JP2007237434A - Heat-shrinkable film - Google Patents
Heat-shrinkable film Download PDFInfo
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- JP2007237434A JP2007237434A JP2006059389A JP2006059389A JP2007237434A JP 2007237434 A JP2007237434 A JP 2007237434A JP 2006059389 A JP2006059389 A JP 2006059389A JP 2006059389 A JP2006059389 A JP 2006059389A JP 2007237434 A JP2007237434 A JP 2007237434A
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- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 24
- 229920000728 polyester Polymers 0.000 claims abstract description 39
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 7
- 229920006267 polyester film Polymers 0.000 abstract description 3
- 238000010030 laminating Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 61
- -1 polyethylene terephthalate Polymers 0.000 description 13
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- CVBWTNHDKVVFMI-LBPRGKRZSA-N (2s)-1-[4-[2-[6-amino-8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]purin-9-yl]ethyl]piperidin-1-yl]-2-hydroxypropan-1-one Chemical compound C1CN(C(=O)[C@@H](O)C)CCC1CCN1C2=NC=NC(N)=C2N=C1SC(C(=C1)Br)=CC2=C1OCO2 CVBWTNHDKVVFMI-LBPRGKRZSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BICHQNPPYNUPKG-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohex-2-yn-1-yl]methanol Chemical compound OCC1(CO)CCCC#C1 BICHQNPPYNUPKG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
本発明は、ポリエステルからなる熱収縮性フィルムに関する。 The present invention relates to a heat shrinkable film made of polyester.
飲料容器として、ポリエステルフィルムを金属板に貼り合わせて作られた缶や、ポリエステルフィルムをシュリンクラベルとして用いたＰＥＴ（ポリエチレンテレフタレート）ボトルが用いられている。飲料容器には、近年ますます美麗な意匠が求められている。 As beverage containers, cans made by bonding polyester films to metal plates and PET (polyethylene terephthalate) bottles using polyester films as shrink labels are used. In recent years, more and more beautiful designs are required for beverage containers.
シュリンクラベル用のフィルムには、熱収縮特性、接着性、ハンドリング性、耐薬品性などの改良が求められる。従来、種々の改良はなされているものの包装材料としての意匠性を向上させるために、印刷柄による差別化が図られてきた。 Films for shrink labels are required to have improved heat shrink characteristics, adhesiveness, handling properties, chemical resistance, and the like. Conventionally, although various improvements have been made, differentiation by printed patterns has been attempted in order to improve the design as a packaging material.
他方、多層積層フィルムは、相対的に低い屈折率の層と高い屈折率の層とを交互に多層積層することで、層間の構造的な光干渉によって特定の波長の光を選択的に反射し、他の波長の光を透過する特性を得ることができる。この多層積層フィルムは、染料を使用しないで発色させることができ、退色することがなく、意匠性に優れたフィルムを得ることができる。 On the other hand, multilayer laminated films selectively reflect light of a specific wavelength by structural optical interference between layers by alternately laminating relatively low refractive index layers and high refractive index layers. The characteristic which permeate | transmits the light of another wavelength can be acquired. This multilayer laminated film can be colored without using a dye, and can be obtained without fading and having excellent design.
しかし、従来の多層積層フィルムはシュリンクラベルとして満足に使用できる特性ではなかった。本発明の目的は、特定の波長の光を高い選択性で反射させ、発色性に優れ、玉虫色の金属光沢を有し、フィルムに施される絵柄印刷を美麗なものとすることができる熱収縮性フィルムを提供することにある。 However, the conventional multilayer laminated film has not been able to be used satisfactorily as a shrink label. It is an object of the present invention to reflect light of a specific wavelength with high selectivity, has excellent color developability, has an iridescent metallic luster, and can provide a beautiful image printing applied to a film. It is to provide a sex film.
すなわち本発明は、ガラス転移温度が５０〜７０℃のポリエステルからなる厚み０．０５〜０．５μｍの第１の層と、第１の層を構成するポリエステルとは組成を異にする熱可塑性樹脂からなる厚み０．０５〜０．５μｍの第２の層と、を交互に１１層以上積層してなり、フィルム厚みに対する第１の層の層厚みの総計が５０〜９５％であり、１００℃の熱風中に５分間放置したときの熱収縮率がフィルム長手方向および幅方向の少なくともいずれか一方において３０％以上であることを特徴とする熱収縮性フィルムである。 That is, the present invention relates to a thermoplastic resin having a composition different from that of the first layer made of polyester having a glass transition temperature of 50 to 70 ° C. and having a thickness of 0.05 to 0.5 μm and the polyester constituting the first layer. 11 or more layers having a thickness of 0.05 to 0.5 μm are alternately laminated, and the total thickness of the first layer with respect to the film thickness is 50 to 95%, and 100 ° C. The heat shrinkable film has a heat shrinkage rate of 30% or more in at least one of the longitudinal direction and the width direction when left in the hot air for 5 minutes.
本発明によれば、特定の波長の光を高い選択性で反射させ、発色性に優れ、玉虫色の金属光沢を有し、フィルムに施される絵柄印刷を美麗なものとすることができる熱収縮性フィルムを提供することができる。 According to the present invention, heat shrinkage that reflects light of a specific wavelength with high selectivity, has excellent color developability, has an iridescent metallic luster, and can make a beautiful pattern printing on a film. A protective film can be provided.
以下、本発明を詳細に説明する。
＜第１の層＞
本発明における第１の層は、ガラス転移温度が５０〜７０℃のポリエステルからなる。ガラス転移温度が５０℃未満ではシュリンクラベルとしての十分な強度が得らず、７０℃を超えるとシュリンクラベルとしての十分な収縮特性が得られない。
Hereinafter, the present invention will be described in detail.
<First layer>
The 1st layer in this invention consists of polyester with a glass transition temperature of 50-70 degreeC. If the glass transition temperature is less than 50 ° C., sufficient strength as a shrink label cannot be obtained, and if it exceeds 70 ° C., sufficient shrinkage characteristics as a shrink label cannot be obtained.
第１の層のポリエステルとしては、結晶化を抑制し熱収縮特性を満足する観点から、ポリエチレンテレフタレートにジカルボン酸成分またはジオール成分を共重合したポリエステルが好ましい。共重合成分のジカルボン酸成分としては、イソフタル酸、２，６―ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸といった芳香族カルボン酸；アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸といった脂肪族ジカルボン酸；シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸を用いることができ、ジオール成分としては、ブタンジオール、ヘキサンジオールといった脂肪族ジオール；シクロヘキサンジメタノールの如き脂環族ジオールを用いることができる。 The polyester of the first layer is preferably a polyester obtained by copolymerizing polyethylene terephthalate with a dicarboxylic acid component or a diol component from the viewpoint of suppressing crystallization and satisfying heat shrinkage characteristics. Examples of the dicarboxylic acid component of the copolymer component include aromatic carboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. Acid: An alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid can be used. As the diol component, an aliphatic diol such as butanediol and hexanediol; and an alicyclic diol such as cyclohexanedimethanol can be used.
＜第２の層＞
第２の層は、第１の層を構成するポリエステルとは組成を異にする熱可塑性樹脂からなる。ここで、「組成を異にする」とは、ポリマーを構成する繰り返し単位の主たる成分が異なるか、少なくとも共重合成分として用いられる従たる成分の種類か量が異なることを意味する。他方、ポリマーを構成する成分の組成が同じであって滑剤等ポリマー物性に影響を与えない成分のみが異なる場合は、ここでは「組成を異にする」とはいわない。
<Second layer>
The second layer is made of a thermoplastic resin having a composition different from that of the polyester constituting the first layer. Here, “different in composition” means that the main component of the repeating unit constituting the polymer is different, or at least the type or amount of the subordinate component used as the copolymerization component is different. On the other hand, when the composition of the components constituting the polymer is the same and only the components that do not affect the physical properties of the polymer such as a lubricant are different, it is not said that “the compositions are different”.
熱可塑性樹脂は、第１の層との積層に必要な相溶性を確保する観点からポリエステルが好ましく、良好な収縮特性を得る観点から結晶性ポリエステルにジカルボン酸成分またはジオール成分の共重合成分を共重合した共重合ポリエステルがさらに好ましい。 The thermoplastic resin is preferably a polyester from the viewpoint of ensuring compatibility required for lamination with the first layer, and a copolymer of a dicarboxylic acid component or a diol component is added to the crystalline polyester from the viewpoint of obtaining good shrinkage characteristics. A polymerized copolyester is more preferred.
結晶性ポリエステルとしては、例えば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を用いることができる。共重合成分としては、ジカルボン酸成分として、イソフタル酸、２，６―ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸といった芳香族カルボン酸；アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸といった脂肪族ジカルボン酸；シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸を用いることができる。ジオール成分として、ブタンジオール、ヘキサンジオール、ネオペンチルグリコールといった脂肪族ジオール；シクロヘキサンジメタノールの如き脂環族ジオールを用いることができる。 For example, polyethylene terephthalate or polybutylene terephthalate can be used as the crystalline polyester. As copolymerization component, dicarboxylic acid component, aromatic carboxylic acid such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid; aliphatic such as adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid Dicarboxylic acid; An alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid can be used. As the diol component, an aliphatic diol such as butanediol, hexanediol, or neopentylglycol; and an alicyclic diol such as cyclohexanedimethanol can be used.
この共重合ポリエステルは、良好な延伸性を得る観点から、第１の層のポリエステルのガラス転移温度（Ｔｇ１）と第２の層のポリエステルのガラス転移温度（Ｔｇ２）との差（Ｔｇ１−Ｔｇ２）が下記式を満足することが好ましい。
−２０℃≦（Ｔｇ１−Ｔｇ２）≦５０℃
上記（Ｔｇ１−Ｔｇ２）が−２０℃未満であると第１の層の延伸に追従して第２の層が配向して屈折率が大きくなるために屈折率差が小さくなり発色が得られにくく好ましくなく、５０℃を超えるとガラス転移温度差が大きすぎて均一な延伸が難しく好ましくない。
From the viewpoint of obtaining good stretchability, the copolymer polyester has a difference (Tg1−Tg2) between the glass transition temperature (Tg1) of the polyester of the first layer and the glass transition temperature (Tg2) of the polyester of the second layer. Preferably satisfies the following formula.
−20 ° C. ≦ (Tg1-Tg2) ≦ 50 ° C.
If the above (Tg1-Tg2) is less than −20 ° C., the second layer is oriented following the stretching of the first layer to increase the refractive index. Unfavorably, if it exceeds 50 ° C., the glass transition temperature difference is too large, and uniform stretching is difficult and undesirable.
また、第２の層のポリエステルの融点は、第１の層のポリエステルの融点よりも２０〜５０℃低いことが好ましい。融点の差が２０℃未満であると得られる多層延伸フィルムの層間に十分な屈折率差を付与することが困難であり好ましくない。融点の差が５０℃を超えると２つの層の密着性を維持することが難しくなり好ましくない。 Moreover, it is preferable that melting | fusing point of polyester of a 2nd layer is 20-50 degreeC lower than melting | fusing point of polyester of 1st layer. If the difference in melting point is less than 20 ° C., it is difficult to provide a sufficient difference in refractive index between the layers of the obtained multilayer stretched film, which is not preferable. If the difference between the melting points exceeds 50 ° C., it is difficult to maintain the adhesion between the two layers, which is not preferable.
＜フィルム特性＞
本発明の熱収縮性フィルムは、１００℃の熱風中に５分間放置したときの熱収縮率がフィルム長手方向および幅方向の少なくともいずれか一方において３０％以上であることが必要である。３０％未満であるとシュリンクラベルとして用いたときにボトルへの十分な密着性を示さない。
<Film characteristics>
The heat-shrinkable film of the present invention needs to have a heat shrinkage rate of 30% or more in at least one of the film longitudinal direction and width direction when left in hot air at 100 ° C. for 5 minutes. When it is less than 30%, sufficient adhesion to a bottle is not exhibited when used as a shrink label.
本発明の熱収縮性フィルムは、フィルム厚みに対する第１の層の層厚みの総計が５０〜９５％である。５０％未満であると所望の収縮率を得ることができず、９５％を超えると積層構造がみだれ発色が十分に発現しない。 In the heat-shrinkable film of the present invention, the total thickness of the first layer with respect to the film thickness is 50 to 95%. If it is less than 50%, the desired shrinkage rate cannot be obtained, and if it exceeds 95%, the laminated structure is squeezed and color development is not sufficiently exhibited.
光の干渉による発色性を効果的に発現するために、各層の厚みは０．０５〜０．５μｍとし、第１の層と第２の層とを交互に１１層以上積層する。各層の厚みをこの範囲とすることにより、可視光での発色を得ることができる。各層の厚みが０．０５μｍ未満では反射波長が紫外線領域になるために発色せず、０．５μｍを超えると赤外線領域の反射となるために発色しない。 In order to effectively develop color development due to light interference, the thickness of each layer is 0.05 to 0.5 μm, and 11 or more layers of the first layer and the second layer are alternately laminated. By setting the thickness of each layer within this range, color development with visible light can be obtained. When the thickness of each layer is less than 0.05 μm, the reflection wavelength is in the ultraviolet region, so that no color is generated, and when it exceeds 0.5 μm, the infrared region is reflected, so that no color is generated.
この構成をとる本発明の熱収縮性フィルムは、波長３５０〜２０００ｎｍの光に対する反射率曲線において反射率のベースラインよりも２０％以上高い最大反射率ピークが観察される。
なお、光学干渉機能に寄与しない厚膜層を別途設けてもよい。その場合には、厚膜層の厚みは０．５μｍを超えてよい。
In the heat-shrinkable film of the present invention having this configuration, a maximum reflectance peak that is 20% or more higher than the reflectance baseline is observed in the reflectance curve for light having a wavelength of 350 to 2000 nm.
A thick film layer that does not contribute to the optical interference function may be provided separately. In that case, the thickness of the thick film layer may exceed 0.5 μm.
＜製造方法＞
つぎに、本発明の熱収縮性フィルムの製造方法について、一例を詳述する。
まず、第１の押出し機より供給された第１の層のポリエステルと、第２の押出し機より供給された第１の層の熱可塑性樹脂とを、溶融状態で交互に少なくとも１１層を重ね合わせた状態を形成し、ダイを用いてこれを回転するドラム上にキャストすることにより、多層未延伸フィルム（シート状物とする工程）とする。得られた多層未延伸フィルムを、製膜方向またはそれに直交する方向に少なくとも１軸方向（フィルム面に沿った方向）に延伸する。このときの延伸温度は、好ましくは第１の層のポリエステルのガラス転移点の温度（Ｔｇ）〜Ｔｇ＋５０℃の範囲とする。面積倍率は好ましくは２〜１０倍とする。延伸倍率が大きい程、第１の層と第２の層の個々の層における面方向のバラツキが延伸による薄層化により小さくなり、多層延伸フィルムの光干渉が面方向に均一になるので好ましい。この延伸工程でプライマー層などを塗設してもよい。この場合、例えば縦延伸後にフィルムの片面または両面に水分散性の塗剤を塗布し、横延伸の前に乾燥してフィルムに皮膜を形成させるとよい。塗工方法は、例えばリバースロールコーターによる塗工を用いることができる。
なお、原料に用いるポリエステルのガラス転移温度および融点は、用いる共重合成分の量を変更することによって適宜調整することができる。
<Manufacturing method>
Next, an example of the method for producing the heat-shrinkable film of the present invention will be described in detail.
First, at least 11 layers of the first layer polyester supplied from the first extruder and the first layer thermoplastic resin supplied from the second extruder are alternately superposed in a molten state. And forming a multi-layer unstretched film (a step of forming a sheet-like material) by casting it on a rotating drum using a die. The obtained multilayer unstretched film is stretched in at least one axial direction (direction along the film surface) in the film forming direction or a direction perpendicular thereto. The stretching temperature at this time is preferably in the range of the temperature (Tg) to Tg + 50 ° C. of the glass transition point of the polyester of the first layer. The area magnification is preferably 2 to 10 times. The larger the draw ratio, the smaller the variation in the plane direction between the individual layers of the first layer and the second layer, and the more preferable the optical interference of the multilayer stretched film becomes in the plane direction. You may coat a primer layer etc. by this extending process. In this case, for example, a water-dispersible coating agent may be applied to one or both sides of the film after longitudinal stretching and dried before lateral stretching to form a film on the film. As the coating method, for example, coating by a reverse roll coater can be used.
In addition, the glass transition temperature and melting | fusing point of polyester used for a raw material can be suitably adjusted by changing the quantity of the copolymerization component to be used.
以下、実施例に基づき本発明を説明する。
各特性値ならびに評価法は下記の方法によって測定、評価した。
Hereinafter, the present invention will be described based on examples.
Each characteristic value and evaluation method were measured and evaluated by the following methods.
（ア）熱収縮率
幅１０ｍｍ、長さ２５０ｍｍのフィルムサンプルに標線間隔を２００ｍｍの標線を付して１００℃の熱風中に５分間放置した。放置前と放置後での標線間の長さを測定し、寸法変化の原寸法に対する割合としてフィルムの熱収縮率（％）を算出した。そして、ＭＤとＴＤ方向の収縮率の平均が３０％以上を○、２０％以上３０％未満を△、２０％未満を×として評価した。
(A) Thermal contraction rate A film sample having a width of 10 mm and a length of 250 mm was marked with a marked line having a marked line interval of 200 mm and left in hot air at 100 ° C. for 5 minutes. The length between the marked lines before and after being allowed to stand was measured, and the heat shrinkage rate (%) of the film was calculated as the ratio of the dimensional change to the original dimension. And the average of the shrinkage | contraction rate of MD and TD direction evaluated as 30% or more as (circle), 20% or more and less than 30% as (triangle | delta), and less than 20% as x.
（イ）フィルム外観
上記熱処理による収縮後に白化等の外観不良を生じたものを×、良好なものを○として評価した。
(A) Film appearance Evaluation was made with x for those having poor appearance such as whitening after shrinkage due to the heat treatment, and ◯ for good.
（ウ）最大反射率波長、最大反射率ピーク高さ
分光光度計（島津製作所製、ＭＰＣ−３１００）を用い、波長３５０ｎｍから２０００ｎｍの範囲にわたり、アルミ蒸着したミラーとの相対鏡面反射率を測定した。波長ごとに測定された反射率の中で最大のものを最大反射率としその波長を最大反射率波長とした。最大反射率とベースラインと差を最大反射率ピーク高さとした。
(C) Maximum reflectance wavelength, maximum reflectance peak height Using a spectrophotometer (manufactured by Shimadzu Corporation, MPC-3100), the relative specular reflectance with an aluminum-deposited mirror was measured over a wavelength range of 350 nm to 2000 nm. . Among the reflectances measured for each wavelength, the maximum reflectance was defined as the maximum reflectance, and the wavelength was defined as the maximum reflectance wavelength. The difference between the maximum reflectance and the baseline was taken as the maximum reflectance peak height.
（エ）収縮フィルムとしての評価
フィルムを収縮ラベルとして円筒形にした後、ＰＥＴボトルに被せ、設定温度７５℃のシュリンクトンネルを通過させて収縮させた。トンネル通過後、フィルムがボトルに十分に密着しているかどうかを目視で判定し、密着の良好なものをＯ．良好でないものを×として評価した。
また、フィルムの収縮斑を目視で判定し、上端部または下端部が収縮後斜めになったり歪んでいないものを○、斜めになったりゆがんでいるものを×として評価した。
総合評価として、上記２項目を満足し、さらに収縮後のフィルムに白化、シワ等が全く見られないものをＯ、そうでないものを×として評価した。
(D) Evaluation as shrink film
The film was made into a cylindrical shape as a shrinkable label, and then covered with a PET bottle, and shrunk by passing through a shrink tunnel having a set temperature of 75 ° C. After passing through the tunnel, it is visually determined whether the film is sufficiently adhered to the bottle. Those not good were evaluated as x.
Moreover, the shrinkage spot of the film was visually determined, and the upper end portion or the lower end portion was evaluated as ◯ when the upper end portion or the lower end portion was not slanted or distorted after shrinkage, and the case where the slanted or distorted portion was evaluated as x.
As a comprehensive evaluation, the above two items were satisfied, and the film after shrinkage in which no whitening, wrinkles, etc. were observed was evaluated as O, and the other film was evaluated as x.
（オ）層間の密着性
サンプルフィルム（１０ｍｍｘ５０ｍｍ）の両面に２４ｍｍ幅の粘着テープ（ニチバン社製、商品名：セロテープ(登録商標)）を１００ｍｍ貼り付け、１８０度の剥離角度で剥がした後、剥離面を観察した。これを各１０サンプルについて行い、層間剥離の生じた回数を算出した。
(E) Interlayer adhesion A 24 mm wide adhesive tape (product name: cello tape (registered trademark)) of 100 mm is pasted on both sides of a sample film (10 mm x 50 mm), and then peeled off at a peeling angle of 180 degrees. The surface was observed. This was performed for each 10 samples, and the number of delaminations was calculated.
（カ）色相の斑
Ａ４サイズのサンプルフィルムを１０枚用意し、それぞれのサンプルフィルムを白色の普通紙に重ね、３０ルクスの照明の下、目視にてサンプルフィルム内の透過色の色相の斑を評価した。また、Ａ４サイズのサンプルフィルムを１０枚用意し、それぞれのサンプルフィルムの裏面を黒色のスプレーにて着色した後、３０ルクスの照明の下、目視にてサンプルフィルム内の反射色の色相の斑を評価した。
(F) Hue spots 10 A4 size sample films were prepared, and each sample film was layered on white plain paper, and visually visible hue spots in the sample film under 30 lux illumination. evaluated. In addition, 10 A4 size sample films were prepared, and the back surface of each sample film was colored with a black spray, and then the reflected color spots in the sample film were visually observed under 30 lux illumination. evaluated.
［実施例１］
第１の層のポリエステルとして、固有粘度（オルソクロロフェノール、３５℃）０．６５のポリエチレンテレフタレート−イソフタレート共重合体（イソフタル酸成分含有量１５モル％、「ＩＡ１５ＰＥＴ」という）を用意し、第２の層のポリエステルとして、０．６５のポリエチレンテレフタレート−セバシン酸共重合体（セバシン酸成分含有量１５モル％、「ＳＡ１５ＰＥＴ」という）を用意し、このポリエステルのペレットを攪拌しながら１１０℃で１０時間加熱し表面を結晶化させたものを用意した。
[Example 1]
As a polyester of the first layer, a polyethylene terephthalate-isophthalate copolymer (isophthalic acid component content 15 mol%, referred to as “IA15PET”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.65 is prepared. A 0.65 polyethylene terephthalate-sebacic acid copolymer (15 mol% sebacic acid component content, referred to as “SA15PET”) is prepared as the polyester of
そして、第１の層のポリエステルおよび第２の層のポリエステルを、それぞれ１７０℃で３時間乾燥後、第１、２の押出し機に供給し、２９０℃まで加熱して溶融状態とし、第１の層のポリエステルを２０１層、第２の層のポリエステルを２００層に分岐させた後、第１の層と第２の層が交互に積層するような多層フィードブロック装置を使用して、積層状態の溶融体とし、その積層状態を保持したまま、キャスティングドラム上にキャストして、押出量の比を第１の層のポリエステルを８０％、第２の層のポリエステルを２０％に調整し、第１の層と第２の層が交互に積層された総数４０１層の未延伸多層積層フィルムを作成した。この多層未延伸フィルムを８５℃の温度で製膜方向に４．０倍延伸し、７０℃で３秒間熱固定処理を行い、熱収縮性フィルムを得た。得られた熱収縮性フィルムの特性を前述の方法で評価した。結果を表１および表２にまとめる。 Then, the polyester of the first layer and the polyester of the second layer are each dried at 170 ° C. for 3 hours, then supplied to the first and second extruders, heated to 290 ° C. to be in a molten state, After branching the polyester of the layer to 201 and the polyester of the second layer to 200, using a multilayer feed block device in which the first layer and the second layer are alternately laminated, The melt was cast on a casting drum while maintaining the laminated state, and the ratio of the extrusion amount was adjusted to 80% for the first layer polyester and 20% for the second layer polyester. A total of 401 unstretched multilayer laminated films in which the above layers and second layers were alternately laminated were prepared. This multilayer unstretched film was stretched 4.0 times in the film forming direction at a temperature of 85 ° C., and heat-fixed at 70 ° C. for 3 seconds to obtain a heat-shrinkable film. The characteristics of the obtained heat-shrinkable film were evaluated by the method described above. The results are summarized in Table 1 and Table 2.
［実施例２］
第１の層のポリエステルを、固有粘度（オルソクロロフェノール、３５℃）０．６５のポリエチレンテレフタレート−シクロヘキンジメタノール共重合体（シクロヘキンジメタノール成分含有量２０モル％、「ＣＨＤＭ２０ＰＥＴ」という）とした以外は実施例１と同様にして、熱収縮性フィルムを得た。得られた熱収縮性フィルムの特性を前述の方法で評価した。結果を表１および表２にまとめる。
[Example 2]
The polyester of the first layer is a polyethylene terephthalate-cyclohexynedimethanol copolymer having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.65 (
［実施例３］
第１の層のポリエステルを、固有粘度（オルソクロロフェノール、３５℃）０．６５のポリエチレンテレフタレート−イソフタレート共重合体（イソフタル酸成分含有量２０モル％、「ＩＡ２０ＰＥＴ」という）とした以外は実施例１と同様にして熱収縮性フィルムを得た。得られたフィルムの特性を前述の方法で評価した。結果を表１および表２にまとめる。
[Example 3]
Implemented except that the polyester of the first layer was a polyethylene terephthalate-isophthalate copolymer (isophthalic
［比較例１］
押出量の比を第１の層用ポリエステルを９９％、第２の層のポリエステルを１％に調整した以外は実施例１と同様にして熱収縮性フィルムを得た。得られた熱収縮性フィルムの特性を前述の方法で評価した。結果を表１および表２にまとめる。
[Comparative Example 1]
A heat-shrinkable film was obtained in the same manner as in Example 1 except that the ratio of the extrusion amount was adjusted to 99% for the first layer polyester and 1% for the second layer polyester. The characteristics of the obtained heat-shrinkable film were evaluated by the method described above. The results are summarized in Table 1 and Table 2.
［比較例２］
第１の層のポリエステルを、固有粘度（オルソクロロフェノール、３５℃）０．６５のポリエチレン−２，６−ナフタレート（「ＰＥＮ」という）とし、第２の層のポリエステルを、固有粘度（オルソクロロフェノール、３５℃）０．６５のポリエチレンテレフタレート−イソフタレート共重合体（イソフタル酸成分含有量１５モル％、「ＩＡ１５ＰＥＴ」という）とし、縦方向延伸時の予熱温度を１１５℃とした以外は実施例１と同様にして熱収縮性フィルムを得た。得られた熱収縮性フィルムの特性を前述の方法で評価した。結果を表１および表２にまとめる。
[Comparative Example 2]
The polyester of the first layer is polyethylene-2,6-naphthalate (referred to as “PEN”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.65, and the polyester of the second layer is made of intrinsic viscosity (orthochloro. Phenol, 35 ° C.) 0.65 polyethylene terephthalate-isophthalate copolymer (isophthalic acid component content 15 mol%, referred to as “IA15PET”), except that the preheating temperature during longitudinal stretching was 115 ° C. In the same manner as in No. 1, a heat-shrinkable film was obtained. The characteristics of the obtained heat-shrinkable film were evaluated by the method described above. The results are summarized in Table 1 and Table 2.
本発明の熱収縮性フィルムは、屈折率の高い層と低い層を規則的に配置させ、層間の構造的な干渉によって、光を選択的に反射させることにより、フィルムに施される絵柄印刷を美麗なものとすることができる。そのため、ＰＥＴボトルなどの容器の外面を覆う包装用フィルムとして好適に用いることができる。 The heat-shrinkable film of the present invention has a pattern printing applied to the film by regularly arranging a layer having a high refractive index and a layer having a low refractive index and selectively reflecting light by structural interference between the layers. It can be beautiful. Therefore, it can be suitably used as a packaging film that covers the outer surface of a container such as a PET bottle.
１ 最大反射率と反射率のベースラインの差
２ 反射率のベースライン
1 Difference between maximum reflectance and baseline of
Claims (3)
−２０℃≦（Ｔｇ１−Ｔｇ２）≦５０℃ The thermoplastic resin of the second layer is polyester, and the difference (Tg1-Tg2) between the glass transition temperature (Tg1) of the polyester of the first layer and the glass transition temperature (Tg2) of the polyester of the second layer is as follows. The heat-shrinkable film according to claim 1, which satisfies the formula.
−20 ° C. ≦ (Tg1-Tg2) ≦ 50 ° C.
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| JP2006059389A JP2007237434A (en) | 2006-03-06 | 2006-03-06 | Heat-shrinkable film |
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| JP2006059389A JP2007237434A (en) | 2006-03-06 | 2006-03-06 | Heat-shrinkable film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010100002A (en) * | 2008-10-27 | 2010-05-06 | Teijin Dupont Films Japan Ltd | Heat-shrinkable polyester-based film |
| JP2016060525A (en) * | 2014-09-19 | 2016-04-25 | 株式会社フジシールインターナショナル | Shrink label |
| WO2016199809A1 (en) * | 2015-06-11 | 2016-12-15 | 東洋紡株式会社 | Heat-shrinkable polyester film and packaging material |
-
2006
- 2006-03-06 JP JP2006059389A patent/JP2007237434A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010100002A (en) * | 2008-10-27 | 2010-05-06 | Teijin Dupont Films Japan Ltd | Heat-shrinkable polyester-based film |
| JP2016060525A (en) * | 2014-09-19 | 2016-04-25 | 株式会社フジシールインターナショナル | Shrink label |
| WO2016199809A1 (en) * | 2015-06-11 | 2016-12-15 | 東洋紡株式会社 | Heat-shrinkable polyester film and packaging material |
| JP2017213682A (en) * | 2015-06-11 | 2017-12-07 | 東洋紡株式会社 | Heat-shrinkable polyester-based film and package |
| CN107708966A (en) * | 2015-06-11 | 2018-02-16 | 东洋纺株式会社 | Heat-contractable ployester series film and package body |
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