JP4804193B2 - Biaxially stretched multilayer laminated film - Google Patents
Biaxially stretched multilayer laminated film Download PDFInfo
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Description
本発明は、屈折率の低い層と屈折率の高い層とを交互に規則的に配置させ、層間の屈折率差および各層の厚みによって特定の波長帯域の光を選択的に反射する、ポリエステルからなる二軸延伸多層積層フィルムに関する。 The present invention provides a polyester having a low refractive index layer and a high refractive index layer arranged alternately and regularly, and selectively reflecting light in a specific wavelength band according to the refractive index difference between the layers and the thickness of each layer. It is related with the biaxial stretching multilayer laminated film which becomes.
近年、食品包装（例えば、トレー、アイスクリームカップ等）、薬品包装（例えば、カプセル、錠剤等のＰＴＰ薬品包装）、ラミネート成形（例えば、家具、屋内外装飾品、電化製品、自動車部品等の、フィルムと紙、木材、金属、もしくは樹脂とのラミネート成形）、ＩＣ・磁気記録用カード材料（例えば、キャッシュカード、ＩＤカード、クレジットカード）、農業（例えば、グリーンハウス）といった幅広い分野で、ポリエステルのフィルムが用いられている。 In recent years, food packaging (for example, trays, ice cream cups, etc.), medicine packaging (for example, PTP medicine packaging for capsules, tablets, etc.), laminate molding (for example, furniture, interior / exterior decorations, electrical appliances, automobile parts, etc.) Polyester film in a wide range of fields, such as paper and wood, metal, or resin laminates, IC and magnetic recording card materials (for example, cash cards, ID cards, credit cards), and agriculture (for example, greenhouses). Is used.
ところで多層積層フィルムは、屈折率の低い層と高い層とを交互に多数積層したものであり、層間の構造的な光干渉によって、特定波長の光を選択的に反射または透過する光学干渉フィルムとすることができる。この多層積層フィルムは、選択的に反射または透過する光の波長を可視光領域とすれば、構造的な発色により意匠性に優れた、例えば、玉虫色に見える真珠光沢フィルムとすることができる。ここで得られる意匠性は、多層積層フィルムの構造的な発色によることから、染料などによる発色と異なり退色の問題もない。また、このような多層積層フィルムは、膜厚を徐々に変化させたり、異なる反射ピークを有するフィルムを貼り合せることで金属を使用したフィルムと同等の高い反射率を得ることができ、金属光沢フィルムや反射ミラーとして使用することができる。 By the way, the multilayer laminated film is one in which a large number of layers having a low refractive index and high layers are alternately laminated, and an optical interference film that selectively reflects or transmits light of a specific wavelength by structural optical interference between the layers. can do. This multilayer laminated film can be made into a pearly luster film that looks superior in design, for example, looks like an iridescent color, due to structural color development, when the wavelength of light that is selectively reflected or transmitted is in the visible light region. Since the design property obtained here is based on the structural coloration of the multilayer laminated film, there is no problem of fading unlike coloration with dyes. In addition, such a multilayer laminated film can obtain a high reflectance equivalent to a film using metal by gradually changing the film thickness or by laminating films having different reflection peaks. It can be used as a reflection mirror.
これまで、光干渉による発色を呈する多層積層フィルムとして、例えば特開昭５６−９９３０７号公報でポリエチレンテレフタレートとポリメチルメタクリレートといった相互に異なる熱可塑性樹脂を用いた多層積層フィルムが提案されている。また、例えば特表平９−５０６８３７号公報や国際公開第０１／４７７１１号パンフレットでは、屈折率の高い層としてポリエチレン−２，６−ナフタレンジカルボキシレートからなる層を用いた多層積層フィルムが提案されている。 So far, as a multilayer laminated film exhibiting color development due to light interference, for example, JP-A-56-99307 has proposed a multilayer laminated film using different thermoplastic resins such as polyethylene terephthalate and polymethyl methacrylate. In addition, for example, Japanese Patent Publication No. 9-506737 and International Publication No. 01/47711 pamphlet propose a multilayer laminated film using a layer made of polyethylene-2,6-naphthalenedicarboxylate as a layer having a high refractive index. ing.
しかし、このような光干渉により発色する従来の多層積層フィルムは、意匠性にこそ優れているものの、成形性には乏しいものばかりであった。
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ながら、成形・加工性に優れ、経時安定性、耐溶剤性、寸法安定性等にも優れた多層積層フィルムを提供することにある。
However, the conventional multilayer laminated film that develops color by such light interference is excellent in design but has poor moldability.
The object of the present invention is to reflect light of a specific wavelength with high selectivity, excellent color developability, iridescent metallic luster, excellent molding / workability, stability over time, solvent resistance, dimensional stability It is providing the multilayer laminated film excellent also in the property etc.
すなわち本発明は、第１のポリエステルの厚み０．０５〜０．５μｍの層と、第１のポリエステルより融点が１５℃以上低い第２のポリエステルの厚み０．０５〜０．５μｍの層とを１１層以上交互に積層してなる二軸延伸多層積層フィルムであり、第１のポリエステルおよび第２のポリエステルともに共重合ポリエチレンテレフタレートであって、かつ第１のポリエステルより融点が１５℃以上低い第２のポリエステルが共重合成分を１０〜１２モル％共重合した共重合ポリエチレンテレフタレートであり、第１のポリエステルの層の合計厚みが第１のポリエステルの層と第２のポリエステルの層との合計厚みの４０％以下であり、該積層フィルムの製膜方向および幅方向の２方向において８０℃における破断伸度が３００％以上かつ破断強度が３０ＭＰａ以下であって、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ことを特徴とするモールディング加工用二軸延伸多層積層フィルムである。 That is, the present invention comprises a layer having a thickness of 0.05 to 0.5 μm of the first polyester and a layer having a thickness of 0.05 to 0.5 μm of the second polyester having a melting point 15 ° C. or more lower than that of the first polyester. A biaxially stretched multi-layer laminated film in which 11 layers or more are alternately laminated, and the first polyester and the second polyester are both copolyethylene terephthalate and have a melting point of 15 ° C. or more lower than that of the first polyester. Is a copolymerized polyethylene terephthalate copolymerized with 10 to 12 mol% of a copolymer component, and the total thickness of the first polyester layer is the total thickness of the first polyester layer and the second polyester layer. 40% or less, and the breaking elongation at 80 ° C. is 300% or more and the breaking strength in two directions, ie, the film forming direction and the width direction of the laminated film. A biaxially stretched multilayer for molding , characterized in that a maximum reflectance peak of 20% or more higher than the reflectance baseline is observed in the reflectance curve for light having a wavelength of 30 MPa or less and a wavelength of 350 to 2000 nm It is a laminated film.
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ながら、成形・加工性に優れ、経時安定性、耐溶剤性、寸法安定性等にも優れた多層積層フィルムを提供することができる。 According to the present invention, light of a specific wavelength is reflected with high selectivity, excellent color developability, iridescent metallic luster, excellent molding / workability, stability over time, solvent resistance, dimensional stability It is possible to provide a multilayer laminated film having excellent properties.
以下、本発明を詳細に説明する。
［層構成］
第１のポリエステルの層および第２のポリエステルの層は、層間の光干渉によって選択的に光を反射するために、それぞれ１層の厚みが０．０５〜０．５μｍである。本発明の多層積層フィルムが示す選択反射は、紫外光、可視光、近赤外光の範囲において、適宜、その層厚を調整することで実現できる。それぞれの１層厚みが０．０５μｍ未満であるとその反射光はポリエステル組成分の吸収によって反射性能が得られなくなる。０．５μｍを超えると層間の光干渉によって選択的に反射する光が赤外光の領域に達し、光学的特性としての有用性が得られなくなる。第１のポリエステルの層と第２のポリエステルの層とは、交互に１１層以上積層される。１１層未満であると、所望の波長帯域での十分な反射率を得ることができない。
Hereinafter, the present invention will be described in detail.
[Layer structure]
Each of the first polyester layer and the second polyester layer has a thickness of 0.05 to 0.5 μm in order to selectively reflect light by optical interference between the layers. The selective reflection exhibited by the multilayer laminated film of the present invention can be realized by appropriately adjusting the layer thickness in the range of ultraviolet light, visible light, and near infrared light. When the thickness of each layer is less than 0.05 μm, the reflected light cannot be reflected by absorption of the polyester composition. If it exceeds 0.5 μm, the light selectively reflected by the light interference between layers reaches the infrared light region, and the usefulness as an optical characteristic cannot be obtained. Eleven or more layers of the first polyester layer and the second polyester layer are alternately laminated. If it is less than 11 layers, sufficient reflectance in a desired wavelength band cannot be obtained.
本発明において、第１のポリエステルの層の合計厚みは、第１のポリエステルの層と第２のポリエステルの層の合計厚みの４０％以下、好ましくは３５％以下である。４０％を超えると成形加工性が損なわれる。本発明では第２のポリエステルの層によって優れた成型加工性が確保される。そのため、第２のポリエステルの層の厚みは第１のポリエステルの層と第２のポリエステルの層の合計厚みの６０％以上を占めることが必要である。なお、第１のポリエステルの層の合計厚みは、光を安定して反射する積層構造を維持する観点から好ましくは２％以上である。 In the present invention, the total thickness of the first polyester layer is 40% or less, preferably 35% or less, of the total thickness of the first polyester layer and the second polyester layer. If it exceeds 40%, the moldability is impaired. In the present invention, excellent moldability is ensured by the second polyester layer. Therefore, the thickness of the second polyester layer needs to occupy 60% or more of the total thickness of the first polyester layer and the second polyester layer. The total thickness of the first polyester layer is preferably 2% or more from the viewpoint of maintaining a laminated structure that stably reflects light.
［破断伸度および破断強度］
本発明の二軸延伸多層積層フィルムは、高い成型加工性を得る観点から、少なくとも１方向において８０℃における破断伸度が、好ましくは２５０％以上、さらに好ましくは３００％以上、特に好ましくは４００％以上である。８０℃における破断伸度が２５０％未満であると、ＰＴＰ（プシュ スルー パッケージ Push Through Package）成形機で加工する際に十分な成形性が得られないので好ましくない。なお、破断伸度の上限は高々１０００％である。
[Elongation at break and strength at break]
From the viewpoint of obtaining high moldability, the biaxially stretched multilayer laminated film of the present invention has a breaking elongation at 80 ° C. in at least one direction of preferably 250% or more, more preferably 300% or more, and particularly preferably 400%. That's it. When the elongation at break at 80 ° C. is less than 250%, sufficient formability cannot be obtained when processing with a PTP (Push Through Package) molding machine. The upper limit of elongation at break is 1000% at most.
本発明の二軸延伸多層積層フィルムは、高い成型加工性を得る観点から、少なくとも１方向において８０℃における破断強度が、好ましくは３０ＭＰａ以下、さらに好ましくは２５ＭＰａ以下である。８０℃における破断強度が３０ＭＰａを超えると、ＰＴＰ成形機で加工した際にフィルム表面にひび、割れなどが生じて好ましくない。 From the viewpoint of obtaining high moldability, the biaxially stretched multilayer laminated film of the present invention has a breaking strength at 80 ° C. in at least one direction of preferably 30 MPa or less, more preferably 25 MPa or less. When the breaking strength at 80 ° C. exceeds 30 MPa, it is not preferable because the film surface is cracked or cracked when processed by a PTP molding machine.
［反射率］
本発明の二軸延伸多層積層フィルムは、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好ましくは２０％以上、さらに好ましくは３０％以上、特に好ましくは５０％以上高い最大反射率ピークが観察される。２０％未満であると所望の波長帯域での十分な反射率を得ることができず好ましくない。
[Reflectance]
The biaxially stretched multilayer laminated film of the present invention is preferably a maximum of 20% or more, more preferably 30% or more, particularly preferably 50% or more higher than the baseline of reflectance in the reflectance curve for light having a wavelength of 350 to 2000 nm. A reflectance peak is observed. If it is less than 20%, sufficient reflectance in a desired wavelength band cannot be obtained, which is not preferable.
［ポリエステル］
第１のポリエステルとしては結晶性ポリエステル、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、ポリエチレン−２，６−ナフタレンジカルボキシレートやその共重合体を用いることができる。
[polyester]
As the first polyester, a crystalline polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate or a copolymer thereof can be used.
第１のポリエステルとしては、好ましくはポリエチレンテレフタレート、さらに好ましくは全繰返し単位の８０モル％以上がエチレンテレフタレート成分からなるポリエチレンテレフタレートを用いる。共重合成分としては、例えばイソフタル酸、ナフタレンジカルボン酸を例示することができる。 The first polyester is preferably polyethylene terephthalate, more preferably polyethylene terephthalate in which 80 mol% or more of all repeating units are composed of an ethylene terephthalate component. Examples of the copolymer component include isophthalic acid and naphthalenedicarboxylic acid.
第２のポリエステルは、第１のポリエステルの融点より少なくとも１５℃は低い融点のポリエステルを用いる。第２のポリエステルの融点が、第１のポリエステルの融点より少なくと１５℃低くないと、２つのポリエステルの融点差が十分でなく、結果として、得られる多層延伸フィルムの層間に十分な屈折率差が付与できない。第１のポリエステルの融点と第２のポリエステルの融点との差は両者の密着性を維持する観点から高々５０℃であることが好ましい。 As the second polyester, a polyester having a melting point that is at least 15 ° C. lower than the melting point of the first polyester is used. If the melting point of the second polyester is at least 15 ° C. lower than the melting point of the first polyester, the difference in melting point between the two polyesters is not sufficient, and as a result, a sufficient difference in refractive index between the layers of the resulting multilayer stretched film. Cannot be granted. The difference between the melting point of the first polyester and the melting point of the second polyester is preferably at most 50 ° C. from the viewpoint of maintaining the adhesion between them.
第２のポリエステルとしては、例えば、共重合ポリエチレンテレフタレート、共重合ポリブチレンテレフタレート、共重合ポリエチレン−２，６−ナフタレンジカルボキシレートを用いることができる。第１のポリエステルとしてポリエチレンテレフターレートを用いる場合、第２のポリエステルとして共重合ポリエチレンテレフタレートを用いることが好ましい。 As the second polyester, for example, copolymerized polyethylene terephthalate, copolymerized polybutylene terephthalate, or copolymerized polyethylene-2,6-naphthalenedicarboxylate can be used. When polyethylene terephthalate is used as the first polyester, it is preferable to use copolymerized polyethylene terephthalate as the second polyester.
共重合ポリエステルの融点は、共重合成分の種類と量をコントロールすることによりコントロールすることができる。融点をコントロールするために用いる共重合成分としては、例えばイソフタル酸、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とった脂環族ジカルボン酸を用いることができる。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といった脂環族ジオールを用いてもよい。 The melting point of the copolyester can be controlled by controlling the type and amount of the copolymerization component. Examples of copolymer components used to control the melting point include aromatic carboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid Aliphatic dicarboxylic acids such as cycloaliphatic dicarboxylic acid can be used. Aliphatic diols such as hexanediol; alicyclic diols such as cyclohexanedimethanol may be used.
例えば第１のポリエステルとしてホモのポリエチレンテレフタレートを用いる場合、これより１５〜５０℃融点の低い第２のポリエステルとしては、例えばイソフタル酸、ナフタレンジカルボン酸、ヘキサメチレングリコールといった共重合成分を通常３〜６０モル％、好ましくは４〜４０モル％共重合した共重合ポリエチレンテレフタレートを用いればよい。 For example, when homopolyethylene terephthalate is used as the first polyester, a copolymer component such as isophthalic acid, naphthalenedicarboxylic acid or hexamethylene glycol is usually used in the range of 3 to 60 as the second polyester having a melting point of 15 to 50 ° C. A copolymerized polyethylene terephthalate copolymerized with mol%, preferably 4 to 40 mol% may be used.
［製造方法］
本発明の二軸延伸多層積層フィルムは、第１の押出し機より供給された第１のポリエステルと、第２の押出し機より供給された第２のポリエステルと、を溶融状態で交互に少なくとも１１層以上重ね合わせて多層未延伸シートとする。これを回転するドラム上にキャストすることにより、未延伸多層積層フィルムとする。このようにして得られた未延伸多層積層フィルムを、製膜方向とそれに直交する幅方向の二軸方向（フィルム面に沿った方向）に延伸する。延伸温度は、第１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。延伸の面積倍率は５〜５０倍とすることが好ましい。延伸倍率が大きい程、第１の層および第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、二軸延伸多層積層フィルムの光干渉が面方向に均一になるので、延伸倍率はこの範囲で大きいことが好ましい。延伸方法は、逐次二軸延伸、同時二軸延伸のいずれの方法であってもよい。必要があればさらに熱固定を行ってもよい。
[Production method]
The biaxially stretched multilayer laminated film of the present invention comprises at least 11 layers alternately in a molten state of a first polyester supplied from a first extruder and a second polyester supplied from a second extruder. A multilayer unstretched sheet is obtained by superimposing the above. By casting this on a rotating drum, an unstretched multilayer laminated film is obtained. The unstretched multilayer laminated film thus obtained is stretched in the biaxial direction (the direction along the film surface) in the width direction perpendicular to the film forming direction. The stretching temperature is in the range of the glass transition temperature (Tg) to Tg + 50 ° C. of the first polyester. The stretching area ratio is preferably 5 to 50 times. The larger the draw ratio, the smaller the variation in the plane direction in the individual layers of the first layer and the second layer due to the thinning by stretching, and the light interference of the biaxially stretched multilayer laminated film becomes uniform in the plane direction. Therefore, the draw ratio is preferably large in this range. The stretching method may be either sequential biaxial stretching or simultaneous biaxial stretching. If necessary, heat setting may be further performed.
以下、実施例をもって本発明をさらに説明する。
なお、実施例中の物性や特性は、下記の方法にて測定または評価した。
The present invention will be further described below with reference to examples.
In addition, the physical property and characteristic in an Example were measured or evaluated by the following method.
（１）ガラス転移温度（Ｔｇ）および融点
試料１０ｍｇについて、ＤＳＣ（ＴＡインスツルメンツ社製、商品名：ＤＳＣ２９２０）を用い、２０℃／ｍｉｎ．の昇温速度でガラス転移温度および融点を測定した。
(1) Glass transition temperature (Tg) and melting point About 10 mg of sample, DSC (TA Instruments make, brand name: DSC2920) is used, and 20 degreeC / min. The glass transition temperature and the melting point were measured at a temperature increase rate of.
（２）層厚み
サンプルを三角形に切り出し、包埋カプセルに固定後、エポキシ樹脂にて包埋した。そして、包埋されたサンプルをミクロトーム（ＵＬＴＲＡＣＵＴ−Ｓ、製造元：ライヘルト社）で製膜方向と厚み方向に沿って切断し、厚さ５０ｎｍの薄膜切片にした。得られた薄膜切片を、透過型電子顕微鏡（製造元：日本電子（株）、商品名：ＪＥＭ２０１０）を用いて、加速電圧１００ｋＶにて観察・撮影し、写真から各層の厚みを測定した。
(2) Layer thickness A sample was cut into a triangle, fixed in an embedded capsule, and then embedded in an epoxy resin. And the embedded sample was cut | disconnected along the film forming direction and thickness direction with the microtome (ULTRACUT-S, manufacturer: Reichert), and it was set as the thin film slice | slice of thickness 50nm. The obtained thin film slices were observed and photographed at an accelerating voltage of 100 kV using a transmission electron microscope (manufacturer: JEOL Ltd., trade name: JEM2010), and the thickness of each layer was measured from the photograph.
（３）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。
(3) 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.
（４）８０℃における破断伸度および破断強度
製膜方向の破断強度は、サンプルフィルムを試料幅（幅方向）１０ｍｍ、長さ（製膜方向）１５０ｍｍに切り出し、チャック間１００ｍｍ、引っ張り速度１００ｍｍ／ｍｉｎで、チャート速度５００ｍ／ｍｉｎの条件で外部環境を８０℃に保持した状態で、インストロンタイプの万能引っ張り試験装置にてサンプルを引張り、得られた荷重―伸び曲線から破断伸度、および破断強度を測定した。また、幅方向の破断強度は、サンプルフィルムを試料幅（製膜方向）１０ｍｍ、長さ（幅方向）１５０ｍｍに切り出す以外は、製膜方向の破断強度の測定と同様に行った。
(4) Elongation at break and breaking strength at 80 ° C. The breaking strength in the film forming direction was obtained by cutting a sample film into a sample width (width direction) of 10 mm and a length (film forming direction) of 150 mm, 100 mm between chucks, and a pulling speed of 100 mm / In a state where the external environment is maintained at 80 ° C. with a chart speed of 500 m / min, the sample is pulled with an Instron type universal tensile testing device, and the elongation at break and breakage are determined from the obtained load-elongation curve. The strength was measured. The breaking strength in the width direction was the same as the measurement of breaking strength in the film forming direction, except that the sample film was cut into a sample width (film forming direction) of 10 mm and a length (width direction) of 150 mm.
（５）成形加工性１
フィルムをエンボスローラーに圧着させ、前面にＲｚが５００μｍのエンボスが付与されたエンボスフィルムを作成した。なお、ここで言うＲｚは断面曲線から基準長さだけ抜き取った部分の平均線に平行な直線のうち、高い方から１〜５番目までの山の平均と、深い方から１〜５番目までの谷の平均との間隔をμｍ単位で表したものを指す。下記の基準で評価した。
◎：エンボス付与しても、エンボスフィルムに割れ発生は全くない。
○：エンボス付与の際、エンボスフィルムに微細な割れが発生する。
×：エンボス付与の際、エンボスフィルムに大きな割れが発生する。
(5)
The film was pressure-bonded to an embossing roller, and an embossed film with an embossing having an Rz of 500 μm on the front surface was prepared. In addition, Rz said here is the average of the 1st to 5th mountain from the highest, and the 1st to 5th from the deepest among the straight lines parallel to the average line of the part extracted by the reference length from the cross-sectional curve. The distance between the average of the valleys is expressed in μm. Evaluation was made according to the following criteria.
(Double-circle): Even if embossing is given, there is no crack generation in an embossed film.
○: During embossing, fine cracks occur in the embossed film.
X: During embossing, large cracks occur in the embossed film.
（６）成形加工性２
加熱プラグを有したＰＴＰ（Push Through Package）成形機にて、フィルムを８０℃にて、プレス成形して、長さ２０ｍｍ、幅１０ｍｍ、深さ１０ｍｍのポケットを１０ｍｍ間隔で付与したパック用フィルムを作成した。下記の基準で評価した。
◎：ポケットの形状は金型通りであり、ポケット間のフィルムにしわの発生もない。
○：ポケットの形状は金型通りであるが、ポケット間のフィルムに若干のしわの発生がある。
×：ポケットのしわがあり、また形状も金型通りでないものがある。さらに、ポケット間のフィルムにしわの発生が多い。
(6) Formability 2
A pack film in which a 20 mm long, 10 mm wide, 10 mm deep pocket is provided at 10 mm intervals by press molding the film at 80 ° C. with a PTP (Push Through Package) molding machine having a heating plug. Created. Evaluation was made according to the following criteria.
(Double-circle): The shape of a pocket is as a metal mold | die, and there is no wrinkle generation | occurrence | production in the film between pockets.
○: The shape of the pocket is the same as the mold, but some wrinkles occur in the film between the pockets.
X: There is a wrinkle of a pocket, and there is a shape which does not follow the mold Furthermore, wrinkles are often generated on the film between the pockets.
（７）印刷性
メチルエチルケトンで顔料を分散したインクにて、グラビアロールを使用して、フィルムロールの片面に連続印刷した。なお、この印刷性評価は、耐溶剤性評価の代替手段である。
○：フィルムロールの印刷反対面（無印刷面）に、印刷面からのインクの転写はない。
×：フィルムロールの印刷反対面（無印刷面）に、印刷面からのインクの転写が前面にある。
(7) Printability Continuous printing was performed on one side of a film roll using a gravure roll with an ink in which a pigment was dispersed with methyl ethyl ketone. This printability evaluation is an alternative to solvent resistance evaluation.
◯: There is no transfer of ink from the printing surface to the opposite surface (non-printing surface) of the film roll.
X: The transfer of the ink from a printing surface exists in the front surface on the printing opposite surface (non-printing surface) of a film roll.
（８）層間の密着性
サンプルフィルム（１０ｍｍ×５０ｍｍ）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。
(8) Interlayer adhesion After applying 100 mm of 24 mm wide adhesive tape (product name: cello tape (registered trademark)) on both sides of the sample film (10 mm × 50 mm) and peeling it off at 180 ° peel angle The peeled surface was observed. This was performed for each 10 samples, and the number of delaminations was calculated.
（９）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。そして、透過色および反射色の色相の斑を総合して、以下の評価基準で判断した。
○：サンプル内に視認できる色相の斑がない。
△：サンプル内に一部、色相の異なる部分が見られる。
×：明らかに斑や筋となって見える色相斑が確認できる。
(9) Hue spots 10 A4 size sample films are prepared, and each sample film is layered on white plain paper. Under the illumination of 30 lux, visible hue spots in the sample film are visually observed. 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. Then, the patches of the hues of the transmitted color and the reflected color were synthesized and judged according to the following evaluation criteria.
◯: There are no visible hue spots in the sample.
(Triangle | delta): The part from which a hue differs partially in a sample is seen.
X: Hue spots that clearly appear as spots or streaks can be confirmed.
［実施例１］
第１のポリエステルとしてイソフタル酸を４モル％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６２の共重合ポリエチレンテレフタレート（以下「ＩＡ４ＰＥＴ」という）を、第２のポリエステルとしてイソフタル酸を１２モル％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６５の共重合ポリエチレンテレフタレート（以下「ＩＡ１２ＰＥＴ」という）に真球状シリカ粒子（平均粒径：１．５μｍ）を０．１０ｗｔ％添加したもの、をそれぞれ準備した。そして、第１のポリエステルおよび第２のポリエステルを、それぞれ１７０℃で３時間乾燥後、押出機に供給し、２８０℃まで加熱して溶融状態とし、第１のポリエステルを３０１層、第２のポリエステルを３００層に分岐させた後、第１のポリエステルの層と第２のポリエステルの層とを交互に積層する多層フィードブロック装置を使用して積層し、その積層状態を保持したままダイへと導き、キャスティングドラム上にキャストして各層の厚みが等しくなるように第１のポリエステルの層と第２のポリエステルの層が交互に積層された総数６０１層の未延伸多層積層フィルムを作成した。このとき第１のポリエステルと第２のポリエステルの押出し量が２０：８０になるように調整し、かつ、両端層が第１のポリエステルになるように積層した。この多層未延伸フィルムを９０℃の温度で製膜方向に３．６倍延伸し、さらに９５℃の温度で幅方向に３．９倍に延伸し、２３０℃で３秒間熱固定処理を行った。得られた二軸延伸多層積層フィルムの物性を表２に示す。
[Example 1]
A copolymerized polyethylene terephthalate (hereinafter referred to as “IA4PET”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62 copolymerized with 4 mol% of isophthalic acid as the first polyester, and 12 of isophthalic acid as the second polyester. Add 0.10 wt% of spherical silica particles (average particle size: 1.5 μm) to 0.65 copolymerized polyethylene terephthalate (hereinafter referred to as “IA12PET”) having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.6%. We prepared for each. Then, the first polyester and the second polyester are each dried at 170 ° C. for 3 hours, and then supplied to an extruder, heated to 280 ° C. to be in a molten state, the first polyester is 301 layers, the second polyester Is branched into 300 layers, and then laminated using a multilayer feed block device in which the first polyester layer and the second polyester layer are alternately laminated, and led to a die while maintaining the laminated state. The film was cast on a casting drum to produce a total of 601 unstretched multilayer laminated films in which the first polyester layer and the second polyester layer were alternately laminated so that the thickness of each layer was equal. At this time, the extrusion amount of the first polyester and the second polyester was adjusted to 20:80, and the both end layers were laminated so as to be the first polyester. This multilayer unstretched film was stretched 3.6 times in the film forming direction at a temperature of 90 ° C., further stretched 3.9 times in the width direction at a temperature of 95 ° C., and heat-set at 230 ° C. for 3 seconds. . Table 2 shows the physical properties of the obtained biaxially stretched multilayer laminated film.
［実施例２〜３および比較例１〜４］
第１のポリエステルおよび第２のポリエステルならびに製造条件を表１に示すように変更した以外は実施例１と同様にして二軸延伸多層積層フィルムを製造した。得られた二軸延伸多層積層フィルムの物性を表２に示す。
[Examples 2 to 3 and Comparative Examples 1 to 4 ]
A biaxially stretched multilayer laminated film was produced in the same manner as in Example 1 except that the first polyester, the second polyester, and the production conditions were changed as shown in Table 1. Table 2 shows the physical properties of the obtained biaxially stretched multilayer laminated film.
なお、表において用いたポリエステルは以下のとおりである。
ＩＡ４ＰＥＴ：
イソフタル酸を４モル％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６２の共重合ポリエチレンテレフタレート
ＩＡ１２ＰＥＴ：
イソフタル酸を１２モル％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６５の共重合ポリエチレンテレフタレート
ＮＤＣ１０ＰＥＴ：
２，６−ナフタレンジカルボン酸を１０モル％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６３の共重合ポリエチレンテレフタレート
ＣＨＤＭ２０ＰＥＴ：
シクロヘキサンジメタノールを２０モル％共重合した固有粘度（オルトクロロフェノール、３５℃）０．６０の共重合ポリエチレンテレフタレート
ＰＥＴ：
固有粘度（オルトクロロフェノール、３５℃）０．６２のポリエチレンテレフタレート
ＰＥＮ：
固有粘度（オルトクロロフェノール、３５℃）０．６２のポリエチレン−２，６−ナフタレンジカルボキシレート
The polyester used in the table is as follows.
IA4PET:
Copolymerized polyethylene terephthalate IA12PET having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62 copolymerized with 4 mol% of isophthalic acid:
Copolymerized polyethylene terephthalate NDC10PET having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.65 obtained by copolymerization of 12 mol% of isophthalic acid:
Copolymerized polyethylene terephthalate CHDM20PET having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.63 copolymerized with 10 mol% of 2,6-naphthalenedicarboxylic acid:
Copolymerized polyethylene terephthalate PET having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.60 copolymerized with 20 mol% of cyclohexanedimethanol:
Polyethylene terephthalate PEN having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62:
Polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.62
本発明の二軸延伸多層積層フィルムは、モールディング加工、エンボス加工など変形加工する用途、フィルムを保持金具に挟んで固定して使用する用途に特に有用であり、例えば食品包装、薬品包装、ラミネート成形、ＩＣ・磁気記録用カード材料、農業といった分野での使用に有用である。 The biaxially stretched multilayer laminated film of the present invention is particularly useful for applications such as molding and embossing, and applications in which the film is fixed by holding it between holding metal fittings, such as food packaging, chemical packaging, and laminate molding. It is useful for use in fields such as IC and magnetic recording card materials and agriculture.
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 reflectance 2 Baseline of reflectance
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