JPH0693062A - Polypropylene block copolymer and film therefrom - Google Patents
Polypropylene block copolymer and film therefromInfo
- Publication number
- JPH0693062A JPH0693062A JP4246160A JP24616092A JPH0693062A JP H0693062 A JPH0693062 A JP H0693062A JP 4246160 A JP4246160 A JP 4246160A JP 24616092 A JP24616092 A JP 24616092A JP H0693062 A JPH0693062 A JP H0693062A
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- weight
- block copolymer
- polymerization
- propylene
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- Extrusion Moulding Of Plastics Or The Like (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリプロピレンブロック
共重合体及びそのフィルムに関する。さらに詳しくは、
フィッシュアイ等の発生がなく、外観が良好であり、か
つ低温での耐衝撃性，耐熱性、耐ブロッキング性及び食
品衛生性に優れたポリプロピレンブロック共重合体及び
そのフィルムに関する。This invention relates to polypropylene block copolymers and films thereof. For more details,
The present invention relates to a polypropylene block copolymer having a good appearance without generation of fish eyes and the like, and having excellent impact resistance at low temperature, heat resistance, blocking resistance and food hygiene, and a film thereof.
【０００２】[0002]
【従来の技術】ポリプロピレンのフィルムは、外観、機
械的性質、包装適性等が優れていることから食品包装、
繊維包装などの包装分野で広く使用されている。2. Description of the Related Art Polypropylene films are excellent in appearance, mechanical properties, packaging suitability, etc.
Widely used in the packaging field such as textile packaging.
【０００３】ポリプロピレン未延伸フィルムにおいても
プロピレン単独重合体、プロピレンとα−オレフィンの
ランダム共重合体、およびプロピレンブロック共重合体
がそれぞれの特徴を生かして各種の包装用途に使用され
ているが、従来公知のフィルムでは、外観、低温での耐
衝撃性、耐熱性、耐ブロッキング性などの点でいずれも
不十分であり、それぞれ使用に制限がある。Also in polypropylene unstretched films, propylene homopolymers, random copolymers of propylene and α-olefins, and propylene block copolymers have been used for various packaging applications by taking advantage of their respective characteristics. Known films are insufficient in terms of appearance, impact resistance at low temperature, heat resistance, blocking resistance, etc., and their use is limited.
【０００４】すなわち、プロピレン単独重合体では、外
観、耐熱性、耐ブロッキング性が優れるものの低温での
耐衝撃性が劣り、またプロピレンとα−オレフィンのラ
ンダム共重合体では、外観、低温での耐衝撃性、耐熱性
が劣り、プロピレンブロック共重合体では、低温での耐
衝撃性においてある程度優れるものの、フィッシュアイ
が発生して外観が不良であるか耐ブロッキング性が劣る
ものであり、それぞれ使用に制限がある。このため、外
観、低温での耐衝撃性、耐熱性、耐ブロッキング性など
が良好なポリプロピレンフィルムの開発が要望されてき
た。That is, a propylene homopolymer is excellent in appearance, heat resistance and blocking resistance, but inferior in impact resistance at low temperature, and a random copolymer of propylene and α-olefin is excellent in appearance and resistance at low temperature. The impact resistance and heat resistance are poor, and the propylene block copolymer is somewhat excellent in impact resistance at low temperatures, but it has poor appearance or poor blocking resistance due to the occurrence of fish eyes. There is a limit. Therefore, there has been a demand for the development of a polypropylene film having good appearance, impact resistance at low temperature, heat resistance, blocking resistance, and the like.
【０００５】このようなことから、主にポリプロピレン
ブロック共重合体を用いて上記の特性を改良する試みが
いくつかなされている。Under these circumstances, several attempts have been made to improve the above-mentioned properties mainly by using a polypropylene block copolymer.
【０００６】特開平１−２２５６４８号公報には、溶剤
重合法で重合された、Ｂ成分の極限粘度が１．９２ dｌ
／g 以下であるプロピレン共重合体の組成物が開示され
ている。しかしながら、この組成物は、低温での耐衝撃
性および耐ブロッキング性が劣る、あるいはフィッシュ
アイの発生による外観の悪化、または加工性が劣るもの
であった。またこれらの組成物をレトルト食品包装用の
フィルムに使用しようとした場合、食品衛生性で問題が
あり、ヘキサンに対する耐溶剤性が劣るかまたは外観が
不良であるなど、不満足なものであった。JP-A 1-225648 discloses that the intrinsic viscosity of the B component polymerized by the solvent polymerization method is 1.92 dl.
Compositions of propylene copolymers of less than or equal to / g are disclosed. However, this composition was inferior in impact resistance and blocking resistance at low temperature, or was deteriorated in appearance due to generation of fish eyes, or was inferior in processability. Further, when these compositions were used for a film for packaging a retort food, there was a problem in food hygiene, and the solvent resistance to hexane was poor or the appearance was unsatisfactory.
【０００７】特開昭５９−１１５３１２号公報、特開昭
５９−７４１０９号公報には、レトルトフィルム用重合
体組成物の製造法、及びレトルト食品包装袋用フィルム
が開示され、具体的には第１段階の重合体が融点が１３
５〜１５５℃の範囲の共重合体であり、第２段階以降の
重合体が、含有量５〜４０重量％、プロピレン単位１０
〜５０モル％、エチレン単位５０〜９０モル％、他のα
−オレフィン単位３モル％以下でかつ溶液粘度〔η〕が
２．５以上であるように重合し、メルトフローインデッ
クスが０．５〜１５ｇ／１０分になるよう各成分の生成
量、組成、分子量を調整したレトルトフィルム用重合体
組成物の製造法及び前記組成物を用いた動的貯蔵弾性率
が特定の範囲にあるレトルト食品包装袋用フィルムが示
され、さらに具体的には第１段融点１３２〜１４９℃
で、第２段重合量１４．８〜２２．０重量％、または第
１段融点１５９．６℃で、第２段重合量１５．２重量％
の範囲の組成物及びフィルムが示されている。しかしな
がら、この発明で示された第１段融点が１３２〜１５５
℃の範囲の組成物においては、耐熱性が劣り、さらに低
温での耐衝撃性が不十分であり、また第１段融点１５
９．６℃の組成物においては、低温での耐衝撃性が不十
分なものであった。JP-A-59-115312 and JP-A-59-74109 disclose a method for producing a polymer composition for a retort film and a film for a retort food packaging bag. One-step polymer has a melting point of 13
It is a copolymer in the range of 5 to 155 ° C., and the polymer after the second stage has a content of 5 to 40% by weight and a propylene unit of 10%.
~ 50 mol%, ethylene unit 50-90 mol%, other α
-Polymerization so that the olefin unit content is 3 mol% or less and the solution viscosity [η] is 2.5 or more, and the production amount, composition, and molecular weight of each component are adjusted so that the melt flow index becomes 0.5 to 15 g / 10 minutes. A method for producing a polymer composition for a retort film, in which the above-mentioned composition is adjusted, and a film for a retort food packaging bag having a dynamic storage elastic modulus in a specific range using the composition are shown, and more specifically, the first stage melting point. 132-149 ° C
And the second stage polymerization amount is 14.8 to 22.0% by weight, or the first stage melting point is 159.6 ° C. and the second stage polymerization amount is 15.2% by weight.
A range of compositions and films are indicated. However, the first stage melting point shown in the present invention is 132 to 155.
In the case of the composition in the range of ° C, the heat resistance is inferior, the impact resistance at low temperature is insufficient, and the first stage melting point is 15
The composition at 9.6 ° C had insufficient impact resistance at low temperatures.
【０００８】これらのことから、１３０〜１４０℃の高
温処理を行うハイレトルト食品包装用フィルムに従来公
知のポリプロピレンブロック共重合体を使用する場合に
は、低温での耐衝撃性を補うために、耐熱性、食品衛生
性の限度の範囲で低結晶性のＥＰＲやＬ−ＬＤＰＥなど
を配合した組成物が用いられてきた。From these facts, when a conventionally known polypropylene block copolymer is used in a high retort food packaging film which is subjected to a high temperature treatment at 130 to 140 ° C., in order to supplement the impact resistance at a low temperature, A composition containing EPR or L-LDPE having low crystallinity within the limits of heat resistance and food hygiene has been used.
【０００９】[0009]
【発明が解決しようとする課題】本発明者らは、前述の
従来公知のプロピレン系共重合体の欠点を解消し、耐熱
性などポリプロピレンブロック共重合体が本来有する好
ましい特性を損なうことなく、また、低結晶性のＥＰＲ
やＬ−ＬＤＰＥなどを配合することなく、低温での耐衝
撃性が良好であり、外観、耐ブロッキング性、食品衛生
性が良好で、ハイレトルト食品包装用途に好適なポリプ
ロピレンブロック共重合体及びフィルムを開発するべく
検討を行った。DISCLOSURE OF THE INVENTION The present inventors have solved the above-mentioned drawbacks of the conventionally known propylene-based copolymers, without impairing the desirable characteristics inherent to polypropylene block copolymers such as heat resistance, and , Low crystalline EPR
Polypropylene block copolymer and film that have good impact resistance at low temperature, good appearance, blocking resistance, and food hygiene, and are suitable for high retort food packaging applications, without the addition of L-LDPE, etc. I examined to develop.
【００１０】[0010]
【課題を解決するための手段】従来公知の溶剤重合法や
塊状重合法では、低温での耐衝撃性に有効な成分である
エチレン−プロピレン共重合体部分が溶剤または液体の
モノマーに溶解するため、低温での耐衝撃性の点で不十
分なものであり、前記課題の解決が困難であった。In the conventionally known solvent polymerization method or bulk polymerization method, the ethylene-propylene copolymer moiety, which is an effective component for impact resistance at low temperature, is dissolved in a solvent or liquid monomer. However, the impact resistance at low temperature is insufficient, and it is difficult to solve the above-mentioned problems.
【００１１】本発明者らは種々の検討の結果、実質的に
溶剤の不存在下に重合して得られた特定範囲のブロック
共重合体を溶融混練してなり、溶融混練後の全重合体中
の２０℃キシレン可溶部の特定の低分子量成分の含有量
を特定の範囲にしたポリプロピレンブロック共重合体と
することによって前記課題が解決できることを見出し、
本発明に到達した。As a result of various studies, the inventors of the present invention melt-knead a block copolymer in a specific range obtained by polymerizing in the substantially absence of a solvent, and the whole polymer after melt-kneading is obtained. It was found that the above problems can be solved by using a polypropylene block copolymer in which the content of the specific low molecular weight component of the 20 ° C. xylene-soluble part in the specific range is within a specific range,
The present invention has been reached.
【００１２】すなわち、本発明は、少なくともチタン、
マグネシウム、ハロゲンを必須とするチーグラー・ナッ
タ型触媒を用いて、第１工程で実質的に不活性溶剤の不
存在下にプロピレンを主体とした重合体部分（Ａ成分）
を全重合量の６０〜８０重量％重合し、ついで第２工程
で気相中でエチレン含有量が２０〜５０重量％のエチレ
ン−プロピレン共重合部分（Ｂ成分）を全重合量の２０
〜４０重量％重合して得られるブロック共重合体であっ
て、かつＢ成分の極限粘度（〔η〕B ）が２．０ dｌ／
g 以上、Ｂ成分の極限粘度（〔η〕B ）とＡ成分の極限
粘度（〔η〕A ）の比（〔η〕B ／〔η〕A ）が１．８
以下のブロック共重合体を溶融混練してなり、溶融混練
後の全重合体中の２０℃キシレン可溶部の分子量５万以
下の成分の含有量が２．０重量％以下であることを特徴
とするポリプロピレンブロック共重合体、および該ポリ
プロピレンブロック共重合体を、溶融押出し製膜してな
るフィルムである。That is, the present invention is at least titanium,
Polymer portion mainly composed of propylene (component A) in the first step in the absence of an inert solvent by using a Ziegler-Natta type catalyst which essentially requires magnesium and halogen
Is polymerized in an amount of 60 to 80% by weight based on the total polymerization amount, and then, in the second step, the ethylene-propylene copolymerized portion (component B) having an ethylene content of 20 to 50% by weight is added to 20% by weight of the total polymerization amount.
Block copolymer obtained by polymerizing up to 40% by weight, and having an intrinsic viscosity ([η] B) of component B of 2.0 dl /
The ratio ([η] B / [η] A) of the intrinsic viscosity ([η] B) of the component B and the intrinsic viscosity ([η] A) of the component A is 1.8 or more.
The following block copolymers are melt-kneaded, and the content of the component having a molecular weight of 50,000 or less in the 20 ° C. xylene-soluble part in the whole polymer after melt-kneading is 2.0% by weight or less. And a film obtained by melt-extruding the polypropylene block copolymer.
【００１３】以下、本発明を具体的に詳述する。本発明
のポリプロピレンブロック共重合体は、チーグラー・ナ
ッタ型触媒を用いて、第１工程で実質的に不活性溶剤の
不存在下にプロピレンを主体とした重合体部分（Ａ成
分）を重合し、ついで第２工程で気相中でエチレン−プ
ロピレン共重合部分（Ｂ成分）を重合して得られるブロ
ック共重合体を溶融混練してなるものである。The present invention will be described in detail below. The polypropylene block copolymer of the present invention uses a Ziegler-Natta type catalyst to polymerize a polymer portion (component A) mainly composed of propylene in the first step in the substantial absence of an inert solvent, Then, in the second step, the block copolymer obtained by polymerizing the ethylene-propylene copolymer portion (component B) in the gas phase is melt-kneaded.
【００１４】プロピレンを主体とした重合体（Ａ成分）
とエチレン−プロピレン共重合体（Ｂ成分）の割合は、
Ａ成分が６０〜８０重量％、Ｂ成分が２０〜４０重量％
の範囲であることが必要である。Ｂ成分が２０重量％未
満であると低温での耐衝撃性が悪化し、が４０重量％を
越えると重合時にトラブルが発生し生産性が大幅に悪化
するかまたは得られたポリプロピレンブロック共重合体
の耐熱性が悪化するなどの問題が発生する。Ａ成分とＢ
成分の割合は、低温での耐衝撃性の点から、Ａ成分が６
０〜７５重量％、Ｂ成分が２５〜４０重量％の範囲が好
ましい。Polymer mainly composed of propylene (component A)
The ratio of ethylene-propylene copolymer (component B) is
A component is 60 to 80% by weight, B component is 20 to 40% by weight
Must be within the range. If the content of the component B is less than 20% by weight, the impact resistance at low temperature is deteriorated, and if it exceeds 40% by weight, a trouble occurs during the polymerization to significantly deteriorate the productivity or the obtained polypropylene block copolymer. However, there is a problem that the heat resistance of is deteriorated. A component and B
From the viewpoint of impact resistance at low temperature, the ratio of the components is 6 for A component.
A range of 0 to 75% by weight and a content of B component of 25 to 40% by weight is preferable.
【００１５】プロピレンを主体とした重合体（Ａ成分）
は、耐熱性、剛性などの点から、融点が１６０℃以上の
プロピレン単独重合体が好ましいが、融点が１５７℃以
上の範囲のものであれば、プロピレンと少量のエチレ
ン、ブテン−１などのα−オレフィンとの共重合体であ
ってもよい。Polymer mainly composed of propylene (component A)
Is preferably a propylene homopolymer having a melting point of 160 ° C. or higher from the viewpoint of heat resistance and rigidity, but if the melting point is in the range of 157 ° C. or higher, propylene and a small amount of ethylene, butene-1, etc. α -It may be a copolymer with an olefin.
【００１６】エチレン−プロピレン共重合体（Ｂ成分）
は、エチレン含有量が２０〜５０重量％であり、極限粘
度（〔η〕B ）が２．０ dｌ／g 以上の範囲のものであ
ることが必要である。エチレン含有量が２０重量％未満
であると低温での耐衝撃性が低下し、エチレン含有量が
５０重量％を越えるとフィルムの外観および低温での耐
衝撃性が劣り、一方〔η〕B が２．０ dｌ／g 未満であ
ると耐ブロッキング性、低温での耐衝撃性が劣り、いず
れの場合も本発明の目的を達成できない。Ｂ成分のエチ
レン含有量は、外観と耐衝撃性の点から、２５〜４５重
量％の範囲が好ましく、〔η〕B は２．５ dｌ／g 以上
が好ましく、２．５〜４．５ dｌ／g の範囲がさらに好
ましい。Ethylene-propylene copolymer (component B)
Has an ethylene content of 20 to 50% by weight and an intrinsic viscosity ([η] B) of 2.0 dl / g or more. When the ethylene content is less than 20% by weight, the impact resistance at low temperature is lowered, and when the ethylene content exceeds 50% by weight, the appearance of the film and the impact resistance at low temperature are deteriorated, while [η] B is If it is less than 2.0 dl / g, the blocking resistance and the impact resistance at low temperature are poor, and the object of the present invention cannot be achieved in any case. From the viewpoint of appearance and impact resistance, the ethylene content of the component B is preferably in the range of 25 to 45% by weight, and [η] B is preferably 2.5 dl / g or more, and 2.5 to 4.5 dl. The range of / g is more preferable.
【００１７】さらに、Ｂ成分とＡ成分との極限粘度の比
（〔η〕B ／〔η〕A ）が１．８以下であることが必要
である。〔η〕B ／〔η〕A が１．８を越えるものは、
フィルムにフィッシュアイが発生して外観が損なわれる
ため使用できない。〔η〕B ／〔η〕A は、低温での耐
衝撃性と外観の点から、０．８〜１．７の範囲が好まし
い。Further, the ratio ([η] B / [η] A) of the intrinsic viscosities of the B component and the A component must be 1.8 or less. [Η] B / [η] A exceeding 1.8,
It cannot be used because fish eyes are generated on the film and the appearance is impaired. [Η] B / [η] A is preferably in the range of 0.8 to 1.7 from the viewpoint of impact resistance at low temperature and appearance.
【００１８】さらに、本発明では、溶融混練後のポリプ
ロピレンブロック共重合体中の２０℃キシレン可溶部の
分子量５万以下の成分（Ｌ−ＣＸＳ）の含有量が２．０
重量％以下であることが重要である。全重合体中のＬ−
ＣＸＳの含有量が２．０重量％を越えると食品衛生性で
重要な因子であるヘキサン抽出量が増加して、レトルト
食品包装用フィルムとしての使用に制限がある。Furthermore, in the present invention, the content of the component (L-CXS) having a molecular weight of 50,000 or less in the 20 ° C. xylene-soluble portion in the polypropylene block copolymer after melt-kneading is 2.0.
It is important that it is less than or equal to wt. L- in all polymers
When the content of CXS exceeds 2.0% by weight, the amount of hexane extracted, which is an important factor in food hygiene, increases, which limits the use as a retort food packaging film.
【００１９】本発明のポリプロピレンブロック共重合体
は、低温での耐衝撃性、耐熱性および耐溶剤性などの点
から、２０℃キシレン可溶部（ＣＸＳ）の含有量が１０
重量％以上で２５重量％未満の範囲のものが好ましい。
ＣＸＳの含有量が１０重量％未満では低温での耐衝撃性
が劣り、ＣＸＳの含有量が２５重量％を越えると食品衛
生性のキシレン可溶分の点および耐熱性が劣り好ましく
ない。The polypropylene block copolymer of the present invention has a xylene-soluble part (CXS) content of 20 ° C. of 10 from the viewpoint of impact resistance at low temperature, heat resistance and solvent resistance.
It is preferably in the range of not less than 25% by weight and not less than 25% by weight.
When the content of CXS is less than 10% by weight, impact resistance at low temperature is poor, and when the content of CXS exceeds 25% by weight, the xylene-soluble component of food hygiene and heat resistance are unfavorable.
【００２０】本発明のポリプロピレンブロック共重合体
は、少なくともチタン、マグネシウム、ハロゲンを必須
とするチーグラー・ナッタ型触媒を用いて、同一の重合
槽中においてＡ成分を重合した後、引き続いてＢ成分を
重合する回分式重合法、または少なくとも２槽からなる
重合槽を使用してＡ成分とＢ成分を連続的に重合する連
続式重合法などで製造が可能である。The polypropylene block copolymer of the present invention is obtained by polymerizing the A component in the same polymerization tank using a Ziegler-Natta type catalyst which essentially contains at least titanium, magnesium and halogen, and then continuously purifying the B component. The production can be carried out by a batch polymerization method in which polymerization is carried out, or a continuous polymerization method in which a component A and a component B are continuously polymerized using a polymerization tank comprising at least two tanks.
【００２１】具体的には、例えば、 (a) Ｓｉ−Ｏ結合を有する有機ケイ素化合物の共存下、
一般式Ｔｉ（ＯＲ1 ) nＸ4-n （Ｒ1 は炭素数が１〜２
０の炭化水素基、Ｘはハロゲン原子、ｎは０＜ｎ≦４の
数字を表わす。）で表されるチタン化合物を、有機マグ
ネシウム化合物で還元して得られる固体生成物を、エス
テル化合物及び、エーテル化合物と四塩化チタンとの混
合物で処理して得られる三価のチタン化合物含有固体触
媒成分、 (b) 有機アルミニウム化合物(c) Ｓｉ−ＯＲ2 結合（Ｒ
2 は炭素数が１〜２０の炭化水素基である。）を有する
ケイ素化合物よりなる触媒系 などのチーグラー・ナッタ型触媒を用いて、(b) 成分中
のＡｌ原子／(a) 成分中のＴｉ原子のモル比を１〜１０
００、好ましくは５〜６００、(c) 成分／(b) 成分中の
Ａｌ原子のモル比を０．０２〜５００、好ましくは０．
０５〜１０となるように使用し、重合温度２０〜１５０
℃、好ましくは５０〜９５℃、重合圧力は大気圧〜４０
ｋｇ／ｃｍ2 Ｇ、好ましくは２〜３０ｋｇ／ｃｍ2 Ｇの
条件下に、第１工程で実質的に不活性溶剤の不存在下に
プロピレンと分子量調節のため水素を供給してプロピレ
ンを主体とした重合体部分（Ａ）を重合した後、引き続
いて第２工程で気相中でプロピレンとエチレンと水素を
供給してエチレン−プロピレン共重合体部分（Ｂ）を重
合することによって製造できる。Specifically, for example, (a) in the coexistence of an organosilicon compound having a Si--O bond,
General formula Ti (OR 1 ) n X 4-n (R 1 has 1 to 2 carbon atoms.
0 represents a hydrocarbon group, X represents a halogen atom, and n represents a number of 0 <n ≦ 4. ) A trivalent titanium compound-containing solid catalyst obtained by treating a solid product obtained by reducing a titanium compound represented by (4) with an organomagnesium compound with a mixture of an ester compound and an ether compound and titanium tetrachloride. Component, (b) organoaluminum compound (c) Si—OR 2 bond (R
2 is a hydrocarbon group having 1 to 20 carbon atoms. A Ziegler-Natta type catalyst such as a catalyst system made of a silicon compound having a), the molar ratio of Al atoms in the component (b) / Ti atoms in the component (a) is 1 to 10
00, preferably 5 to 600, and the molar ratio of Al atoms in the component (c) / component (b) is 0.02 to 500, preferably 0.1.
It is used so as to be from 05 to 10, and the polymerization temperature is from 20 to 150.
℃, preferably 50 ~ 95 ℃, the polymerization pressure is atmospheric pressure ~ 40
kg / cm 2 G, preferably the principal under the conditions of 2~30kg / cm 2 G, substantially propylene by supplying hydrogen for the adjustment of propylene and molecular weight in the absence of an inert solvent in the first step After polymerizing the polymer portion (A), the ethylene-propylene copolymer portion (B) is polymerized by subsequently supplying propylene, ethylene and hydrogen in the gas phase in the second step.
【００２２】本発明のポリプロピレンブロック共重合体
フィルムは、前記のブロック共重合体を溶融混練してな
り、かつメルトフローレイトが０．５〜１０ g／１０分
の範囲であるポリプロピレンブロック共重合体から得ら
れる。メルトフローレイトが０．５ g／１０分未満であ
ると製膜性、外観の点で不十分であり、１０ g／１０分
を越えるとフィッシュアイが発生し外観の点で劣り、本
発明の目的が達成されない。メルトフローレイトは、高
速製膜安定性などの点から、１．０〜１０ g／１０分の
範囲であることが好ましく、１．０〜５．０ g／１０分
の範囲がさらに好ましい。The polypropylene block copolymer film of the present invention is obtained by melt-kneading the above block copolymer and has a melt flow rate of 0.5 to 10 g / 10 min. Obtained from When the melt flow rate is less than 0.5 g / 10 minutes, the film-forming property and the appearance are insufficient, and when it exceeds 10 g / 10 minutes, fish eyes are generated and the appearance is inferior. The purpose is not achieved. The melt flow rate is preferably from 1.0 to 10 g / 10 minutes, more preferably from 1.0 to 5.0 g / 10 minutes, from the viewpoint of high-speed film forming stability.
【００２３】本発明に規定したブロック共重合体から、
メルトフローレイト０．５〜１０ g／１０分のポリプロ
ピレンブロック共重合体を得る方法としては、有機過酸
化物の存在下、不存在下に公知の方法で溶融混練を行う
方法であれば特に限定されない。」From the block copolymer defined in the present invention,
The method for obtaining a polypropylene block copolymer having a melt flow rate of 0.5 to 10 g / 10 min is not particularly limited as long as it is a method of melt-kneading by a known method in the presence or absence of an organic peroxide. Not done. "
【００２４】本発明のポリプロピレンブロック共重合体
フィルムは、Ｔダイ法、またはチューブラー法などの公
知のフィルムの製膜法で製造することが可能であるが、
特にＴダイ法による未延伸フィルムの製造法により好適
に製造される。The polypropylene block copolymer film of the present invention can be produced by a known film forming method such as a T-die method or a tubular method.
Particularly, it is preferably manufactured by the method of manufacturing an unstretched film by the T-die method.
【００２５】本発明のフィルムの厚みは、特に限定され
ないが、１０〜５００μが好ましくさらに好ましくは１
０〜１００μである。The thickness of the film of the present invention is not particularly limited, but is preferably 10 to 500 μm, more preferably 1
It is 0 to 100 μ.
【００２６】本発明のポリプロピレンブロック共重合体
フィルムは、外観、低温での耐衝撃性、耐ブロッキング
性、耐熱性、食品衛生性が良好なものであるので、高温
での加熱処理を行うレトルト食品包装用途や低温下での
重量物包装用途で特に好適に使用される。Since the polypropylene block copolymer film of the present invention has good appearance, impact resistance at low temperature, blocking resistance, heat resistance and food hygiene, it is a retort food product which is heat-treated at high temperature. It is particularly preferably used for packaging applications and heavy-weight packaging applications at low temperatures.
【００２７】また、その他のフィルム、例えばポリプロ
ピレン二軸延伸フィルム、未延伸ナイロンフィルム、延
伸ポリテレフタール酸エチルフィルムやアルミニウム箔
等とドライラミネート法、又は押出ラミネート法等の方
法で製造される複合フィルムの少なくとも一層としても
好適に使用が可能である。A composite film produced by another film, for example, a biaxially stretched polypropylene film, an unstretched nylon film, a stretched polyethylterephthalate film, an aluminum foil or the like by a dry laminating method or an extrusion laminating method. Can be suitably used as at least one layer.
【００２８】本発明のポリプロピレンブロック共重合体
フィルムは、通常工業的に採用されている方法によって
コロナ放電処理、あるいは火炎処理、プラズマ処理、オ
ゾン処理等の表面処理を施すこともできる。The polypropylene block copolymer film of the present invention can be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc., by a method usually adopted in industry.
【００２９】本発明のポリプロピレンブロック共重合体
とフィルムには、酸化防止剤、紫外線吸収剤、帯電防止
剤、防曇剤、滑剤、抗ブロッキング剤、造核剤等を必要
に応じて含むことができる。The polypropylene block copolymer and film of the present invention may optionally contain an antioxidant, an ultraviolet absorber, an antistatic agent, an antifogging agent, a lubricant, an antiblocking agent, a nucleating agent and the like. it can.
【００３０】[0030]
【実施例】以下、実施例によって本発明を具体的に説明
するが、本発明の範囲は実施例のみに限定されるもので
はない。なお、発明の詳細な説明および実施例中の各項
目の測定値は、下記の方法で測定した。EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to the examples. The measured values of each item in the detailed description of the invention and Examples were measured by the following methods.
【００３１】（１）Ａ成分、Ｂ成分の含有量 Ａ成分およびＢ成分の重合時の物質収支から、Ａ成分の
含有量（ＰA ）、およびＢ成分の含有量（ＰB ）を求め
た。(1) Content of Component A and Component B The content of Component A (PA) and the content of Component B (PB) were determined from the material balance of Component A and Component B during polymerization.
【００３２】（２）極限粘度（〔η〕） ウベローデ型粘度計を用いて１３５℃テトラリン中で測
定を行った。 Ａ成分、Ｂ成分の極限粘度（〔η〕A 、〔η〕B ） 第１工程のＡ成分の重合終了後に測定した極限粘度
〔η〕A と、第２工程の重合終了後に測定した極限粘度
〔η〕AB、およびＡ成分の含有量（ＰA ）、Ｂ成分の含
有量（ＰB ）から、次式によりＢ成分の極限粘度〔η〕
B を決定した。 〔η〕A ×ＰA ／１００＋〔η〕B ×ＰB ／１００＝
〔η〕AB(2) Intrinsic Viscosity ([η]) Measurement was carried out in tetralin at 135 ° C. using an Ubbelohde viscometer. Intrinsic Viscosity of Components A and B ([η] A, [η] B) Intrinsic Viscosity [η] A Measured After Completion of Polymerization of Component A in the First Step and Intrinsic Viscosity Measured after Completion of Polymerization in the Second Step [Η] AB, the content of component A (PA), the content of component B (PB), the intrinsic viscosity of component B by the following formula [η]
B has been decided. [Η] A × PA / 100 + [η] B × PB / 100 =
[Η] AB
【００３３】（３）エチレン含有量 高分子分析ハンドブック（１９８５年、朝倉書店発行）
の２５６〜２５７ページ「（ii）ブロック共重合体」の
項記載の方法によってＩＲスペクトル法で決定した。(3) Ethylene content Polymer analysis handbook (1985, published by Asakura Shoten)
IR spectroscopy by the method described in the section "(ii) Block copolymer" on pages 256-257 of the above.
【００３４】（４）メルトフローレイト（ＭＦＲ） ＪＩＳ Ｋ７２１０に従い、条件−１４の方法で測定し
た。(4) Melt Flow Rate (MFR) The melt flow rate (MFR) was measured by the method of condition -14 according to JIS K7210.
【００３５】（５）２０℃キシレン可溶部（ＣＸＳ） ポリプロピレン５ｇを沸騰キシレン５００ｍｌに完全に
溶解させた後、２０℃に降温し、４時間以上放置する。
その後、これを析出物と溶液とに濾別し、濾液を乾固し
て減圧下７０℃で乾燥した。その重量を測定して含有量
（重量％）を求めた。(5) 20 ° C. xylene-soluble part (CXS) After completely dissolving 5 g of polypropylene in 500 ml of boiling xylene, the temperature is lowered to 20 ° C. and left for 4 hours or more.
Then, this was separated by filtration into a precipitate and a solution, and the filtrate was dried and dried at 70 ° C. under reduced pressure. The weight was measured to determine the content (% by weight).
【００３６】（６）２０℃キシレン可溶部（ＣＸＳ）の
分子量５万以下の成分量（Ｌ−ＣＸＳ） ２０℃キシレン可溶部を分取して、ＧＰＣ測定を行い、
得られた分子量分布図において、ポリスチレン換算の分
子量５万以下の成分の含有量（Ｗ）を求め、次式により
Ｌ−ＣＸＳを決定した。 Ｌ−ＣＸＳ＝ 全ＣＸＳ含有量 × Ｗ(6) Amount of components having a molecular weight of 50,000 or less (L-CXS) in the 20 ° C. xylene-soluble part (CXS): The 20 ° C. xylene-soluble part is collected and subjected to GPC measurement.
In the obtained molecular weight distribution chart, the content (W) of the component having a polystyrene equivalent molecular weight of 50,000 or less was obtained, and L-CXS was determined by the following formula. L-CXS = total CXS content × W
【００３７】ＧＰＣ測定条件 ゲルパーミエーションクロマトグラフィー（ＧＰＣ）に
より、下記の条件で測定した。また、検量線は標準ポリ
スチレンを用いて作成した。 機種 ：ミリポアウォーターズ社製 １５０ＣＶ型 カラム：Ｓｈｏｄｅｘ Ｍ／Ｓ ８０ 測定温度：１４５℃、溶媒オルトジクロルベンゼン サンプロ濃度：５ｍｇ／８ｍｌ なお、本条件でＮＢＳ（National Bureau of Standard
s）の Standard Reference Material７０６（Ｍｗ／Ｍ
ｎ＝２．１のポリスチレン）を測定したところ、分子量
分布（Ｍｗ／Ｍｎ＝２．１が得られた。GPC measurement conditions: It was measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was prepared using standard polystyrene. Model: Millipore Waters 150 CV Column: Shodex M / S 80 Measurement temperature: 145 ° C, solvent ortho-dichlorobenzene sunpro concentration: 5 mg / 8 ml Under these conditions, NBS (National Bureau of Standard)
s) Standard Reference Material 706 (Mw / M
When a polystyrene of n = 2.1 was measured, a molecular weight distribution (Mw / Mn = 2.1) was obtained.
【００３８】（７）融点（Ｔｍ） 示差走査熱量計（パーキンエルマー社製ＤＳＣ）を用い
て、あらかじめ試片１０ｍｇを窒素雰囲気下で２２０℃
で５分間溶融した後、５℃／分の降温速度で４０℃まで
降温する。その後、５℃／分で昇温させて、得られた融
解吸熱カーブの最大ピークのピーク温度を融点（Ｔｍ）
とした。なお、本測定器を用いて５℃／分の昇温速度で
測定したインジウム（Ｉｎ）の融点は、１５６．６℃で
あった。(7) Melting point (Tm) Using a differential scanning calorimeter (DSC manufactured by Perkin Elmer Co., Ltd.), 10 mg of a test piece was previously prepared at 220 ° C. under a nitrogen atmosphere.
After melting for 5 minutes, the temperature is lowered to 40 ° C at a rate of 5 ° C / min. Then, the temperature is raised at 5 ° C./min, and the peak temperature of the maximum peak of the obtained melting endothermic curve is determined by the melting point (Tm).
And The melting point of indium (In) measured with this measuring device at a temperature rising rate of 5 ° C./min was 156.6 ° C.
【００３９】フィルム特性：厚み３０μのフィルムにつ
いて、下記の方法で測定した。 （８）外観 目視により、直径が２００μ以上のフィッシュアイ（Ｆ
Ｅ）を観測して、ＦＥ個数が約１０個／１０００ｃｍ2
以下のものを良好、約１５個／１０００ｃｍ2以上のも
のを不良とした。Film characteristics: A film having a thickness of 30 μ was measured by the following methods. (8) Appearance Visually, fish eyes (F
Observing E), the number of FE is about 10/1000 cm 2
The following were evaluated as good, and those of about 15/1000 cm 2 or more were evaluated as bad.
【００４０】（９）耐衝撃性 −１０℃において、東洋精機製フィルムインパクトテス
ターを使用して、直径１５ｍｍの半球状衝撃頭を用い
て、フィルムの衝撃強度を測定した。(9) Impact resistance The impact strength of the film was measured at -10 ° C using a film impact tester manufactured by Toyo Seiki Co., Ltd. and a hemispherical impact head having a diameter of 15 mm.
【００４１】（１０）耐ブロッキング性 ２２５ｍｍ×５０ｍｍのフィルムを用いて、フィルム同
志を重ね合わせ、１００ｍｍ×５０ｍｍの範囲を４０ｇ
／ｃｍ2 の荷重下で６０℃、３時間状態調整を行った。
その後、２３℃、湿度５０％の雰囲気下に３０分以上放
置し、島津製作所製ブロッキングテスターを用いて２０
ｇ／分の剥離荷重速度で、試料の剥離に要する強度を測
定した。(10) Blocking resistance Using a film of 225 mm × 50 mm, the films are superposed on each other, and 40 g in the range of 100 mm × 50 mm.
The condition was adjusted at 60 ° C. for 3 hours under a load of / cm 2 .
Then, leave it in an atmosphere of 23 ° C. and a humidity of 50% for 30 minutes or more, and use a Shimadzu blocking tester for 20 minutes.
The strength required for peeling the sample was measured at a peeling load rate of g / min.
【００４２】（１１）ヒートシール温度 フィルム同志を重ね合わせ、所定の温度に加熱されたヒ
ートシーラー（東洋精機製）で２ｋｇ／ｃｍ2 Ｇの荷重
で２秒間圧着してヒートシールする。一夜放置後、２３
℃で剥離速度２００ｍｍ／分、剥離角度１８０℃で剥離
した時の剥離抵抗力が３００ｇ／ｍｍになるシール温度
を求め、ヒートシール温度とした。(11) Heat Sealing Temperature Films are superposed on each other, and heat sealed by a heat sealer (manufactured by Toyo Seiki) heated to a predetermined temperature under a load of 2 kg / cm 2 G for 2 seconds. 23 after left overnight
The heat-sealing temperature was obtained by determining the sealing temperature at which the peeling resistance was 300 g / mm when peeled at a peeling speed of 200 mm / min at 180 ° C. and a peeling angle of 180 ° C.
【００４３】食品衛生性： 厚み６０μのフィルムにつ
いて、以下の方法で測定した。 （１２）ヘキサン抽出量 ＦＤＡ１７７．１５２０（ｄ）（３）（ｉｉ）に記載の
方法に従って、厚み６０μのフィルムの５０℃、ｎ−ヘ
キサン抽出量を測定した。なお、レトルト食品包装用に
使用する場合の本項目の規制値は、２．６重量％以下で
ある。Food Hygiene: A 60 μm thick film was measured by the following method. (12) Extraction amount of hexane According to the method described in FDA 177.1520 (d) (3) (ii), the extraction amount of n-hexane of a film having a thickness of 60 µC was measured at 50 ° C. When used for packaging retort food, the regulation value of this item is 2.6% by weight or less.
【００４４】（１３）キシレン可溶分 ＦＤＡ１７７．１５２０（ｄ）（４）に記載の方法に従
って、２５℃キシレン可溶分量を測定した。なお、食品
包装用に使用する場合の本項目の規制値は、３０重量％
以下である。(13) Xylene Soluble Content The amount of xylene soluble content at 25 ° C. was measured according to the method described in FDA 177.1520 (d) (4). The regulatory value of this item when used for food packaging is 30% by weight.
It is the following.
【００４５】参考例 （ａ）有機マグネシウム化合物の合成 攪拌機、還流冷却器、滴下ロート、温度計を備えた１Ｌ
のフラスコをアルゴンで置換した後、グリニヤール用削
状マグネシウム３２．０ｇを投入した。滴下ロートにブ
チルクロリド１２０ｇとジブチルエーテル５００ｍｌを
仕込み、フラスコ中のマグネシウムに約３０ｍｌ滴下
し、反応を開始させた。反応開始後、５０℃で４時間か
けて滴下を続け、滴下終了後、６０℃で更に１時間反応
を続けた。その後、反応溶液を室温に冷却し、固形分を
濾別した。ジブチルエーテル中のブチルマグネシウムク
ロリドを１規定硫酸で加水分解し、指示薬としてフェノ
ールフタレインを使用して１規定水酸化ナトリウム水溶
液で逆滴定して濃度を決定したところ、濃度は２．１ｍ
ｏｌ／Ｌであった。Reference Example (a) Synthesis of Organomagnesium Compound 1 L equipped with stirrer, reflux condenser, dropping funnel, and thermometer
After the flask was replaced with argon, 32.0 g of ground magnesium for Grignard was charged. To the dropping funnel, 120 g of butyl chloride and 500 ml of dibutyl ether were charged, and about 30 ml was added dropwise to magnesium in the flask to start the reaction. After the reaction was started, the dropping was continued at 50 ° C. for 4 hours, and after the dropping was completed, the reaction was continued at 60 ° C. for another hour. Then, the reaction solution was cooled to room temperature, and the solid content was filtered off. Butyl magnesium chloride in dibutyl ether was hydrolyzed with 1N sulfuric acid, and the concentration was determined by back titration with 1N sodium hydroxide aqueous solution using phenolphthalein as an indicator.
It was ol / L.
【００４６】（ｂ）固体生成物の合成 攪拌機、滴下ロートを備えた５００ｍｌのフラスコをア
ルゴンで置換したのち、ヘキサン２４０ｍｌ、テトラブ
トキシチタン５．４ｇ（１５．８ｍｍｏｌ）およびテト
ラエトキシシラン６１．４ｇ（２９５ｍｍｏｌ）を投入
し、均一溶液とした。次に、（ａ）で合成した有機マグ
ネシウム化合物１５０ｍｌを、フラスコ内の温度を５℃
に保ちながら、滴下ロートから４時間かけて除々に滴下
した。滴下終了後、室温で更に１時間攪拌したのち室温
で固液分離し、ヘキサン２４０ｍｌで３回洗浄を繰り返
したのち減圧乾燥して、茶褐色の固体生成物４５．０ｇ
を得た。固体生成物中にはチタン原子が１．７重量％、
エトキシ基が３３．８重量％、ブトキシ基が２．９重量
％含有されていた。又、この固体生成物のＣｕ−Ｋａ線
による広角Ｘ線回析図には、明瞭な回析ピークは全く認
められず、非晶構造であった。(B) Synthesis of solid product After replacing a 500 ml flask equipped with a stirrer and a dropping funnel with argon, 240 ml of hexane, 5.4 g (15.8 mmol) of tetrabutoxytitanium and 61.4 g of tetraethoxysilane ( 295 mmol) was added to make a uniform solution. Next, 150 ml of the organomagnesium compound synthesized in (a) was heated to a temperature of 5 ° C. in the flask.
While maintaining the above, the solution was gradually added dropwise from the dropping funnel over 4 hours. After completion of dropping, the mixture was stirred at room temperature for 1 hour, solid-liquid separated at room temperature, washed with 240 ml of hexane three times, and dried under reduced pressure to obtain 45.0 g of a brown solid product.
Got 1.7% by weight of titanium atoms in the solid product,
It contained 33.8% by weight of ethoxy groups and 2.9% by weight of butoxy groups. Moreover, no clear diffraction peak was observed in the wide-angle X-ray diffraction diagram of the solid product by Cu-Ka line, and the solid product had an amorphous structure.
【００４７】（ｃ）エステル処理固体の合成 １００ｍｌのフラスコをアルゴンで置換した後、（ｂ）
で合成した固体生成物６．５ｇ、トルエン１６．２ｍｌ
およびフタル酸ジイソブチル４．３ｍｌ（１６ｍｍｏ
ｌ）を加え、９５℃で１時間反応を行った。反応後、固
液分離し、トルエン３３ｍｌで３回洗浄を行った。(C) Synthesis of ester-treated solid After replacing a 100 ml flask with argon, (b)
6.5 g of the solid product synthesized in 1. and 16.2 ml of toluene
And diisobutyl phthalate 4.3 ml (16 mmo
1) was added and the reaction was carried out at 95 ° C. for 1 hour. After the reaction, solid-liquid separation was performed, and washing with 33 ml of toluene was performed three times.
【００４８】（ｄ）固体触媒の合成（活性化処理） 上記（ｃ）での洗浄終了後、フラスコにトルエン１６．
２ｍｌ、フタル酸ジイソブチル０．３６ｍｌ（１．３ｍ
ｍｏｌ）、ブチルエーテル２．２ｍｌ（１３ｍｍｏｌ）
および四塩化チタン３８．０ｍｌ（３４６ｍｍｏｌ）を
加え、９５℃で３時間反応を行った。反応終了後、９５
℃で固液分離した後、同温度でトルエン３３ｍｌで２回
洗浄を行った。上述したフタル酸ジイソブチルとブチル
エーテル及び四塩化チタンとの混合物による処理を同一
条件で更にもう一度繰り返し、ヘキサン３３ｍｌで３回
洗浄して、黄土色の固体触媒５．０ｇを得た。固体触媒
中には、チタン原子が２．１重量％、マグネシウム原子
が１９．９重量％、フタル酸エステルが１２．７重量％
含まれていた。(D) Synthesis of solid catalyst (activation treatment) After completion of washing in (c) above, toluene 16.
2 ml, diisobutyl phthalate 0.36 ml (1.3 m
mol), butyl ether 2.2 ml (13 mmol)
And 38.0 ml (346 mmol) of titanium tetrachloride were added, and the reaction was carried out at 95 ° C for 3 hours. 95 after completion of reaction
After solid-liquid separation at ℃, it was washed twice with 33 ml of toluene at the same temperature. The above-mentioned treatment with a mixture of diisobutyl phthalate, butyl ether and titanium tetrachloride was repeated once more under the same conditions, and the mixture was washed 3 times with 33 ml of hexane to obtain 5.0 g of an ocher solid catalyst. The solid catalyst contained 2.1% by weight of titanium atoms, 19.9% by weight of magnesium atoms, and 12.7% by weight of phthalates.
Was included.
【００４９】実施例１ （ａ）触媒成分 十分に精製したヘキサン１５０Ｌを２５０Ｌの攪拌機付
反応器に添加し、系内を十分チッソ置換したのち、トリ
エチルアルミニウム（以下ＴＥＡと略す）３．２ｍｏ
ｌ、シクロヘキシルエチルジメトキシシラン（以下ＣＨ
ＥＤＭＳと略す）０．３２ｍｏｌおよび前記参考例で得
た固体触媒をＴｉ原子に換算して５１．８ｇ添加する。
２５℃を維持しながらプロピレン２．８ｋｇを２時間に
わたって連続的に添加した。Example 1 (a) Catalyst component 150 L of sufficiently purified hexane was added to a 250 L reactor equipped with a stirrer and the inside of the system was sufficiently replaced with nitrogen, and then triethylaluminum (hereinafter abbreviated as TEA) 3.2 mo.
1, cyclohexylethyldimethoxysilane (hereinafter referred to as CH
(Abbreviated as EDMS) 0.32 mol and 51.8 g of the solid catalyst obtained in the above-mentioned reference example are added in terms of Ti atoms.
While maintaining 25 ° C, 2.8 kg of propylene was continuously added over 2 hours.
【００５０】（ｂ）重合 各槽が内容積２０〜４５ｍ3 の直列の気相重合槽３槽か
らなる装置を用いた。３槽をそれぞれＸ、Ｙ、Ｚとす
る。Ｘ、Ｙ槽でプロピレンの単独重合を行う。圧力は、
Ｘ槽２０ｋｇ／ｃｍ2 Ｇ、Ｙ槽１７ｋｇ／ｃｍ2 Ｇ、温
度はＸ、Ｙ槽共に８０℃で重合を行った。反応時間は
Ｘ、Ｙ槽の合計した平均の滞留時間７時間となるように
（ａ）で調製した触媒成分を連続的にＸ槽に供給した。
同時にＸ槽にＴＥＡ ２ｍｏｌ／ｈｒ、ＣＨＥＤＭＳ
０．３ｍｏｌ／ｈｒ供給し、さらにＸ、Ｙ槽でのＨ2 濃
度が０．０１％になるようにＨ2 を連続的に供給した。
Ｙ槽を出たポリマーをＺ槽に移送し、圧力１４ｋｇ／ｃ
ｍ2 Ｇ、温度７０℃、滞留時間３時間でプロピレンとエ
チレンを重合した。エチレン濃度は２２％、Ｈ 2 濃度が
０．５％になるようにエチレン、プロピレン、Ｈ2 を供
給した。(B) Polymerization Each tank has an internal volume of 20 to 45 m.33 gas-phase polymerization tanks in series
A device consisting of The three tanks are designated as X, Y, and Z, respectively.
It Homopolymerization of propylene is carried out in the X and Y tanks. Pressure is
X tank 20kg / cm2G, Y tank 17kg / cm2G, warm
Polymerization was performed at 80 ° C. in both X and Y tanks. The reaction time is
The average residence time in the X and Y tanks should be 7 hours.
The catalyst component prepared in (a) was continuously supplied to the X tank.
At the same time, TEA 2 mol / hr, CHEDMS in the X tank
Supply 0.3 mol / hr, H in X and Y tanks2Dark
H so that the degree is 0.01%2Was continuously fed.
Polymer discharged from Y tank is transferred to Z tank and pressure is 14 kg / c
m2G, temperature 70 ° C, residence time 3 hours
The ethylene was polymerized. Ethylene concentration is 22%, H 2Concentration
Ethylene, propylene, H to be 0.5%2Together with
I paid.
【００５１】得られたブロック共重合体は、Ａ成分の含
有量７２重量％、極限粘度（〔η〕A ）３．１ ｄｌ／
ｇ、Ｂ成分が含有量２８重量％、エチレン含有量３４重
量％、極限粘度（〔η〕B ）２．９ ｄｌ／ｇ、〔η〕
B ／〔η〕A ＝０．９であった。The obtained block copolymer had an A component content of 72% by weight and an intrinsic viscosity ([η] A) of 3.1 dl /
g, content of B component 28% by weight, ethylene content 34% by weight, intrinsic viscosity ([η] B) 2.9 dl / g, [η]
B / [η] A = 0.9.
【００５２】このブロック共重合体粉末１００重量部
に、ステアリン酸カルシウム０．１重量部、スミライザ
ーＢＨＴ（住友化学工業（株）製）０．２重量部、イル
ガノックス１０１０（チバガイギー社製）０．１重量
部、２，５−ジメチル−２，５−ジ（ターシャリーブチ
ルパーオキシ）ヘキサン ０．０２重量部を加えヘンシ
ェルミキサーで混合した後、溶融押出しを行いペレット
化した。ペレットは、メルトフローレイト １．６ｇ／
１０分、２０℃キシレン可溶部１６．８重量％、融点１
６３℃であった。100 parts by weight of this block copolymer powder, 0.1 part by weight of calcium stearate, 0.2 part by weight of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), 0.1 part of Irganox 1010 (manufactured by Ciba Geigy). After addition of 0.02 part by weight of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane was mixed with a Henschel mixer, the mixture was melt-extruded and pelletized. Pellets have a melt flow rate of 1.6 g /
10 minutes, 20 ° C xylene-soluble part 16.8% by weight, melting point 1
It was 63 ° C.
【００５３】次いで、得られたペレットを５０ｍｍφＴ
−ダイ製膜機で、ダイ温度２８０℃で溶融押出しを行
い、３０℃の冷却水を通水した冷却ロールで冷却して、
厚さ３０μ、６０μの未延伸フィルムを得た。得られた
フィルムの外観、衝撃強度、耐ブロッキング性、食品衛
生性、耐熱性（ヒートシール温度）を表２に示した。Then, the obtained pellets are 50 mmφT
-In a die film forming machine, melt extrusion is performed at a die temperature of 280 ° C, and cooling is performed with a cooling roll in which cooling water of 30 ° C is passed,
An unstretched film having a thickness of 30μ and 60μ was obtained. Table 2 shows the appearance, impact strength, blocking resistance, food hygiene, and heat resistance (heat sealing temperature) of the obtained film.
【００５４】実施例２〜３ 重合工程において、第１工程でＨ2 濃度、第２工程でエ
チレン、Ｈ2 濃度および重合量を変更した以外は、実施
例１と同様に実施し、また混合、ペレット化工程以降に
おいては、２，５−ジメチル−２，５−ジ（ターシャリ
ーブチルパーオキシ）ヘキサンの配合量を変更した以外
は、実施例１と同様に実施した。実施例２および３で得
られたペレットは、融点１６４℃であった。このペレッ
トを用いて、実施例１と同様に製膜、評価を実施した。
評価結果を表２に示した。[0054] In Examples 2-3 the polymerization step, concentration of H 2 in a first step, ethylene in the second step, except for changing the concentration of H 2 and the polymerization amount, in the same manner as in Example 1, also mixed, After the pelletizing step, the same procedure as in Example 1 was performed except that the compounding amount of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane was changed. The pellets obtained in Examples 2 and 3 had a melting point of 164 ° C. Using this pellet, film formation and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 2.
【００５５】比較例１ 内容積２３ｍ3 の攪拌機付重合槽を使用して、特公平３
−４６００１号公報に記載の固体触媒、ジエチルアルミ
ニウムクロライド、電子供与体及び水素の共存下にヘプ
タンを溶媒として重合温度６０℃、重合圧力９ｋｇ／ｃ
ｍ2 Ｇ、気相水素濃度１．５％でプロピレンを６時間重
合し、引き続いて、同一の重合槽において、重合温度５
０℃、重合圧力５ｋｇ／ｃｍ2 Ｇで、３時間プロピレン
とエチレンを重合した。エチレン濃度３２％、Ｈ2 濃度
４．５％になるように、エチレン、プロピレン、Ｈ2 を
供給した。得られたプロピレンブロック共重合体は、Ａ
成分の含有量７４重量％、極限粘度（〔η〕A ）３．１
ｄｌ／ｇ、Ｂ成分が含有量２６重量％、エチレン含有
量３２重量％、極限粘度（〔η〕B ）３．１ ｄｌ／
ｇ、〔η〕B ／〔η〕A ＝１．０であった。[0055] Using an agitator with polymerization vessel of Comparative Example 1 inner volume 23m 3, KOKOKU 3
-60001 in the presence of a solid catalyst, diethylaluminum chloride, an electron donor and hydrogen in the presence of heptane as a solvent at a polymerization temperature of 60 ° C. and a polymerization pressure of 9 kg / c.
Propylene was polymerized for 6 hours at m 2 G and a vapor phase hydrogen concentration of 1.5%, and subsequently, in the same polymerization tank, at a polymerization temperature of 5
Propylene and ethylene were polymerized for 3 hours at 0 ° C. and a polymerization pressure of 5 kg / cm 2 G. Ethylene, propylene and H 2 were supplied so that the ethylene concentration was 32% and the H 2 concentration was 4.5%. The obtained propylene block copolymer has A
Ingredient content 74% by weight, intrinsic viscosity ([η] A) 3.1
dl / g, B component content 26% by weight, ethylene content 32% by weight, intrinsic viscosity ([η] B) 3.1 dl /
g, [η] B / [η] A = 1.0.
【００５６】このブロック共重合体を用いて、実施例１
と同様にペレット化した。ペレットは、メルトフローレ
イト１．９ｇ／１０分、２０℃キシレン可溶部１１．７
重量％、融点１６３℃であった。このペレットについ
て、実施例１と同様に製膜、評価を実施した。評価結果
を表２に示した。Example 1 was prepared using this block copolymer.
Pelletized as in. The pellets had a melt flow rate of 1.9 g / 10 minutes and a xylene-soluble portion of 11.7 at 20 ° C.
% By weight, melting point 163 ° C. The pellets were subjected to film formation and evaluation in the same manner as in Example 1. The evaluation results are shown in Table 2.
【００５７】比較例２ 特公平３−４６００１号公報に記載のＴｉＣｌ3 型の固
体触媒とジエチルアルミニウムクロライドと電子供与体
としてメチルメタクリレートを組み合わせた触媒系を用
いて、第１工程で重合温度、Ｈ2 濃度、第２工程で重合
温度、エチレン、Ｈ2 濃度および重合量を変更して、実
施例１と同様に実施し、Ａ成分の含有量６９重量％、極
限粘度（〔η〕A ）２．４ ｄｌ／ｇ、Ｂ成分が含有量
３１重量％、エチレン含有量４０重量％、極限粘度
（〔η〕B ）３．７ ｄｌ／ｇのブロック共重合体粉末
を得た。Comparative Example 2 Using the TiCl 3 type solid catalyst described in JP-B-3-46001 and a catalyst system in which diethylaluminum chloride and methyl methacrylate as an electron donor are combined, the polymerization temperature, H 2 concentration, in the second step, the polymerization temperature, ethylene, H 2 concentration and the amount of polymerization were changed, and the same procedure as in Example 1 was carried out, the content of component A was 69% by weight, the intrinsic viscosity ([η] A) 2 A block copolymer powder having a content of 0.4 dl / g, a B component content of 31% by weight, an ethylene content of 40% by weight, and an intrinsic viscosity ([η] B) of 3.7 dl / g was obtained.
【００５８】このブロック共重合体を用いて、ステアリ
ン酸カルシウム０．１重量部、スミライザーＢＨＴ
０．２重量部、イルガノックス１０１０ ０．１重量部
を加え実施例１と同様にペレット化した。ペレットは、
メルトフローレイト １．４ｇ／１０分、２０℃キシレ
ン可溶部２４．０重量％、融点１６３℃であった。この
ペレットについて、実施例１と同様に製膜、評価を実施
した。評価結果を表２に示した。Using this block copolymer, 0.1 part by weight of calcium stearate and Sumilizer BHT
0.2 parts by weight and 0.1 parts by weight of Irganox 1010 were added and pelletized in the same manner as in Example 1. Pellets
The melt flow rate was 1.4 g / 10 minutes, the xylene-soluble portion at 20 ° C. was 24.0% by weight, and the melting point was 163 ° C. The pellets were subjected to film formation and evaluation in the same manner as in Example 1. The evaluation results are shown in Table 2.
【００５９】比較例３〜５ 重合工程において、第１工程でＨ2 濃度、第２工程でエ
チレン、Ｈ2 濃度および重合量を変更した以外は、実施
例１と同様に実施し、また混合、ペレット化工程以降に
おいては、２，５−ジメチル−２，５−ジ（ターシャリ
ーブチルパーオキシ）ヘキサンの配合量を変更した以外
は実施例１と同様に実施した。評価結果を表２に示し
た。[0059] In Comparative Example 3-5 the polymerization step, concentration of H 2 in a first step, ethylene in the second step, except for changing the concentration of H 2 and the polymerization amount, in the same manner as in Example 1, also mixed, After the pelletizing step, the same procedure as in Example 1 was performed except that the compounding amount of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane was changed. The evaluation results are shown in Table 2.
【００６０】比較例６ 住友化学工業（株）製住友ノーブレンＦＳ２０１１Ｄ
（〔η〕＝２．２８ｄｌ／ｇ）７５重量部と、実施例１
の固体触媒とＴＥＡ、ＣＨＥＤＭＳとを組み合わせた触
媒系を用いて、エチレン濃度２８％、Ｈ2 濃度２３％、
重合温度６０℃、重合圧力３ｋｇ／ｃｍ2 の条件下に、
プロピレンとエチレンの混合ガスを重合して得たエチレ
ン含有量２５重量％、極限粘度１．０ ｄｌ／ｇのエチ
レン−プロピレン共重合体２５重量部を混合し、ステア
リン酸カルシウム、スミライザーＢＨＴ、イルガノック
ス１０１０を各０．０５重量部配合してペレット化し
た。ペレットは、メルトフローレイト３．６ｇ／１０
分、２０℃キシレン可溶部１９．１重量％であった。こ
のペレットについて、実施例１と同様に製膜、評価を実
施した。評価結果を表２に示した。Comparative Example 6 Sumitomo Chemical Co., Ltd. Sumitomo Noblen FS2011D
([Η] = 2.28 dl / g) 75 parts by weight
Ethylene catalyst 28%, H 2 concentration 23%, using a catalyst system combining the solid catalyst of TEA and CHEDMS
Under the conditions of a polymerization temperature of 60 ° C. and a polymerization pressure of 3 kg / cm 2 ,
25 parts by weight of an ethylene-propylene copolymer having an ethylene content of 25% by weight and an intrinsic viscosity of 1.0 dl / g obtained by polymerizing a mixed gas of propylene and ethylene were mixed, and calcium stearate, Sumilizer BHT, and Irganox 1010 were mixed. 0.05 part by weight of each was mixed and pelletized. Pellets have a melt flow rate of 3.6 g / 10
Min, the xylene-soluble portion at 20 ° C. was 19.1% by weight. The pellets were subjected to film formation and evaluation in the same manner as in Example 1. The evaluation results are shown in Table 2.
【００６１】比較例７ 重合工程において、第１工程でＨ2 濃度、第２工程でエ
チレン、Ｈ2 濃度および重合量を変更した以外は、実施
例１と同様に実施し、また混合、ペレット化工程以降に
おいては、２，５−ジメチル−２，５−ジ（ターシャリ
ーブチルパーオキシ）ヘキサンの配合量を０．１重量部
に変更した以外は、実施例１と同様に実施した。評価結
果を表２に示した。[0061] In Comparative Example 7 the polymerization step, concentration of H 2 in a first step, ethylene in the second step, except for changing the concentration of H 2 and the polymerization amount, in the same manner as in Example 1, also mixed, pelletized After the steps, the same procedure as in Example 1 was performed except that the compounding amount of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane was changed to 0.1 part by weight. The evaluation results are shown in Table 2.
【００６２】[0062]
【表１】 [Table 1]
【００６３】[0063]
【表２】 [Table 2]
【００６４】[0064]
【発明の効果】本発明により、耐熱性などのポリプロピ
レンブロック共重合体が本来有する好ましい特性を損な
うことなく、また低結晶性のＥＰＲやＬ−ＬＤＰＥなど
を配合することなく、低温での耐衝撃性が良好であり、
外観、耐ブロッキング性、食品衛生性が良好で、特にレ
トルト食品包装用途に好適なポリプロピレンブロック共
重合体のフィルムを得ることができる。INDUSTRIAL APPLICABILITY According to the present invention, impact resistance at low temperature can be achieved without impairing the desirable characteristics inherent to polypropylene block copolymers such as heat resistance, and without compounding low crystalline EPR or L-LDPE. Is good,
It is possible to obtain a polypropylene block copolymer film which has good appearance, blocking resistance and food hygiene and is particularly suitable for retort food packaging applications.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森 二郎 千葉県市原市姉崎海岸５の１ 住友化学工 業株式会社内 (72)発明者 白谷 英助 千葉県市原市姉崎海岸５の１ 住友化学工 業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jiro Mori 1-5 Anezaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Eisuke Shiratani 5-1 Anesaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd. Within the corporation
Claims (2)
ンを必須とするチーグラー・ナッタ型触媒を用いて、第
１工程で実質的に不活性溶剤の不存在下にプロピレンを
主体とした重合体部分（Ａ成分）を全重合量の６０〜８
０重量％重合し、ついで第２工程で気相中でエチレン含
有量が２０〜５０重量％のエチレン−プロピレン共重合
部分（Ｂ成分）を全重合量の２０〜４０重量％重合して
得られるブロック共重合体であって、かつＢ成分の極限
粘度（〔η〕B ）が２．０ dｌ／g 以上、Ｂ成分の極限
粘度（〔η〕B ）とＡ成分の極限粘度（〔η〕A ）の比
（〔η〕B ／〔η〕A ）が１．８以下のブロック共重合
体を溶融混練してなり、溶融混練後の全重合体中の２０
℃キシレン可溶部の分子量５万以下の成分の含有量が
２．０重量％以下であることを特徴とするポリプロピレ
ンブロック共重合体。1. A polymer portion (component A) containing propylene as a main component in the first step in the substantially absence of an inert solvent by using a Ziegler-Natta type catalyst in which at least titanium, magnesium and halogen are essential. ) Is 60 to 8 of the total polymerization amount.
It is obtained by polymerizing 0% by weight, and then polymerizing the ethylene-propylene copolymer part (component B) having an ethylene content of 20 to 50% by weight in the gas phase in the second step in an amount of 20 to 40% by weight of the total amount of polymerization. It is a block copolymer and has an intrinsic viscosity ([η] B) of component B of 2.0 dl / g or more, an intrinsic viscosity of component B ([η] B) and an intrinsic viscosity of component A ([η]). The block copolymer having a ratio (A) ([η] B / [η] A) of 1.8 or less is melt-kneaded to obtain 20% of all polymers after melt-kneading.
A polypropylene block copolymer, characterized in that the content of components having a molecular weight of 50,000 or less in the xylene-soluble part at 2.0 ° C. is 2.0% by weight or less.
重合体を、溶融押出し製膜してなるフィルム。2. A film obtained by melt-extruding the polypropylene block copolymer according to claim 1.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4246160A JP2998448B2 (en) | 1992-09-16 | 1992-09-16 | Polypropylene block copolymer and its film |
| CA002105834A CA2105834A1 (en) | 1992-09-16 | 1993-09-09 | Polypropylene block copolymer and the film thereof |
| DE69313056T DE69313056T2 (en) | 1992-09-16 | 1993-09-13 | Propylene block copolymers and films made therefrom |
| EP93307190A EP0588581B1 (en) | 1992-09-16 | 1993-09-13 | Polypropylene block copolymers and films thereof |
| SG1996009449A SG55195A1 (en) | 1992-09-16 | 1993-09-13 | Polypropylene block copolymer and the films thereof |
| KR1019930018420A KR100295028B1 (en) | 1992-09-16 | 1993-09-14 | Polypropylene Block Copolymer and Films thereof |
| TW082107657A TW307774B (en) | 1992-09-16 | 1993-09-16 | |
| US08/611,759 US5654372A (en) | 1992-09-16 | 1996-03-08 | Polypropylene composition and the film thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4246160A JP2998448B2 (en) | 1992-09-16 | 1992-09-16 | Polypropylene block copolymer and its film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0693062A true JPH0693062A (en) | 1994-04-05 |
| JP2998448B2 JP2998448B2 (en) | 2000-01-11 |
Family
ID=17144398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4246160A Expired - Fee Related JP2998448B2 (en) | 1992-09-16 | 1992-09-16 | Polypropylene block copolymer and its film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2998448B2 (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10211683A (en) * | 1996-11-29 | 1998-08-11 | Sumitomo Chem Co Ltd | Packing stretch film |
| KR19980042888A (en) * | 1997-11-28 | 1998-08-17 | 고오사이아끼오 | Stretch wrapping film |
| US6300415B1 (en) | 1995-11-24 | 2001-10-09 | Chisso Corporation | Propylene composition, process for preparing the same, polypropylene composition, and molded articles |
| US6319991B1 (en) | 1997-05-22 | 2001-11-20 | Chisso Corporation | Propylene polymer blends, processes of producing the same and polypropylene resin compositions |
| US6355736B1 (en) | 1999-11-02 | 2002-03-12 | Chisso Corporation | Propylene block copolymer compositions |
| JP2003041068A (en) * | 2001-07-26 | 2003-02-13 | Idemitsu Unitech Co Ltd | Resin composition for retort, its film and laminate |
| CN1117779C (en) * | 1996-06-04 | 2003-08-13 | 住友化学工业株式会社 | Propylene block copolymer |
| US6657910B2 (en) | 2001-10-10 | 2003-12-02 | Nec Electronics Corporation | Semiconductor device having internal power terminals including a positive power terminal and a negative power terminal |
| JP2006089513A (en) * | 2004-09-21 | 2006-04-06 | Sumitomo Chemical Co Ltd | Propylene-based resin composition, its film and laminate |
| JP2006161033A (en) * | 2004-11-10 | 2006-06-22 | Sumitomo Chemical Co Ltd | Propylene resin composition and film made thereof |
| JP2006212785A (en) * | 2005-02-01 | 2006-08-17 | Okamoto Ind Inc | Light barrier film, laminate and container |
| DE102008063120A1 (en) | 2007-12-26 | 2009-09-03 | Sumitomo Chemical Co., Ltd. | Polypropylene-based copolymer and film comprising the polypropylene-based copolymer |
| KR101007785B1 (en) * | 2008-11-25 | 2011-01-14 | 삼성토탈 주식회사 | Ethylene propylene block copolymer for protective film |
| WO2014054673A1 (en) | 2012-10-03 | 2014-04-10 | サンアロマー株式会社 | Propylene resin composition for retort pouch-packaging film |
| KR101598715B1 (en) * | 2014-11-12 | 2016-02-29 | 한화토탈 주식회사 | Polypropylene resin composition and film produced by the same |
| JP2016530378A (en) * | 2013-08-28 | 2016-09-29 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Polypropylene resin for protective film and protective film |
| KR20240053004A (en) | 2015-08-31 | 2024-04-23 | 도레이 필름 카코우 가부시키가이샤 | Retort-packaging polypropylene-based sealant film and laminate using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638309A (en) * | 1979-09-07 | 1981-04-13 | Mitsui Toatsu Chem Inc | Propylene copolymer for forming film |
| JPH01272612A (en) * | 1988-04-25 | 1989-10-31 | Idemitsu Petrochem Co Ltd | Production of propylene copolymer composition |
| JPH06172465A (en) * | 1992-08-31 | 1994-06-21 | Mitsui Toatsu Chem Inc | Production of propylene-ethylene block copolymer |
-
1992
- 1992-09-16 JP JP4246160A patent/JP2998448B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638309A (en) * | 1979-09-07 | 1981-04-13 | Mitsui Toatsu Chem Inc | Propylene copolymer for forming film |
| JPH01272612A (en) * | 1988-04-25 | 1989-10-31 | Idemitsu Petrochem Co Ltd | Production of propylene copolymer composition |
| JPH06172465A (en) * | 1992-08-31 | 1994-06-21 | Mitsui Toatsu Chem Inc | Production of propylene-ethylene block copolymer |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6300415B1 (en) | 1995-11-24 | 2001-10-09 | Chisso Corporation | Propylene composition, process for preparing the same, polypropylene composition, and molded articles |
| CN1117779C (en) * | 1996-06-04 | 2003-08-13 | 住友化学工业株式会社 | Propylene block copolymer |
| JPH10211683A (en) * | 1996-11-29 | 1998-08-11 | Sumitomo Chem Co Ltd | Packing stretch film |
| US6319991B1 (en) | 1997-05-22 | 2001-11-20 | Chisso Corporation | Propylene polymer blends, processes of producing the same and polypropylene resin compositions |
| KR19980042888A (en) * | 1997-11-28 | 1998-08-17 | 고오사이아끼오 | Stretch wrapping film |
| US6355736B1 (en) | 1999-11-02 | 2002-03-12 | Chisso Corporation | Propylene block copolymer compositions |
| JP2003041068A (en) * | 2001-07-26 | 2003-02-13 | Idemitsu Unitech Co Ltd | Resin composition for retort, its film and laminate |
| US6657910B2 (en) | 2001-10-10 | 2003-12-02 | Nec Electronics Corporation | Semiconductor device having internal power terminals including a positive power terminal and a negative power terminal |
| JP2006089513A (en) * | 2004-09-21 | 2006-04-06 | Sumitomo Chemical Co Ltd | Propylene-based resin composition, its film and laminate |
| JP2006161033A (en) * | 2004-11-10 | 2006-06-22 | Sumitomo Chemical Co Ltd | Propylene resin composition and film made thereof |
| JP2006212785A (en) * | 2005-02-01 | 2006-08-17 | Okamoto Ind Inc | Light barrier film, laminate and container |
| DE102008063120A1 (en) | 2007-12-26 | 2009-09-03 | Sumitomo Chemical Co., Ltd. | Polypropylene-based copolymer and film comprising the polypropylene-based copolymer |
| KR101007785B1 (en) * | 2008-11-25 | 2011-01-14 | 삼성토탈 주식회사 | Ethylene propylene block copolymer for protective film |
| WO2014054673A1 (en) | 2012-10-03 | 2014-04-10 | サンアロマー株式会社 | Propylene resin composition for retort pouch-packaging film |
| JP2016530378A (en) * | 2013-08-28 | 2016-09-29 | ハンファ トータル ペトロケミカル カンパニー リミテッド | Polypropylene resin for protective film and protective film |
| KR101598715B1 (en) * | 2014-11-12 | 2016-02-29 | 한화토탈 주식회사 | Polypropylene resin composition and film produced by the same |
| WO2016076490A1 (en) * | 2014-11-12 | 2016-05-19 | 한화토탈주식회사 | Polypropylene resin composition and film prepared therefrom |
| KR20240053004A (en) | 2015-08-31 | 2024-04-23 | 도레이 필름 카코우 가부시키가이샤 | Retort-packaging polypropylene-based sealant film and laminate using same |
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|---|---|
| JP2998448B2 (en) | 2000-01-11 |
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