
【従来の技術】ポリプロピレン樹脂は、高剛性及び成形
性が良好で、しかも安価であるなどの点から自動車内外
装部品、例えばバンパー、モール、フロントグリル、イ
ンパネ等や、電気機器外装部品等の分野において、近
年、加速度的にその用途が拡大されている。しかしなが
ら、このようなポリプロピレン樹脂でも、その用途によ
っては耐衝撃性が不十分であるという問題点を有してい
た。このような問題点を改善するために、従来から、ポ
リプロピレン樹脂にエチレン・プロピレン共重合体ゴ
ム、エチレン・ブテン共重合体ゴム、エチレン・プロピ
レン・ジエン共重合体ゴム等のゴム状弾性物質をブレン
ドすることが行なわれていた。2. Description of the Related Art Polypropylene resin has high rigidity, good moldability, and is inexpensive, and is used in the field of interior and exterior parts of automobiles, such as bumpers, moldings, front grilles, instrument panels, and exterior parts of electric equipment. In recent years, its applications have been rapidly expanding. However, even such a polypropylene resin has a problem that its impact resistance is insufficient depending on its use. In order to solve such problems, conventionally, rubber-like elastic materials such as ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene-propylene-diene copolymer rubber are blended with polypropylene resin. Was being done.
【0003】[0003]
【発明が解決しようとする課題】しかし、これらのゴム
状弾性物質をブレンドして、上記問題点を改善し、しか
も、ポリプロピレン樹脂の本来の長所である剛性を高度
に保とうとしても、耐衝撃性と剛性の物性バランスが高
度に良好な組成物を得ることは困難なことであった。本
発明の目的は、ポリプロピレン樹脂の長所である剛性を
高度に保ちながら、衝撃に対する問題点を改善して、耐
衝撃性と剛性の物性バランスが高度に優れた射出成形用
プロピレン系樹脂組成物を提供することにある。However, these rubber-like elastic materials are blended to solve the above-mentioned problems, and even if the rigidity which is the original advantage of the polypropylene resin is to be maintained at a high level, the impact resistance is high. It has been difficult to obtain a composition having a good balance between physical properties of rigidity and rigidity. An object of the present invention is to provide a propylene-based resin composition for injection molding, which has a high rigidity, which is an advantage of a polypropylene resin, while improving the problem of impact while maintaining a high level of rigidity, which is an advantage of a polypropylene resin. To provide.
【0004】[0004]
【課題を解決するための手段】[発明の概要] 本発明は、プロピレン重合体に、特定の性状を有するエ
チレン・α−オレフィン共重合体を特定の割合で配合し
て得られたプロピレン系樹脂組成物が、上記目的を達成
することができるとの知見を得て完成されるに至ったも
のである。すなわち、本発明による射出成形用プロピレ
ン系樹脂組成物は、下記の成分(A) および(B) を含んで
なること、を特徴とするものである。 成分(A) : MFRが15〜200g/10分のプロピ
レン・α−オレフィン(ただし、α−オレフィンの炭素
数は2または4〜12である)共重合体50〜97重量
%、 成分(B) : メタロセン系触媒で製造され、かつ下記
(a)〜(d) の性状を有するエチレン・α−オレフィン
(ただし、α−オレフィンの炭素数は4〜18である)
共重合体50〜3重量% (a) 密度が0.913g/cm3 以下、 (b) MFRが0.01〜20g/10分、 (c) α−オレフィン含量が10〜60重量% (d) ASTM D747による曲げ剛性が2,000k
g/cm2 以下。[Summary of the Invention] The present invention relates to a propylene resin obtained by blending an ethylene / α-olefin copolymer having a specific property with a specific ratio in a propylene polymer. The composition has been completed with the knowledge that the above object can be achieved. That is, the propylene resin composition for injection molding according to the present invention is characterized by comprising the following components (A) and (B). Component (A): 50 to 97% by weight of a propylene / α-olefin (α-olefin has 2 or 4 to 12 carbon atoms) copolymer having an MFR of 15 to 200 g / 10 min, Component (B) : Produced with a metallocene catalyst and the following
Ethylene / α-olefin having properties (a) to (d) (however, α-olefin has 4 to 18 carbon atoms)
50 to 3% by weight of copolymer (a) density of 0.913 g / cm 3 or less, (b) MFR of 0.01 to 20 g / 10 minutes, (c) α-olefin content of 10 to 60% by weight (d ) Flexural rigidity of 2,000k according to ASTM D747
g / cm 2 or less.
【0005】[発明の具体的説明] [I] 射出成形用プロピレン系樹脂組成物 (1) 構成成分 本発明による射出成形用プロピレン系樹脂組成物は、成
分(A) および(B) を含んでなるものである。ここで、本
発明によるプロピレン系樹脂組成物が成分(A) および
(B) を含んでなるということは、この組成物が挙示の成
分、すなわち成分(A) および(B) 、の外に本発明の趣旨
を損なわない限り、各種の補助成分(下記の成分(C) )
を含んでいてもよいことを意味する。 (a) 成分(A) 本発明のプロピレン系樹脂組成物を構成する成分(A) の
プロピレン系重合体は、プロピレンと少量のα−オレフ
ィンとのランダム又はブロック共重合体である。その製
造方法については特別に限定されるものではなく、一般
的には、いわゆるチタン含有固体状遷移金属成分と有機
金属成分を組合せて用いるチーグラー・ナッタ型触媒、
特には遷移金属成分がチタン、マグネシウム及びハロゲ
ンを必須成分とし、電子供与性化合物を任意成分とする
固体成分又は三塩化チタンとし、有機金属成分が有機ア
ルミニウム化合物である触媒、を用いて、スラリー重
合、気相重合、バルク重合、溶液重合等又はこれらを組
み合わせた重合法で、一段又は多段で、プロピレンと炭
素数2又は4〜12のα−オレフィン、好ましくはエチ
レンとを一段又は多段で共重合させることによって得ら
れるプロピレン・α−オレフィン共重合体である。前記
プロピレン系重合体が共重合体である場合には、ランダ
ム共重合体の場合、該共重合体中の他のα−オレフィン
の共重合割合は、一般に10重量%以下、好ましくは、
0.5〜7重量%であり、ブロック共重合体の場合、該
共重合体中の他のα−オレフィンの共重合割合は一般に
1〜40重量%、好ましくは1〜25重量%、さらには
2〜20重量%、特に好ましくは3〜15重量%であ
る。また、この共重合体はランダム共重合体でも、ブロ
ック共重合体でも良いが、本発明の目的である物性バラ
ンスをより高度化することができる点でプロピレン・エ
チレンブロック共重合体を使用することが好ましい。ま
た、これらのプロピレン系重合体は、2種以上の重合体
を併用したものであっても良い。[I] Propylene resin composition for injection molding (1) Constituents The propylene resin composition for injection molding according to the present invention contains components (A) and (B). It becomes. Here, the propylene-based resin composition according to the present invention comprises the component (A) and
The fact that the composition contains (B) means that the composition does not impair the purpose of the present invention in addition to the listed components, that is, components (A) and (B). (C))
Means that it may be included. (a) Component (A) The propylene polymer of the component (A) constituting the propylene resin composition of the present invention is a random or block copolymer of propylene and a small amount of α-olefin. The production method is not particularly limited, and generally, a Ziegler-Natta type catalyst using a combination of a so-called titanium-containing solid transition metal component and an organic metal component,
Particularly, a slurry polymerization is performed using a catalyst in which a transition metal component is titanium, magnesium and halogen as essential components, an electron donating compound is an optional component, a solid component or titanium trichloride, and an organic metal component is an organic aluminum compound. , Gas phase polymerization, bulk polymerization, solution polymerization, or a combination thereof, in one or more stages, copolymerizing propylene with an α-olefin having 2 or 4 to 12 carbon atoms, preferably ethylene in one or more stages And a propylene / α-olefin copolymer obtained by the reaction. When the propylene-based polymer is a copolymer, in the case of a random copolymer, the copolymerization ratio of the other α-olefin in the copolymer is generally 10% by weight or less, preferably,
0.5 to 7% by weight, and in the case of a block copolymer, the copolymerization ratio of the other α-olefin in the copolymer is generally 1 to 40% by weight, preferably 1 to 25% by weight, and more preferably 1 to 25% by weight. It is 2 to 20% by weight, particularly preferably 3 to 15% by weight. In addition, this copolymer may be a random copolymer or a block copolymer, but the use of a propylene / ethylene block copolymer in that the physical property balance which is the object of the present invention can be further enhanced. Is preferred. Further, these propylene-based polymers may be those obtained by using two or more kinds of polymers in combination.
【0006】MFR プロピレン系重合体のMFRは、一般に15〜200g
/10分、好ましくは15〜150g/10分、特に好
ましくは15〜100g/10分のものである。該MF
Rの値が低すぎると成形(射出成形)することが困難と
なってくるので好ましくない。また、MFRの値が高す
ぎると衝撃強度が低下するので好ましくない。[0006] The MFR of the MFR propylene polymer is generally 15 to 200 g.
/ 10 minutes, preferably 15 to 150 g / 10 minutes, particularly preferably 15 to 100 g / 10 minutes. The MF
If the value of R is too low, molding (injection molding) becomes difficult, which is not preferable. On the other hand, if the value of MFR is too high, the impact strength is undesirably reduced.
【0007】曲げ弾性率 プロピレン系重合体のJIS K7203による曲げ弾
性率は、5,000kg/cm2 以上、好ましくは6,
000〜20,000kg/cm2 、特には8,000
〜18,000kg/cm2 であるものが好ましく用い
られる。パルス法NMRによる特性 本発明に用いるプロピレン系重合体は、K.Fujimoto, T.
Nishi ahd R.Kado,Polym.J., Vol.3,448-462 (1972)に
記載の方法で求めた結晶成分(I)、拘束された非晶成
分(II)及び拘束されていない非晶成分(III )のそれ
ぞれの比率が、(I)/(II)が重量比で1.5〜4、
好ましくは2〜3.5で、かつ(III)が3〜30重量
%、好ましくは5〜20重量%、である。(I)/(I
I)が上記範囲より小さいと、耐熱性が劣り好ましくな
く、上記範囲を越えると、引張伸び特性が不足となり好
ましくない。(III )が上記範囲より小さいと、耐衝撃
性が劣り好ましくなく、上記範囲を越えると、製品表面
に傷が付き易くなり、製品の価値を低下させる原因とな
るので好ましくない。The flexural modulus of the propylene polymer according to JIS K7203 is 5,000 kg / cm 2 or more, preferably 6,5 kg / cm 2 or more.
000-20,000 kg / cm 2 , especially 8,000
What is ~ 18,000 kg / cm < 2 > is used preferably. Characteristics by pulse method NMR The propylene polymer used in the present invention is K. Fujimoto, T.
Nishi ahd R. Kado, Polym. J., Vol. 3, 448-462 (1972), the crystal component (I), the constrained amorphous component (II) and the unconstrained amorphous component ( III), the ratio of (I) / (II) is 1.5 to 4 by weight,
Preferably it is 2 to 3.5 and (III) is 3 to 30% by weight, preferably 5 to 20% by weight. (I) / (I
If I) is smaller than the above range, the heat resistance is inferior, which is not preferable. If it exceeds the above range, the tensile elongation properties become insufficient, which is not preferable. If (III) is smaller than the above range, the impact resistance is poor, which is not preferable. If it exceeds the above range, the surface of the product is liable to be scratched and the value of the product is reduced, which is not preferable.
【0008】(b) 成分(B) 本発明のプロピレン系樹脂組成物においてに用いられる
成分(B) は、下記(a)〜(d) の性状を有するエチレン・
α−オレフィン(ただし、α−オレフィンの炭素数は4
〜18である)共重合体である。 (a) 密度が0.913g/cm3 以下、 (b) MFRが0.01〜20g/10分、 (c) α−オレフィン含量が10〜60重量%、 (d) ASTM D747による曲げ剛性が2,000k
g/cm2 以下。(B) Component (B) The component (B) used in the propylene-based resin composition of the present invention is ethylene / ethylene having the following properties (a) to (d):
α-olefin (however, the carbon number of the α-olefin is 4
~ 18) copolymer. (a) density of 0.913 g / cm 3 or less, (b) MFR of 0.01 to 20 g / 10 min, (c) α-olefin content of 10 to 60% by weight, (d) flexural rigidity according to ASTM D747. 2,000k
g / cm 2 or less.
【0009】(a) 密 度 本発明に用いられるエチレン・α−オレフィン共重合体
の密度は、0.913g/cm3 以下、好ましくは0.
853〜0.900g/cm3 、更に好ましくは0.8
53〜0.890g/cm3 、特には0.853〜0.
880g/cm3 の値を示すものである。現在の工業的
技術では0.850g/cm3 の値より低い密度の製品
を製造することは困難ではあるが、これの値以下でも本
発明の効果を奏することができるものと推定する。上記
密度が高すぎると十分な衝撃強度が得られないので好ま
しくない。(A) Density The density of the ethylene / α-olefin copolymer used in the present invention is 0.913 g / cm 3 or less, preferably 0.1 g / cm 3 or less.
853-0.900 g / cm 3 , more preferably 0.8
53-0.890 g / cm 3 , especially 0.853-0.
It shows a value of 880 g / cm 3 . Although it is difficult to produce a product having a density lower than the value of 0.850 g / cm 3 with the current industrial technology, it is presumed that the effect of the present invention can be exerted even below this value. If the density is too high, a sufficient impact strength cannot be obtained, which is not preferable.
【0010】(b) MFR 本発明に用いられるエチレン・α−オレフィン共重合体
のMFRは、一般に0.01〜20g/10分、好まし
くは0.1〜10g/10分、更に好ましくは0.3〜
5g/10分、最も好ましくは0.5〜2g/10分で
ある。上記MFRが低すぎるとプロピレン重合体への分
散不良が起こり好ましくない。また、MFRが高すぎる
と十分な衝撃強度が得られないので好ましくない。(B) MFR The MFR of the ethylene / α-olefin copolymer used in the present invention is generally 0.01 to 20 g / 10 min, preferably 0.1 to 10 g / 10 min, and more preferably 0.1 to 10 g / 10 min. 3 ~
5 g / 10 min, most preferably 0.5 to 2 g / 10 min. If the MFR is too low, poor dispersion in the propylene polymer occurs, which is not preferable. On the other hand, if the MFR is too high, sufficient impact strength cannot be obtained, which is not preferable.
【0011】(c) オレフィン及びその含量 本発明のプロピレン系樹脂組成物において、用いられる
成分(B) のエチレン・α−オレフィン共重合体を構成す
る単量体として、エチレンと共重合される炭素数4〜1
8のα−オレフィンとしては、1−ブテン、1−ペンテ
ン、1−ヘキセン、1−オクテン、1−ヘプテン、4−
メチル−ペンテン−1、4−メチル−ヘキセン−1、
4,4−ジメチルペンテン−1、1−オクタデセン等を
挙げることができる。これらの中で好ましくは炭素数6
〜12の、特に好ましくは炭素数6〜10のα−オレフ
ィンである。これらのα−オレフィンは1種または2種
以上を用いてエチレンと共重合させることができる。上
記エチレン・α−オレフィン共重合体の中でも殊にエチ
レン・1−ヘキセンランダム共重合体が好ましい。エチ
レン・α−オレフィン共重合体におけるα−オレフィン
の含量は、一般に10〜60重量%、好ましくは20〜
55重量%、特に好ましくは20〜50重量%である。
このα−オレフィンの含量が少なすぎると改良効果が低
下するので好ましくない。また、高すぎると非結晶性成
分が増大し成形品が「べとつく」ので好ましくない。(C) Olefin and Its Content In the propylene-based resin composition of the present invention, as a monomer constituting the ethylene / α-olefin copolymer of the component (B) used, carbon which is copolymerized with ethylene is used. Number 4-1
8 as the α-olefin, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-
Methyl-pentene-1, 4-methyl-hexene-1,
4,4-dimethylpentene-1, 1-octadecene and the like can be mentioned. Of these, preferably those having 6 carbon atoms
And particularly preferably an α-olefin having 6 to 10 carbon atoms. One or more of these α-olefins can be copolymerized with ethylene. Among the above ethylene / α-olefin copolymers, an ethylene / 1-hexene random copolymer is particularly preferred. The content of α-olefin in the ethylene / α-olefin copolymer is generally 10 to 60% by weight, preferably 20 to 60% by weight.
It is 55% by weight, particularly preferably 20 to 50% by weight.
If the content of the α-olefin is too small, the improving effect is undesirably reduced. On the other hand, if it is too high, the amount of non-crystalline components increases and the molded product becomes "sticky", which is not preferable.
【0012】(d) 曲げ剛性 本発明に用いられる成分(B) のエチレン・α−オレフィ
ン共重合体のASTMD747による曲げ剛性は、2,
000kg/cm2 以下、好ましくは1,000kg/
cm2 以下、更には500kg/cm2 以下、最も好ま
しくは300kg/cm2 以下である。成分(B) の製造 本発明のプロピレン系樹脂組成物において、用いられる
成分(B) のエチレン・α−オレフィン共重合体の製造
は、特開昭58−19309号、特開昭59−9529
2号、特開昭60−35005号、特開昭60−350
06号、特開昭60−35007号、特開昭60−35
008号、特開昭60−35009号、好ましくは特開
平3−163088号の各公報、ヨーロッパ特許出願公
開第420436号明細書、米国特許第5055438
号明細書及び特に好ましくは国際公表公報WO 91/
04257号明細書等に記載の、1個又は2個のシクロ
ペンタジエニル骨格を有する配位子が周期律表IVb〜VI
b族の遷移金属、好ましくは、チタン、ジルコニウム又
はハフニウムに配位した公知のメタロセン化合物とアル
モキサンとを組み合わせた触媒、いわゆるメタロセン系
触媒を使用して、エチレンと炭素数4〜18のα−オレ
フィンとを共重合させて行うことができる。(D) Flexural rigidity The flexural rigidity according to ASTM D747 of the ethylene / α-olefin copolymer of the component (B) used in the present invention is 2,
000 kg / cm 2 or less, preferably 1,000 kg / cm 2
cm 2 or less, more preferably 500 kg / cm 2 or less, most preferably 300 kg / cm 2 or less. Production of Component (B) In the propylene resin composition of the present invention, the production of the ethylene / α-olefin copolymer of the component (B) used in the propylene resin composition is described in JP-A-58-19309 and JP-A-59-9529.
No. 2, JP-A-60-35005, JP-A-60-350
No. 06, JP-A-60-35007, JP-A-60-35
008, JP-A-60-35009, preferably JP-A-3-1630088, EP-A-420436, U.S. Pat. No. 5,055,438.
And particularly preferably International Publication WO 91 /
Ligand having one or two cyclopentadienyl skeletons described in JP-A-04257 is used in the periodic table IVb to VI
Using a so-called metallocene catalyst, which is a combination of a known metallocene compound and alumoxane coordinated to a transition metal of group b, preferably titanium, zirconium or hafnium, ethylene and an α-olefin having 4 to 18 carbon atoms Can be copolymerized.
【0013】重 合 このエチレン・α−オレフィン共重合体の製造方法とし
ては、気相法、スラリー法、溶液法、高圧イオン重合法
等を挙げることができる。これらの中では生成する共重
合体の融点以上280℃までの温度で重合する、高圧イ
オン重合法、溶液法で製造することが好ましく、本発明
の効果を大きく発揮することができる高圧イオン重合法
にて製造することが特に好ましい。なお、高圧イオン重
合法とは、特開昭56−18607号、特開昭58−2
25106号各公報により公知の、圧力が200kg/
cm2 以上、好ましくは300〜2,000kg/cm
2 、温度が125℃以上、好ましくは130〜250
℃、特に好ましくは150〜200℃の反応条件下にて
行なわれるエチレン系重合体の連続的製造法である。本
発明においては、上記製造、重合法によって得られたエ
チレン・α−オレフィン共重合体は、前記(a) 〜(d) の
性状を有することが必要である。[0013] As a method for producing Polymerization the ethylene · alpha-olefin copolymer, mention may be made of gas phase method, slurry, solution, high pressure ion polymerization method. Among these, it is preferable to produce by a high-pressure ionic polymerization method or a solution method, in which polymerization is performed at a temperature from the melting point of the produced copolymer to 280 ° C. It is particularly preferred to produce them at The high pressure ionic polymerization method is described in JP-A-56-18607 and JP-A-58-2607.
The pressure is 200 kg /
cm 2 or more, preferably 300 to 2,000 kg / cm
2. The temperature is 125 ° C or higher, preferably 130 to 250
C., particularly preferably a continuous method for producing an ethylene polymer, which is carried out under a reaction condition of 150 to 200.degree. In the present invention, the ethylene / α-olefin copolymer obtained by the above-mentioned production and polymerization method needs to have the above-mentioned properties (a) to (d).
【0014】(c) その他の配合成分(C) 本発明のプロピレン系樹脂組成物には、一般に樹脂組成
物の製造方法において用いられている補助添加成分、例
えば、酸化防止剤、熱安定剤、光安定剤、紫外線吸収
剤、中和剤、着色剤、滑剤、帯電防止剤等を添加するこ
とができる。また、炭酸カルシウム、カオリン、タル
ク、マイカ、中空ガラス球、酸化チタン、シリカ、カー
ボンブラック、アスベスト、ガラス繊維、チタン酸カリ
ウム繊維等の充填剤、本発明において用いられる上記成
分(B) 以外のオレフィン系共重合体、ポリスチレン樹
脂、アクリロニトリル・ブタジエン・スチレン共重合体
樹脂、エチレン・酢酸ビニル共重合樹脂、エチレン・プ
ロピレン系ゴム、スチレン・ブタジエン系ゴム、ポリブ
タジエン等の樹脂やゴム等をブレンドすることもでき
る。(C) Other Ingredients (C) The propylene-based resin composition of the present invention contains auxiliary additives generally used in a method for producing a resin composition, such as an antioxidant, a heat stabilizer, Light stabilizers, ultraviolet absorbers, neutralizing agents, coloring agents, lubricants, antistatic agents and the like can be added. In addition, fillers such as calcium carbonate, kaolin, talc, mica, hollow glass spheres, titanium oxide, silica, carbon black, asbestos, glass fibers, potassium titanate fibers, etc., and olefins other than the above-mentioned component (B) used in the present invention It is also possible to blend resins and rubbers such as a copolymer, a polystyrene resin, an acrylonitrile / butadiene / styrene copolymer resin, an ethylene / vinyl acetate copolymer resin, an ethylene / propylene rubber, a styrene / butadiene rubber, and a polybutadiene. it can.
【0015】(2) 組成比 本発明のプロピレン系樹脂組成物において用いられる上
記成分(A) と成分(B)の各成分の配合割合は、重量比
で、一般に成分(A) :成分(B) =97:3〜50:5
0、好ましくは成分(A) :成分(B) =93:7〜55:
45、更に好ましくは成分(A) :成分(B) =90:10
〜60:40、特に好ましくは成分(A) :成分(B) =8
0:20〜65:35である。上記成分(B) の配合割合
が多すぎると剛性が損なわれてしまうので好ましくな
く、少なすぎると改良効果が低下するので好ましくな
い。(2) Composition Ratio The mixing ratio of each of the above components (A) and (B) used in the propylene-based resin composition of the present invention is generally expressed in terms of weight ratio, in general, component (A): component (B) ) = 97: 3 to 50: 5
0, preferably component (A): component (B) = 93: 7 to 55:
45, more preferably component (A): component (B) = 90: 10
~ 60: 40, particularly preferably component (A): component (B) = 8
0:20 to 65:35. If the proportion of the component (B) is too large, the rigidity is impaired, which is not preferable. If the proportion is too small, the improvement effect is undesirably reduced.
【0016】[II] 樹脂組成物の製造 (1) 溶融・混練 本発明のプロピレン系樹脂組成物は、上記構成成分を上
記割合で配合する以外は通常の樹脂組成物の製造方法と
同様にして製造することができる。例えば、成分(A) と
成分(B) を押出機、ブラベンダープラストグラフ、バン
バリーミキサー、ニーダーブレンダー等を用いて溶融、
混練して、通常に用いられている方法でペレット状とす
るのが普通である。[II] Production of resin composition (1) Melting and kneading The propylene resin composition of the present invention is prepared in the same manner as in the production of a normal resin composition except that the above components are blended in the above proportions. Can be manufactured. For example, the components (A) and (B) are melted using an extruder, a Brabender plastograph, a Banbury mixer, a kneader blender, etc.
It is common to knead and form pellets by a commonly used method.
【0017】(2) 成 形 そして、このペレットを成形して各種成形体に成形する
ことができる。これらの中でも本発明の組成物を射出成
形用に用いるのが、本発明の効果を最も発揮することが
できるので好ましい。(2) Molding The pellets can be molded into various molded articles. Among them, it is preferable to use the composition of the present invention for injection molding because the effects of the present invention can be exhibited most.
【0018】[0018]
【実施例】以下に本発明の実験例を記載して、本発明を
より具体的に説明する。 (1) 評価方法 実施例及び比較例における物性の評価・測定方法は、次
に示す通りである。 (a) MFR:JIS K7210に準拠 (b) 密度 :JIS K7112に準拠 (c) α−オレフィン含量 エチレン/ブテン−1共重合体:「Macromolecules」 15 353-360、(1982) エチレン/ヘキセン−1共重合体:「Macromolecules」15,402-1406(1982) プロピレン/エチレン共重合体:「Macromolecules」、17,1950-1955(1984) に記載されているC13−MNRによる測定方法に準拠 (測定条件) 装置 :JEOL−GSX270(日本電子(株)製) 溶媒 :o−ジクロロベンゼン(70)/ds−ベンゼン(30) (v/v)% 測定濃度 :10(Wt/V)% 温度 :130℃ スペクトル幅 :11,000Hz データポイント数:16k パルス幅 :16μs(60゜) パルス間隔 :4s 積算回数 :3,000回 (d) 曲げ剛性 :ASTM D747に準拠 (e) 曲げ弾性率 :JIS K7203に準拠 (三点曲げ弾性率) (f) アイゾット衝撃機強度:JIS K7110に準拠(測定温度:23℃、 −40℃)して行なった。 (g) 耐熱性 :JIS K7207のHDT試験による (h) 引張伸び特性 :JIS K7113の引張試験による (i) 表面硬度 :JIS K7202のロックウェル硬度による (j) パルス法NMR :JEOL−GSX270(日本電子(株)製) を用い、30℃の試料に対して、90゜パルス幅 1.8μsでソリッドエコーの測定を行う。得ら れた磁化減衰曲線を対数プロットし、文献 K.Fuj imoto,T.Nishi and R.Kado, Polym.J., Vol.3 、 448-462(1972) に記載の方法で成分分離を行い、 各成分の分率を求める。The present invention will be described more specifically with reference to experimental examples of the present invention. (1) Evaluation method The evaluation and measurement methods of the physical properties in Examples and Comparative Examples are as follows. (a) MFR: compliant with JIS K7210 (b) Density: compliant with JIS K7112 (c) α-olefin content Ethylene / butene-1 copolymer: “Macromolecules” 15 353-360, (1982) ethylene / hexene-1 Copolymer: “Macromolecules” 15 , 402-1406 (1982) Propylene / ethylene copolymer: “Macromolecules”, 17 , 1950-1955 (1984), conforming to the measurement method by C 13 -MNR (measurement Conditions) Apparatus: JEOL-GSX270 (manufactured by JEOL Ltd.) Solvent: o-dichlorobenzene (70) / ds-benzene (30) (v / v)% Measurement concentration: 10 (Wt / V)% Temperature: 130 ° C Spectral width: 11,000 Hz Number of data points: 16 k Pulse width: 16 μs (60 °) Pulse interval: 4 s Number of integrations: 3,000 times (d) Flexural rigidity: Conforms to ASTM D747 (e) Flexural modulus: JIS K7 Compliant 03 (three-point bending modulus) (f) Izod impact machine strength: compliant JIS K7110 (measurement temperature: 23 ℃, -40 ℃) was performed to. (g) Heat resistance: by HDT test of JIS K7207 (h) Tensile elongation property: by tensile test of JIS K7113 (i) Surface hardness: by Rockwell hardness of JIS K7202 (j) Pulse method NMR: JEOL-GSX270 (Japan The solid echo is measured on a sample at 30 ° C. with a 90 ° pulse width of 1.8 μs using an electronic device. The obtained magnetization decay curve was logarithmically plotted, and the components were separated by the method described in K. Fujimoto, T. Nishi and R. Kado, Polym. J., Vol. 3, 448-462 (1972). Find the fraction of each component.
【0019】(2) 実験例 実施例1 [成分(A) の製造] 内容積200リットルの攪拌式オートクレーブをプロピ
レンで充分置換した後、脱水、脱酸素したn−ヘプタン
60リットルを導入し、ジエチルアルミニウムクロライ
ド38g、丸紅ソルベイ社製三塩化チタン12.7gを
60℃でプロピレン雰囲気下で導入した。前段重合は、
オートクレーブを65℃に昇温した後、水素濃度を10
%に保ちながら、プロピレンを9kg/時間のスピード
で導入することによって開始した。203分後、プロピ
レンの導入を止め、さらに重合を65℃で90分間継続
させた。そして、気相部プロピレンを0.2kg/cm
2 Gとなるまでパージした。次に、オートクレーブを6
0℃に降温した後、後段重合はα‐オレフィンとしての
エチレンを2.70kg/時間、プロピレンを4.06
kg/時間で30分間導入する事により実施した。この
ようにして得られたスラリーをろ過、乾燥して35.4
kgの粉末状重合体を得た。得られた試料のMFRは3
0g/10min、α‐オレフィン含量は4wt%、曲
げ弾性率は15000kg/cm2 であった。 [エチレン・α−オレフィン共重合体=成分(B) の合
成] 触媒成分の合成は国際公表公報WO 91/04257
号明細書に記載された方法で実施した。上記で得た錯体
Me2 Si(C5 Me4 )(NC12H23)TiCl
2 2.1ミリモルに東洋ストーファー製メチルアルモキ
サンを上記錯体に対し1,000倍モル加え、トルエン
で10リットルに希釈して触媒溶液を調製し、以下の方
法で重合を行なった。内容積1.5リットルの攪拌式オ
ートクレーブ型連続反応器に、エチレンと1−ヘキセン
との混合物を1−ヘキセンの組成が78重量%となるよ
うに供給した。反応器の圧力を1,000kg/cm2
に保ち、180℃で重合反応を行なった。反応後、MF
Rが3.9g/10分、密度が0.861g/cm3 、
ポリマー中の1−ヘキセン含量48重量%のエチレン共
重合体[成分(B) ]を得た。(2) Experimental example Example 1 [Production of component (A)] After sufficiently replacing a stirred autoclave having an internal volume of 200 liters with propylene, 60 liters of dehydrated and deoxygenated n-heptane were introduced, and diethyl ether was introduced. 38 g of aluminum chloride and 12.7 g of titanium trichloride manufactured by Marubeni Solvay were introduced at 60 ° C. in a propylene atmosphere. The pre-stage polymerization is
After raising the temperature of the autoclave to 65 ° C., the hydrogen concentration was increased to 10%.
%, Started by introducing propylene at a speed of 9 kg / h. After 203 minutes, the introduction of propylene was stopped and the polymerization was continued at 65 ° C. for 90 minutes. And propylene in the gas phase is 0.2 kg / cm
It was purged until the 2 G. Next, autoclave 6
After the temperature was lowered to 0 ° C., the post-stage polymerization was conducted using 2.70 kg / hour of ethylene as an α-olefin and 4.06 kg of propylene.
It was carried out by introducing at a rate of 30 kg / hour for 30 minutes. The slurry thus obtained was filtered and dried to give 35.4.
kg of a powdery polymer was obtained. The MFR of the obtained sample was 3
0 g / 10 min, the α-olefin content was 4 wt%, and the flexural modulus was 15000 kg / cm 2 . [Synthesis of ethylene / α-olefin copolymer = component (B)] The synthesis of the catalyst component is described in International Publication WO 91/04257.
This was performed in the manner described in the specification. Complex Me 2 Si (C 5 Me 4 ) (NC 12 H 23 ) TiCl obtained above
2. To 2.1 mmol of methylalumoxane (manufactured by Toyo Stoffer) was added 1,000 times by mole to the above complex, diluted with toluene to 10 liter to prepare a catalyst solution, and polymerized by the following method. A mixture of ethylene and 1-hexene was supplied to a stirred autoclave continuous reactor having an internal volume of 1.5 liters so that the composition of 1-hexene was 78% by weight. The pressure of the reactor is 1,000 kg / cm 2
And a polymerization reaction was carried out at 180 ° C. After the reaction, MF
R is 3.9 g / 10 min, density is 0.861 g / cm 3 ,
An ethylene copolymer [component (B)] having a 1-hexene content of 48% by weight in the polymer was obtained.
【0020】[組成物の製造] プロピレン系重合体としてα−オレフィン含量が4重量
%、MFRが30g/10分、JIS K7203によ
る曲げ弾性率が15,000kg/cm2 のプロピレン
・エチレンブロック共重合体[成分(A) ]を70重量%
と、上記の、MFRが1.5g/10分、密度が0.8
61g/cm3 、α−オレフィン含量が48重量%、曲
げ剛性が0kg/cm2 のエチレン・α−オレフィン共
重合体[成分(B) ]30重量%を均一にドライブレンド
し、シリンダー温度210℃で二軸押出機を用いて溶融
混和した後、造粒した。得られたペレットを、射出成形
機を用いて試験片を成形し、アイゾット衝撃強度、三点
曲げ弾性率を測定した。結果は表1の通りである。[Production of Composition] A propylene / ethylene block copolymer having an α-olefin content of 4% by weight, an MFR of 30 g / 10 min, and a flexural modulus of 15,000 kg / cm 2 according to JIS K7203 as a propylene polymer. 70% by weight of the combined [Component (A)]
And an MFR of 1.5 g / 10 min and a density of 0.8
61 g / cm 3 , an α-olefin content of 48% by weight, and a flexural rigidity of 0 kg / cm 2 30% by weight of an ethylene / α-olefin copolymer [component (B)] were uniformly dry-blended, and the cylinder temperature was 210 ° C. The mixture was melt-mixed using a twin screw extruder and granulated. A test piece was formed from the obtained pellet using an injection molding machine, and the Izod impact strength and the three-point bending modulus were measured. Table 1 shows the results.
【0021】実施例2〜17 実施例1で用いたプロピレン系重合体[成分(A) ]70
重量%と、エチレンとα−オレフィン混合物の組成を変
えて供給した以外は実施例1と同様にエチレン・α−オ
レフィン共重合体を製造して得られた表1に示す物性の
各エチレン・α−オレフィン共重合体[成分(B) ]30
重量%をそれぞれ用い、実施例1と同様に成形し、評価
した。その結果を表1〜3に示す。Examples 2 to 17 Propylene polymer [component (A)] 70 used in Example 1
% By weight and the ethylene / α-olefin properties shown in Table 1 obtained by producing the ethylene / α-olefin copolymer in the same manner as in Example 1 except that the ethylene / α-olefin mixture was supplied while changing the composition. -Olefin copolymer [Component (B)] 30
Using each of the weight%, molding and evaluation were performed in the same manner as in Example 1. The results are shown in Tables 1 to 3.
【0022】実施例18 実施例1において、成分(A) のプロピレン系重合体を9
0重量%用い、成分(B) のエチレン・α−オレフィン共
重合体を10重量%配合した以外は実施例1と同様に成
形し、評価した。その結果を表3に示す。Example 18 In Example 1, the propylene polymer of the component (A)
It was molded and evaluated in the same manner as in Example 1 except that 0% by weight was used and 10% by weight of the ethylene / α-olefin copolymer of the component (B) was blended. Table 3 shows the results.
【0023】実施例19 JIS K7203による曲げ弾性率が10,000k
g/cm2 のプロピレン重合体を用いた以外は実施例1
と同様に成形し、評価した。その結果を表3に示す。Example 19 The flexural modulus according to JIS K7203 is 10,000 k.
Example 1 except that g / cm 2 of a propylene polymer was used.
It was molded and evaluated in the same manner as described above. Table 3 shows the results.
【0024】比較例1〜3 実施例1で用いたプロピレン系重合体70重量%と、カ
ミンスキー系触媒を用いて製造したエチレン・α−オレ
フィン共重合体の代わりにバナジウム系触媒を用いて製
造した三井石油化学(株)製「タフマーA4085」
(比較例1)日本合成ゴム(株)製「EP02P」(比
較例2)又は「EP07P」(比較例3)30重量%を
用いて、実施例1と同様に成形し、評価した。その結果
を表4に示す。Comparative Examples 1 to 3 70% by weight of the propylene-based polymer used in Example 1 and a vanadium-based catalyst produced in place of the ethylene / α-olefin copolymer produced by using a Kaminski-based catalyst Mitsui Petrochemical Co., Ltd. “Tuffmer A4085”
(Comparative Example 1) Using "EP02P" (Comparative Example 2) or "EP07P" (Comparative Example 3) manufactured by Nippon Synthetic Rubber Co., Ltd., 30% by weight was molded and evaluated in the same manner as in Example 1. Table 4 shows the results.
【0025】比較例4 実施例1で用いた成分(A) のプロピレン系重合体70重
量%と、成分(B) をカミンスキー系触媒を用いて製造し
たエチレン・α−オレフィン共重合体の代わりにチタン
系触媒を用いて高圧イオン重合法で製造したMFRが
1.2g/10分、密度が0.890g/cm3 、α−
オレフィン含量が22重量%のエチレン・α−オレフィ
ン共重合体30重量%に変えた以外は実施例1と同様に
成形し、評価した。その結果を表4に示す。COMPARATIVE EXAMPLE 4 70% by weight of the propylene polymer of the component (A) used in Example 1 and the component (B) in place of the ethylene / α-olefin copolymer produced using a Kaminski catalyst were used. MFR produced by high-pressure ion polymerization using a titanium-based catalyst was 1.2 g / 10 min, the density was 0.890 g / cm 3 , α-
Molding and evaluation were performed in the same manner as in Example 1 except that the olefin content was changed to 30% by weight of an ethylene / α-olefin copolymer having 22% by weight. Table 4 shows the results.
【0026】比較例5 実施例1で用いた成分(A) のプロピレン系重合体の代わ
りに、MFRが300g/10分、曲げ弾性率が15,
000kg/cm2 のα−オレフィンを含有しないプロ
ピレン重合体、に変えた以外は実施例1と同様に成形
し、評価した。その結果を表4に示す。Comparative Example 5 Instead of the propylene polymer of the component (A) used in Example 1, the MFR was 300 g / 10 min, the flexural modulus was 15,
Molding and evaluation were conducted in the same manner as in Example 1 except that the propylene polymer containing no 000 kg / cm 2 α-olefin was used. Table 4 shows the results.
【0027】比較例6 実施例1において、成分(A) のプロピレン系重合体40
重量%と、実施例1で用いたと同じエチレン・α−オレ
フィン共重合体を60重量%配合した以外は、実施例1
と同様に成形し、評価した。その結果を表4に示す。Comparative Example 6 In Example 1, the propylene polymer 40 of the component (A) was used.
Example 1 except that the same ethylene / α-olefin copolymer as used in Example 1 was blended at 60% by weight.
It was molded and evaluated in the same manner as described above. Table 4 shows the results.
【0028】比較例7 実施例1において成分(A) のプロピレン系重合体70重
量%と、成分(B) の実施例1で用いたエチレン・α−オ
レフィン共重合体を表4に示すMFR、密度及びコモノ
マーの種類並びに含量のMFRが大きいエチレン・α−
オレフィン共重合体を30重量%、用いたこと、以外は
実施例1と同様に成形し、評価した。その結果を表4に
示す。Comparative Example 7 70% by weight of the propylene polymer of the component (A) in Example 1 and the ethylene / α-olefin copolymer used in Example 1 of the component (B) were obtained by MFR shown in Table 4. Ethylene-α- with high MFR of density and comonomer type and content
Molding and evaluation were performed in the same manner as in Example 1 except that 30% by weight of the olefin copolymer was used. Table 4 shows the results.
【0029】比較例8 実施例1で用いた成分(A) のプロピレン系重合体70重
量%と、成分(B) を表5に示すMFR、密度及びコモノ
マーの種類並びに含量の、密度及びコモノマー含量が範
囲外であるエチレン・α−オレフィン共重合体30重量
%、に変えた以外は実施例1と同様に成形し、評価し
た。その結果を表5に示す。COMPARATIVE EXAMPLE 8 70% by weight of the propylene polymer of the component (A) used in Example 1 and the component (B) in Table 5 showing the MFR, the density and the type and content of the comonomer, the density and the comonomer content Was molded and evaluated in the same manner as in Example 1, except that the ethylene / α-olefin copolymer was out of the range. Table 5 shows the results.
【0030】比較例9 実施例1で用いた成分(A) のプロピレン系重合体70重
量%と、成分(B) を表5に示すMFR、密度及びコモノ
マーの種類並びに含量の、コモノマー含量が大きすぎる
エチレン・α−オレフィン含有量30重量%、に変えた
以外は実施例1と同様に成形し、評価した。その結果を
表5に示す。COMPARATIVE EXAMPLE 9 70% by weight of the propylene polymer of the component (A) used in Example 1 and the comonomer content of the component (B) having a large MFR, a density and a kind and content of a comonomer shown in Table 5 were large. Molding and evaluation were performed in the same manner as in Example 1 except that the content of ethylene / α-olefin, which was too high, was changed to 30% by weight. Table 5 shows the results.
【0031】比較例10 実施例1で用いた成分(A) のプロピレン系重合体70重
量%と、成分(B) を表5に示すMFR、密度及びα−オ
レフィンの種類並びに含量の、コモノマーがプロピレン
であるエチレン・α−オレフィン含有量30重量%、と
を用いた以外は実施例1と同様に成形し、評価した。そ
の結果を表5に示す。COMPARATIVE EXAMPLE 10 70% by weight of the propylene polymer of the component (A) used in Example 1 and the comonomer of the component (B) having the MFR, the density and the type and content of the α-olefin shown in Table 5 were used. Molding and evaluation were performed in the same manner as in Example 1 except that the content of ethylene / α-olefin, which was propylene, was 30% by weight. Table 5 shows the results.
【0032】比較例11 対象として、実施例1で使用した成分(A) のプロピレン
系重合体のみを用いた以外は、実施例1と同様に成形
し、評価した。その結果を表5に示す。Comparative Example 11 A molding was performed and evaluated in the same manner as in Example 1 except that only the propylene polymer of the component (A) used in Example 1 was used. Table 5 shows the results.
【0033】比較例12 成分(A) としてMFRが3g/10分、曲げ弾性率が1
5,000kg/cm2 であるプロピレン系重合体70
重量%と、実施例1で用いたと同じエチレン・α−オレ
フィン共重合体30重量%、を用いた以外は実施例1と
同様に成形し、評価した。その結果を表5に示す。Comparative Example 12 As the component (A), the MFR was 3 g / 10 min, and the flexural modulus was 1
Propylene polymer 70 of 5,000 kg / cm 2
Molding and evaluation were performed in the same manner as in Example 1 except that the same weight% and 30% by weight of the same ethylene / α-olefin copolymer as used in Example 1 were used. Table 5 shows the results.
【0034】実施例20〜24、比較例13〜17 実施例1と同様な方法で製造した成分(A) の種類を変え
た以外は実施例1と同様の方法で配合試料を作成し、前
記の方法にて諸物性を測定した。使用した成分(A) 、
(B) の物性、配合量、及び、配合試料の物性を表−6、
7に示した。Examples 20 to 24, Comparative Examples 13 to 17 A blended sample was prepared in the same manner as in Example 1 except that the type of the component (A) produced in the same manner as in Example 1 was changed. Various physical properties were measured by the methods described above. Ingredients used (A),
Table 6 shows the physical properties, blending amount, and physical properties of the blended sample of (B).
7 is shown.
【0035】比較例18 実施例1で用いた成分(A) のプロピレン系重合体の代わ
りに、MFRが100g/10分、曲げ弾性率が15,
000kg/cm2 のα−オレフィンを含有しないプロ
ピレン重合体に変えた以外は実施例1と同様に成形し、
評価した。その結果を表3に示す。Comparative Example 18 Instead of the propylene polymer of the component (A) used in Example 1, the MFR was 100 g / 10 min, the flexural modulus was 15,
Molding was performed in the same manner as in Example 1 except that the propylene polymer did not contain 000 kg / cm 2 α-olefin.
evaluated. Table 3 shows the results.
【0036】 [0036]
【0037】 [0037]
【0038】 [0038]
【0039】 [0039]
【0040】 [0040]
【0041】 [0041]
【0042】 [0042]
【0043】[0043]
【発明の効果】本発明の射出成形用プロピレン系樹脂組
成物は、従来のゴム状弾性体を混合したものと比較し
て、常温耐衝撃性及び低温耐衝撃性が改良され、飛躍的
に剛性と耐衝撃性の物性バランスが改良されており、成
形性に優れた樹脂組成物であることから、バンパー、イ
ンパネ等の自動車内外装部品や、電気機器外装部品等の
各種分野において有用な素材である。The propylene-based resin composition for injection molding of the present invention has improved room-temperature impact resistance and low-temperature impact resistance as compared with those obtained by mixing a conventional rubber-like elastic material, and has a remarkably high rigidity. It is a resin composition that has an improved balance of physical properties of impact resistance and impact resistance, and is a material that is useful in various fields such as automotive interior and exterior parts such as bumpers and instrument panels, and electrical equipment exterior parts because it is a resin composition with excellent moldability. is there.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−13838(JP,A) 特開 昭62−121709(JP,A) 特開 昭62−256856(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08L 23/00 - 23/36 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-13838 (JP, A) JP-A-62-121709 (JP, A) JP-A-62-256856 (JP, A) (58) Field (Int.Cl. 7 , DB name) C08L 23/00-23/36
Claims (6)
とを特徴とする、射出成形用プロピレン系樹脂組成物。 成分(A) : MFRが15〜200g/10分のプロピ
レン・α−オレフィン(ただし、α−オレフィンの炭素
数は2または4〜12である)共重合体50〜97重量
%、 成分(B) : メタロセン系触媒で製造され、かつ下記
(a)〜(d) の性状を有するエチレン・α−オレフィン
(ただし、α−オレフィンの炭素数は4〜18である)
共重合体50〜3重量% (a) 密度が0.913g/cm3 以下、 (b) MFRが0.01〜20g/10分、 (c) α−オレフィン含量が10〜60重量% (d) ASTM D747による曲げ剛性が2,000k
g/cm2 以下。1. A propylene-based resin composition for injection molding, comprising the following components (A) and (B). Component (A): 50 to 97% by weight of a propylene / α-olefin (α-olefin has 2 or 4 to 12 carbon atoms) copolymer having an MFR of 15 to 200 g / 10 min, Component (B) : Produced with a metallocene catalyst and the following
Ethylene / α-olefin having properties (a) to (d) (however, α-olefin has 4 to 18 carbon atoms)
50 to 3% by weight of copolymer (a) density of 0.913 g / cm 3 or less, (b) MFR of 0.01 to 20 g / 10 minutes, (c) α-olefin content of 10 to 60% by weight (d ) Flexural rigidity of 2,000k according to ASTM D747
g / cm 2 or less.
共重合体がプロピレン・エチレンブロック共重合体であ
る、請求項1記載の射出成形用プロピレン系樹脂組成
物。2. The propylene resin composition for injection molding according to claim 1, wherein the propylene / α-olefin copolymer of the component (A) is a propylene / ethylene block copolymer.
(ただし、α−オレフィンの炭素数は2または4〜12
である)共重合体が、パルス法NMRで求めた結晶成分
(I)、拘束された非晶成分(II)、及び拘束されてい
ない非晶成分(III )のそれぞれの比率が、(I)/
(II)の重量比で1.5〜4で、かつ、(III )が3〜
30重量%である、請求項1記載の射出成形用プロピレ
ン系樹脂組成物。3. A propylene / α-olefin of the component (A) wherein the α-olefin has 2 or 4 to 12 carbon atoms.
The copolymer has a ratio of each of the crystalline component (I), the constrained amorphous component (II), and the unconstrained amorphous component (III) determined by pulsed NMR, which is (I) /
1.5 to 4 in weight ratio of (II) and 3 to 3 in (III)
The propylene-based resin composition for injection molding according to claim 1, which is 30% by weight.
下である、請求項1記載の射出成形用プロピレン系樹脂
組成物。4. The propylene resin composition for injection molding according to claim 1, wherein the density of the component (B) is 0.90 g / cm 3 or less.
下である、請求項1記載の射出成形用プロピレン系樹脂
組成物。5. The propylene resin composition for injection molding according to claim 1, wherein the density of the component (B) is 0.89 g / cm 3 or less.
10のα‐オレフィンである、請求項1記載の射出成形
用プロピレン系樹脂組成物。6. The component (B) wherein the α-olefin has 6 to 6 carbon atoms.
The propylene-based resin composition for injection molding according to claim 1, which is an α-olefin of No. 10.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24715293A JP3234070B2 (en) | 1992-10-15 | 1993-10-01 | Propylene resin composition for injection molding |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4-277407 | 1992-10-15 | ||
JP27740792 | 1992-10-15 | ||
JP24715293A JP3234070B2 (en) | 1992-10-15 | 1993-10-01 | Propylene resin composition for injection molding |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06192500A JPH06192500A (en) | 1994-07-12 |
JP3234070B2 true JP3234070B2 (en) | 2001-12-04 |
Family
ID=26538076
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24715293A Expired - Fee Related JP3234070B2 (en) | 1992-10-15 | 1993-10-01 | Propylene resin composition for injection molding |
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JP (1) | JP3234070B2 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3418957B2 (en) * | 1995-01-17 | 2003-06-23 | 出光石油化学株式会社 | Polypropylene resin composition |
US5608008A (en) * | 1995-02-03 | 1997-03-04 | Tosoh Corporation | Polypropylene resin composition and molded product |
CA2187407C (en) * | 1995-10-09 | 2006-03-14 | Tomohiko Akagawa | Polypropylene resin composition for exterior parts of automobiles |
US6048942A (en) * | 1996-09-30 | 2000-04-11 | Montell North America Inc. | Thermoplastic olefin articles having high surface gloss and mar resistance |
DE19821718A1 (en) | 1997-05-15 | 1998-11-19 | Sumitomo Chemical Co | Polypropylene]=based resin composition used for injection moulded article |
US6011102A (en) * | 1997-05-16 | 2000-01-04 | Toyota Jidosha Kabushiki Kaisha | Polypropylene-based resin composition and injection molded article thereof |
KR100598192B1 (en) * | 1998-06-05 | 2006-07-07 | 닛폰 포리프로 가부시키가이샤 | Propylene block copolymer and propylene resin composition |
JP4344421B2 (en) | 1999-04-26 | 2009-10-14 | 住友化学株式会社 | Thermoplastic resin composition and injection-molded body thereof |
CN1231505C (en) | 2000-05-16 | 2005-12-14 | 三井化学株式会社 | Ethylene copolymer and ethylene/& alpha,-olefin copolymer compsn. and propylene polymer compsn. both contg. ethylene copolymer |
JP2003073524A (en) | 2001-09-03 | 2003-03-12 | Sumitomo Chem Co Ltd | Basic magnesium sulfate-fiber reinforced polypropylene resin composition and injection molded product obtained by using the same resin composition |
EP1517954B1 (en) * | 2002-06-26 | 2014-05-28 | Basell Poliolefine Italia S.r.l. | Impact-resistant polyolefin compositions |
PL372196A1 (en) * | 2002-06-26 | 2005-07-11 | Basell Poliolefine Italia S.P.A. | Impact-resistant polyolefin compositions |
US7259211B2 (en) | 2003-12-12 | 2007-08-21 | Mitsui Chemicals, Inc. | Ethylene type ternary copolymer and propylene type resin composition |
BRPI0511307A (en) * | 2004-06-08 | 2007-12-04 | Basell Poliolefine Srl | Polyolefin composition having a high balance of hardness, impact resistance and elongation at break and low thermal shrinkage |
JP4844091B2 (en) * | 2004-11-10 | 2011-12-21 | 住友化学株式会社 | Propylene resin composition and film thereof |
AU2006227666A1 (en) * | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of propylene/alpha-olefins |
BRPI0609851B1 (en) * | 2005-03-17 | 2016-12-13 | Dow Global Technologies Inc | fiber obtainable from or comprising an ethylene / (alpha) olefin interpolymer, fiber obtainable from or comprising at least one ethylene interpolymer and a c3-c20 (alpha) olefin, cloth, yarn and method for making a fiber or cloth |
JP2007056145A (en) * | 2005-08-25 | 2007-03-08 | Asahi Kasei Chemicals Corp | Thermoplastic resin composition |
US7906599B2 (en) | 2006-04-19 | 2011-03-15 | Japan Polypropylene Corporation | Transition metal compound, catalyst for olefin polymerization containing the same, and method for producing propylene/ethylene-α-olefin block copolymer by using the catalyst |
JP5595733B2 (en) * | 2006-11-23 | 2014-09-24 | サンアロマー株式会社 | Polyolefin composition |
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1993
- 1993-10-01 JP JP24715293A patent/JP3234070B2/en not_active Expired - Fee Related
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