JPS59226012A - Ethylene copolymer - Google Patents

Abstract

PURPOSE:To provide the titled copolymer composed of ethylene and a specific alpha-olefin, having specific intrinsic viscosity, density and flow rate ratio, excellent mechanical strength and inflation moldability, and suitable as a material of packaging film, etc. CONSTITUTION:The objective copolymer having an intrinsic viscosity of 3.10- 3.80dl/g, a density of 0.950-0.965g/cm<3> and a flow rate ratio of 110-240, preferably 160-220 is obtained by copolymerizing ethylene (preferably 97.0-99.8wt%) with a 5-7C straight-chain alpha-olefin (preferably hexene-1) (preferably 3.0- 0.2wt%) preferably by two-stage polymerization (polymerizing ethylene, and then copolymerizing ethylene and the 5-7C straight-chain alpha-olefin to the resultant polyethylene).

Description

【発明の詳細な説明】 本発明はエチレン共重合体に関し、詳しくは機械的強度
が高く、かつインフレーション成形性にすぐれたエチレ
ン共重合体に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ethylene copolymer, and more particularly to an ethylene copolymer that has high mechanical strength and excellent inflation moldability.

近年、ポリエチレン、ポリプロピレンなどのフィルムは
包装分野において広く用いられており、機械設備による
自動包装、自動充填が一般的に行なわれている。しかも
、その処理速度は次第に早くなっておシ、かつ大容量化
の傾向にある。また、フィルムから製袋する際の速度も
装置の改良に伴ない急速に早くなっている。In recent years, films such as polyethylene and polypropylene have been widely used in the packaging field, and automatic packaging and filling using mechanical equipment are generally performed. Moreover, the processing speed is gradually increasing and the capacity is increasing. Furthermore, the speed at which bags are made from film is rapidly increasing as equipment improves.

したがって、これらの要求に対応するためには、フィル
ムが所定の物性を具備していることが必要であシ、とり
わけ十分な機械的強度と腰の強さを有することが重要で
ある。Therefore, in order to meet these demands, it is necessary for the film to have certain physical properties, and in particular, it is important to have sufficient mechanical strength and stiffness.

フィルムの強度と腰の強さを向上させる手段としてフィ
ルムの厚みを増すことが採用されている。Increasing the thickness of the film has been adopted as a means to improve the strength and stiffness of the film.

しかし、この方法はフィルムの製造コスト、生産性の面
から制約を受ける。フィルム強度については衝撃強度、
引裂強度、引裂強度の縦横のバランスが良いことが重要
であシ、腰の強さについては高密度、高剛性であシ、か
つ引張弾性率が高いことが重要である〇 本発明者らはエチレン系重合体のフィルムに関し、上記
のような諸物性を同時に満足するものを開発すべく検討
を重ねた結果、該重合体の極限粘度、密度および流出量
比をそれぞれ特定することによって目的とするフィルム
が得られることを見出し、本発明を完成するに到った。However, this method is subject to limitations in terms of film manufacturing cost and productivity. Regarding film strength, impact strength,
It is important that tear strength and tear strength are well balanced in the vertical and horizontal directions, and for waist strength, it is important that the material has high density, high rigidity, and high tensile modulus.〇The present inventors As a result of repeated studies to develop an ethylene polymer film that simultaneously satisfies the various physical properties listed above, we determined the intrinsic viscosity, density, and outflow ratio of the polymer to achieve the desired goals. It was discovered that a film could be obtained, and the present invention was completed.

すなわち本発明は、エチレンと炭素数５〜７の直鎖α−
オレフィンの共重合体であって、極限粘度！１．１０〜
１８０　ｄｉ／ｆ　、密度０．９５０　ＮＯ，９６５ｆ
／ｃｄ。That is, the present invention deals with ethylene and a straight chain α-
It is an olefin copolymer and has an intrinsic viscosity! 1.10～
180 di/f, density 0.950 NO, 965f
/cd.

流出量比１１０〜２４０であるエチレン共重合体に関す
るものである。This relates to an ethylene copolymer having an outflow ratio of 110 to 240.

本発明においてエチレンとの共重合成分として用いるα
−オレフィンは炭素数５〜７の直鎖α−オレフィンであ
る。炭素数５未満のものや炭素数７を超えるもの、さら
には炭素数５〜７であってモ側鎖を有するα−オレフィ
ンをコモノマーとして用いて得られる共重合体は衝撃強
度が低く、がつ引裂強度の縦横バランスが悪いものとな
る◎炭素数５〜７の直鎖α−オレアインの中では特にヘ
キセン−１が好ましい。α used as a copolymerization component with ethylene in the present invention
-Olefin is a straight chain α-olefin having 5 to 7 carbon atoms. Copolymers with fewer than 5 carbon atoms, those with more than 7 carbon atoms, and copolymers obtained by using α-olefins with 5 to 7 carbon atoms and a mo side chain as comonomers have low impact strength and are tough. The vertical and horizontal balance of tear strength is poor. Among linear α-olein having 5 to 7 carbon atoms, hexene-1 is particularly preferred.

次に、エチレンと上記α−オレフィンの配合割合につい
てはエチレン９４．０〜９９．９重量％、好ましくは９
７．０〜９９．８重ａｇおよびα−オレフィン６．０〜
０．１重量％、好ましくは１０−０．２重量％である。Next, regarding the blending ratio of ethylene and the above α-olefin, ethylene is 94.0 to 99.9% by weight, preferably 9% by weight.
7.0~99.8 heavy ag and α-olefin 6.0~
0.1% by weight, preferably 10-0.2% by weight.

本発明のエチレン共重合体は極限粘度（１５５℃、？）
う９ｙ溶液中で測定）が１１０〜５．Ｂ　Ｏｄｌ／ｆテ
ア夛、５．１０　ｄ／７未満のものはフィルムの衝撃強
度が低下し、かつ溶融張力が低下するため、フィルム成
形の際にバブルが不安定となる。一方、５．８０ｄｌ／
ｙを超えるものはフィルムの衝撃強度が低下し、かつ流
動性が低下してフィルム外観が不良となシ、さらにフィ
ルム成形の際のバブルが不安定となる。The ethylene copolymer of the present invention has an intrinsic viscosity (155°C, ?)
(measured in a 9y solution) is 110-5. If the B Odl/f tear value is less than 5.10 d/7, the impact strength of the film and the melt tension will decrease, resulting in unstable bubbles during film forming. On the other hand, 5.80dl/
If the value exceeds y, the impact strength of the film will decrease, fluidity will decrease, the appearance of the film will be poor, and furthermore, bubbles during film molding will become unstable.

また、エチレン共重合体の密度（Ｊ工ＦＪＫ６７６０１
１Ｃよる）が０．９５０　ｆ／ｄｉ未満のものはフィル
ムの引張弾性率が低下し、かつ引張強度の縦横のバラン
スが悪化し、ｏ、９６ｓｙ／−を超えるとフィルムの引
裂強度が低下し、かつ引裂強度の縦横のバランスが悪化
するほか衝撃強度も低下するので好ましくない。In addition, the density of ethylene copolymer (J Engineering FJK67601
1C) is less than 0.950 f/di, the tensile modulus of the film decreases and the vertical and horizontal balance of tensile strength deteriorates, and when it exceeds 96 sy/-, the tear strength of the film decreases. Moreover, it is not preferable because the vertical and horizontal balance of the tear strength deteriorates and the impact strength also decreases.

さらに、エチレン共重合体の流出量比は１１０〜２４０
、好ましくは１６０〜２２０であシ、　。Furthermore, the outflow ratio of ethylene copolymer is 110 to 240.
, preferably 160-220.

１１０未満のものは流動性が悪く、シかもバブルが不安
定となるため、インフレーション成形に適さない。また
、２４０を超えると分子量分布が広くなシ、フィルムの
衝撃強度が低下し、好ましくない。なお、流出量比はＡ
８ＴＭ　１）　１２３８　Ｋ基づくメルトインデックス
（Ｍ工）測定において荷重１ゆ（Ｍ工、）と１０ｋｐ（
Ｍ工、。、・）の比（Ｍ工、６７Ｍ工訃）で表わしたも
のである。If it is less than 110, the fluidity is poor and the bubbles become unstable, so it is not suitable for inflation molding. Moreover, if it exceeds 240, the molecular weight distribution will become broad and the impact strength of the film will decrease, which is not preferable. In addition, the outflow ratio is A
8TM 1) In the melt index (M-work) measurement based on 1238 K, the load is 1 Yu (M-work,) and 10 kp (
M engineering. , .) (M-work, 67M-work).

本発明のエチレン共重合体は種々の方法で製造すること
ができ、たとえばチーグラー型触媒を用いて単段で所定
量のエチレンと炭素数５〜７の直鎖α−オレフィンを圧
力０．５〜１５　ｋｙ／ｃＩｌ、温度５０〜９５℃の条
件下で共重合させる方法などがあるが、特に効率よく製
造するためＫは、下記のような２段階による方法が好ま
しい。The ethylene copolymer of the present invention can be produced by various methods. For example, a predetermined amount of ethylene and a linear α-olefin having 5 to 7 carbon atoms are heated in a single stage using a Ziegler type catalyst at a pressure of 0.5 to 7. There is a method of copolymerizing under conditions of 15 ky/cIl and a temperature of 50 to 95° C., but for particularly efficient production, the following two-step method for K is preferred.

まず、第１段階においてエチレンのみを高活性のチーグ
ラー型触媒の存在下で極限粘度が０．１〜１．３ｔ＆／
ｆＩ−１好ましく　ハ０．４〜０．８　ｄ／　ｆ、エチ
レン重合量２５〜８０重社％、好ましくは３５〜６５重
量％となるような条件下で反応させる。さらに、第２段
階においては、得られたポリエチレンにエチレンおよび
炭素数５〜７の直鎖α−オレフィンを加えてエチレン含
量および該α−オレフィン含敞がそれぞれ所定量となる
ように重合を行なう。この第２段階では反応生成物の極
限粘度が４．０〜１０．０ｄｌ／ｆ、好ましくは５．０
〜８．０ｄｌ／ｆ。First, in the first step, only ethylene is processed in the presence of a highly active Ziegler type catalyst so that the intrinsic viscosity is 0.1 to 1.3t&/
The reaction is carried out under conditions such that fI-1 is preferably 0.4 to 0.8 d/f and the ethylene polymerization amount is 25 to 80% by weight, preferably 35 to 65% by weight. Furthermore, in the second step, ethylene and a linear α-olefin having 5 to 7 carbon atoms are added to the obtained polyethylene, and polymerization is carried out so that the ethylene content and the α-olefin content are respectively predetermined amounts. In this second stage, the intrinsic viscosity of the reaction product is 4.0 to 10.0 dl/f, preferably 5.0 dl/f.
~8.0dl/f.

重合量７５〜２０重景％、重量しくは６５〜３５重量％
となるような条件で反応を行ない、前記した物性を有す
る本発明のエチレン共重合体を得る。Polymerization amount: 75-20% by weight, 65-35% by weight
The reaction is carried out under conditions such that the ethylene copolymer of the present invention having the above-mentioned physical properties is obtained.

ここで、高活性のチーグラー型触媒としては各種のもの
を使用でき、たとえば特願昭５８−６６９２０号明細書
に開示されている触媒は好適に使用することができる。Various kinds of highly active Ziegler type catalysts can be used here, and for example, the catalyst disclosed in Japanese Patent Application No. 58-66920 can be suitably used.

上記２段階による重合方法において懸濁重合。Suspension polymerization in the above two-step polymerization method.

溶液重合、気相重合などいずれも適用可能であシ、また
重合は連続式１回分式などいずれの方式で行なうことも
できる。たとえば懸濁２段重合を行なう場合、溶媒とし
てペンタン、ｎ−ヘキサン、ヘプタン、ベンゼン、トル
エン、シクロヘキサンなどの不活性溶媒を用い、第１段
階では温度７０〜９５℃、好ましくは８０〜９０℃、圧
力０．５〜１５＃／ｄ、好ましくは４〜１０に９／ｄ、
反応時間１〜３時間で重合を行ない、第２段階では温度
５０〜９０℃、好ましくは６０〜８０℃、圧力０．５〜
１５に９７ｍ、好ましくは３〜１０ｋＩｉ／ｄ、反応時
間０．５〜１．５時間で重合を行なうことＫより本発明
のエチレン共重合体を得ることができる。また、物性の
うち極限粘度については分子量調節剤（たとえば水素な
ど）の種類、濃度などを変化させることによって調節す
ることも可能である。Solution polymerization, gas phase polymerization, and the like can be applied, and the polymerization can be carried out by any method such as a continuous method or a single batch method. For example, when performing suspension two-stage polymerization, an inert solvent such as pentane, n-hexane, heptane, benzene, toluene, or cyclohexane is used as the solvent, and the temperature in the first stage is 70 to 95°C, preferably 80 to 90°C. Pressure 0.5 to 15 #/d, preferably 4 to 10 to 9/d,
Polymerization is carried out for a reaction time of 1 to 3 hours, and in the second stage, the temperature is 50 to 90°C, preferably 60 to 80°C, and the pressure is 0.5 to 90°C.
The ethylene copolymer of the present invention can be obtained by carrying out polymerization at a reaction time of 0.5 to 97 m, preferably 3 to 10 kI/d, and a reaction time of 0.5 to 1.5 hours. In addition, among the physical properties, the intrinsic viscosity can be adjusted by changing the type, concentration, etc. of the molecular weight modifier (for example, hydrogen).

本発明のエチレン共重合体は機械的強度、特にフィルム
強度にすぐれておシ、かつフィルム強度た場合に十分に
腰の強いフィルムを得ることができる。したがって、薄
肉化フィルムの製造用素材として適している。さらに、
成形加工性にすぐれておシ、特にバブル安定性が良好で
あるので、インフレーション成形に好適である。それ故
、本発明のエチレン共重合体は包装用フィルムの素材と
して極めて有用である。The ethylene copolymer of the present invention has excellent mechanical strength, particularly film strength, and can provide a sufficiently stiff film. Therefore, it is suitable as a material for manufacturing thin films. moreover,
It has excellent moldability and particularly good bubble stability, so it is suitable for inflation molding. Therefore, the ethylene copolymer of the present invention is extremely useful as a material for packaging films.

次に１本発明の実施例を示す。Next, an example of the present invention will be shown.

製造例 固体触媒成分の製造 ｎ−へブタン５０ｄ中にマグネシウムジェトキシド１．
Ｏｆ　（８，８ミリモル）および市販の無水硫酸マグネ
シウム１．０６７　（８，８ミリモル）を懸濁させ、さ
らに四塩化ケイ素１．５　ｆ　（８，８ミリモル）とエ
タノール１．６ｆ　（３５，２ミリモル）を加えて８０
℃で１時間反応を行なった。次いで、四塩化チタン５７
（４５ミリモル）を加えて９８℃で３時間反応させた。Preparation Example Preparation of Solid Catalyst Component Magnesium jetoxide 1.
Of (8,8 mmol) and 1.067 (8,8 mmol) of commercially available anhydrous magnesium sulfate are suspended, together with 1.5 f (8,8 mmol) of silicon tetrachloride and 1.6 f (35,2 mmol) of ethanol. mmol) and 80
The reaction was carried out at ℃ for 1 hour. Next, titanium tetrachloride 57
(45 mmol) was added and reacted at 98°C for 3 hours.

反応後、冷却静置し上澄液を傾斜法によ）除去した。次
いで、新たにｎ−へブタン１００Ｎｌを加えて攪拌、静
置、上澄液除去の洗浄操作を３回行なった後、ｎ−へブ
タン２００ｄを加えて固体触媒成分の分散液を得た。こ
のもののチタン担持量を比色法によシ求めた結果、４２
冨ｙ−ｒｉ／を一担体であった。After the reaction, the mixture was left to cool and stand, and the supernatant liquid was removed by decanting. Next, 100 Nl of n-hebutane was newly added and washing operations of stirring, standing still, and removing the supernatant liquid were performed three times, and then 200 d of n-hebutane was added to obtain a dispersion of the solid catalyst component. As a result of determining the amount of titanium supported on this material using a colorimetric method, it was found that 42
Fuji-ri/ was one carrier.

実施例１〜６および比較例１〜７ ７を容のステンレス製、オートクレーブを乾燥窒素で置
換した後、乾燥ヘキサン２．５ｔ、上記製造例で製造し
た固体触媒成分を０．２５ミリモル。Examples 1 to 6 and Comparative Examples 1 to 7 7 was made of stainless steel, the autoclave was replaced with dry nitrogen, 2.5 t of dry hexane, and 0.25 mmol of the solid catalyst component produced in the above production example.

トリエチルアルミニウム１．０ミリモルおよびジエチル
アルミニウムクルライドを４．０ミリモル加えた。1.0 mmol of triethylaluminum and 4.0 mmol of diethylaluminum chloride were added.

次に１ポリエチレンが第１表に示す極限粘度となるよう
計量された水素および反応器の全圧が８、ｙｋｇ／ｃｄ
ａ　ＩＩＣなるようにエチレンを連続的に供給し、９０
℃で１２０分間攪拌しながら反応を行なった。Next, hydrogen was measured so that 1 polyethylene had the intrinsic viscosity shown in Table 1, and the total pressure of the reactor was 8, ykg/cd.
a Continuously supply ethylene so that IIC is 90
The reaction was carried out at 120° C. with stirring for 120 minutes.

次いで、反応器を４０℃まで冷却後、脱気して乾燥窒素
置換した後、２．５１の乾燥へキサンを追加投入した。Next, the reactor was cooled to 40° C., degassed and replaced with dry nitrogen, and then 2.51 g of dry hexane was added.

しかる後、エチレンおよび炭素数５〜７の直鎖α−オレ
フィンの各所定量と第１表に示す極限粘度となるように
計量された水素を加え１全圧４．０　ｋｇ／ｄａ　ｓ　
温度８０℃で３０分間攪拌しながら反応を行なった。Thereafter, predetermined amounts of ethylene and linear α-olefin having 5 to 7 carbon atoms and hydrogen weighed to give the intrinsic viscosity shown in Table 1 were added to give a total pressure of 4.0 kg/da s.
The reaction was carried out at a temperature of 80°C for 30 minutes with stirring.

反応終了後、得られたエチレン共重合体を洗浄、乾燥し
た後、その物性を測定した。結果を第１表に示す。After the reaction was completed, the obtained ethylene copolymer was washed and dried, and its physical properties were measured. The results are shown in Table 1.

Claims (1)

【特許請求の範囲】 エチレンと炭素数５〜７の直鎖α−オレフィンの共重合
体であって、極限粘度３．１０〜３．８０４／ｐ。 密度０．９５０〜０．９６５　ｆｆ／ｄｉ　、流出量比
１１０〜２４０であるエチレン共重合体。[Claims] A copolymer of ethylene and a linear α-olefin having 5 to 7 carbon atoms, and has an intrinsic viscosity of 3.10 to 3.804/p. An ethylene copolymer having a density of 0.950 to 0.965 ff/di and an outflow ratio of 110 to 240.