JP4915749B2 - Polyolefin multilayer shrink film - Google Patents
Polyolefin multilayer shrink filmInfo
- Publication number
- JP4915749B2 JP4915749B2 JP2008221985A JP2008221985A JP4915749B2 JP 4915749 B2 JP4915749 B2 JP 4915749B2 JP 2008221985 A JP2008221985 A JP 2008221985A JP 2008221985 A JP2008221985 A JP 2008221985A JP 4915749 B2 JP4915749 B2 JP 4915749B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- film
- shrink film
- inner layer
- multilayer shrink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006300 shrink film Polymers 0.000 title claims description 30
- 229920000098 polyolefin Polymers 0.000 title claims description 28
- 239000010410 layer Substances 0.000 claims description 68
- 239000004743 Polypropylene Substances 0.000 claims description 39
- -1 polypropylene Polymers 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 229920001155 polypropylene Polymers 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 239000002344 surface layer Substances 0.000 claims description 14
- 229920013716 polyethylene resin Polymers 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 229920005604 random copolymer Polymers 0.000 claims description 7
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 description 70
- 238000007789 sealing Methods 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 14
- 238000000137 annealing Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005678 polyethylene based resin Polymers 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は収縮包装材料に関し、より詳しくは、腰強度と低温収縮性が共に優れ、自動包装機における高速包装機適性と収縮包装仕上がり性を保持しつつ、溶断シール時のシール線が良好なポリオレフィン系多層シュリンクフィルムに関する。 The present invention relates to shrink wrapping materials, and more specifically, polyolefin having excellent waist strength and low-temperature shrinkability, and maintaining good suitability for high-speed wrapping machines and finish of shrink wrapping in an automatic wrapping machine, and having a good seal line during fusing sealing The present invention relates to a multilayer shrink film.
従来、熱収縮性包装材料として、ポリ塩化ビニル系フィルム、ポリプロピレン系フィルム、ポリエチレン系フィルム等が知られているが、低価格、使用後の廃棄処理の容易さなどの点でポリプロピレン、ポリエチレン等のポリオレフィン系シュリンクフィルムが好んで用いられている。しかしながら、ポリプロピレン系シュリンクフィルムは腰強度、耐熱性等に優れるものの、低温収縮性、耐衝撃性、耐引裂性に乏しい等の欠点を有している。一方、ポリエチレン系シュリンクフィルムは、低温収縮性、耐衝撃性、耐引裂性等に優れるものの、腰強度、耐熱性に乏しい等の欠点を有している。このような問題を解決すべく、ポリプロピレン系樹脂を両表面層に、ポリエチレン系樹脂を内部層に用いたポリオレフィン系多層シュリンクフィルムが開示(特許文献1)されている。
これらポリオレフィン系多層シュリンクフィルムは、低温収縮性と耐熱性に優れているため、美麗な収縮包装仕上がりが得られると共に、耐衝撃性、耐引裂性も比較的高いという特徴を有している。しかしながら、腰強度と低温収縮性という特性を両立させることは難しいという問題点があった。
Conventionally, polyvinyl chloride films, polypropylene films, polyethylene films, and the like are known as heat-shrinkable packaging materials. However, polypropylene, polyethylene, etc. are low in terms of cost and ease of disposal after use. Polyolefin shrink films are preferred. However, although the polypropylene-based shrink film is excellent in waist strength, heat resistance, etc., it has drawbacks such as poor low temperature shrinkage, impact resistance, and tear resistance. On the other hand, the polyethylene-based shrink film is excellent in low-temperature shrinkage, impact resistance, tear resistance, and the like, but has drawbacks such as poor waist strength and heat resistance. In order to solve such problems, a polyolefin multilayer shrink film using a polypropylene resin as both surface layers and a polyethylene resin as an inner layer is disclosed (Patent Document 1).
Since these polyolefin multilayer shrink films are excellent in low-temperature shrinkage and heat resistance, they have a feature that a beautiful shrink-wrapped finish is obtained and that impact resistance and tear resistance are relatively high. However, there is a problem that it is difficult to achieve both the properties of waist strength and low-temperature shrinkability.
本出願人は、先に、かかる欠点を有しない、腰強度と低温収縮性が共に優れたポリオレフィン系多層シュリンクフィルム(特許文献2)を提案した。該シュリンクフィルムは、自動包装機における高速包装機適性と収縮包装仕上がり性を両立させたものであるが、包装機としてL型シール式半折包装機を用いた場合には、溶断シール時に包装機のシールバーと受け台に樹脂が付着する事によって、フィルムとシールバーの間に溶融樹脂が糸のようになり(以下、糸引きという)、シール線が汚くなり、包装体の見栄えが悪くなるという問題があった。
本発明は、上記状況を鑑みてなされたもので、腰強度と低温収縮性が共に優れ、自動包
装機における高速包装機適性と収縮包装仕上がり性を保持しつつ、溶断シール時のシール
線も良好で、包装体の見栄えの良いポリオレフィン系多層シュリンクフィルムを提供する
ことを課題とする。
The present invention has been made in view of the above circumstances, and has excellent waist strength and low-temperature shrinkability, and maintains high-speed packaging machine suitability and shrink-wrapping finish in an automatic packaging machine, and also has a good seal line during fusing sealing. Thus, an object of the present invention is to provide a polyolefin-based multilayer shrink film having a good package appearance.
本発明者らは、前記の問題点を解決すべく鋭意検討した結果、内部層にプロピレン/3
-メチルブテン−1コポリマー共重合体を添加する事で、課題を解決できることを見い出
し、本発明に到達した。
すなわち本発明は、
(1)示差走査熱量計(以下DSCと記す)によって測定される融解ピーク温度が135〜165℃、メルトフローレート(以下MFRと記す。測定温度230℃、荷重2.16kgf)が1.0〜10.0g/10分であるポリプロピレン系樹脂(A)からなる両表面層(X)と、DSCによって測定される融解ピーク温度が110〜135℃であり、メタロセン触媒によって重合された結晶性プロピレン−α−オレフィンランダム共重合体(B;以下、メタロセンPPと記す)を主体とする内部層(Y)と、23℃における密度が0.900〜0.940g/cm3のポリエチレン系樹脂(C)を主体とする内部層(Z)を含有し、縦横それぞれ3倍以上に延伸した、少なくとも4層以上からなるポリオレフィン系多層多層シュリンクフィルムであって、前記内部層(Y)及び/又は前記内部層(Z)に、プロピレン/3-メチルブテン−1共重合体(D)が0.5〜10重量%添加されたものである、ポリオレフィン系多層シュリンクフィルム、
(2)内部層(Y)の厚みが全体の10%以上45%以下であり、両表面層の厚みが各々1μm以上である、上記(1)記載のポリオレフィン系多層シュリンクフィルム、
(3)ポリプロピレン系樹脂(A)が、結晶性プロピレン−α−オレフィンランダム共重
合体である、上記(1)乃至(2)のいずれか一に記載のポリオレフィン系多層シュリン
クフィルム、
(4)ポリエチレン系樹脂(C)が、直鎖状低密度ポリエチレンである、上記(1)乃至
(3)のいずれか一に記載のポリオレフィン系多層シュリンクフィルム、
(5)ポリプロピレン系樹脂(A)の融解ピーク温度(Tma)とメタロセンPP(B)
の融解ピーク温度(Tmb)との差(Tma−Tmb)が10℃以上である、上記(1)
乃至(4)のいずれか一に記載のポリオレフィン系多層シュリンクフィルム、
(6)ポリオレフィン系多層シュリンクフィルムが、下記特性(1)、(2)を同時に満
足するものである、上記(1)乃至(5)のいずれか一に記載のポリオレフィン系多層シ
ュリンクフィルム、
特性(1):MD、TD引張弾性率がそれぞれ0.80GPa以上。
特性(2):100℃におけるMD、TD熱収縮率の平均値が25%以上、
(7)前記延伸において、縦と横の延伸倍率の値の差が0.2以下で、縦横の延伸倍率が各4.3倍以上である上記(1)乃至(6)のいずれか一に記載のポリオレフィン系多層シュリンクフィルム、
を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have found that propylene / 3 is contained in the inner layer.
The inventors have found that the problem can be solved by adding a methylbutene-1 copolymer copolymer, and have reached the present invention.
That is, the present invention
(1) Melting peak temperature measured by a differential scanning calorimeter (hereinafter referred to as DSC) is 135 to 165 ° C., and melt flow rate (hereinafter referred to as MFR; measuring temperature 230 ° C., load 2.16 kgf) is 1.0 to Both surface layers (X) made of polypropylene resin (A) at 10.0 g / 10 min, a crystalline propylene polymerized by a metallocene catalyst having a melting peak temperature measured by DSC of 110 to 135 ° C. An inner layer (Y) mainly composed of an α-olefin random copolymer (B; hereinafter referred to as metallocene PP), and a polyethylene resin (C) having a density of 0.900 to 0.940 g / cm 3 at 23 ° C. A polyolefin-based multilayer multilayer shrink film comprising at least four layers, which contains an inner layer (Z) mainly composed of bismuth and stretched at least three times in length and width. And 0.5 to 10% by weight of propylene / 3-methylbutene-1 copolymer (D) is added to the inner layer (Y) and / or the inner layer (Z). Polyolefin multilayer shrink film,
(2) The polyolefin-based multilayer shrink film according to (1), wherein the thickness of the inner layer (Y) is 10% or more and 45% or less of the whole, and the thicknesses of both surface layers are each 1 μm or more,
(3) The polyolefin-based multilayer shrink film according to any one of (1) to (2), wherein the polypropylene-based resin (A) is a crystalline propylene-α-olefin random copolymer,
(4) The polyolefin-based multilayer shrink film according to any one of (1) to (3), wherein the polyethylene-based resin (C) is a linear low-density polyethylene,
(5) Melting peak temperature (Tma) of polypropylene resin (A) and metallocene PP (B)
The difference (Tma−Tmb) from the melting peak temperature (Tmb) is 10 ° C. or higher (1)
Thru | or the polyolefin-type multilayer shrink film as described in any one of thru | or (4),
(6) The polyolefin multilayer shrink film according to any one of the above (1) to (5), wherein the polyolefin multilayer shrink film satisfies the following characteristics (1) and (2) simultaneously:
Characteristic (1): MD and TD tensile elastic moduli are each 0.80 GPa or more.
Characteristic (2): MD, TD heat shrinkage average value at 100 ° C. is 25% or more,
(7) In any one of the above (1) to (6), in the stretching, the difference between the longitudinal and lateral stretching ratios is 0.2 or less, and the longitudinal and lateral stretching ratios are each 4.3 times or more. The polyolefin-based multilayer shrink film as described,
Is to provide.
本発明のポリオレフィン系多層シュリンクフィルムは、両表面層に腰強度と耐熱性に優
れた特定のポリプロピレン系樹脂からなる層を、内部層に腰強度と低温収縮性に優れた特
定のメタロセンPPを主体とする層と低温収縮性と耐引裂性に優れた特定のポリエチレン
系樹脂を主体とする層を設けるとともに、内部層に、プロピレン/3-メチルブテン−1
共重合体を添加する事で、腰強度と低温収縮性が共に優れ、自動包装機における高速包装
機適性と収縮包装仕上がり性とを両立するとともに、L型シール式半折包装機を用いて包
装しても、溶断シール時のシール線も良好で、収縮包装後にもクラウドを発生しない包装体の見栄えが良い、という効果を奏する
。
The polyolefin-based multilayer shrink film of the present invention is mainly composed of a layer made of a specific polypropylene resin excellent in waist strength and heat resistance on both surface layers, and a specific metallocene PP excellent in waist strength and low-temperature shrinkability as an inner layer. And a layer mainly composed of a specific polyethylene-based resin excellent in low-temperature shrinkage and tear resistance, and propylene / 3-methylbutene-1
By adding a copolymer, both waist strength and low-temperature shrinkability are excellent, and both high-speed packaging machine suitability and shrink-wrapping finish in an automatic packaging machine are compatible, and packaging is performed using an L-shaped seal-type half-fold packaging machine. However, the sealing line at the time of fusing sealing is also good, and there is an effect that the appearance of the package that does not generate a cloud after shrink wrapping is good.
以下、本発明を詳細に説明する。
本発明において、両表面層(X)に用いられるポリプロピレン系樹脂(A)は、DSC
によって測定される融解ピーク温度が135〜165℃、MFRが1.0〜10.0g/
10分の範囲のもので、ポリプロピレン単独重合体、プロピレンとα−オレフィンの共重
合体、例えばプロピレン−エチレン、プロピレン−ブテン共重合体等、及びプロピレン−
エチレン−ブテン3元共重合体の中から選ばれる少なくとも1種以上からなり、主に耐熱
性、腰強度を付与する作用を成す。これらの内、耐熱性、腰強度と熱収縮特性のバランス
を考慮して、結晶性プロピレン−α−オレフィンランダム共重合体が好適に用いられる。
ポリプロピレン系樹脂(A)の融解ピーク温度が135℃未満では耐熱性が低いため好
ましくなく、165℃を超えると低温収縮性が低下するため好ましくない。また、MFR
が1.0g/10分未満では、溶融押出時のモーター負荷が高くなる等の問題点があり、
10.0g/10分を超えると溶断シール性が低下するため好ましくない。
Hereinafter, the present invention will be described in detail.
In the present invention, the polypropylene resin (A) used for both surface layers (X) is DSC.
The melting peak temperature measured by is 135 to 165 ° C., and the MFR is 1.0 to 10.0 g /
In the range of 10 minutes, polypropylene homopolymers, copolymers of propylene and α-olefins such as propylene-ethylene, propylene-butene copolymers, and propylene-
It consists of at least one selected from ethylene-butene terpolymers, and mainly serves to impart heat resistance and waist strength. Among these, a crystalline propylene-α-olefin random copolymer is preferably used in consideration of the balance of heat resistance, waist strength and heat shrinkage characteristics.
When the melting peak temperature of the polypropylene resin (A) is less than 135 ° C., the heat resistance is low, which is not preferable. When the melting temperature exceeds 165 ° C., the low temperature shrinkability is decreased, which is not preferable. Also, MFR
Is less than 1.0 g / 10 min, there are problems such as high motor load during melt extrusion,
Exceeding 10.0 g / 10 minutes is not preferable because the fusing and sealing properties are reduced.
両表面層(X)の厚みは、各々1μm以上が好ましく、1μm未満では、溶断シール性
、耐熱性、腰強度が低下する恐れがある。
The thicknesses of both surface layers (X) are each preferably 1 μm or more, and if it is less than 1 μm, the fusing sealing properties, heat resistance, and waist strength may be reduced.
表面層(X)には、希望により、滑剤、ブロッキング防止剤、帯電防止剤、防曇剤、酸
化防止剤等の添加剤がそれぞれの有効な作用を具備させる目的で適宜使用することができ
る。
In the surface layer (X), additives such as a lubricant, an antiblocking agent, an antistatic agent, an antifogging agent, and an antioxidant can be appropriately used for the purpose of providing each effective action as desired.
本発明の内部層(Y)の主体であるメタロセンPP(B)は、メタロセン触媒によって
重合された結晶性プロピレン−α−オレフィンランダム共重合体であり、コモノマーが主
鎖に導入されたものである。この触媒で重合したポリマーは、狭い分子量分布、狭い結晶
性分布、均一なコモノマー組成分布を有している。このようなメタロセンPPは、例えば
特開2001−240711号公報、特開2002−60566号公報等に記載の方法に
より製造することができる。プロピレンと共重合されるα−オレフィンとしては、エチレ
ン、または炭素数4〜20のα−オレフィン或いはこれらの混合物が挙げられるが、好ま
しくはエチレンとの共重合体が用いられる。
メタロセンPP(B)は、融解ピーク温度が110〜135℃の範囲のものであり、1
10℃未満では多層フィルム全体としての耐熱性が低くなるため好ましくなく、135℃
を超えると低温収縮性が低下するため好ましくない。MFR(測定温度230℃、荷重2
.16kgf)は、0.5〜10.0g/10分のものが好適に用いられる。0.5g/
10分未満では溶融押出時のモーター負荷が高くなる等の問題点があり、10.0g/1
0分を超えると多層フィルム全体としての耐熱性が低くなるため好ましくない。
本発明に用いられるメタロセンPP(B)は、高腰強度、低温収縮性等の特性を有して
おり、ポリプロピレン系樹脂を両表面層に、ポリエチレン系樹脂を内部層に用いたポリオ
レフィン系多層シュリンクフィルムの内部層に用いることで高速包装機適性、且つ、収縮
包装仕上がり性を向上させる作用を成すことができる。
The metallocene PP (B) that is the main component of the inner layer (Y) of the present invention is a crystalline propylene-α-olefin random copolymer polymerized by a metallocene catalyst, and a comonomer is introduced into the main chain. . The polymer polymerized with this catalyst has a narrow molecular weight distribution, a narrow crystallinity distribution, and a uniform comonomer composition distribution. Such a metallocene PP can be produced by a method described in, for example, JP-A Nos. 2001-240711 and 2002-60566. Examples of the α-olefin copolymerized with propylene include ethylene, an α-olefin having 4 to 20 carbon atoms, or a mixture thereof. Preferably, a copolymer with ethylene is used.
Metallocene PP (B) has a melting peak temperature in the range of 110 to 135 ° C.
Less than 10 ° C is not preferable because the heat resistance of the entire multilayer film is lowered, and 135 ° C is not preferable.
Exceeding this is not preferable because the low-temperature shrinkage is reduced. MFR (measurement temperature 230 ° C, load 2
. As for 16 kgf), 0.5 to 10.0 g / 10 min is preferably used. 0.5g /
If it is less than 10 minutes, there is a problem that the motor load at the time of melt extrusion becomes high, and 10.0 g / 1
If it exceeds 0 minutes, the heat resistance of the multilayer film as a whole is lowered, which is not preferable.
The metallocene PP (B) used in the present invention has characteristics such as high waist strength and low temperature shrinkage, and is a polyolefin-based multilayer shrink using a polypropylene resin as both surface layers and a polyethylene resin as an inner layer. By using it as the inner layer of the film, it is possible to achieve the effect of improving the suitability of the high-speed packaging machine and the finish of shrink packaging.
本発明の内部層(Y)には、本発明の目的に支障をきたさない範囲で、メタロセンPP
(B)の他に、ポリプロピレン系樹脂あるいはポリエチレン系樹脂を混合することができ
る。混合できるポリプロピレン系樹脂、ポリエチレン系樹脂は、それぞれ両表面層(X)
に用いるポリプロピレン系樹脂(A)、内部層(Z)に用いるポリエチレン系樹脂(C)
と同じであり、スクラップの再利用として用いることもできる。これら樹脂を混合する場
合、メタロセンPP(B)の混合率としては、内部層(Y)の総重量に対して40重量%
以上となることが好ましい。40重量%未満では、腰強度、低温収縮性の向上レベルが低
くなるため好ましくない。
In the inner layer (Y) of the present invention, the metallocene PP is used within the range not hindering the object of the present invention.
In addition to (B), a polypropylene resin or a polyethylene resin can be mixed. Polypropylene resin and polyethylene resin that can be mixed are both surface layers (X)
Polypropylene resin (A) used for coating, polyethylene resin (C) used for inner layer (Z)
It can be used for scrap reuse. When these resins are mixed, the mixing ratio of the metallocene PP (B) is 40% by weight with respect to the total weight of the inner layer (Y).
It is preferable to become above. If it is less than 40% by weight, the improvement level of waist strength and low-temperature shrinkage is lowered, which is not preferable.
内部層(Y)の厚みは、全体の10%以上、45%以下が好ましく、10%未満では腰
強度と低温収縮性を両立できないため、また、45%を越えると耐引き裂き性が劣る場合
がある。
The thickness of the inner layer (Y) is preferably 10% or more and 45% or less of the whole, and if it is less than 10%, it is not possible to achieve both waist strength and low temperature shrinkage, and if it exceeds 45%, the tear resistance may be inferior. is there.
内部層(Y)には、希望により、滑剤、ブロッキング防止剤、帯電防止剤、防曇剤、酸
化防止剤等の添加剤がそれぞれの有効な作用を具備させる目的で適宜使用することができ
る。
In the inner layer (Y), additives such as a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, and an antioxidant can be appropriately used for the purpose of providing each effective action as desired.
内部層(Z)の主体であるポリエチレン系樹脂(C)は、23℃における密度が0.9
00〜0.940g/cm3の範囲のもので、長鎖分岐を有する低密度ポリエチレン、エ
チレンとブテン−1、ペンテン−1、ヘキセン−1、4−メチルペンテン−1、オクテン
−1を含む炭素数4〜20個のα−オレフィンとの共重合体である直鎖状低密度ポリエチ
レン、エチレン−酢酸ビニル共重合体、エチレン−脂肪族不飽和カルボン酸共重合体、エ
チレン−脂肪族不飽和カルボン酸エステル共重合体、アイオノマー樹脂から選ばれる少な
くとも1種以上からなり、低温収縮性、耐引裂性、耐衝撃性を付与する作用をなす。これ
らの内、優れた低温収縮性を付与できる点から直鎖状低密度ポリエチレンが好適に用いら
れる。
ポリエチレン系樹脂(C)の密度が0.900g/cm3未満では引張破断強度が低下
するため好ましくなく、0.940g/cm3を超えると低温収縮性が低下するため好ま
しくない。また、MFR(測定温度190℃、荷重2.16kgf)は、0.3〜5.0
g/10分のものが好適に用いられる。0.3g/10分未満では押出時のモーター負荷
が高くなる等の問題点があり、5.0g/10分を超えると延伸安定性が低下するため好
ましくない。
The polyethylene resin (C) which is the main component of the inner layer (Z) has a density at 0.9C of 0.9.
Low density polyethylene having a long chain branch, carbon containing ethylene and butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1 in a range of 00 to 0.940 g / cm 3 Linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-aliphatic unsaturated carboxylic acid copolymer, ethylene-aliphatic unsaturated carboxylic acid which is a copolymer with several to 20 α-olefins It consists of at least one selected from an acid ester copolymer and an ionomer resin, and has the effect of imparting low-temperature shrinkage, tear resistance, and impact resistance. Of these, linear low-density polyethylene is preferably used because it can impart excellent low-temperature shrinkage.
When the density of the polyethylene resin (C) is less than 0.900 g / cm 3 , the tensile strength at break is unfavorable, and when it exceeds 0.940 g / cm 3 , the low-temperature shrinkage property is undesirably lowered. Moreover, MFR (measurement temperature 190 degreeC, load 2.16kgf) is 0.3-5.0.
Those having g / 10 minutes are preferably used. If it is less than 0.3 g / 10 minutes, there is a problem that the motor load at the time of extrusion becomes high, and if it exceeds 5.0 g / 10 minutes, the stretching stability is lowered, which is not preferable.
本発明の内部層(Z)には、本発明の目的に支障をきたさない範囲で、ポリエチレン系
樹脂の他に、ポリプロピレン系樹脂、及びメタロセンPPを混合することができる。混合
するポリプロピレン系樹脂、メタロセンPPは、それぞれ両表面層(X)に用いるポリプ
ロピレン系樹脂(A)、内部層(Y)に用いるメタロセンPP(B)と同じであり、スク
ラップの再利用として用いることもできる。これら樹脂を混合する場合、ポリエチレン系
樹脂(C)の混合率としては、内部層(Z)の総重量に対して40重量%以上となること
が好ましい。40重量%未満では、低温収縮性、耐引裂性、耐衝撃性が低下するため好ま
しくない。
In the inner layer (Z) of the present invention, a polypropylene resin and a metallocene PP can be mixed in addition to the polyethylene resin as long as the object of the present invention is not hindered. The polypropylene resin and metallocene PP to be mixed are the same as the polypropylene resin (A) used for both surface layers (X) and the metallocene PP (B) used for the inner layer (Y), respectively, and should be used for scrap recycling. You can also. When these resins are mixed, the mixing ratio of the polyethylene resin (C) is preferably 40% by weight or more based on the total weight of the inner layer (Z). If it is less than 40% by weight, the low-temperature shrinkage, tear resistance and impact resistance are lowered, which is not preferable.
内部層(Z)の厚みは、全体の10%以上が好ましく、10%未満では低温収縮性、耐
引裂性が低下するため好ましくない。
The thickness of the inner layer (Z) is preferably 10% or more of the whole, and less than 10% is not preferable because the low-temperature shrinkage and tear resistance deteriorate.
内部層(Z)には、希望により、滑剤、ブロッキング防止剤、帯電防止剤、防曇剤、酸
化防止剤等の添加剤がそれぞれの有効な作用を具備させる目的で適宜使用することができ
る。
In the inner layer (Z), additives such as a lubricant, an antiblocking agent, an antistatic agent, an antifogging agent, and an antioxidant can be appropriately used for the purpose of providing each effective action as desired.
本発明において、内部層(Y)及び/又は内部層(Z)には、プロピレン/3-メチル
ブテン−1共重合体(D)が添加される。
共重合体(D)の添加量は、添加する層に対して0.5〜10重量%である。添加量が
0.5重量%未満では糸引きが発生し、シール線が汚くなり、包装体の見栄えが悪くなる
場合がある。一方、10重量%を超えると熱収縮性が劣り、良好な包装仕上がり性が得ら
れず包装体の見栄えが悪くなる場合がある。
共重合体(D)は、内部層に添加する事で、メタロセンPP、あるいは直鎖状低密度ポ
リエチレンの結晶化温度が上昇し、溶断シール時のフィルムとシールバーとの融着を抑制
し、溶断シール時の良好なシール線が得られるという作用をなす。
かかる共重合体(D)の具体例としては、プライムポリマー(株)F132等を例示す
ることができる。
In the present invention, propylene / 3-methylbutene-1 copolymer (D) is added to the inner layer (Y) and / or the inner layer (Z).
The addition amount of the copolymer (D) is 0.5 to 10% by weight with respect to the layer to be added. If the added amount is less than 0.5% by weight, stringing may occur, the seal line becomes dirty, and the appearance of the package may be deteriorated. On the other hand, if it exceeds 10% by weight, the heat shrinkability is inferior, and good packaging finish cannot be obtained, and the appearance of the package may be deteriorated.
By adding the copolymer (D) to the inner layer, the crystallization temperature of the metallocene PP or linear low-density polyethylene is increased, and the fusion between the film and the seal bar during fusing sealing is suppressed, An effect is obtained in that a good seal wire at the time of fusing sealing is obtained.
Specific examples of such a copolymer (D) include Prime Polymer F132.
本発明において、ポリプロピレン系樹脂(A)の融解ピーク温度(Tma)とメタロセ
ンPP(B)の融解ピーク温度(Tmb)との差(Tma−Tmb)は、10℃以上であ
ることが好ましい。10℃未満では、熱収縮特性が低下するため、良好な収縮包装仕上が
り性が得られるトンネル温度範囲が狭くなり、好ましくない。
In the present invention, the difference (Tma−Tmb) between the melting peak temperature (Tma) of the polypropylene resin (A) and the melting peak temperature (Tmb) of the metallocene PP (B) is preferably 10 ° C. or more. If it is less than 10 ° C., the heat shrinkage characteristics are deteriorated, so that the tunnel temperature range in which good shrinkage packaging finish can be obtained becomes narrow, which is not preferable.
本発明のポリオレフィン系多層シュリンクフィルムは、下記特性(1)、(2)を同時
に満足するものであることが好ましい。
特性(1):MD、TD引張弾性率がそれぞれ0.80GPa以上。
特性(2):100℃におけるMD、TD熱収縮率の平均値が25%以上。
特性(1)、(2)を同時に満足しないものは、高速包装機適性、収縮包装仕上がり性
の両立レベルが低いため、好ましくない。
The polyolefin multilayer shrink film of the present invention preferably satisfies the following characteristics (1) and (2) at the same time.
Characteristic (1): MD and TD tensile elastic moduli are each 0.80 GPa or more.
Characteristic (2): The average value of MD and TD thermal shrinkage at 100 ° C. is 25% or more.
What does not satisfy the characteristics (1) and (2) at the same time is not preferable because the compatibility level of high-speed packaging machine suitability and shrink packaging finish is low.
本発明において、内部層は必ずしも2層である必要はなく、必要に応じて2層以上にす
ることができ、全体として4層以上の層構成を採用することができる。例えばX/Y/Z
/Xの4層構成、X/Y/Z/Y/X、X/Z/Y/Z/Xの5層構成、X/Y/Z/Y
/Z/Xの6層構成等の層構成が挙げられるが、フィルムのカール現象を防止する観点か
らは対称構成であることが好ましい。
In the present invention, the inner layer does not necessarily have to be two layers, and can be formed into two or more layers as necessary, and a layer configuration of four or more layers as a whole can be adopted. For example, X / Y / Z
/ X 4 layer configuration, X / Y / Z / Y / X, X / Z / Y / Z / X 5 layer configuration, X / Y / Z / Y
Although a layer structure such as a / Z / X six-layer structure is mentioned, a symmetrical structure is preferable from the viewpoint of preventing the curling phenomenon of the film.
次に、本発明のフィルムの製造方法を示す。前記の樹脂を用いて本発明の延伸フィルム
を製造する方法は、公知の方法で行うことができるが、以下、5層積層環状製膜延伸の場
合を例に挙げ、具体的に説明する。
まず、ポリプロピレン系樹脂(A)を両表面層、メタロセンPP(B)を主体とする樹
脂組成物を中間層、ポリエチレン系樹脂(C)を主体とする樹脂組成物を芯層(中間層及
び/又は芯層は共重合体(D)が添加される)となるように、5台の押出機により溶融混
練し、5層環状ダイより環状に共押出し、延伸することなく一旦急冷固化してチューブ状
未延伸フィルムを作製する。
得られたチューブ状未延伸フィルムを、チューブラー延伸装置に供給し、高度の配向可
能な温度範囲、例えば芯層樹脂の融点以下10℃よりも低い温度で、好ましくは融点以下
15℃よりも低い温度でチューブ内部にガス圧を適用して膨張延伸により同時二軸配向を
起こさせる。延伸倍率は、優れた強度、収縮率等の物性を得るためには縦横何れの方向にも3倍以上に延伸するのが好ましい。さらに、縦横の延伸倍率を各4.3以上とし、縦と横の延伸倍率の値の差を0.2以下にすると、収縮包装後のクラウドを抑えることができるため、
特に外観の美麗性を要求される用途や、黒っぽい被包装物を包装するようなクラウドが目立ちやすい用途に、好適に用いることが出来る。
延伸装置から取り出したフィルムは、希望によりアニーリングすることができ、このア
ニーリングにより保存中の自然収縮を抑制することができる。
Next, the manufacturing method of the film of this invention is shown. The method for producing the stretched film of the present invention using the above-mentioned resin can be performed by a known method, and will be specifically described below by taking the case of 5-layer laminated annular film-forming stretch as an example.
First, a polypropylene resin (A) is used for both surface layers, a resin composition mainly composed of metallocene PP (B) is an intermediate layer, and a resin composition mainly composed of polyethylene resin (C) is a core layer (intermediate layer and / or Alternatively, the core layer is added with a copolymer (D), and melted and kneaded by five extruders, co-extruded in a ring shape from a five-layer annular die, and then rapidly cooled and solidified without stretching. An unstretched film is produced.
The obtained tubular unstretched film is supplied to a tubular stretching apparatus, and is in a highly orientable temperature range, for example, at a temperature lower than 10 ° C below the melting point of the core layer resin, preferably lower than 15 ° C below the melting point. Simultaneous biaxial orientation is caused by expansion and stretching by applying gas pressure inside the tube at temperature. In order to obtain excellent physical properties such as strength and shrinkage, the stretching ratio is preferably stretched by 3 times or more in both the longitudinal and lateral directions. Furthermore, if the vertical and horizontal stretch ratios are 4.3 or more and the difference between the vertical and horizontal stretch ratios is 0.2 or less, the cloud after shrink wrapping can be suppressed.
In particular, it can be suitably used for applications that require a beautiful appearance or for applications in which a cloud for packaging a dark packaged item is easily noticeable.
The film taken out from the stretching apparatus can be annealed as desired, and the natural shrinkage during storage can be suppressed by this annealing.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定され
るものではない。
なお、本実施例の中で示した各物性測定は以下の方法によった。
1.フィルム厚み:JIS−Z1709に準じて測定した。
2.厚み比:フィルムの断面を顕微鏡で観察することにより測定した。
3.引張弾性率:JIS−Z7127に準じて測定した。
4.100℃熱収縮率:縦横それぞれ100mmの正方形に切り取ったフィルムを100
℃のグリセリン浴中に10秒間浸漬した後、水中で急冷し、縦横それぞれの長さを測定し
、数1によりMD、TDの熱収縮率を算出した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In addition, each physical property measurement shown in a present Example was based on the following method.
1. Film thickness: measured according to JIS-Z1709.
2. Thickness ratio: Measured by observing the cross section of the film with a microscope.
3. Tensile modulus: measured according to JIS-Z7127.
4. 100 ° C. heat shrinkage: 100 mm of a film cut into a 100 mm square each in length and width
After being immersed in a glycerin bath at 10 ° C. for 10 seconds, it was rapidly cooled in water, the lengths in the vertical and horizontal directions were measured, and the thermal shrinkage ratios of MD and TD were calculated by Equation 1.
5.糸引き評価:協和電機(株)製のL型シール式半折自動包装機(型式:AT-500
)を用いて、溶断シール温度:200℃、溶断シール時間:2秒の条件にて市販のビデオ
テープを30個連続して包装した。その後、包装サンプルの溶断シール部を観察し、以下
の判定基準にて、糸引き性を評価した。
<判定基準>
○:30個中に糸引きが1本も発生しない。
△:糸引きが平均して1包装中に5本以内である。
×:糸引きが平均して1包装中に6本以上である。
6.高速包装機適性:トキワ工業(株)製自動包装機(型式:NEO型、ピロー包装機)
にて、市販のカップラーメンを150個/分のスピードで包装し、フィルムの走行状態を
観察した。
7.収縮包装仕上がり性:トキワ工業(株)製自動包装機(型式:NEO型、ピロー包装
機)にて、市販のカップラーメンを150個/分のスピードで包装し、フィルムヤケド2
〜20℃手前の温度に設定した収縮トンネル内を3秒間滞留させ、トンネル通過後の包装
サンプルの中から無作為に5つを選び、収縮包装仕上がり性を下記の基準で評価した。
<評価基準>
○:包装サンプルの平均角高さが10mm以下となるトンネル温度範囲が10℃を超
える。
△:包装サンプルの平均角高さが7mm以下となるトンネル温度範囲が4〜10℃。
×:包装サンプルの平均角高さが7mm以下となるトンネル温度範囲が4℃未満。
(注:角高さとは、適度に余裕率を持たせた包装予備体を収縮トンネルで熱収縮させた
後、包装体の側面にできる角状突起物の突起高さを意味する。)
8.クラウド評価:協和電機(株)製のL型シール式半折自動包装機(型式:AT-500)を用いて、市販の黒い箱を包装し、フィルムヤケド10℃手前の温度に設定した協和電機製のシュリンクトンネル(L−1500FC)を5秒間滞留させ、トンネル通過後の包装サンプルのフィルム表面を観察し、以下の判定基準にて、クラウド評価した。
<判定基準>
◎:全くクラウドが見られない。
○:わずかにクラウドが見られる。
△:クラウドがやや目立つ。
×:クラウドがかなり目立つ。
5. Thread pull evaluation: Kyowa Denki Co., Ltd. L type seal type half folding automatic packaging machine (model: AT-500
), 30 commercially available video tapes were continuously packaged under the conditions of fusing seal temperature: 200 ° C. and fusing seal time: 2 seconds. Then, the fusing seal part of the packaging sample was observed, and the stringiness was evaluated according to the following criteria.
<Criteria>
○: No threading occurs in 30 pieces.
(Triangle | delta): An average of stringing is 5 or less in 1 packaging.
X: The average number of stringing is 6 or more in one package.
6). High-speed packaging machine suitability: Automatic packaging machine manufactured by Tokiwa Industry Co., Ltd. (model: NEO type, pillow packaging machine)
Then, commercially available cup ramen was packaged at a speed of 150 pieces / min, and the running state of the film was observed.
7). Shrink wrapping finish: Film burned 2 by packaging commercially available cup ramen at a speed of 150 pieces / min with an automatic wrapping machine (model: NEO type, pillow wrapping machine) manufactured by Tokiwa Industry Co., Ltd.
The inside of the shrink tunnel set at a temperature of ˜20 ° C. was allowed to stay for 3 seconds, and 5 samples were randomly selected from the packaging samples after passing through the tunnel, and the shrink packaging finish was evaluated according to the following criteria.
<Evaluation criteria>
○: The tunnel temperature range in which the average angular height of the packaging sample is 10 mm or less exceeds 10 ° C.
(Triangle | delta): The tunnel temperature range from which the average angle height of a packaging sample will be 7 mm or less is 4-10 degreeC.
X: The tunnel temperature range in which the average angular height of the packaging sample is 7 mm or less is less than 4 ° C.
(Note: Angular height means the height of the projections on the side of the package after heat shrinking the packaging preparatory body with a moderate margin with a shrinking tunnel.)
8). Cloud evaluation: Kyowa Denki Co., Ltd., which uses a L-type seal-type half-fold automatic packaging machine (model: AT-500) manufactured by Kyowa Denki Co., Ltd. The shrink tunnel (L-1500FC) made from manufacture was made to stay for 5 seconds, the film surface of the packaging sample after tunnel passage was observed, and cloud evaluation was carried out with the following criteria.
<Criteria>
A: Cloud is not seen at all.
○: Cloud is slightly seen.
Δ: Cloud is slightly noticeable.
×: The cloud is quite conspicuous.
実施例1
表1に示すように、融解ピーク温度が145℃、MFRが2.3g/10分の特性を有
するプロピレン−エチレンランダム共重合体を両表面層(X)とし、融解ピーク温度が1
25℃、MFRが4.0g/10分の特性を有するメタロセンPPに共重合体(D)を6
重量%添加したものを内部層(Y)とし、密度が0.920g/cm3、MIが1.0g
/10分の特性を有する直鎖状低密度ポリエチレンを内部層(Z)として、5台の押出機
でそれぞれ130〜240℃にて溶融混練し、厚み比がX/Y/Z/Y/X=1/1/4
/1/1になるように各押出機の押出量を設定し、240℃に保った5層環状ダイスによ
り下向きに共押出した。形成された5層構成チューブを、内側は冷却水が循環している円
筒状冷却マンドレルの外表面を摺動させながら、外側は水槽を通すことにより冷却して引
き取り、直径75mm、厚さ210μmの未延伸フィルムを得た。
このチューブ状未延伸フィルムをチューブラー二軸延伸装置に導き、90〜110℃で
縦横それぞれ4倍に延伸し、積層二軸延伸フィルムを得た。
次にこの延伸フィルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%
弛緩させた後、室温に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。
最終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表1に示すように、引張弾性率、100℃熱収縮率も共に優
れていた。半折包装機での溶断シール時に糸引きも発生せず、良好なシール線であった。
ピロー包装機での包装評価では、腰が強いためにフィルムの走行性が良好で、また収縮包
装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるトン
ネル温度範囲が広く、良好なものであった。収縮包装後のクラウドはわずかに観察された。
Example 1
As shown in Table 1, a propylene-ethylene random copolymer having a melting peak temperature of 145 ° C. and an MFR of 2.3 g / 10 min is used as both surface layers (X), and the melting peak temperature is 1
The copolymer (D) is added to a metallocene PP having the characteristics of 25 ° C. and MFR of 4.0 g / 10 min.
The inner layer (Y) is added by weight%, the density is 0.920 g / cm 3 , and MI is 1.0 g.
/ 10 min. Linear low density polyethylene having the characteristics of 10 minutes as the inner layer (Z), melt-kneaded at 130-240 ° C. with 5 extruders, respectively, and the thickness ratio is X / Y / Z / Y / X = 1/1/4
The extrusion amount of each extruder was set so as to be 1/1/1, and coextrusion was performed downward using a 5-layer annular die maintained at 240 ° C. The formed five-layer tube is cooled by passing through the water tank while sliding the outer surface of the cylindrical cooling mandrel in which the cooling water circulates on the inner side, and has a diameter of 75 mm and a thickness of 210 μm. An unstretched film was obtained.
This tubular unstretched film was guided to a tubular biaxial stretching apparatus, and stretched at 90 to 110 ° C. four times in length and breadth to obtain a laminated biaxially stretched film.
Next, this stretched film was heated in a tube annealing apparatus with hot air at 75 ° C. for 10% each in length and width.
After relaxing, the film was cooled to room temperature, and both ends of the film were trimmed and wound up separately.
The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 1, the obtained stretched film was excellent in both tensile modulus and 100 ° C. heat shrinkage. Stringing did not occur at the time of fusing and sealing in a half-fold packaging machine, and the seal line was good.
In the packaging evaluation with a pillow packaging machine, the film is easy to run due to its firmness, and the shrinkable packaging finish also has a wide tunnel temperature range where a beautiful finish can be obtained due to its excellent heat shrinkage characteristics. It was good. A slight cloud was observed after shrink wrapping.
実施例2
実施例1において、共重合体(D)を内部層(Y)にかえて内部層(Z)に6重量%添
加した以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィル
ムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛緩させた後、室温に
冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最終のフィルム厚みは
15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表1に示すように、引張弾性率、100℃熱収縮率も共に優
れていた。半折包装機での溶断シール時に糸引きも発生せず、良好なシール線であった。
ピロー包装機での包装評価では、腰が強いためにフィルムの走行性が良好で、また収縮包
装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるトン
ネル温度範囲が広く、良好なものであった。収縮包装後のクラウドはわずかに観察された。
Example 2
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that 6% by weight of the copolymer (D) was added to the internal layer (Z) instead of the internal layer (Y). . Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 1, the obtained stretched film was excellent in both tensile modulus and 100 ° C. heat shrinkage. Stringing did not occur at the time of fusing and sealing in a half-fold packaging machine, and the seal line was good.
In the packaging evaluation with a pillow packaging machine, the film is easy to run due to its firmness, and the shrinkable packaging finish also has a wide tunnel temperature range where a beautiful finish can be obtained due to its excellent heat shrinkage characteristics. It was good. A slight cloud was observed after shrink wrapping.
実施例3
実施例1において、共重合体(D)を内部層(Z)にも2重量%添加した以外は実施例
1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィルムをチューブアニー
リング装置にて75℃の熱風で縦横各々10%弛緩させた後、室温に冷却し、フィルム両
端をトリミングして、二枚別々に巻き取った。最終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表1に示すように、引張弾性率、100℃熱収縮率も共に優
れていた。半折包装機での溶断シール時に糸引きも発生せず、良好なシール線であった。
ピロー包装機での包装評価では、腰が強いためにフィルムの走行性が良好で、また収縮包
装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるトン
ネル温度範囲が広く、良好なものであった。収縮包装後のクラウドはわずかに観察された。
Example 3
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that 2% by weight of the copolymer (D) was also added to the inner layer (Z). Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 1, the obtained stretched film was excellent in both tensile modulus and 100 ° C. heat shrinkage. Stringing did not occur at the time of fusing and sealing in a half-fold packaging machine, and the seal line was good.
In the packaging evaluation with a pillow packaging machine, the film is easy to run due to its firmness, and the shrinkable packaging finish also has a wide tunnel temperature range where a beautiful finish can be obtained due to its excellent heat shrinkage characteristics. It was good. A slight cloud was observed after shrink wrapping.
実施例4
実施例1において、縦横それぞれ4.5倍で延伸した以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛緩させた後、室温に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表1に示すように、引張弾性率、100℃熱収縮率も共に優れていた。半折包装機での溶断シール時に糸引きも発生せず、良好なシール線であった。ピロー包装機での包装評価では、腰が強いためにフィルムの走行性が良好で、また収縮包装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるトンネル温度範囲が広く、良好なものであった。収縮包装後のクラウドも観察されず良好であった。
Example 4
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the film was stretched 4.5 times in length and width. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 1, the obtained stretched film was excellent in both tensile modulus and 100 ° C. heat shrinkage. Stringing did not occur at the time of fusing and sealing in a half-fold packaging machine, and the seal line was good. In the packaging evaluation with a pillow packaging machine, the film is easy to run due to its firmness, and the shrinkable packaging finish also has a wide tunnel temperature range where a beautiful finish can be obtained due to its excellent heat shrinkage characteristics. It was good. The cloud after shrink wrapping was not observed and was good.
実施例5
実施例1において、縦横それぞれ5.0倍で延伸した以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛緩させた後、室温に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表1に示すように、引張弾性率、100℃熱収縮率も共に優れていた。半折包装機での溶断シール時に糸引きも発生せず、良好なシール線であった。ピロー包装機での包装評価では、腰が強いためにフィルムの走行性が良好で、また収縮包装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるトンネル温度範囲が広く、良好なものであった。収縮包装後のクラウドも観察されず良好であった。
Example 5
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the film was stretched 5.0 times in the longitudinal and lateral directions. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 1, the obtained stretched film was excellent in both tensile modulus and 100 ° C. heat shrinkage. Stringing did not occur at the time of fusing and sealing in a half-fold packaging machine, and the seal line was good. In the packaging evaluation with a pillow packaging machine, the film is easy to run due to its firmness, and the shrinkable packaging finish also has a wide tunnel temperature range where a beautiful finish can be obtained due to its excellent heat shrinkage characteristics. It was good. The cloud after shrink wrapping was not observed and was good.
実施例6
実施例1において、縦5.0倍、横4.3倍で延伸した以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛緩させた後、室温に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表1に示すように、引張弾性率、100℃熱収縮率も共に優れていた。半折包装機での溶断シール時に糸引きも発生せず、良好なシール線であった。ピロー包装機での包装評価では、腰が強いためにフィルムの走行性が良好で、また収縮包装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるトンネル温度範囲が広く、良好なものであった。収縮包装後のクラウドはわずかに観察された。
Example 6
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the film was stretched 5.0 times in length and 4.3 times in width. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 1, the obtained stretched film was excellent in both tensile modulus and 100 ° C. heat shrinkage. Stringing did not occur at the time of fusing and sealing in a half-fold packaging machine, and the seal line was good. In the packaging evaluation with a pillow packaging machine, the film is easy to run due to its firmness, and the shrinkable packaging finish also has a wide tunnel temperature range where a beautiful finish can be obtained due to its excellent heat shrinkage characteristics. It was good. A slight cloud was observed after shrink wrapping.
比較例1
実施例1において、内部層(Y)に共重合体(D)を添加しなかった以外は実施例1と
同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィルムをチューブアニーリン
グ装置にて75℃の熱風で縦横各々10%弛緩させた後、室温に冷却し、フィルム両端を
トリミングして、二枚別々に巻き取った。最終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表2に示すように、引張弾性率、100℃熱収縮率は十分で
、ピロー包装機での包装評価でも、腰が強いためにフィルムの走行性が良好で、また収縮
包装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるト
ンネル温度範囲が広く、良好なものであった。しかしながら、半折包装機では、溶断シー
ル時の糸引きが発生し、シール線は汚くなった。収縮包装後のクラウドはわずかに観察された。
Comparative Example 1
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the copolymer (D) was not added to the inner layer (Y). Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 2, the obtained stretched film has sufficient tensile elastic modulus and 100 ° C. heat shrinkage, and even in packaging evaluation with a pillow wrapping machine, the stretchability of the film is strong, and the running property of the film is good. As for the shrink-wrapping finish, the tunnel temperature range in which a beautiful finish can be obtained is excellent due to the excellent heat-shrinkage characteristics, and it was good. However, in the half-fold packaging machine, stringing occurs at the time of fusing sealing, and the sealing wire becomes dirty. A slight cloud was observed after shrink wrapping.
比較例2
実施例1において、内部層(Y)に添加する共重合体(D)を6重量%から0.1重量
%にかえた以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フ
ィルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛緩させた後、室
温に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最終のフィルム厚
みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表2に示すように、引張弾性率、100℃熱収縮率は十分で
、ピロー包装機での包装評価でも、腰が強いためにフィルムの走行性が良好で、また収縮
包装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるト
ンネル温度範囲が広く、良好なものであった。しかしながら、半折包装機では、溶断シー
ル時の糸引きが発生し、シール線は汚くなった。収縮包装後のクラウドはわずかに観察された。
Comparative Example 2
In Example 1, a five-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the copolymer (D) added to the inner layer (Y) was changed from 6% by weight to 0.1% by weight. It was. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 2, the obtained stretched film has sufficient tensile elastic modulus and 100 ° C. heat shrinkage, and even in packaging evaluation with a pillow wrapping machine, the stretchability of the film is strong, and the running property of the film is good. As for the shrink-wrapping finish, the tunnel temperature range in which a beautiful finish can be obtained is excellent due to the excellent heat-shrinkage characteristics, and it was good. However, in the half-fold packaging machine, stringing occurs at the time of fusing sealing, and the sealing wire becomes dirty. A slight cloud was observed after shrink wrapping.
比較例3
実施例1において、内部層(Y)に添加する共重合体(D)を6重量%から20重量%
にかえた以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。次にこの延伸フィ
ルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛緩させた後、室温
に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最終のフィルム厚み
は15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表2に示すように、引張弾性率は十分で、ピロー包装機での
包装評価でも、腰が強いためにフィルムの走行性が良好で、半折包装機での溶断シール時
に糸引きも発生せず、良好なシール線であった。しかしながら、収縮率が25%以下で、
ピロー包装機での収縮包装仕上がり性も角立ちがおおきく、良好な仕上がり性が得られな
かった。収縮包装後のクラウドはわずかに観察された。
Comparative Example 3
In Example 1, the copolymer (D) added to the inner layer (Y) was added in an amount of 6% by weight to 20% by weight.
A 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the change was made. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 2, the obtained stretched film has a sufficient tensile elastic modulus, and even in packaging evaluation with a pillow wrapping machine, the stretchability of the film is strong and the film travels well. There was no stringing at the time of sealing, and the sealing wire was good. However, the shrinkage rate is 25% or less,
The shrink-wrapping finish in the pillow wrapping machine was also very sharp, and good finish was not obtained. A slight cloud was observed after shrink wrapping.
比較例4
実施例1において、内部層(Y)に添加する重合体をポリプロピレン単独重合体(E)
にかえて6重量%添加した以外は実施例1と同様の方法で5層二軸延伸フィルムを得た。
次にこの延伸フィルムをチューブアニーリング装置にて75℃の熱風で縦横各々10%弛
緩させた後、室温に冷却し、フィルム両端をトリミングして、二枚別々に巻き取った。最
終のフィルム厚みは15μmであった。
延伸性は良好で、延伸点の上下動や延伸チューブの揺動もなく、またネッキングなどの
不均一延伸状態も観察されなかった。
得られた延伸フィルムは、表2に示すように、引張弾性率、100℃熱収縮率は十分で
、ピロー包装機での包装評価でも、腰が強いためにフィルムの走行性が良好で、また収縮
包装仕上がり性についても、熱収縮特性が優れているために美麗な仕上がりが得られるト
ンネル温度範囲が広く、良好なものであった。しかしながら、半折包装機では、溶断シー
ル時の糸引きが発生し、シール線は汚くなった。収縮包装後のクラウドはわずかに観察された。
Comparative Example 4
In Example 1, the polymer added to the inner layer (Y) is a polypropylene homopolymer (E).
Instead of adding 6% by weight, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1.
Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and non-uniform stretching conditions such as necking were not observed.
As shown in Table 2, the obtained stretched film has sufficient tensile elastic modulus and 100 ° C. heat shrinkage, and even in packaging evaluation with a pillow wrapping machine, the stretchability of the film is strong, and the running property of the film is good. As for the shrink-wrapping finish, the tunnel temperature range in which a beautiful finish can be obtained is excellent due to the excellent heat-shrinkage characteristics, and it was good. However, in the half-fold packaging machine, stringing occurs at the time of fusing sealing, and the sealing wire becomes dirty. A slight cloud was observed after shrink wrapping.
本発明のポリオレフィン系多層シュリンクフィルムは、腰強度と低温収縮性が共に優れ
、自動包装機における高速包装機適性と収縮包装仕上がり性を保持しつつ、L型シール式
半折包装機を用いる包装において溶断シール時のシール線が良好で、収縮包装後のクラウドの発生が抑えられるため、各種収縮包装に好適に用いることができる。
The polyolefin-based multilayer shrink film of the present invention is excellent in both waist strength and low-temperature shrinkage, and in packaging using an L-type seal-type half-fold packaging machine while maintaining high-speed packaging machine suitability and shrink packaging finish in an automatic packaging machine. Since the seal line at the time of fusing sealing is good and the generation of cloud after shrink packaging is suppressed, it can be suitably used for various shrink packaging.
Claims (7)
特性(1):MD、TD引張弾性率がそれぞれ0.80GPa以上。
特性(2):100℃におけるMD、TD熱収縮率の平均値が25%以上。 The polyolefin multilayer shrink film according to any one of claims 1 to 5, wherein the polyolefin multilayer shrink film satisfies the following characteristics (1) and (2) simultaneously.
Characteristic (1): MD and TD tensile elastic moduli are each 0.80 GPa or more.
Characteristic (2): The average value of MD and TD thermal shrinkage at 100 ° C. is 25% or more.
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JP2011068844A (en) * | 2009-08-24 | 2011-04-07 | Mitsubishi Plastics Inc | Stretch wrap film |
JP5476533B2 (en) * | 2009-12-14 | 2014-04-23 | 興人フィルム&ケミカルズ株式会社 | Heat shrinkable film for polyolefin sleeve packaging |
JP5545627B2 (en) * | 2009-12-21 | 2014-07-09 | 興人フィルム&ケミカルズ株式会社 | Polyolefin thin film multilayer shrink film |
JP5771459B2 (en) * | 2011-06-28 | 2015-09-02 | 旭化成ケミカルズ株式会社 | Heat-shrinkable stretched laminated film, and top seal package and pillow shrink package including the same |
CN104275900B (en) * | 2014-08-29 | 2017-06-06 | 安徽紫金新材料科技股份有限公司 | A kind of aerated food three-layer coextru-laminated film |
JP2018076081A (en) * | 2016-11-07 | 2018-05-17 | 住友ベークライト株式会社 | Freshness-keeping bag for sprout or fungus, package containing sprout or fungus and method to keep freshness of sprout or fungus |
WO2023132301A1 (en) * | 2022-01-06 | 2023-07-13 | 興人フィルム&ケミカルズ株式会社 | Polyolefin-based biomass shrink film |
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