JP7355591B2 - Stretched film and its uses - Google Patents
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Description
本発明は、低温熱収縮性を有し、熱収縮率に優れ、かつ自然収縮率が低く、引張弾性率が高い延伸フィルムおよびその用途に関する。 The present invention relates to a stretched film that has low-temperature heat shrinkability, excellent heat shrinkage rate, low natural shrinkage rate, and high tensile modulus, and uses thereof.
食品包装に用いる延伸フィルムの用途の一つであるシュリンクフィルムは、ポリ塩化ビニル、ポリエチレン、ポリプロピレン等の熱可塑性樹脂が用いられている。ポリ塩化ビニルシュリンクフィルムは収縮性、透明性に優れるが、環境への問題が懸念されている。ポリエチレンシュリンクフィルムは収縮性や耐突き刺し強度に優れるものの、透明性、剛性、耐熱性等は高くない。一方、ポリプロピレンシュリンクフィルムは透明性、耐熱性、剛性に優れるが、成形に高温を要し、収縮性に乏しいという問題がある。 Thermoplastic resins such as polyvinyl chloride, polyethylene, and polypropylene are used for shrink films, which are one of the applications of stretched films used in food packaging. Although polyvinyl chloride shrink film has excellent shrinkability and transparency, there are concerns about environmental issues. Although polyethylene shrink film has excellent shrinkability and puncture resistance, it does not have high transparency, rigidity, heat resistance, etc. On the other hand, although polypropylene shrink film has excellent transparency, heat resistance, and rigidity, it requires high temperatures for molding and has poor shrinkability.
かかる問題点の解決方法として、低融点化したポリプロピレン（プロピレン・α‐オレフィンランダム共重合体）を主材、もしくは改質材として用いることで収縮率を向上させる方法が提案されている（たとえば、特許文献１、２）。さらには、柔軟性や収縮性を改良する方法として、プロピレン系重合体に、ポリブテン系重合体を加えたオレフィン系重合体組成物を使用する方法が提案されている（たとえば、特許文献３～５）。 As a solution to this problem, a method has been proposed in which the shrinkage rate is improved by using polypropylene (propylene/α-olefin random copolymer) with a lower melting point as the main material or modifier (for example, Patent Documents 1, 2). Furthermore, as a method for improving flexibility and shrinkage, a method has been proposed that uses an olefin polymer composition in which a polybutene polymer is added to a propylene polymer (for example, Patent Documents 3 to 5 ).
一方で、提案された手法においては、主材の弾性率や融点が低いために、フィルムの弾性率すなわちコシに乏しく、製膜後経時での自然収縮が発生する恐れがあることから、後工程における作業性に難点が残る。これを解決する方法として、主材に高剛性かつ高融点なポリプロピレンを用いることが考えられるが、加熱収縮率が不足する問題が生じる。 On the other hand, in the proposed method, because the elastic modulus and melting point of the main material are low, the elastic modulus of the film, that is, the stiffness, is poor, and there is a risk of natural shrinkage occurring over time after film formation. Difficulties remain in terms of workability. One possible solution to this problem is to use polypropylene, which has high rigidity and a high melting point, as the main material, but this poses the problem of insufficient heat shrinkage.
本発明の目的は、低温熱収縮性を有し、熱収縮率に優れ、かつ自然収縮率が低く、引張弾性率が高い延伸フィルムを得ることにある。 An object of the present invention is to obtain a stretched film that has low-temperature heat shrinkability, excellent heat shrinkage rate, low natural shrinkage rate, and high tensile modulus.
本発明は、示差走査熱量測定（ＤＳＣ）により測定した融点（Ｔｍ）が１５０～１８０℃の範囲にあるプロピレン系重合体（Ａ）を４０～９０質量％、および示差走査熱量測定（ＤＳＣ）により測定した融点（Ｔｍ）が１２０℃未満または融点が観測されないプロピレン系共重合体（Ｂ）を１０～６０質量％〔但し、（Ａ）と（Ｂ）の合計を１００質量％とする。〕含む重合体組成物からなる縦方向（ＭＤ）の引張弾性率が１．５ＧＰａ以上であることを特徴とする延伸フィルムに係る。 The present invention contains 40 to 90% by mass of a propylene polymer (A) having a melting point (Tm) in the range of 150 to 180°C as measured by differential scanning calorimetry (DSC), and 10 to 60% by mass of a propylene copolymer (B) with a measured melting point (Tm) of less than 120° C. or no observed melting point [however, the total of (A) and (B) is 100% by mass. ] This relates to a stretched film characterized in that the tensile modulus in the machine direction (MD) is 1.5 GPa or more and is made of a polymer composition containing the present invention.
本発明の延伸フィルムは、低温熱収縮性を有し、加熱収縮率に優れ、かつ自然収縮率が低く、引張弾性率が高いので、食品包装材等に好適に用い得る。 The stretched film of the present invention has low-temperature heat shrinkability, excellent heat shrinkage rate, low natural shrinkage rate, and high tensile modulus, so it can be suitably used for food packaging materials and the like.
＜プロピレン系重合体（Ａ）＞
本発明の延伸フィルムを形成する重合体組成物の成分の一つであるプロピレン系重合体（Ａ）は、示差走査熱量測定（ＤＳＣ）により測定した融点（Ｔｍ）が１４０～１８０℃の範囲、好ましくは１５０～１７０℃の範囲にある。
<Propylene polymer (A)>
The propylene polymer (A), which is one of the components of the polymer composition forming the stretched film of the present invention, has a melting point (Tm) in the range of 140 to 180°C as measured by differential scanning calorimetry (DSC), Preferably it is in the range of 150 to 170°C.
本発明に係わるプロピレン系重合体（Ａ）の示差走査熱量測定（ＤＳＣ）による融点（Ｔｍ）の測定は、実施例に記載する方法で行った値である。
本発明に係わるプロピレン系重合体（Ａ）は、通常、プロピレンから導かれる構成単位が５０モル％を超え、好ましくは６０モル％以上、より好ましくは７０モル％以上である。
The melting point (Tm) of the propylene polymer (A) according to the present invention was measured by differential scanning calorimetry (DSC) using the method described in the Examples.
The propylene polymer (A) according to the present invention usually contains more than 50 mol% of structural units derived from propylene, preferably 60 mol% or more, and more preferably 70 mol% or more.
本発明に係わるプロピレン系重合体（Ａ）は、プロピレンの単独重合体（ホモポリプロピレン）であっても、プロピレンと炭素原子数２～２０のα－オレフィン（ただしプロピレンを除く）とのランダム共重合体であっても、プロピレンブロック共重合体であっても良い。 The propylene polymer (A) according to the present invention may be a propylene homopolymer (homopolypropylene) or a random copolymer of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). It may be a combination or a propylene block copolymer.
本発明に係わるプロピレン系重合体（Ａ）は、延伸製膜後の引張弾性率が１．５ＧＰａ以上のものを得るため、プロピレン単独重合体であることがより好ましい。
プロピレンと共重合させる炭素数が２～２０のα－オレフィンとしては、例えば、エチレン、１－ブテン、１－ペンテン、３－メチル－１－ブテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン、１－デセン、１－ドデセン、１－テトラセン、１－ヘキサデセン、１－オクタデセン、１－エイコセンが挙げられる。二種類以上のα－オレフィンを用いることも好ましい形態の一つである。
The propylene polymer (A) according to the present invention is more preferably a propylene homopolymer in order to obtain a tensile modulus of 1.5 GPa or more after film formation by stretching.
Examples of α-olefins having 2 to 20 carbon atoms to be copolymerized with propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, Examples include 1-octene, 1-decene, 1-dodecene, 1-tetracene, 1-hexadecene, 1-octadecene, and 1-eicosene. One preferable embodiment is to use two or more types of α-olefins.
本発明に係わるプロピレン系重合体（Ａ）は、延伸製膜後の引張弾性率が１．５ＧＰａ以上のものを得るため、アイソタクティックプロピレン系重合体が好ましい。アイソタクティックプロピレン系重合体とは、ＮＭＲ法により測定したアイソタクティックペンタッド分率が０.９以上、好ましくは０.９５以上であるプロピレン系重合体である。このアイソタクティックペンタッド分率を百分率で表すと９０％以上、好ましくは９５％以上である。 The propylene polymer (A) according to the present invention is preferably an isotactic propylene polymer in order to obtain a tensile modulus of 1.5 GPa or more after stretching film formation. The isotactic propylene polymer is a propylene polymer whose isotactic pentad fraction measured by NMR is 0.9 or more, preferably 0.95 or more. This isotactic pentad fraction, expressed as a percentage, is 90% or more, preferably 95% or more.
アイソタクティックペンタッド分率（ｍｍｍｍ分率）は、13Ｃ－ＮＭＲを使用して測定される分子鎖中のペンタッド分率単位でのアイソタクティック連鎖の存在割合を示すものであり、プロピレンモノマー単位が５個連続してメソ結合した連鎖の中心にあるプロピレンモノマー単位の分率である。具体的には、13Ｃ－ＮＭＲスペクトルで観測されるメチル炭素領域の全吸収ピーク中に占めるｍｍｍｍピークの分率として算出される。 The isotactic pentad fraction (mmmm fraction) indicates the proportion of isotactic chains present in the pentad fraction unit in the molecular chain measured using 13 C-NMR, and is It is the fraction of propylene monomer units at the center of a chain of five consecutive meso-bonded units. Specifically, it is calculated as the fraction of the mmmm peak in the total absorption peak in the methyl carbon region observed in the 13 C-NMR spectrum.
ｍｍｍｍ分率は、13Ｃ－ＮＭＲスペクトルにおけるＰｍｍｍｍ（プロピレン単位が５単位連続してアイソタクティック結合した部位における第３番目のメチル基に由来する吸収強度）およびＰｗ（プロピレン単位の全メチル基に由来する吸収強度）の吸収強度から下記式により求められる。
ｍｍｍｍ分率＝Ｐｍｍｍｍ／Ｐｗ
The mmmm fraction is defined as Pmmmm (absorption intensity derived from the third methyl group at the site where five propylene units are consecutively bonded isotactically) and Pw (total methyl groups of the propylene units) in the 13 C-NMR spectrum. It is determined by the following formula from the absorption intensity of the derived absorption intensity).
mmmm fraction=Pmmmm/Pw
ＮＭＲ測定は、ＮＭＲ測定装置を用いて例えば次のようにして行われる。すなわち、試料０.３５ｇをヘキサクロロブタジエン２.０ｍＬに加熱溶解させる。この溶液をグラスフィルター（Ｇ２）で濾過した後、重水素化ベンゼン０.５ｍＬを加え、内径１０ｍｍのＮＭＲチューブに装入する。そして１２０℃で13Ｃ－ＮＭＲ測定を行う。積算回数は１０,０００回以上とする。 NMR measurement is performed using an NMR measuring device, for example, as follows. That is, 0.35 g of the sample is heated and dissolved in 2.0 mL of hexachlorobutadiene. After filtering this solution through a glass filter (G2), 0.5 mL of deuterated benzene was added, and the solution was placed in an NMR tube with an inner diameter of 10 mm. Then, 13 C-NMR measurement is performed at 120°C. The cumulative number of times shall be 10,000 or more.
本発明に係わるプロピレン系重合体（Ａ）は、メルトフローレート（ＭＦＲ）〔ＡＳＴＭ Ｄ１２３８、２３０℃、２.１６ｋｇ荷重下）は、後述のプロピレン系重合体（Ｂ）と混合して得られる重合体組成物がフィルム形成能を有する限り特に限定はされないが、０．１～１０ｇ／１０分が好適であり、中でも０．５～８ｇ／１０分が特に好適である。このような範囲であれば、フィルム成形が良好である。 The propylene polymer (A) according to the present invention has a melt flow rate (MFR) [ASTM D1238, 230°C, under a load of 2.16 kg] of a polymer obtained by mixing with the propylene polymer (B) described below. There is no particular limitation as long as the combined composition has film-forming ability, but 0.1 to 10 g/10 minutes is preferred, and 0.5 to 8 g/10 minutes is particularly preferred. Within this range, film formation is good.
《プロピレン系重合体（Ａ）の製造方法》
本発明に係るプロピレン系重合体（Ａ）は、通常、ポリプロピレンとして、製造・販売されているオレフィン系重合体の一種であり、種々公知の製造方法、例えば、チーグラー・ナッタ系触媒、メタロセン系触媒などの公知の触媒の存在下に、モノマーを気相法、バルク法、スラリー法などの公知の重合法により製造し得る。
<<Production method of propylene polymer (A)>>
The propylene polymer (A) according to the present invention is a type of olefin polymer that is usually produced and sold as polypropylene, and can be produced using various known production methods, such as Ziegler-Natta catalysts and metallocene catalysts. The monomer can be produced by a known polymerization method such as a gas phase method, a bulk method, or a slurry method in the presence of a known catalyst such as.
＜プロピレン系共重合体（Ｂ）＞
本発明の延伸フィルムを形成する重合体組成物の成分の一つであるプロピレン系共重合体（Ｂ）は、示差走査熱量測定（ＤＳＣ）により測定した融点（Ｔｍ）が１２０℃未満または融点が観測されない。
<Propylene copolymer (B)>
The propylene copolymer (B), which is one of the components of the polymer composition forming the stretched film of the present invention, has a melting point (Tm) of less than 120°C or a melting point measured by differential scanning calorimetry (DSC). Not observed.
本発明に係わるプロピレン系共重合体（Ｂ）は、好ましくは、示差走査熱量測定（ＤＳＣ）により測定した融点（Ｔｍ）が１１０℃以下である。
本発明に係わるプロピレン系共重合体（Ｂ）は、好ましくは、13Ｃ－ＮＭＲで測定されるトリアドタクティシティ（ｍｍ分率）が８５％以上、より好ましくは９０～９８％の範囲にある。
The propylene copolymer (B) according to the present invention preferably has a melting point (Tm) of 110° C. or lower as measured by differential scanning calorimetry (DSC).
The propylene copolymer (B) according to the present invention preferably has a triad tacticity (mm fraction) measured by 13 C-NMR of 85% or more, more preferably in the range of 90 to 98%. .
本発明に係わるプロピレン系共重合体（Ｂ）の示差走査熱量測定（ＤＳＣ）による融点（Ｔｍ）の測定は、実施例に記載する方法で行った値である。
本発明に係わるプロピレン系共重合体（Ｂ）のトリアドタクティシティ（ｍｍ分率）は、具体的にポリマー鎖中に存在するプロピレン単位を含む３連鎖として、(i)頭－尾結合したプロピレン単位３連鎖、および(ii)頭－尾結合したプロピレン単位とα－オレフィン単位とからなりかつ第２単位目がプロピレン単位であるプロピレン単位・α－オレフィン単位３連鎖について、ｍｍ分率が測定される。これら３連鎖(i)および(ii)中の第２単位目（プロピレン単位）の側鎖メチル基のピーク強度からｍｍ分率が求められる。
The melting point (Tm) of the propylene copolymer (B) according to the present invention was measured by differential scanning calorimetry (DSC) using the method described in the Examples.
The triad tacticity (mm fraction) of the propylene copolymer (B) according to the present invention is specifically defined as three chains containing propylene units present in the polymer chain, (i) head-to-tail propylene The mm fraction is measured for three chains of units, and (ii) three chains of propylene units and α-olefin units consisting of a head-to-tail bonded propylene unit and an α-olefin unit, and the second unit is a propylene unit. Ru. The mm fraction is determined from the peak intensity of the side chain methyl group of the second unit (propylene unit) in these three chains (i) and (ii).
本発明に係るプロピレン系共重合体（Ｂ）は、通常、プロピレンから導かれる構成単位１０～９５モル％、好ましくは５０～９５モル％、より好ましくは６０～９０モル％並びに、炭素原子数２または４～２０のα－オレフィンから導かれる構成単位５～９０モル％、好ましくは５～５０モル％、より好ましくは１０～４０モル％［ここで、プロピレンから導かれる構成単位と炭素原子数２または４～２０のα－オレフィンから導かれる構成単位の合計量は１００モル％である。］を含有するプロピレン系重合体である。 The propylene copolymer (B) according to the present invention usually has a structural unit derived from propylene of 10 to 95 mol%, preferably 50 to 95 mol%, more preferably 60 to 90 mol%, and a carbon atom number of 2. or 5 to 90 mol% of structural units derived from 4 to 20 α-olefins, preferably 5 to 50 mol%, more preferably 10 to 40 mol% [here, structural units derived from propylene and carbon atoms of 2 Alternatively, the total amount of structural units derived from 4 to 20 α-olefins is 100 mol%. ] It is a propylene-based polymer containing.
本発明に係わるプロピレン系共重合体（Ｂ）において、プロピレンと共重合させる炭素数２または４～２０のα－オレフィンとしては、例えば、エチレン、１－ブテン、１－ペンテン、３－メチル－１－ブテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン、１－デセン、１－ドデセン、１－テトラセン、１－ヘキサデセン、１－オクタデセン、１－エイコセンが挙げられる。これらα－オレフィンは二種類以上のα－オレフィンであってもよい。これらα－オレフィンの中では、１－ブテンがより好ましい。 In the propylene copolymer (B) according to the present invention, the α-olefin having 2 or 4 to 20 carbon atoms to be copolymerized with propylene includes, for example, ethylene, 1-butene, 1-pentene, 3-methyl-1 -butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetracene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins may be two or more types of α-olefins. Among these α-olefins, 1-butene is more preferred.
本発明に係わるプロピレン系共重合体（Ｂ）のゲルパーミエイションクロマトグラフィー（ＧＰＣ）により求められる分子量分布（Ｍｗ／Ｍｎ）は、好ましくは３.０以下、より好ましくは２.０～３.０、特に好ましくは２.０～２.５である。Ｍｗ／Ｍｎを上記範囲に設定することで、プロピレン系共重合体（Ｂ）中の低分子量成分の含有量を抑制できる。その結果、延伸フィルムの表層からブリードが起こり難くなり、延伸フィルムの保管時における表層のべた付き、ブロッキングを抑制できる。 The molecular weight distribution (Mw/Mn) determined by gel permeation chromatography (GPC) of the propylene copolymer (B) according to the present invention is preferably 3.0 or less, more preferably 2.0 to 3. 0, particularly preferably 2.0 to 2.5. By setting Mw/Mn within the above range, the content of low molecular weight components in the propylene copolymer (B) can be suppressed. As a result, bleeding from the surface layer of the stretched film is less likely to occur, and stickiness and blocking of the surface layer during storage of the stretched film can be suppressed.
本発明に係わるプロピレン系共重合体（Ｂ）のＭｗ／Ｍｎの測定方法は、実施例に記載した方法で測定した値である。
本発明に係わるプロピレン系共重合体（Ｂ）のメルトフローレート（ＭＦＲ；ＡＳＴＭ Ｄ１２３８、２３０℃、２.１６ｋｇ荷重下）は、前記プロピレン系重合体（Ａ）と混合して得られる重合体組成物がフィルム形成能を有する限り特に限定はされないが、好ましくは０.１～３０ｇ／１０分、より好ましくは０.５～２０ｇ／１０分、特に好ましくは１.０～１０ｇ／１０分である。
The method for measuring Mw/Mn of the propylene copolymer (B) according to the present invention is the value measured by the method described in the Examples.
The melt flow rate (MFR; ASTM D1238, 230°C, under 2.16 kg load) of the propylene copolymer (B) according to the present invention is the polymer composition obtained by mixing with the propylene polymer (A). There is no particular limitation as long as the material has film-forming ability, but it is preferably 0.1 to 30 g/10 minutes, more preferably 0.5 to 20 g/10 minutes, particularly preferably 1.0 to 10 g/10 minutes. .
《プロピレン系共重合体（Ｂ）の製造方法》
本発明に係わるプロピレン系共重合体（Ｂ）は、プロピレンとα－オレフィンをメタロセン化合物を含む触媒の存在下に共重合することにより好適に製造できる。具体的には、例えば、ＷＯ２００４／０８７７７５号パンフレットまたはＷＯ２００１／２７１２４号パンフレットに記載の方法などに従いメタロセン触媒によって好適に製造できる。また、チーグラー・ナッタ触媒を用いてもよい。
<<Production method of propylene copolymer (B)>>
The propylene copolymer (B) according to the present invention can be suitably produced by copolymerizing propylene and α-olefin in the presence of a catalyst containing a metallocene compound. Specifically, it can be suitably produced using a metallocene catalyst, for example, according to the method described in WO2004/087775 pamphlet or WO2001/27124 pamphlet. Alternatively, a Ziegler-Natta catalyst may be used.
＜重合体組成物＞
本発明の延伸フィルムを形成する重合体組成物は、本発明に係わる上記プロピレン系重合体（Ａ）を４０～９５質量％、好ましくは５０～９５質量％、より好ましくは６０～９０質量％、および、本発明に係わる上記プロピレン系共重合体（Ｂ）を５～６０質量％、好ましくは５～５０質量％、より好ましくは１０～４０質量％の範囲で含む組成物である〔但し、（Ａ）と（Ｂ）の合計を１００質量％とする。〕。
<Polymer composition>
The polymer composition forming the stretched film of the present invention contains 40 to 95% by mass, preferably 50 to 95% by mass, more preferably 60 to 90% by mass of the propylene polymer (A) according to the present invention. and a composition containing the propylene copolymer (B) according to the present invention in an amount of 5 to 60% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass [provided that ( The total of A) and (B) is 100% by mass. ].
本発明に係わる重合体組成物は、プロピレン系重合体（Ａ）とプロピレン系共重合体（Ｂ）とを上記範囲で含むことにより、低温熱収縮性を有し、熱収縮率に優れ、かつ自然収縮率が低く、引張弾性率が高い延伸フィルムを得ることができる。 The polymer composition according to the present invention contains the propylene polymer (A) and the propylene copolymer (B) in the above range, so that it has low-temperature heat shrinkability, excellent heat shrinkage rate, and A stretched film with low natural shrinkage and high tensile modulus can be obtained.
本発明に係わる重合体組成物は、あるいは、上記プロピレン系重合体（Ａ）、上記プロピレン系共重合体（Ｂ）には、その目的を損なわない範囲内において通常用いられる耐熱安定剤、酸化防止剤、紫外線吸収剤、抗ブロッキング剤、スリップ剤、帯電防止剤、対候安定剤、防曇剤、結晶核剤、塩基吸収剤、滑剤、難燃剤などを、本発明の目的を損なわない範囲で添加することができる。 Alternatively, the polymer composition according to the present invention may contain heat-resistant stabilizers and antioxidants that are commonly used in the propylene-based polymer (A) and the propylene-based copolymer (B) within a range that does not impair the purpose. additives, ultraviolet absorbers, anti-blocking agents, slip agents, antistatic agents, weather stabilizers, antifogging agents, crystal nucleating agents, base absorbers, lubricants, flame retardants, etc., within the range that does not impair the purpose of the present invention. Can be added.
本発明に係わる重合体組成物のメルトフローレート（ＭＦＲ；ＡＳＴＭ Ｄ１２３８、２３０℃、２.１６ｋｇ荷重下）は、重合体組成物がフィルム形成能を有する限り特に限定はされないが、好ましくは０．１～１００ｇ／１０分、より好ましくは０．５～３０ｇ／１０分、特に好ましくは１～１０ｇ／１０分である。 The melt flow rate (MFR; ASTM D1238, 230°C, under a load of 2.16 kg) of the polymer composition according to the present invention is not particularly limited as long as the polymer composition has film-forming ability, but is preferably 0. The rate is 1 to 100 g/10 minutes, more preferably 0.5 to 30 g/10 minutes, particularly preferably 1 to 10 g/10 minutes.
＜延伸フィルム＞
本発明の延伸フィルムは、本発明に係わる上記重合体組成物を延伸してなる縦方向（ＭＤ）の引張弾性率が１．５ＧＰａ以上、好ましくは１．５～６．０ＧＰａの範囲にあることを特徴とする延伸フィルムである。
<Stretched film>
The stretched film of the present invention is obtained by stretching the above polymer composition according to the present invention, and has a tensile modulus in the machine direction (MD) of 1.5 GPa or more, preferably in the range of 1.5 to 6.0 GPa. It is a stretched film characterized by:
本発明の延伸フィルムは、一軸延伸フィルムであっても、二軸延伸フィルムであってもよい。
本発明の延伸フィルムは、好ましくは、１３０℃以上の温度で１分間加熱した際の熱収縮率が１０％以上、より好ましくは１０～７０％の範囲にある。
The stretched film of the present invention may be a uniaxially stretched film or a biaxially stretched film.
The stretched film of the present invention preferably has a heat shrinkage rate of 10% or more, more preferably in the range of 10 to 70% when heated for 1 minute at a temperature of 130° C. or higher.
本発明の延伸フィルムは、好ましくは、４０℃雰囲気下で７日間保管後の縦および横の収縮率がいずれも２．５％以下である。
本発明の延伸フィルムの厚さは、延伸フィルムの用途に応じて種々決め得るが、通常、１～１００μｍ、好ましくは５～５０μｍ、より好ましくは１０～３０μｍの範囲にある。
The stretched film of the present invention preferably has both longitudinal and transverse shrinkage percentages of 2.5% or less after being stored in an atmosphere at 40° C. for 7 days.
The thickness of the stretched film of the present invention can be determined variously depending on the use of the stretched film, but is usually in the range of 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 30 μm.
本発明の延伸フィルムは、上記重合体組成物からなる単層の延伸フィルムであってもよいが、延伸フィルムの用途によっては、当該延伸フィルムの片面、あるいは両面に熱融着層が積層された延伸フィルムであってもよい。 The stretched film of the present invention may be a single-layer stretched film made of the above polymer composition, but depending on the use of the stretched film, a heat-sealable layer may be laminated on one or both sides of the stretched film. It may be a stretched film.
《熱融着層》
本発明の延伸フィルムに積層される熱融着層は、延伸フィルムにヒートシール性、好ましくは低温ヒートシール性を付与するための層であり、通常、上記プロピレン系重合体（Ａ）より低い温度で融着し得る重合体であり、例えば、高圧法低密度ポリエチレン、線状低密度ポリエチレン、結晶性あるいは低結晶性のエチレンと炭素数３～１０のα－オレフィンとのランダム共重合体あるいはプロピレンとエチレンもしくは炭素数４以上のα－オレフィンとのランダム共重合体、ポリブテン、エチレン・酢酸ビニル共重合体等の低融点の重合体を単独あるいはそれらの組成物からなる層である。
《Heat adhesive layer》
The heat-sealing layer laminated on the stretched film of the present invention is a layer for imparting heat-sealability, preferably low-temperature heat-sealability, to the stretched film, and is usually at a temperature lower than that of the propylene polymer (A). For example, high-pressure low-density polyethylene, linear low-density polyethylene, random copolymers of crystalline or low-crystalline ethylene and α-olefin having 3 to 10 carbon atoms, or propylene. This layer is made of a random copolymer of ethylene or an α-olefin having 4 or more carbon atoms, a low melting point polymer such as a polybutene, an ethylene/vinyl acetate copolymer, or a composition thereof.
本発明の延伸フィルムに積層される熱融着層の厚さは、用途に応じて種々決め得るが、通常、０．１～１０μｍ、好ましくは０．５～５μｍ、より好ましくは１～３μｍの範囲にある。 The thickness of the heat-sealing layer laminated on the stretched film of the present invention can be determined variously depending on the application, but is usually 0.1 to 10 μm, preferably 0.5 to 5 μm, and more preferably 1 to 3 μm. in range.
《基材層》
本発明の延伸フィルムは、延伸フィルムの用途によっては、基材層を積層した積層フィルムであってもよい。
《Base material layer》
The stretched film of the present invention may be a laminated film in which base layers are laminated, depending on the use of the stretched film.
本発明に係わる基材層は、熱可塑性樹脂からなるシート状またはフィルム状のもの、紙、アルミニウム箔等からなる。熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４－メチル・１－ペンテン、ポリブテン等）、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリアミド（ナイロン－６、ナイロン－６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体の鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエチレンテレフタレート、ポリアミド等、延伸性、透明性が良好な熱可塑性樹脂が好ましい。又、かかる熱可塑性樹脂フィルムからなる基材は、無延伸フィルムであっても、延伸フィルムであっても良いし、１種或いは２種以上の共押し出し品、押出しラミ品、ドライラミ品等の積層体であっても良い。 The base material layer according to the present invention is made of a sheet or film made of thermoplastic resin, paper, aluminum foil, or the like. Examples of the thermoplastic resin include various known thermoplastic resins, such as polyolefins (polyethylene, polypropylene, poly4-methyl-1-pentene, polybutene, etc.), polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), and polyamides. (nylon-6, nylon-66, polymethaxylene adipamide, etc.), polyvinyl chloride, polyimide, saponified products of ethylene/vinyl acetate copolymers, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomers, or these Examples include mixtures and the like. Among these, thermoplastic resins with good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferred. Further, the base material made of such a thermoplastic resin film may be an unstretched film or a stretched film, or may be a laminate of one or more coextruded products, extruded laminated products, dry laminated products, etc. It can also be the body.
又、基材層の片面あるいは両面を、本発明の延伸フィルムとの接着性を改良するために、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理、プライマーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。基材層の厚さは、通常５～１０００μｍ、好ましくは９～１００μｍの範囲にある。 In addition, one or both surfaces of the base material layer may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, flame treatment, etc. in order to improve the adhesion with the stretched film of the present invention. Activation processing may be performed in advance. The thickness of the base layer is usually in the range of 5 to 1000 μm, preferably 9 to 100 μm.
《延伸フィルムの製造方法》
本発明の延伸フィルムは、種々公知の方法、例えば、上記重合体組成物を押出し成形して得たシートを、公知の一軸延伸方法、同時二軸延伸方法あるいは逐次二軸延伸方法等の延伸フィルム製造方法により得られる。
《Method for producing stretched film》
The stretched film of the present invention can be produced by various known methods, for example, a sheet obtained by extrusion molding the above-mentioned polymer composition, and a stretched film such as a known uniaxial stretching method, simultaneous biaxial stretching method, or sequential biaxial stretching method. Obtained by the manufacturing method.
また、本発明の延伸フィルムが上記熱融着層を有する場合は、上記重合体組成物と上記熱融着層を形成する重合体とを共押出し成形してなるシートを用いればよい。
延伸フィルムは、低い温度で延伸するほど低温熱収縮性を有す延伸フィルムを得ることができる。
したがって、本発明の延伸フィルムが二軸延伸フィルムである場合は、その二軸延伸の条件は、公知の二軸延伸ポリプロピレンの製造条件より低い温度で延伸可能である。
Moreover, when the stretched film of the present invention has the above heat sealing layer, a sheet formed by coextruding the above polymer composition and the polymer forming the heat sealing layer may be used.
As the stretched film is stretched at a lower temperature, it is possible to obtain a stretched film having low-temperature heat shrinkability.
Therefore, when the stretched film of the present invention is a biaxially stretched film, the biaxially stretched film can be stretched at a temperature lower than the production conditions for known biaxially stretched polypropylene.
本発明に係わる重合体組成物は、上記プロピレン系重合体（Ａ）と上記プロピレン系共重合体（Ｂ）との組成比で、延伸可能な温度が異なるので、延伸可能な温度を探るために、シートの予熱温度を９０～１５０℃の範囲で行い、予め適正（製膜可能な最も低い温度）を選択すればよい。 Since the temperature at which the polymer composition according to the present invention can be stretched differs depending on the composition ratio of the propylene polymer (A) and the propylene copolymer (B), in order to find the temperature at which it can be stretched, , the sheet may be preheated at a temperature in the range of 90 to 150° C., and an appropriate temperature (the lowest temperature at which film formation is possible) may be selected in advance.
本発明の延伸フィルムは、逐次二軸延伸法では、縦延伸温度１００℃～１４５℃、延伸倍率を４～７倍の範囲、横延伸温度を１１０～１９０℃、延伸倍率を８～１１倍の範囲にすればよい。また、同時二軸延伸法では、延伸温度を１００～１４５℃、延伸（面）倍率を２０～８０倍の範囲にすればよい。 In the sequential biaxial stretching method, the stretched film of the present invention has a longitudinal stretching temperature of 100°C to 145°C, a stretching ratio of 4 to 7 times, a transverse stretching temperature of 110 to 190°C, and a stretching ratio of 8 to 11 times. Just make it a range. Further, in the simultaneous biaxial stretching method, the stretching temperature may be set in the range of 100 to 145° C., and the stretching (area) ratio may be set in the range of 20 to 80 times.
本発明の延伸フィルムが一軸延伸フィルムである場合は、ラベル等や易カット包装フィルム等への適用が考えられ、
本発明の延伸フィルムが二軸延伸フィルムある場合は、食品包装用、非食品包装用、加飾フィルム、キャパシタフィルム等の産業用フィルムへの適用に好適に使用し得る。
When the stretched film of the present invention is a uniaxially stretched film, it can be applied to labels, etc., easy-to-cut packaging films, etc.
When the stretched film of the present invention is a biaxially stretched film, it can be suitably used for food packaging, non-food packaging, decorative films, capacitor films, and other industrial films.
《延伸フィルムの用途》
本発明の延伸フィルムは、一般の包装用フィルムとしても用い得るが、シュリンクフィルム（収縮フィルム）として特に好適に用い得る。収縮包装用とは、包装しようとする物品全体を本発明のシュリンクフィルムが覆うように包装する用途ばかりではなく、包装しようとする物品の一部をシュリンクフィルムが覆うように包装する用途（シュリンクラベルなど）も含む。具体的には、食品包装、日用雑貨品、文具の包装、パレット包装などに用いられる。
《Applications of stretched film》
Although the stretched film of the present invention can be used as a general packaging film, it can be particularly suitably used as a shrink film. Shrink wrapping refers not only to wrapping the entire article to be wrapped with the shrink film of the present invention, but also to wrapping a part of the article to be wrapped with the shrink film (shrink label). etc.) are also included. Specifically, it is used for food packaging, daily necessities, stationery packaging, pallet packaging, etc.
本発明の収縮包装体は、延伸フィルムを熱収縮させて物品を包装する。
延伸フィルムを用いるにあたり、熱収縮に用いる収縮温度に特に制限はないが、例えば７０～１６０℃の範囲の雰囲気で（例えばオーブン中などで）加熱する。
The shrink wrapper of the present invention packages an article by heat-shrinking a stretched film.
When using a stretched film, the shrinkage temperature used for heat shrinkage is not particularly limited, but it is heated, for example, in an atmosphere in the range of 70 to 160°C (eg, in an oven).
本発明の延伸フィルムは、シュリンクフィルム（収縮フィルム）として用い得るが、収縮包装以外にも、種々ＯＰＰフィルムが使用されている分野、例えば、医薬、あるいは食品（被包装材料）などの包装材としても用い得る。 The stretched film of the present invention can be used as a shrink film, but in addition to shrink wrapping, it can be used in various fields where OPP films are used, such as packaging materials for pharmaceuticals or foods (materials to be packaged). can also be used.
《キャパシタフィルム》
本発明の延伸フィルムは、容易に薄肉化することができるので、キャパシタの小型化や、コンデンサー容量の増加に対する要望に対応するキャパシタフィルムとして好適に使用することができる。
《Capacitor film》
Since the stretched film of the present invention can be easily made thin, it can be suitably used as a capacitor film that meets the demand for smaller capacitors and increased capacitance.
《リサイクル品を含む成形体》
本発明の延伸フィルムは、延伸フィルムを成形する際の熱履歴による分子量の低下が少ないので、延伸フィルムあるいはその端材、組成物等を成形体のリサイクル原料として用い、当該リサイクル品を含む成形体とすることができる。
《Molded objects including recycled products》
Since the stretched film of the present invention has a small decrease in molecular weight due to thermal history during forming the stretched film, the stretched film or its scraps, compositions, etc. can be used as recycled raw materials for molded products, and molded products containing the recycled product can be used. It can be done.
本発明の延伸フィルムついて実施例を示してさらに詳細に説明するが、本発明はこれらによって限定されるものではない。
実施例および比較例で用いた（共）重合体を以下に示す。
EXAMPLES The stretched film of the present invention will be described in further detail with reference to Examples, but the present invention is not limited thereto.
The (co)polymers used in Examples and Comparative Examples are shown below.
〔プロピレン系重合体（Ａ）〕
プロピレン系重合体（Ａ）として、以下の重合体を用いた。
（１）プロピレン単独重合体（Ａ－１）〔ｈＰＰ〕
融点（Ｔｍ）：１６０℃、ＭＦＲ：３ｇ／１０分。
[Propylene polymer (A)]
The following polymer was used as the propylene polymer (A).
(1) Propylene homopolymer (A-1) [hPP]
Melting point (Tm): 160°C, MFR: 3g/10min.
〔プロピレン系重合体（Ｂ）〕
プロピレン系重合体（Ｂ）として、以下の製造方法で得たプロピレン・１－ブテン共重合体（Ｂ－１）〔ＰＢＲ－１〕およびプロピレン・１－ブテン共重合体（Ｂ－２）〔ＰＢＲ－２〕を用いた。
[Propylene polymer (B)]
As the propylene polymer (B), propylene/1-butene copolymer (B-1) [PBR-1] and propylene/1-butene copolymer (B-2) [PBR -2] was used.
［合成例］－メタロセン型錯体の合成－
（１）１－ｔｅｒｔ－ブチル－３－メチルシクロペンタジエンの調製
窒素雰囲気下で、ｔｅｒｔ－ブチルマグネシウムクロライド０.９０ｍｏｌ／ジエチルエーテル４５０ｍｌ溶液（２.０ｍｏｌ／Ｌ溶液）に脱水ジエチルエーテル３５０ｍｌを加え、氷冷下で０℃を保ちながら３－メチルシクロペンテノン４３.７ｇ（０.４５ｍｏｌ）／脱水ジエチルエーテル１５０ｍｌ溶液を滴下し、その後室温で１５時間攪拌した。さらにこの反応溶液に、氷冷下で０℃を保ちながら塩化アンモニウム８０.０ｇ（１.５０ｍｏｌ）／水３５０ｍｌ溶液を滴下し、その後水２５００ｍｌを加えて攪拌した。得られた液の有機相を分離し、水で洗浄した。さらにこの有機相に、氷冷下で０℃を保ちながら１０％塩酸水溶液８２ｍｌを加え、その後室温で６時間攪拌した。得られた液の有機相をさらに分離し、水、飽和炭酸水素ナトリウム水溶液、水、飽和食塩水をこの順で用いて洗浄した。次いで無水硫酸マグネシウム（乾燥剤）で乾燥し、乾燥剤を濾過し、濾液から溶媒を留去して液体を得た。この液体を減圧蒸留（４５～４７℃／１０ｍｍＨｇ）することにより１４.６ｇの淡黄色の液体を得た。その分析値を以下に示す。
1Ｈ－ＮＭＲ（２７０ＭＨｚ、ＣＤＣｌ3中、ＴＭＳ基準）δ６.３１＋６.１３＋５.９４＋５.８７（ｓ＋ｓ＋ｔ＋ｄ、２Ｈ）、３.０４＋２.９５（ｓ＋ｓ、２Ｈ）、２.１７＋２.０９（ｓ＋ｓ、３Ｈ）、１.２７（ｄ、９Ｈ）
[Synthesis example] -Synthesis of metallocene complex-
(1) Preparation of 1-tert-butyl-3-methylcyclopentadiene Under a nitrogen atmosphere, 350 ml of dehydrated diethyl ether was added to a solution of 0.90 mol of tert-butylmagnesium chloride/450 ml of diethyl ether (2.0 mol/L solution). A solution of 43.7 g (0.45 mol) of 3-methylcyclopentenone/150 ml of dehydrated diethyl ether was added dropwise to the mixture while maintaining the temperature at 0° C. under ice-cooling, followed by stirring at room temperature for 15 hours. Furthermore, a solution of 80.0 g (1.50 mol) of ammonium chloride/350 ml of water was added dropwise to this reaction solution while maintaining the temperature at 0° C. under ice cooling, and then 2,500 ml of water was added and stirred. The organic phase of the resulting liquid was separated and washed with water. Furthermore, 82 ml of a 10% aqueous hydrochloric acid solution was added to this organic phase while maintaining the temperature at 0° C. under ice cooling, and the mixture was then stirred at room temperature for 6 hours. The organic phase of the obtained liquid was further separated and washed with water, saturated aqueous sodium bicarbonate solution, water, and saturated brine in this order. Next, it was dried over anhydrous magnesium sulfate (desiccant), the desiccant was filtered off, and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (45-47°C/10 mmHg) to obtain 14.6 g of a pale yellow liquid. The analytical values are shown below.
1H -NMR (270MHz, in CDCl3 , TMS standard) δ6.31+6.13+5.94+5.87 (s+s+t+d, 2H), 3.04+2.95 (s+s, 2H), 2.17+2.09 (s+s, 3H) , 1.27 (d, 9H)
（２）３－ｔｅｒｔ－ブチル－１,６,６－トリメチルフルベンの調製
窒素雰囲気下で、上記方法（１）で得られた１－ｔｅｒｔ－ブチル－３－メチルシクロペンタジエン１３.０ｇ（９５.６ｍｍｏｌ）／脱水メタノール１３０ｍｌ溶液に、氷冷下で０℃を保ちながら脱水アセトン５５.２ｇ（９５０.４ｍｍｏｌ）を滴下し、次いでピロリジン６８.０ｇ（９５６.１ｍｍｏｌ）を滴下し、その後室温で４日間攪拌した。この反応液をジエチルエーテル４００ｍｌで希釈し、さらに水４００ｍｌを加えた。得られた液の有機相を分離し、０.５Ｎの塩酸水溶液１５０ｍｌで４回、水２００ｍｌで３回、飽和食塩水１５０ｍｌで１回洗浄した。次いで無水硫酸マグネシウム（乾燥剤）で乾燥し、乾燥剤を濾過し、濾液から溶媒を留去して液体を得た。この液体を減圧蒸留（７０～８０℃／０.１ｍｍＨｇ）することにより１０.５ｇの黄色の液体を得た。その分析値を以下に示す。
1Ｈ－ＮＭＲ（２７０ＭＨｚ、ＣＤＣｌ3中、ＴＭＳ基準）δ６.２３（ｓ、１Ｈ）、６.０５（ｄ、１Ｈ）、２.２３（ｓ、３Ｈ）、２.１７（ｄ、６Ｈ）、１.１７（ｓ、９Ｈ）
(2) Preparation of 3-tert-butyl-1,6,6-trimethylfulvene Under a nitrogen atmosphere, 13.0 g (95.0 g) of 1-tert-butyl-3-methylcyclopentadiene obtained by the above method (1). 6 mmol)/130 ml of dehydrated methanol solution was added dropwise to a solution of 55.2 g (950.4 mmol) of dehydrated acetone while keeping the temperature at 0°C under ice-cooling, and then 68.0 g (956.1 mmol) of pyrrolidine was added dropwise to the solution. The mixture was stirred for several days. This reaction solution was diluted with 400 ml of diethyl ether, and further 400 ml of water was added. The organic phase of the resulting liquid was separated and washed four times with 150 ml of 0.5N aqueous hydrochloric acid, three times with 200 ml of water, and once with 150 ml of saturated brine. Next, it was dried over anhydrous magnesium sulfate (desiccant), the desiccant was filtered off, and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (70-80°C/0.1 mmHg) to obtain 10.5 g of a yellow liquid. The analytical values are shown below.
1H -NMR (270MHz, in CDCl3 , TMS standard) δ6.23 (s, 1H), 6.05 (d, 1H), 2.23 (s, 3H), 2.17 (d, 6H), 1.17 (s, 9H)
（３）２－（３－ｔｅｒｔ－ブチル－５－メチルシクロペンタジエニル）－２－フルオレニルプロパンの調製
フルオレン１０.１ｇ（６０.８ｍｍｏｌ）／ＴＨＦ３００ｍｌ溶液に、氷冷下でｎ－ブチルリチウム６１.６ｍｍｏｌ／ヘキサン４０ｍｌ溶液を窒素雰囲気下で滴下し、その後室温で５時間攪拌した。得られた濃褐色溶液を再度氷冷し、上記方法（２）で得られた３－ｔｅｒｔ－ブチル－１,６,６－トリメチルフルベン１１.７ｇ（６６.５ｍｍｏｌ）／ＴＨＦ３００ｍｌ溶液を窒素雰囲気下で滴下し、その後室温で１４時間攪拌した。さらにこの褐色溶液を氷冷し、水２００ｍｌを加えた。得られた液の有機相を、ジエチルエーテルを用いて抽出、分離した。次いでこの有機相を硫酸マグネシウム（乾燥剤）で乾燥し、乾燥剤を濾過し、濾液から溶媒を減圧下で除去して橙褐色のオイルを得た。このオイルをシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）で精製して、３.８ｇの黄色オイルを得た。その分析値を以下に示す。
1Ｈ－ＮＭＲ（２７０ＭＨｚ、ＣＤＣｌ3中、ＴＭＳ基準）δ７.７０（ｄ、４Ｈ）、７.３４～７.２６（ｍ、６Ｈ）、７.１８～７.１１（ｍ、６Ｈ）、６.１７（ｓ、１Ｈ）、６.０１（ｓ、１Ｈ）、４.４２（ｓ、１Ｈ）、４.２７（ｓ、１Ｈ）、３.０１（ｓ、２Ｈ）、２.８７（ｓ、２Ｈ）、２.１７（ｓ、３Ｈ）、１.９９（ｓ、３Ｈ）、２.１０（ｓ、９Ｈ）、１.９９（ｓ、９Ｈ）、１.１０（ｓ、６Ｈ）、１.０７（ｓ、６Ｈ）
(3) Preparation of 2-(3-tert-butyl-5-methylcyclopentadienyl)-2-fluorenylpropane To a solution of 10.1 g (60.8 mmol) of fluorene/300 ml of THF was added n-butyl under ice cooling. A solution of 61.6 mmol of lithium/40 ml of hexane was added dropwise under a nitrogen atmosphere, and then stirred at room temperature for 5 hours. The obtained dark brown solution was ice-cooled again, and the 3-tert-butyl-1,6,6-trimethylfulvene 11.7 g (66.5 mmol)/THF 300 ml solution obtained in the above method (2) was added under a nitrogen atmosphere. and then stirred at room temperature for 14 hours. Furthermore, this brown solution was cooled with ice, and 200 ml of water was added. The organic phase of the obtained liquid was extracted and separated using diethyl ether. The organic phase was then dried over magnesium sulfate (desiccant), the desiccant was filtered off, and the filtrate was freed from the solvent under reduced pressure to yield an orange-brown oil. This oil was purified by silica gel column chromatography (developing solvent: hexane) to obtain 3.8 g of yellow oil. The analytical values are shown below.
1 H-NMR (270 MHz, in CDCl 3 , TMS standard) δ 7.70 (d, 4H), 7.34-7.26 (m, 6H), 7.18-7.11 (m, 6H), 6 .17 (s, 1H), 6.01 (s, 1H), 4.42 (s, 1H), 4.27 (s, 1H), 3.01 (s, 2H), 2.87 (s, 2H), 2.17 (s, 3H), 1.99 (s, 3H), 2.10 (s, 9H), 1.99 (s, 9H), 1.10 (s, 6H), 1. 07(s, 6H)
（４）ジメチルメチレン（３－ｔｅｒｔ－ブチル－５－メチルシクロペンタジエニル）フルオレニルジルコニウムジクロリド（メタロセン型錯体）の調製
氷冷下で、上記方法（３）で得られた２－（３－ｔｅｒｔ－ブチル－５－メチルシクロペンタジエニル）－２－フルオレニルプロパン１.１４ｇ（３.３ｍｍｏｌ）／ジエチルエーテル２５ｍｌ溶液に、ｎ－ブチルリチウム７.７ｍｍｏｌ／ヘキサン５.０ｍｌ溶液を窒素雰囲気下で滴下し、その後室温で１４時間攪拌した。得られた桃色のスラリーに、－７８℃でジルコニウムテトラクロライド０.７７ｇ（３.３ｍｍｏｌ）を加え、－７８℃で数時間攪拌し、次いで室温で６５時間撹拌した。得られた黒褐色スラリーを濾過し、濾物をジエチルエーテル１０ｍｌで洗浄し、ジクロロメタンで抽出して赤色溶液を得た。この溶液の溶媒を減圧留去して、０.５３ｇの赤橙色の固体状のメタロセン触媒であるジメチルメチレン（３－ｔｅｒｔ－ブチル－５－メチルシクロペンタジエニル）フルオレニルジルコニウムジクロリド（メタロセン型錯体）を得た。その分析値を以下に示す。
1Ｈ－ＮＭＲ（２７０ＭＨｚ、ＣＤＣｌ3中、ＴＭＳ基準）δ８.１１～８.０２（ｍ、３Ｈ）、７.８２（ｄ、１Ｈ）、７.５６～７.４５（ｍ、２Ｈ）、７.２３～７.１７（ｍ、２Ｈ）、６.０８（ｄ、１Ｈ）、５.７２（ｄ、１Ｈ）、２.５９（ｓ、３Ｈ）、２.４１（ｓ、３Ｈ）、２.３０（ｓ、３Ｈ）、１.０８（ｓ、９Ｈ）
(4) Preparation of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride (metallocene type complex) Under ice cooling, the 2-(3) obtained by the above method (3) -tert-Butyl-5-methylcyclopentadienyl)-2-fluorenylpropane 1.14 g (3.3 mmol)/diethyl ether 25 ml solution, n-butyl lithium 7.7 mmol/hexane 5.0 ml solution was added with nitrogen. The mixture was added dropwise under atmosphere, and then stirred at room temperature for 14 hours. To the resulting pink slurry, 0.77 g (3.3 mmol) of zirconium tetrachloride was added at -78°C, stirred at -78°C for several hours, and then stirred at room temperature for 65 hours. The resulting dark brown slurry was filtered, and the filtered residue was washed with 10 ml of diethyl ether and extracted with dichloromethane to obtain a red solution. The solvent of this solution was distilled off under reduced pressure, and 0.53 g of reddish-orange solid metallocene catalyst dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride (metallocene type) was removed. complex) was obtained. The analytical values are shown below.
1 H-NMR (270 MHz, in CDCl 3 , TMS standard) δ8.11-8.02 (m, 3H), 7.82 (d, 1H), 7.56-7.45 (m, 2H), 7 .23-7.17 (m, 2H), 6.08 (d, 1H), 5.72 (d, 1H), 2.59 (s, 3H), 2.41 (s, 3H), 2. 30 (s, 3H), 1.08 (s, 9H)
［調製例１］
プロピレン・１－ブテン共重合体（Ｂ－１）〔ＰＢＲ－１〕の調製
充分に窒素置換した２０００ｍｌの重合装置に、乾燥ヘキサン８７５ｍｌ、１－ブテン７５ｇおよびトリイソブチルアルミニウム１.０ｍｍｏｌを常温で仕込み、重合装置内温を６５℃に昇温し、プロピレンで０.７ＭＰａに加圧した。次いで、上記合成例で得られたメタロセン触媒であるジメチルメチレン（３－ｔｅｒｔ－ブチル－５－メチルシクロペンタジエニル）フルオレニルジルコニウムジクロリド０.００２ｍｍｏｌと、アルミニウム換算で０.６ｍｍｏｌのメチルアルミノキサン（東ソー・ファインケム社製）とを接触させたトルエン溶液を重合器内に添加し、内温６５℃、プロピレン圧０.７５ＭＰａを保ちながら３０分間重合し、２０ｍｌのメタノールを添加し重合を停止した。脱圧後、２Ｌのメタノール中で重合溶液からポリマーを析出し、真空下１３０℃、１２時間乾燥し、１５.２ｇのプロピレン・１－ブテン共重合体を得た。以下の説明では、このプロピレン・１－ブテン共重合体を「ＰＢＲ－１」と略称する。
[Preparation example 1]
Preparation of propylene/1-butene copolymer (B-1) [PBR-1] 875 ml of dry hexane, 75 g of 1-butene, and 1.0 mmol of triisobutylaluminum were charged at room temperature into a 2000 ml polymerization apparatus that was sufficiently purged with nitrogen. The internal temperature of the polymerization apparatus was raised to 65° C., and the pressure was increased to 0.7 MPa using propylene. Next, 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride, which is the metallocene catalyst obtained in the above synthesis example, and 0.6 mmol of methylaluminoxane (in terms of aluminum) were added. A toluene solution in contact with Tosoh Finechem Co., Ltd.) was added into the polymerization vessel, and polymerization was carried out for 30 minutes while maintaining an internal temperature of 65° C. and a propylene pressure of 0.75 MPa, and 20 ml of methanol was added to stop the polymerization. After depressurizing, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130° C. for 12 hours to obtain 15.2 g of propylene/1-butene copolymer. In the following explanation, this propylene/1-butene copolymer will be abbreviated as "PBR-1".
ＰＢＲ－１の１－ブテン含量（Ｍ）は２５モル％、メルトフローレート（ＭＦＲ）は６.５ｇ／１０分、分子量分布（Ｍｗ／Ｍｎ）は２.１１、融点（Ｔｍ）は７５.３℃であった。 The 1-butene content (M) of PBR-1 is 25 mol%, the melt flow rate (MFR) is 6.5 g/10 min, the molecular weight distribution (Mw/Mn) is 2.11, and the melting point (Tm) is 75.3. It was ℃.
［調製例２］
プロピレン・１－ブテン共重合体（Ｂ－２）〔ＰＢＲ－２〕の調製
前記調製例１において、１－ブテンの使用量を４５ｇに、重合時（触媒添加後）のプロピレン圧を０.７ＭＰａに変更した以外は調製例１と同様にしてプロピレン・１－ブテン共重合体を得た。以下の説明では、このプロピレン・１－ブテン共重合体を「ＰＢＲ－２」と略称する。
[Preparation example 2]
Preparation of propylene/1-butene copolymer (B-2) [PBR-2] In Preparation Example 1, the amount of 1-butene used was 45 g, and the propylene pressure during polymerization (after addition of catalyst) was 0.7 MPa. A propylene/1-butene copolymer was obtained in the same manner as in Preparation Example 1 except that the following was changed. In the following explanation, this propylene/1-butene copolymer will be abbreviated as "PBR-2".
ＰＢＲ－２の１－ブテン含量（Ｍ）は１５モル％、メルトフローレート（ＭＦＲ）は６.７ｇ／１０分、分子量分布（Ｍｗ／Ｍｎ）は２.１２、融点（Ｔｍ）は９８.４℃であった。 The 1-butene content (M) of PBR-2 is 15 mol%, the melt flow rate (MFR) is 6.7 g/10 min, the molecular weight distribution (Mw/Mn) is 2.12, and the melting point (Tm) is 98.4. It was ℃.
〔プロピレン系重合体（Ｃ）〕
プロピレン系重合体として、以下の共重合体を用いた。
（１）プロピレン・エチレン・１－ブテンランダム共重合体〔ｔｅｒＰＰ〕
プロピレンターポリマー（ＭＦＲ（２３０℃、２．１６ｋｇ荷重、ＡＳＴＭ Ｄ１２３８に準拠）：５．５ｇ／１０ｍｉｎ、融点：１３２℃、プロピレン含量：９１モル％）。
[Propylene polymer (C)]
The following copolymers were used as propylene polymers.
(1) Propylene/ethylene/1-butene random copolymer [terPP]
Propylene terpolymer (MFR (230° C., 2.16 kg load, according to ASTM D1238): 5.5 g/10 min, melting point: 132° C., propylene content: 91 mol%).
実施例および比較例で用いた（共）重合体の各物性値の測定方法を以下に示す。 The method for measuring each physical property value of the (co)polymer used in Examples and Comparative Examples is shown below.
［分子量分布（Ｍｗ／Ｍｎ）］
分子量分布（Ｍｗ／Ｍｎ）は、Ｗａｔｅｒｓ社製ゲル浸透クロマトグラフＡｌｌｉａｎｃｅ ＧＰＣ－２０００型を用い、以下のようにして測定した。分離カラムとしては、東ソー社製のＴＳＫｇｅｌ（登録商標）ＧＮＨ６－ＨＴを２本およびＴＳＫｇｅｌ（登録商標）ＧＮＨ６－ＨＴＬを２本用い、カラムサイズはいずれも直径７.５ｍｍ、長さ３００ｍｍとし、カラム温度は１４０℃とし、移動相にはｏ－ジクロロベンゼン（和光純薬工業社製）および酸化防止剤としてＢＨＴ（武田薬品社製）０.０２５質量％を用い、１.０ｍｌ／分で移動させ、試料濃度は１５ｍｇ／１０ｍＬとし、試料注入量は５００マイクロリットルとし、検出器として示差屈折計を用いた。標準ポリスチレンは、分子量Ｍｗ＜１０３およびＭｗ＞４×１０６については東ソー社製を用い、１０３≦Ｍｗ≦４×１０６についてはプレッシャーケミカル社製を用いた。
[Molecular weight distribution (Mw/Mn)]
The molecular weight distribution (Mw/Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. As separation columns, two TSKgel (registered trademark) GNH6-HT and two TSKgel (registered trademark) GNH6-HTL manufactured by Tosoh Corporation were used, and the column sizes were 7.5 mm in diameter and 300 mm in length. The temperature was 140°C, and the mobile phase contained o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.025% by mass of BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant, and the mixture was moved at a rate of 1.0 ml/min. The sample concentration was 15 mg/10 mL, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene was manufactured by Tosoh Corporation for molecular weights Mw<103 and Mw>4×106, and manufactured by Pressure Chemical Co., Ltd. for 103≦Mw≦4×106.
［重合体のエチレン、プロピレン、α－オレフィン含量］
エチレン、プロピレン、α－オレフィン含量の定量は、日本電子（株）製ＪＮＭ ＧＸ－５００型ＮＭＲ測定装置を用いて、以下のようにして測定した。試料０.３５ｇをヘキサクロロブタジエン２.０ｍｌに加熱溶解させた。この溶液をグラスフィルター（Ｇ２）で濾過した後、重水素化ベンゼン０.５ｍｌを加え、内径１０ｍｍのＮＭＲチューブに装入して、１２０℃で13Ｃ－ＮＭＲ測定を行った。積算回数は、１０,０００回以上とした。得られた13Ｃ－ＮＭＲスペクトルにより、エチレン、プロピレン、α－オレフィンの組成を定量化した。
[Ethylene, propylene, α-olefin content of polymer]
The contents of ethylene, propylene, and α-olefin were determined using a JNM GX-500 type NMR measuring device manufactured by JEOL Ltd. as follows. 0.35 g of the sample was heated and dissolved in 2.0 ml of hexachlorobutadiene. After filtering this solution with a glass filter (G2), 0.5 ml of deuterated benzene was added, and the mixture was placed in an NMR tube with an inner diameter of 10 mm, and 13 C-NMR measurement was performed at 120°C. The number of times of integration was 10,000 times or more. The composition of ethylene, propylene, and α-olefin was quantified from the obtained 13 C-NMR spectrum.
［プロピレン系重合体（Ａ）およびプロピレン系重合体（Ｃ）の融点（Ｔｍ）］
パーキンエルマー社製ＤＳＣ８０００を用い、窒素雰囲気下（２０ｍｌ／ｍｉｎ）、約５ｍｇの試料を２００℃まで昇温・１０分間保持し、その後１０℃／分で－１００℃まで冷却した。－１００℃で１分間保持した後、１０℃／分で２００℃まで昇温させた時の結晶溶融ピークのピーク頂点から融点（Ｔｍ）を求めた。
[Melting point (Tm) of propylene polymer (A) and propylene polymer (C)]
Using PerkinElmer's DSC8000, about 5 mg of the sample was heated to 200° C. and held for 10 minutes under a nitrogen atmosphere (20 ml/min), and then cooled to −100° C. at 10° C./min. After holding at -100°C for 1 minute, the temperature was raised to 200°C at a rate of 10°C/min, and the melting point (Tm) was determined from the peak apex of the crystal melting peak.
［プロピレン系共重合体（Ｂ）の融点（Ｔｍ）］
セイコーインスツル社製ＤＳＣを用い、測定用アルミパンに約５ｍｇの試料をつめて、１００℃／ｍｉｎで２００℃まで昇温し、２００℃で５分間保持し、その後１０℃／ｍｉｎで－１００℃まで降温し、次いで１０℃／ｍｉｎで２００℃まで昇温し、その吸熱曲線より融点（Ｔｍ）を求めた。
[Melting point (Tm) of propylene copolymer (B)]
Using a Seiko Instruments DSC, approximately 5 mg of a sample was packed in an aluminum pan for measurement, heated at 100°C/min to 200°C, held at 200°C for 5 minutes, and then heated to -100°C at 10°C/min. The temperature was lowered to .degree. C., then raised to 200.degree. C. at a rate of 10.degree. C./min, and the melting point (Tm) was determined from the endothermic curve.
［メルトフローレート（ＭＦＲ）］
メルトフローレート（ＭＦＲ）は、ＡＳＴＭ Ｄ１２３８に準拠し、２３０℃、２.１６ｋｇ荷重下にて測定を行った。
[Melt flow rate (MFR)]
The melt flow rate (MFR) was measured at 230° C. under a load of 2.16 kg in accordance with ASTM D1238.
実施例および比較例で得られた延伸フィルムの物性は、以下の測定方法で行った。 The physical properties of the stretched films obtained in Examples and Comparative Examples were measured using the following measurement method.
〔引張弾性率〕
ＪＩＳ Ｋ７１２７に準拠し、試験片タイプ２（幅１５ｍｍ）を用いた。測定には、株式会社島津製作所ＡＧ－Ｘ－５を用いて、２３℃で、スパン間：１００ｍｍ、引張り速度２００ｍｍ／ｍｉｎで延伸フィルムを引張り〔Ｔ－ダイにおける押出方向（ＭＤ）〕、引張弾性率は、５回の平均値をとった。
[Tensile modulus]
In accordance with JIS K7127, test piece type 2 (width 15 mm) was used. For the measurement, using Shimadzu Corporation AG-X-5, the stretched film was pulled at 23°C with a span of 100 mm and a pulling speed of 200 mm/min [extrusion direction (MD) in the T-die], and tensile elasticity. The rate was the average value of 5 times.
〔熱収縮率〕
延伸フィルムを１０ｍｍ×１００ｍｍ（延伸方向）にスリットして得た試験サンプルをオーブンを用い、１００℃、１３０℃、１４０℃、１５０℃、１６０℃、１７０℃の空気雰囲気下に１分間静置し、この熱処理前後のフィルム寸法差を元の寸法で割り、熱収縮率として算出した。
[Heat shrinkage rate]
A test sample obtained by slitting a stretched film into 10 mm x 100 mm (stretching direction) was placed in an oven at 100°C, 130°C, 140°C, 150°C, 160°C, and 170°C in an air atmosphere for 1 minute. The difference in film dimensions before and after this heat treatment was divided by the original dimensions to calculate the heat shrinkage rate.
〔自然収縮率〕
延伸フィルムの自然収縮率は、熱収縮率試験と同寸法の試験サンプルを、オーブンを用いて４０℃、空気雰囲気下、常圧の条件で７日間熱処理し、熱処理前後のフィルム寸法差を元の寸法で割り、自然収縮率として算出した。
[Natural shrinkage rate]
The natural shrinkage rate of a stretched film is determined by heat-treating a test sample with the same dimensions as the heat shrinkage rate test in an oven at 40°C under an air atmosphere and normal pressure for 7 days, and calculating the difference in film dimensions before and after heat treatment from the original. The natural shrinkage rate was calculated by dividing by the dimensions.
［実施例１］
プロピレン単独重合体（Ａ－１）８０質量％および調製例１で得たプロピレン・１－ブテン共重合体（Ｂ－１）〔ＰＢＲ－１〕２０質量％を造粒機（モダンマシナリー社製 Ｅ－４０）によってブレンドして造粒した。ついで、得られたペレット（組成物）をキャストフィルム成形機（モダンマシナリー社製）によって２００℃で押出しながら、厚さ３５０μｍの単層フィルムを作成した。
[Example 1]
80% by mass of the propylene homopolymer (A-1) and 20% by mass of the propylene/1-butene copolymer (B-1) [PBR-1] obtained in Preparation Example 1 were mixed using a granulator (Modern Machinery Co., Ltd. E). -40) and granulated. Then, the obtained pellets (composition) were extruded at 200° C. using a cast film molding machine (manufactured by Modern Machinery Co., Ltd.) to form a single-layer film with a thickness of 350 μm.
このフィルムから９ｃｍ角の試験片を切り出し、二軸延伸試験機（ブルックナー社製）を用いて同時二軸延伸した。１３０℃で、１分間予熱した後、同温度で、１０ｍ／分の速度で二軸方向へ５倍に延伸した。その後、室温で３０秒間応力緩和させた後に延伸フィルムサンプルとして機器から取り外した。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
A 9 cm square test piece was cut out from this film and subjected to simultaneous biaxial stretching using a biaxial stretching tester (manufactured by Bruckner). After preheating at 130° C. for 1 minute, the film was stretched 5 times in biaxial directions at the same temperature at a speed of 10 m/min. Thereafter, the stress was relaxed for 30 seconds at room temperature, and then removed from the equipment as a stretched film sample.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
［実施例２］
実施例１で得た単層フィルムを用いて、予熱温度、および延伸温度を１２０℃で二軸延伸フィルムを得た。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
[Example 2]
Using the monolayer film obtained in Example 1, a biaxially stretched film was obtained at a preheating temperature and a stretching temperature of 120°C.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
［実施例３〕
実施例１で用いたプロピレン・１－ブテン共重合体（Ｂ－１）〔ＰＢＲ－１〕に替えて、調整例２で得たプロピレン・１－ブテン共重合体（Ｂ－２）〔ＰＢＲ－２〕を用いる以外は実施例１と同様に行い、二軸延伸フィルムを得た。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
[Example 3]
In place of the propylene/1-butene copolymer (B-1) [PBR-1] used in Example 1, the propylene/1-butene copolymer (B-2) [PBR-1] obtained in Preparation Example 2 was used. A biaxially stretched film was obtained in the same manner as in Example 1 except that 2] was used.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
［実施例４］
実施例３で用いたプロピレン・１－ブテン共重合体（Ｂ－１）〔ＰＢＲ－１〕に替えて、調整例２で得たプロピレン・１－ブテン共重合体（Ｂ－２）〔ＰＢＲ－２〕を用いる以外は実施例３と同様に行い、二軸延伸フィルムを得た。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
[Example 4]
In place of the propylene/1-butene copolymer (B-1) [PBR-1] used in Example 3, the propylene/1-butene copolymer (B-2) [PBR-1] obtained in Preparation Example 2 was used. A biaxially stretched film was obtained in the same manner as in Example 3 except that 2] was used.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
［比較例１］
実施例１で用いた組成物に替えて、プロピレン単独重合体（Ａ－１）を単独で用い、予熱温度および延伸温度を１５８℃とする以外は、実施例１と同様に行い、二軸延伸フィルムを得た。
[Comparative example 1]
The same procedure as in Example 1 was carried out except that propylene homopolymer (A-1) was used alone in place of the composition used in Example 1, and the preheating temperature and stretching temperature were 158°C. Got the film.
プロピレン単独重合体（Ａ－１）を単独では実施例１および実施例２で採用した１２０～１３０℃の温度では、延伸できないので１５８℃で行った。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
Propylene homopolymer (A-1) alone could not be stretched at the temperature of 120 to 130°C employed in Examples 1 and 2, so the stretching was carried out at 158°C.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
［比較例２］
比較例１の予熱温度および延伸温度に替えて、予熱温度および延伸温度を１４０℃に替える以外は、比較例２と同様に行い延伸フィルムを得た。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
[Comparative example 2]
A stretched film was obtained in the same manner as Comparative Example 2, except that the preheating temperature and stretching temperature of Comparative Example 1 were changed to 140°C.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
［比較例３］
実施例１で用いた組成物に替えて、プロピレン・エチレン・１－ブテンランダム共重合体〔ｔｅｒＰＰ〕を単独で用い、予熱温度および延伸温度を９０℃とする以外は、実施例１と同様に行い、二軸延伸フィルムを得た。
得られた延伸フィルムの物性を上記記載の方法で評価した。評価結果を表１に示す。
[Comparative example 3]
The same procedure as in Example 1 was carried out, except that propylene/ethylene/1-butene random copolymer [terPP] was used alone in place of the composition used in Example 1, and the preheating temperature and stretching temperature were 90°C. A biaxially stretched film was obtained.
The physical properties of the obtained stretched film were evaluated by the method described above. The evaluation results are shown in Table 1.
表１から明らかなように、実施例１～４で得られた延伸フィルムは、加熱温度が１４０℃でも熱収縮し、加熱温度が１６０～１７０℃では熱収縮率が３０～５０％と大きく収縮しており、自然収縮率も低く、引張弾性率は１．５ＧＰａを超えている。 As is clear from Table 1, the stretched films obtained in Examples 1 to 4 were thermally shrunk even at a heating temperature of 140°C, and the thermal shrinkage rate was as high as 30 to 50% at a heating temperature of 160 to 170°C. It has a low natural shrinkage rate and a tensile modulus of over 1.5 GPa.
それに対し、プロピレン単独重合体から得られる延伸フィルム（比較例１、２）は。自然収縮率は低く、引張弾性率は高いものの、１３０～１７０℃の加熱温度での熱収縮率が低い。 In contrast, stretched films obtained from propylene homopolymer (Comparative Examples 1 and 2). Although the natural shrinkage rate is low and the tensile modulus is high, the heat shrinkage rate at heating temperatures of 130 to 170°C is low.
一方、融点が１３２℃と低いプロピレン・エチレン・１－ブテンランダム共重合体から得られる延伸フィルム（比較例３）は、加熱温度が１００℃でも熱収縮率は４０％と低温熱収縮性に優れるが、自然収縮率が大きく、引張弾性率も低い。 On the other hand, the stretched film obtained from a propylene/ethylene/1-butene random copolymer with a low melting point of 132°C (Comparative Example 3) has excellent low-temperature heat shrinkability with a heat shrinkage rate of 40% even at a heating temperature of 100°C. However, the natural shrinkage rate is large and the tensile modulus is low.
本発明に係る延伸フィルムは食品容器、産業部材の集積包装時に十分な加熱収縮率によって物品の集積を可能とし、十分な剛性をもって外部からの変形に対し内容物を保護することに加え、フィルム加工、包装工程におけるハンドリング性に優れる延伸フィルムとして用いることができる。 The stretched film according to the present invention has a sufficient heat shrinkage rate to enable the stacking of food containers and industrial components when stacking and packaging them, and has sufficient rigidity to protect the contents from external deformation. , it can be used as a stretched film with excellent handling properties in packaging processes.
Claims (7)
縦方向（ＭＤ）の引張弾性率が１．５ＧＰａ以上であり、
１３０℃で１分間加熱した際の熱収縮率が１０％以上であり、
４０℃雰囲気下で７日間保管後の縦および横の収縮率がいずれも２．５％以下であることを特徴とする延伸フィルム。 40 to 90% by mass of a propylene polymer (A) having a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 150 to 180°C, and a melting point (Tm) measured by differential scanning calorimetry (DSC) 10 to 60% by mass of a propylene copolymer (B) having a Tm) of less than 120° C. or no observed melting point [however, the total of (A) and (B) is 100% by mass. [However, after prepolymerizing 3-methyl-1-butene (3MB-1) as a nucleating component, the melting point of homopolymerizing propylene is 167 °C, MFR (230 °C, 2.16 kg Load)=2g/10min, mmmm fraction=0.972, 50% by mass of high melting point propylene resin, and propylene and 23.5mol% of 1-butene were copolymerized with a melting point of 78°C and MFR (230°C). , 2.16 kg load) = 7 g/10 min. (excluding combined compositions) ;
The tensile modulus in the machine direction (MD) is 1.5 GPa or more,
Thermal shrinkage rate when heated at 130°C for 1 minute is 10% or more,
A stretched film having a vertical and horizontal shrinkage rate of 2.5% or less after being stored in an atmosphere at 40°C for 7 days .
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| JP2004059652A (en) | 2002-07-25 | 2004-02-26 | Mitsui Chemicals Inc | Polypropylene resin composition and polypropylene stretched film improved in stretchability and its manufacturing method |
| JP2010087253A (en) | 2008-09-30 | 2010-04-15 | Mitsui Chemicals Inc | Capacitor film |
| JP2014169446A (en) | 2007-11-13 | 2014-09-18 | Prime Polymer Co Ltd | Propylene resin composition for stretched sheet, and stretched sheet and thermo-formed body including the same |
| WO2015064653A1 (en) | 2013-10-31 | 2015-05-07 | 出光興産株式会社 | Polyolefin composition, oriented polyolefin film, and production method for same |
| WO2017018461A1 (en) | 2015-07-28 | 2017-02-02 | 出光興産株式会社 | Monoaxially stretched molded article and method for producing same |
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| JP2004059652A (en) | 2002-07-25 | 2004-02-26 | Mitsui Chemicals Inc | Polypropylene resin composition and polypropylene stretched film improved in stretchability and its manufacturing method |
| JP2014169446A (en) | 2007-11-13 | 2014-09-18 | Prime Polymer Co Ltd | Propylene resin composition for stretched sheet, and stretched sheet and thermo-formed body including the same |
| JP2010087253A (en) | 2008-09-30 | 2010-04-15 | Mitsui Chemicals Inc | Capacitor film |
| WO2015064653A1 (en) | 2013-10-31 | 2015-05-07 | 出光興産株式会社 | Polyolefin composition, oriented polyolefin film, and production method for same |
| WO2017018461A1 (en) | 2015-07-28 | 2017-02-02 | 出光興産株式会社 | Monoaxially stretched molded article and method for producing same |
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