JP4173074B2 - Biaxially oriented multilayer laminated film, decorative yarn and decorative powder - Google Patents
Biaxially oriented multilayer laminated film, decorative yarn and decorative powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims description 14
- 229920000728 polyester Polymers 0.000 claims description 62
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 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 claims description 9
- 239000005001 laminate film Substances 0.000 claims description 7
- 238000005034 decoration Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 212
- 239000010408 film Substances 0.000 description 139
- 230000008018 melting Effects 0.000 description 49
- 238000002844 melting Methods 0.000 description 49
- 229920005989 resin Polymers 0.000 description 38
- 239000011347 resin Substances 0.000 description 38
- 239000002245 particle Substances 0.000 description 31
- -1 polyethylene terephthalate Polymers 0.000 description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
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- 229920001577 copolymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid 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
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920006038 crystalline resin Polymers 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
- 230000007547 defect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 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
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 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
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 241000218202 Coptis Species 0.000 description 1
- 244000062175 Fittonia argyroneura Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Images
Landscapes
- Optical Filters (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
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た、層間の屈折率差および各層の厚みによって任意の波長帯の光を選択的に反射する多層積層フィルムに関する。 The present invention is a multilayer laminated film that selectively reflects light in an arbitrary wavelength band according to the difference in refractive index between layers and the thickness of each layer, in which layers having a low refractive index and layers having a high refractive index are alternately and regularly arranged. About.
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。このような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帯を可視光領域に設定すれば、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できる。しかも、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は少ない。 The multilayer laminated film is obtained by alternately laminating a plurality of layers having a low refractive index and a layer having a high refractive index, and is an optical interference film that selectively reflects or transmits light of a specific wavelength by structural optical interference between the layers. be able to. Such a multilayer laminated film can be made into a pearly luster film that looks superior in design, for example, looks iridescent, by structural coloration, if the wavelength band of light that is selectively reflected or transmitted is set in the visible light region. In addition, since the design properties obtained here are due to the structural color development of the multilayer laminated film, there are few problems of fading unlike the color development due to dyes and the like.
一方で、従来からポリエチレンテレフタレート二軸延伸フィルム上にアルミ蒸着などを施し、1mm以下の幅にマイクロスリットしたフィルム状繊維(金銀糸)が、衣料等の装飾用に使用されてきた。そして近年、さらなる意匠性の向上のために多層積層フィルムの使用も検討されてきている。 On the other hand, conventionally, film-like fibers (gold and silver threads) that have been subjected to aluminum vapor deposition on a polyethylene terephthalate biaxially stretched film and microslit to a width of 1 mm or less have been used for decoration of clothing and the like. In recent years, the use of multilayer laminated films has been studied for further improvement in designability.
上記のような多層積層フィルムとしては、特開昭56−99307号公報など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などの異なる素材の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、特表平9−506837号公報やWO01/47711号公報などで、例えば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多層延伸フィルムも提案されている。
従来から、多層積層フィルムの各層の屈折率差は、各層を構成する樹脂の有する屈折率差に由来していた。例えば、特開昭56−99307号公報に記載されているように、屈折率の高い層には、ポリエチレンテレフタレートを使用し、屈折率の低い層には、ポリメタクリレートのような屈折率の低い樹脂を用いてきていた。しかし、樹脂の有する屈折率に頼って層間の屈折率差を設ける従来の考え方では、各層を構成する樹脂は、どうしても組成の大きく異なる樹脂を選択する必要があり、層間の密着性の劣るものしか得られなかった。さらに特開昭56−99307号公報に記載の多層積層フィルムは、色相の斑が大きいために、用途が限られる上、フィルム強度が十分でないために、支持基材としてポリエチレンテレフタレート二軸延伸フィルムとラミネ−トしたのちにマイクロスリットする必要があり、加工上の欠点などの課題が指摘されている。 Conventionally, the refractive index difference of each layer of the multilayer laminated film is derived from the refractive index difference of the resin constituting each layer. For example, as described in JP-A-56-99307, polyethylene terephthalate is used for a layer having a high refractive index, and a resin having a low refractive index such as polymethacrylate is used for a layer having a low refractive index. Has been used. However, according to the conventional concept of providing a difference in refractive index between layers depending on the refractive index of the resin, it is necessary to select resins having different compositions for each layer, and the adhesion between the layers is inferior. It was not obtained. Furthermore, since the multilayer laminated film described in JP-A-56-99307 has large hue spots, its use is limited and the film strength is not sufficient, so that a polyethylene terephthalate biaxially stretched film as a supporting substrate It is necessary to microslit after lamination, and problems such as processing defects have been pointed out.
また、特表平9−506837号公報やWO01/47711号公報では、屈折率の高い層に屈折率の高いポリエチレン2,6−ナフタレンジカルボキシレート(以下、PENと称することがある。)を使用し、屈折率の低い層に熱可塑性エラストマーを使用した2軸延伸フィルムや屈折率の高い層に屈折率の高いPENを使用し、屈折率の低い層にイソフタル酸を30モル%共重合したPENを使用した1軸延伸多層延伸フィルムが例示されている。これらの多層積層フィルムは屈折率の低い層を実質的に非晶質にしている。 In Japanese Patent Publication No. 9-506837 and WO01 / 47711, polyethylene 2,6-naphthalenedicarboxylate (hereinafter sometimes referred to as PEN) having a high refractive index is used for a layer having a high refractive index. PEN in which a biaxially stretched film using a thermoplastic elastomer for the low refractive index layer, PEN having a high refractive index is used for the high refractive index layer, and 30 mol% of isophthalic acid is copolymerized in the low refractive index layer A uniaxially stretched multilayer stretched film using is used. These multilayer laminated films make the layer with a low refractive index substantially amorphous.
しかしこうしたフィルムは、層間の屈折率差を大きくするために、組成の異なる樹脂を組み合わせるため、各層間の密着が弱く層間剥離現象が発生し、実用に耐えないものであった。またフィルムに延伸処理を施しても、層間密着性が十分に得られなかったり、2軸延伸処理が面方向に均一に行えず、膜質が不均一化したりして、実用上の課題が潜在していた。 However, such a film cannot be put into practical use because a resin having a different composition is combined in order to increase the refractive index difference between the layers, and the adhesion between the layers is weak and the delamination phenomenon occurs. In addition, even if the film is stretched, sufficient adhesion between the layers cannot be obtained, the biaxial stretching process cannot be performed uniformly in the surface direction, and the film quality becomes non-uniform. It was.
本発明はかかる課題を解決して、従来の多層積層フィルムにない高強度でかつ層間の密着性が高く、しかも裂けにくい多層積層フィルムを得ることを目的とする。 An object of the present invention is to solve the above problems and to obtain a multilayer laminated film that has high strength, high interlaminar adhesion, and is difficult to tear, which is not found in conventional multilayer laminated films.
本発明は、第1の層と第2の層とを総層数で11層以上になるよう交互に積層し、なおかつ二軸延伸を施した多層積層フィルムであって、波長350〜2000nmの範囲での光の最大反射率は、波長350〜2000nmの範囲での光反射率曲線から得られる反射率のベースラインよりも20%以上高く、第1の層はポリエステル組成物から構成され、第2の層は第1の層とは組成の異なるポリエステル組成物から構成され、第1の層は第2の層よりも屈折率が高く、第1の層と第2の層は厚みが0.05〜0.5μmの範囲内であり、なおかつ第1の層の厚みと第2の層の厚み比(第1の層/第2の層)が1.2以上5.0以下である二軸延伸多層積層フィルムであって、該二軸延伸多層積層フィルムを1mm角以下に粉砕して装飾用粉末とする用途に用いることを特徴とする、装飾用粉末用二軸延伸多層積層フィルムである。 The present invention is a multilayer laminated film in which the first layer and the second layer are alternately laminated so that the total number of layers is 11 or more and biaxially stretched, and has a wavelength range of 350 to 2000 nm. The maximum reflectance of light at 20% or more higher than the reflectance baseline obtained from the light reflectance curve in the wavelength range of 350 to 2000 nm, the first layer is composed of a polyester composition, The layer is composed of a polyester composition having a composition different from that of the first layer, the first layer has a higher refractive index than the second layer, and the first layer and the second layer have a thickness of 0.05. Biaxial stretching with a thickness ratio of the first layer to the second layer (first layer / second layer) of 1.2 to 5.0 in a range of ˜0.5 μm a multilayer laminate film, decorative powder by pulverizing the biaxially oriented multi-layer laminate film below 1mm square It is characterized by using in applications, a biaxially oriented multi-layer laminated film for decorative powder.
屈折率の高い層と屈折率の低い層を構成する樹脂組成を極限まで近くしても、屈折率の低い層を構成する樹脂の融点を屈折率の高い層を構成する樹脂より低くして、かつ2軸延伸処理後に該融点の低い樹脂からなる層の分子配向を緩和させることにより、層間の屈折率差を発現させつつ、2軸延伸加工性もすぐれ、層間密着性も優れた多層延伸フィルムが得られることを見出し、本発明に到達した。すなわち本発明は、各層を構成する樹脂の組合せとして、従来から層間の屈折率差を発現させ難いとされていた極めて組成の近い樹脂の組合せを採用して、多層積層フィルムに十分な強度と層間の密着性を具備させながら、驚くべきことに層間の屈折率差も十分に具備させたものである。 Even if the resin composition constituting the high refractive index layer and the low refractive index layer is close to the limit, the melting point of the resin constituting the low refractive index layer is lower than the resin constituting the high refractive index layer, In addition, by relaxing the molecular orientation of the layer composed of the resin having a low melting point after the biaxial stretching treatment, the multilayer stretched film has excellent biaxial stretching workability and excellent interlayer adhesion while expressing the refractive index difference between the layers. And the present invention has been achieved. That is, the present invention employs a combination of resins having a very close composition, which has conventionally been difficult to express a difference in refractive index between layers, as a combination of resins constituting each layer, so that the multilayer laminated film has sufficient strength and interlayer. Surprisingly, the difference in refractive index between the layers is sufficiently provided.
本発明の好ましい態様として、次のものがある。フィルムの破断強度が、連続製膜方向および連続製膜方向に垂直な幅方向のいずれにおいても、単位断面積あたり150MPa以上であること。フィルム中のエチレンテレフタレート成分の割合が、ポリエステルの全繰返し単位を基準として、80モル%以上であること。全繰返し単位の1.5〜20モル%がイソフタル酸または2,6−ナフタレンジカルボン酸成分であること。第1の層を構成するポリエステルが、結晶性ポリエステルであり、全繰返し単位の90モル%以上がエチレンテレフタレート成分であって、第2の層を構成するポリエステルが、結晶性ポリエステルであり、全繰返し単位の75〜97モル%がエチレンテレフタレート成分であること。また、別の態様として、本発明の二軸延伸多層積層フィルムを1mm以下にマイクロスリットして形成された装飾用金銀糸や、本発明の二軸延伸多層積層フィルムを1mm角以下に粉砕して形成された装飾用粉末も挙げられる。 Preferred embodiments of the present invention include the following. The breaking strength of the film is 150 MPa or more per unit cross-sectional area in both the continuous film forming direction and the width direction perpendicular to the continuous film forming direction. The ratio of the ethylene terephthalate component in the film is 80 mol% or more based on all repeating units of the polyester. 1.5 to 20 mol% of all repeating units are isophthalic acid or 2,6-naphthalenedicarboxylic acid component. The polyester constituting the first layer is a crystalline polyester, 90 mol% or more of all repeating units are ethylene terephthalate components, the polyester constituting the second layer is a crystalline polyester, and all repeating 75 to 97 mol% of the unit is an ethylene terephthalate component. Moreover, as another aspect, the decorative gold-silver thread formed by microslit the biaxially stretched multilayer laminate film of the present invention to 1 mm or less, or the biaxially stretched multilayer laminate film of the present invention is pulverized to 1 mm square or less. The decorative powder formed can also be mentioned.
本発明の2軸延伸多層積層フィルムは、構造的な発色により玉虫色に見えるなど優れた意匠性を有するだけでなく、マイクロスリットなどの加工にも耐えうる高強度を有し、かつ優れた層間の密着性および高度の破断強度を有することから、装飾用フィルム状繊維や1.0mm以下のフィルム状粉体を始め、各種ラベルなどにも適用できその工業的価値は高い。 The biaxially stretched multilayer laminated film of the present invention not only has excellent design properties such as an iridescent color due to structural coloration, but also has high strength that can withstand processing such as micro slits, and excellent interlayer Since it has adhesiveness and high breaking strength, it can be applied to various labels such as decorative film-like fibers and film-like powders of 1.0 mm or less, and its industrial value is high.
本発明の二軸延伸多層積層フィルムは、ポリエステル組成物からなる第1の層と、同じくポリエステル組成物からなる第2の層とを交互に少なくとも11層積層されたものである。ここで第1の層と第2の層とを構成するポリエステル組成物は、組成は非常に近いものであるが組成を異にすることが必要である。積層数が11層未満だと、多重干渉による選択反射が小さく、十分な反射率が得られない。積層数の上限は、生産性などの観点から高々501層であることが好ましい。 The biaxially stretched multilayer laminated film of the present invention is obtained by alternately laminating at least 11 layers of a first layer made of a polyester composition and a second layer made of the polyester composition. Here, the polyester compositions constituting the first layer and the second layer are very close in composition, but need to have different compositions. If the number of layers is less than 11, selective reflection due to multiple interference is small, and sufficient reflectance cannot be obtained. The upper limit of the number of stacked layers is preferably at most 501 from the viewpoint of productivity.
さらに第1の層および第2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の範囲内で、なおかつ後述の厚み比を満足する必要がある。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。一方、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えられなくなる。なお第1の層が相対的に高屈折率層側で、第2の層が相対的に低屈折率層側である。 Furthermore, the first layer and the second layer each selectively reflect light by optical interference between the layers, so that the thickness of each layer is within a range of 0.05 to 0.5 μm, and the thickness ratio described later Need to be satisfied. 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 due to absorption of the polyester composition. On the other hand, 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. The first layer is on the relatively high refractive index layer side, and the second layer is on the relatively low refractive index layer side.
また本発明の二軸延伸多層積層フィルムは光の最大反射率が、波長350〜2000nmの範囲において、反射率曲線のベースラインよりも20%以上高い。この最大反射率とベースライン反射率との差は、好ましくは30%以上、さらに好ましくは50%以上にすることである。図1は、本発明の二軸延伸多層積層フィルムの反射率曲線の一例を示す。図1中の、1は最大反射率と反射率のベースラインの差、2は反射率のベースラインを示す。二軸延伸多層積層フィルムに、最大反射率が反射率のベースラインよりも20%以上高い反射ピークが存在しないと、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しては使用できない。 In the biaxially stretched multilayer laminated film of the present invention, the maximum light reflectance is 20% or more higher than the baseline of the reflectance curve in the wavelength range of 350 to 2000 nm. The difference between the maximum reflectance and the baseline reflectance is preferably 30% or more, more preferably 50% or more. FIG. 1 shows an example of the reflectance curve of the biaxially stretched multilayer laminated film of the present invention. In FIG. 1, 1 is the difference between the maximum reflectance and the baseline of reflectance, and 2 is the baseline of reflectance. If the biaxially stretched multilayer laminated film does not have a reflection peak whose maximum reflectance is 20% or more higher than the baseline of reflectance, it cannot be used as an optical interference film that selectively reflects or transmits light of a specific wavelength.
ところで、本発明では、上述の厚み構成で、二軸延伸多層積層フィルムを構成する第1の層と第2の層に、従来の樹脂の屈折率差に頼らず、十分な屈折率差を付与している。樹脂の屈折率差に頼らずに二軸延伸多層積層フィルムを構成する第1の層と第2の層に十分な屈折率差を付与するには、例えば延伸後の熱処理によって屈折率差を付与する方法が挙げられる。すなわち、高融点を持った第一の層の樹脂は、延伸により配向が進み、高屈折率を示し、低融点を示す第2の層の樹脂は、熱処理により無配向化することで、屈折率が低下する。その結果として、樹脂として屈折率がほぼ同等である樹脂の組み合わせにおいても、十分な屈折率差を付与することができる。ここで得られる屈折率差は、好ましくは0.03以上、より好ましくは0.05以上である。なお、多層フィルムの個々の層の屈折率を、積層状態において測定することには困難さが伴うが、光学的に十分に厚い状態でのフィルムの屈折率から判断することができる。 By the way, in this invention, sufficient refractive index difference is given to the 1st layer and 2nd layer which comprise a biaxial stretching multilayer laminated film by the above-mentioned thickness structure without depending on the refractive index difference of the conventional resin. is doing. In order to give a sufficient refractive index difference to the first layer and the second layer constituting the biaxially stretched multilayer laminated film without depending on the refractive index difference of the resin, for example, the refractive index difference is given by heat treatment after stretching. The method of doing is mentioned. That is, the first layer resin having a high melting point is oriented by stretching and exhibits a high refractive index, and the second layer resin having a low melting point is rendered non-oriented by heat treatment, thereby providing a refractive index. Decreases. As a result, a sufficient difference in refractive index can be imparted even in a combination of resins having substantially the same refractive index as the resin. The refractive index difference obtained here is preferably 0.03 or more, more preferably 0.05 or more. Although it is difficult to measure the refractive index of each layer of the multilayer film in the laminated state, it can be determined from the refractive index of the film in a sufficiently optically thick state.
本発明の二軸延伸多層積層フィルムは、極めて組成の類似した樹脂を第1の層および第2の層を構成する樹脂として選択でき、そのような組成の類似した樹脂の選択によって層間の密着性が飛躍的に向上されたものである。したがって、本発明の二軸延伸多層積層フィルムは、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のポリエステルからなる。エチレンテレフタレート成分が全繰返し単位の80モル%未満だと、層間の密着性が低下する。 In the biaxially stretched multilayer laminated film of the present invention, a resin having a very similar composition can be selected as a resin constituting the first layer and the second layer, and the adhesion between the layers can be determined by selecting a resin having a similar composition. Is a dramatic improvement. Therefore, in the biaxially stretched multilayer laminated film of the present invention, 80 mol% or more of all repeating units are made of polyester having an ethylene terephthalate component. When the ethylene terephthalate component is less than 80 mol% of all repeating units, the adhesion between the layers is lowered.
なお、エチレンテレフタレート成分以外の共重合成分としては、融点を低下させやすいことから、2,6−ナフタレンジカルボン酸またはイソフタル酸成分が好ましい。2,6−ナフタレンジカルボン酸またはイソフタル酸成分の共重合割合は、繰返し単位を基準として、1.5〜20モル%の範囲である。2,6−ナフタレンジカルボン酸またはイソフタル酸成分のモル数が、下限よりも少ないと、第1の層と第2の層に十分な屈折率差を付与しがたく、他方、2,6−ナフタレンジカルボン酸またはイソフタル酸成分のモル数が上限よりも多いと、第1の層と第2の層を構成するポリエステルの組成が大きく異なり、層間の密着性が低下しやすい。上記のような製造方法によって極めて密着性の高い二軸延伸多層積層フィルムを製造できるが、一方で第2の層は、熱処理によりほぼ無配向となるために、従来のポリエチレンテレフタレートフィルムよりも大きく機械強度が低下する。 The copolymer component other than the ethylene terephthalate component is preferably a 2,6-naphthalenedicarboxylic acid or isophthalic acid component because the melting point is likely to be lowered. The copolymerization ratio of the 2,6-naphthalenedicarboxylic acid or isophthalic acid component is in the range of 1.5 to 20 mol% based on the repeating unit. If the number of moles of the 2,6-naphthalenedicarboxylic acid or isophthalic acid component is less than the lower limit, it is difficult to give a sufficient refractive index difference between the first layer and the second layer, while 2,6-naphthalene When the number of moles of the dicarboxylic acid or isophthalic acid component is larger than the upper limit, the composition of the polyester constituting the first layer and the second layer is greatly different, and the adhesion between the layers tends to be lowered. A biaxially stretched multilayer laminated film with extremely high adhesion can be produced by the production method as described above. On the other hand, since the second layer becomes almost non-oriented by heat treatment, it is larger than the conventional polyethylene terephthalate film. Strength decreases.
そこで発明では、機械的に十分な強度を有する第1の層を大きくすることにより、従来にない高強度でかつ密着性が高い二軸延伸多層積層フィルムを発明するにいたった。 Therefore, the present invention has invented a biaxially stretched multilayer laminated film that has high strength and high adhesion that has never been achieved by enlarging the first layer having sufficient mechanical strength.
すなわち、本発明では、二軸延伸多層積層フィルムを構成する第1の層と第2の層の単層での厚み比率(第1の層/第2の層)を1.2以上5.0以下にすることが必要であり、第1の層と第2の層の比率が1.2より小さいとマイクロスリットなどの加工に十分な機械強度を保つことができない。第1の層と第2の層の比率が5.0以上であると光学的に十分な反射が得られなくなる。好ましい上限は、3.0以下、より好ましくは、2.5以下である。好ましい下限は1.5以上、より好ましくは、1.8以上である。 That is, in the present invention, the thickness ratio (first layer / second layer) of the first layer and the second layer constituting the biaxially stretched multilayer laminated film is 1.2 or more and 5.0. It is necessary to make the following, and if the ratio of the first layer to the second layer is smaller than 1.2, the mechanical strength sufficient for processing such as a micro slit cannot be maintained. When the ratio between the first layer and the second layer is 5.0 or more, optically sufficient reflection cannot be obtained. A preferable upper limit is 3.0 or less, more preferably 2.5 or less. A preferable lower limit is 1.5 or more, and more preferably 1.8 or more.
[第1の層]
本発明の好ましい例において、第1の層を構成する樹脂は、主たる繰返し単位がエチレンテレフタレート成分からなるポリエステルである。好ましくは、後述の第2の層を構成するポリエステルよりも融点を高度に維持できることから、ホモポリエチレンテレフタレートまたは繰返し単位の95モル%以上がエチレンテレフタレート成分からなる共重合ポリエチレンテレフタレートである。エチレンテレフタレート成分のモル数が繰返し単位の95モル%未満だと、融点が低下し、後述の第2の層を構成するポリエステルとの融点差が得られがたく、結果として、多層延伸フィルムに十分な屈折率差を付与しがたい。これらの中でも、融点を高度に維持できることから、ホモポリエチレンテレフタレートが好ましい。エチレンテレフタレート成分以外の共重合成分としては、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のような他の芳香族カルボン酸;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等の如き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等の酸成分や、ブタンジオール、ヘキサンジオール等の如き脂肪族ジオ−ル;シクロヘキサンジメタノールの如き脂環族ジオール等、グリコール成分を好ましく挙げることができる。
[First layer]
In a preferred example of the present invention, the resin constituting the first layer is a polyester whose main repeating unit is an ethylene terephthalate component. Preferably, homopolyethylene terephthalate or copolymer polyethylene terephthalate in which 95 mol% or more of repeating units are composed of an ethylene terephthalate component can be maintained at a higher melting point than the polyester constituting the second layer described later. When the number of moles of the ethylene terephthalate component is less than 95% by mole of the repeating unit, the melting point is lowered, and it is difficult to obtain a difference in melting point from the polyester constituting the second layer to be described later. It is difficult to give a large difference in refractive index. Among these, homopolyethylene terephthalate is preferable because the melting point can be maintained at a high level. Examples of copolymer components other than the ethylene terephthalate component include other aromatic carboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid An aliphatic dicarboxylic acid such as an acid; an acid component such as an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; an aliphatic diol such as butanediol or hexanediol; an alicyclic diol such as cyclohexanedimethanol; A glycol component can be mentioned preferably.
ところで、第1の層を構成する樹脂の融点は、250〜260℃の範囲であることが、後述の第2の層を構成する樹脂との融点差を比較的大きくできることから好ましい。第1の層を構成する樹脂の融点が下限よりも低いと、第2の層を構成する樹脂との融点差が小さくなり、結果として、得られる多層延伸フィルムに十分な屈折率差を付与することが困難になる。なお、共重合していないポリエチレンテレフタレートの融点は、通常256℃近傍である。 By the way, the melting point of the resin constituting the first layer is preferably in the range of 250 to 260 ° C., since the difference in melting point from the resin constituting the second layer described later can be relatively large. When the melting point of the resin constituting the first layer is lower than the lower limit, the melting point difference from the resin constituting the second layer is reduced, and as a result, a sufficient refractive index difference is imparted to the resulting multilayer stretched film. It becomes difficult. In addition, the melting point of non-copolymerized polyethylene terephthalate is usually around 256 ° C.
[第2の層]
本発明の好ましい例において、第2の層を構成する樹脂は、主たる繰返し単位がエチレンテレフタレート成分からなるポリエステルである。特に2軸延伸における製膜性の観点から、結晶性ポリエステルであることが好ましい。また、前述の第1の層を構成するポリエステルよりも融点を低くできることから、繰返し単位の75〜97モル%がエチレンテレフタレート成分からなり、3〜25モル%がそれ以外の共重合成分からなる共重合ポリエチレンテレフタレートである。エチレンテレフタレート成分のモル数が繰返し単位の75モル%未満であるか共重合成分のモル数が25モル%を超えると、実質的にポリマーが非晶性を示し、2軸延伸での製膜性が低下し、かつ前述の第1の層を構成するポリエステルとの組成が大きく異なり、層間の密着性が低下しやすい。他方、エチレンテレフタレート成分のモル数が繰返し単位の97モル%を超えるか共重合成分のモル数が3モル%未満だと、前述の第1の層を構成するポリエステルとの融点差が小さくなり、結果として、多層延伸フィルムに十分な反射率を付与することが困難となる。エチレンテレフタレート成分以外の共重合成分としては、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のような他の芳香族カルボン酸;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等の如き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等の酸成分や、ブタンジオール、ヘキサンジオ−ル等の如き脂肪族ジオール;シクロヘキサンジメタノールの如き脂環族ジオール等、グリコール成分を好ましく挙げることができる。これらの中でも、比較的、延伸性を維持しながら融点を低下させやすいことから2,6−ナフタレンジカルボン酸またはイソフタル酸が好ましい。
[Second layer]
In a preferred example of the present invention, the resin constituting the second layer is a polyester whose main repeating unit is an ethylene terephthalate component. In particular, from the viewpoint of film forming property in biaxial stretching, a crystalline polyester is preferable. Further, since the melting point can be made lower than that of the polyester constituting the first layer, 75 to 97 mol% of the repeating units are composed of an ethylene terephthalate component, and 3 to 25 mol% is a copolymer composed of other copolymer components. Polymerized polyethylene terephthalate. When the number of moles of the ethylene terephthalate component is less than 75 mol% of the repeating unit or the number of moles of the copolymer component exceeds 25 mol%, the polymer is substantially amorphous and film-forming properties by biaxial stretching And the composition of the polyester constituting the first layer is greatly different, and the adhesion between the layers tends to decrease. On the other hand, if the number of moles of the ethylene terephthalate component exceeds 97 mol% of the repeating unit or the number of moles of the copolymer component is less than 3 mol%, the melting point difference from the polyester constituting the first layer is reduced, As a result, it becomes difficult to give sufficient reflectivity to the multilayer stretched film. Examples of copolymer components other than the ethylene terephthalate component include other 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 acids; acid components such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aliphatic diols such as butanediol and hexanediol; alicyclic diols such as cyclohexanedimethanol, glycols Preferable components can be mentioned. Among these, 2,6-naphthalenedicarboxylic acid or isophthalic acid is preferable because it is relatively easy to lower the melting point while maintaining stretchability.
ところで、第2の層を構成する樹脂の融点は、200〜245℃の範囲であることが、前述の第1の層を構成する樹脂との融点差を比較的大きくできることから好ましい。第2の層を構成する樹脂の融点が上限よりも高いと、第1の層を構成する樹脂との融点差が小さくなり、結果として、得られる多層延伸フィルムに十分な屈折率差を付与することが困難になる。一方、第2の層を構成する樹脂の融点が下限よりも低くするには、第1の層を構成する樹脂との組成が大きく変更することになり、得られる二軸延伸多層積層フィルムに十分な層間の密着性を付与することが困難になる。なお、第2の層を構成する樹脂の融点は、フィルムにする前の段階から低い必要はなく、延伸処理後に低くなっていれば良い。例えば、ホモポリエチレンテレフタレートとそれ以外の他のポリエステルとを用意し、これらを溶融混練時にエステル交換させたものであってもよいことは容易に理解されるであろう。 By the way, the melting point of the resin constituting the second layer is preferably in the range of 200 to 245 ° C., since the difference in melting point from the resin constituting the first layer can be relatively large. When the melting point of the resin constituting the second layer is higher than the upper limit, the melting point difference from the resin constituting the first layer is reduced, and as a result, a sufficient refractive index difference is imparted to the resulting multilayer stretched film. It becomes difficult. On the other hand, in order for the melting point of the resin constituting the second layer to be lower than the lower limit, the composition with the resin constituting the first layer will be greatly changed, which is sufficient for the obtained biaxially stretched multilayer laminated film. It becomes difficult to provide adhesion between layers. Note that the melting point of the resin constituting the second layer does not need to be low from the stage before forming the film, and may be low after the stretching treatment. For example, it will be easily understood that homopolyethylene terephthalate and other polyesters other than that may be prepared and transesterified at the time of melt kneading.
[二軸延伸多層積層フィルム]
本発明の二軸延伸多層積層フィルムは、上述の第1の層および第2の層を、交互に少なくとも11層積層したものである。なお、本発明の二軸延伸多層積層フィルムは、前述のとおり、十分な機械的強度を具備する観点から、2軸方向に延伸されていることが必要である。
[Biaxially stretched multilayer laminated film]
The biaxially stretched multilayer laminated film of the present invention is obtained by alternately laminating at least 11 layers of the above-mentioned first layer and second layer. In addition, as mentioned above, the biaxially stretched multilayer laminate film of the present invention needs to be stretched in the biaxial direction from the viewpoint of having sufficient mechanical strength.
特に、本発明の二軸延伸多層積層フィルムは、層間の密着性及び2軸延伸加工の製膜性を確保する観点から、第1の層、第2の層ともに、結晶性を示し、かつ第2の層の樹脂は、延伸後には、少なくとも部分的に溶融されていることが好ましい。このようにして得られた二軸延伸多層積層フィルムは、DSC(示差走査熱量計)で測定される融点が2つ以上存在し、かつそれらの融点か5℃以上異なることが好ましい。ここで、測定される融点は、高融点側が高屈折率を示す第1の層であり、低融点側は、低屈折率を示す第2の層であることは容易に想像がつくであろう。また、さらに好ましくは、延伸後に第2の層は少なくとも部分的に溶融されているために、DSCで測定される結晶化ピークが100℃〜190℃の範囲に存在することが好ましい。結晶化ピ−クが100℃以下であると、フィルムの延伸時に一方の層が急激に結晶化し、製膜時の製膜性が低下しやすく、かつ、膜質の均質性が低下しやすく、結果として、色相の斑などが発生することがある。一方で結晶化ピークが190℃以上であると、熱固定処理で第二の層を融解するときに、結晶化が同時に起こり、十分な屈折率差を発現させ難くなる。 In particular, the biaxially stretched multilayer laminated film of the present invention exhibits crystallinity in both the first layer and the second layer from the viewpoint of ensuring adhesion between layers and film forming properties of biaxial stretching. The resin of the second layer is preferably at least partially melted after stretching. The biaxially stretched multilayer laminated film thus obtained preferably has two or more melting points measured by DSC (differential scanning calorimeter), and their melting points are preferably different by 5 ° C. or more. Here, it can be easily imagined that the measured melting point is the first layer exhibiting a high refractive index on the high melting point side, and the second layer exhibiting the low refractive index on the low melting point side. . More preferably, since the second layer is at least partially melted after stretching, the crystallization peak measured by DSC is preferably in the range of 100 ° C. to 190 ° C. When the crystallization peak is 100 ° C. or lower, one of the layers is crystallized rapidly when the film is stretched, the film-forming property at the time of film formation is likely to deteriorate, and the homogeneity of the film quality is likely to decrease. As a result, hue spots or the like may occur. On the other hand, when the crystallization peak is 190 ° C. or higher, when the second layer is melted by heat setting, crystallization occurs at the same time, making it difficult to express a sufficient refractive index difference.
このように、本発明の二軸延伸多層積層フィルムは、ともに結晶性を示す第一の層の樹脂と第二の層の樹脂を延伸することによって、均質な膜質のフィルムが得られ、かつ延伸工程の後に第二の層を融解することで、層間密着性を向上させることと同時に反射性能を向上させることができる。従って、本発明の二軸延伸多層積層フィルムでは、DSCによる結晶ピ−クが100℃〜190℃に存在し、融点差が5℃以上異なる2つ以上の融解ピ−クが観測される二軸延伸多層積層フィルムが好ましい。 As described above, the biaxially stretched multilayer laminated film of the present invention is obtained by stretching the resin of the first layer and the resin of the second layer, both of which exhibit crystallinity, to obtain a film having a uniform film quality and stretching. By melting the second layer after the process, the interlayer adhesion can be improved and simultaneously the reflection performance can be improved. Therefore, in the biaxially stretched multilayer laminated film of the present invention, the biaxial stretching peak is observed in which the crystal peak due to DSC exists at 100 ° C. to 190 ° C. and the difference in melting point is 5 ° C. or more. A stretched multilayer laminated film is preferred.
また、本発明の二軸延伸多層積層フィルムは、延伸処理された方向の破断強度は、それぞれ150MPa以上であることが好ましい。破断強度が150MPa未満だと、マイクロスリットなど加工時が困難となる。好ましい破断強度は、縦方向が180MPa以上、特に200MPa以上で、横方向が180MPa以上、特に200MPa以上である。また、縦方向と横方向の強度比は、3以下であることが耐引裂き性を十分に具備できることから好ましい。特に縦方向と横方向の強度比が2以下であると、さらに耐引裂き性を向上できることから好ましい。破断強度の上限は、特に限定はされないが、延伸工程の安定性を維持する観点から、高々500MPaであることが好ましい。 In addition, the biaxially stretched multilayer laminated film of the present invention preferably has a breaking strength in the stretched direction of 150 MPa or more. When the breaking strength is less than 150 MPa, it becomes difficult to process such as micro slits. The preferred breaking strength is 180 MPa or more in the longitudinal direction, particularly 200 MPa or more, and 180 MPa or more, particularly 200 MPa or more in the transverse direction. In addition, the strength ratio in the longitudinal direction and the transverse direction is preferably 3 or less because tear resistance can be sufficiently obtained. In particular, the strength ratio in the longitudinal direction and the transverse direction is preferably 2 or less because tear resistance can be further improved. The upper limit of the breaking strength is not particularly limited, but is preferably at most 500 MPa from the viewpoint of maintaining the stability of the stretching process.
また、本発明の二軸延伸多層積層フィルムは、熱寸法安定性が高いことが特徴であり、延伸処理された方向(製膜方向および幅方向)の150℃で30分間処理したときの熱収縮率が、それぞれ3.0%以下が好ましい。より好ましくは、2.5%以下、更に好ましくは、2.0%以下である。また、本発明の二軸延伸多層積層フィルムの200℃で10分間処理したときの製膜方向および幅方向の熱収縮率は、それぞれ5.0%以下が好ましい。より好ましい熱収縮率はそれぞれ4.0%以下、更に好ましい熱収縮率はそれぞれ3.0%以下である。熱寸法安定性が高いことから、本発明の二軸延伸多層積層フィルムは、PVCシートとの貼り合せや、エンボス加工などの工程適性に優れているといえる。 Further, the biaxially stretched multilayer laminated film of the present invention is characterized by high thermal dimensional stability, and heat shrinkage when treated at 150 ° C. for 30 minutes in the stretched direction (film forming direction and width direction). Each rate is preferably 3.0% or less. More preferably, it is 2.5% or less, and further preferably 2.0% or less. Moreover, when the biaxially stretched multilayer laminated film of the present invention is treated at 200 ° C. for 10 minutes, the thermal shrinkage in the film forming direction and the width direction is preferably 5.0% or less, respectively. A more preferable heat shrinkage rate is 4.0% or less, and a still more preferable heat shrinkage rate is 3.0% or less. Since the thermal dimensional stability is high, it can be said that the biaxially stretched multilayer laminated film of the present invention is excellent in process suitability such as bonding with a PVC sheet and embossing.
また、本発明の二軸延伸多層積層フィルムは、第1の層および第2の層を構成する樹脂が、ともに結晶性樹脂であることが好ましい。第1の層および第2の層を構成する樹脂がともに結晶性樹脂であると、延伸などの処理が不均一になりがたく、結果としてフィルムの厚み斑を小さくすることができる。好ましい厚み斑の範囲は、下記式で示される厚み変動率が10%未満、好ましくは5%未満、より好ましくは3%未満である。フィルム厚みの変動率が10%以上になると、反射する光の色が変化してしまい、色の斑となって現れる。
厚みの変動率(%)={(Tmax−Tmin)/Tave}×100
ここで、上記式中のTaveは平均厚み、Tmaxは最大厚みおよびTminは最小厚みである。
In the biaxially stretched multilayer laminated film of the present invention, it is preferable that the resins constituting the first layer and the second layer are both crystalline resins. If both the resin constituting the first layer and the second layer are crystalline resins, the treatment such as stretching is unlikely to be uneven, and as a result, the thickness unevenness of the film can be reduced. A preferable range of thickness unevenness is a thickness variation rate represented by the following formula of less than 10%, preferably less than 5%, more preferably less than 3%. When the variation rate of the film thickness is 10% or more, the color of the reflected light changes and appears as a color spot.
Variation rate of thickness (%) = {(T max −T min ) / T ave } × 100
Here, T ave in the above formula is an average thickness, T max is a maximum thickness, and T min is a minimum thickness.
本発明の二軸延伸多層積層フィルムは、フィルムの巻取り性を向上させるため、第1の層または第2の層の少なくとも1方に、平均粒径が0.01μm〜2μmの不活性粒子を、多層延伸フィルムの重量を基準として、0.001重量%〜0.5重量%含有することが好ましい。不活性粒子の平均粒径が下限よりも小さいか、含有量が下限よりも少ないと、多層延伸フィルムの巻取り性を向上させる効果が不十分になりやすく、他方、不活性粒子の含有量が上限を超えるか、平均粒径が上限を超えると、粒子による多層延伸フィルムの光学特性の悪化が顕著になる。好ましい不活性粒子の平均粒径は、0.05〜1μm、特に0.1〜0.3μmの範囲である。また、好ましい不活性粒子の含有量は、0.005〜0.2重量%の範囲である。 In order to improve the rollability of the film, the biaxially stretched multilayer laminated film of the present invention has inert particles having an average particle diameter of 0.01 μm to 2 μm in at least one of the first layer and the second layer. The content is preferably 0.001 to 0.5% by weight based on the weight of the multilayer stretched film. If the average particle size of the inert particles is smaller than the lower limit or the content is less than the lower limit, the effect of improving the winding property of the multilayer stretched film tends to be insufficient, while the content of the inert particles is When the upper limit is exceeded or the average particle diameter exceeds the upper limit, the deterioration of the optical properties of the multilayer stretched film due to the particles becomes remarkable. Preferred average particle diameter of the inert particles is in the range of 0.05 to 1 μm, particularly 0.1 to 0.3 μm. Moreover, content of a preferable inert particle is the range of 0.005-0.2 weight%.
二軸延伸多層積層フィルムに含有させる不活性粒子としては、例えばシリカ、アルミナ、炭酸カルシウム、燐酸カルシウム、カオリン、タルクのような無機不活性粒子、シリコーン、架橋ポリスチレン、スチレン−ジビニルベンゼン共重合体のような有機不活性粒子を挙げることができる。これらの不活性粒子は、その長径と短径の比が1.2以下、さらには1.1以下である球状粒子(以下、真球状粒子ということがある)であることが、フィルムの滑り性と光学特性を高度に維持できることから好ましい。また、これらの不活性粒子は、粒度分布がシャープであることが好ましく、例えば相対標準偏差が0.3未満、さらには0.2未満のものが好ましい。相対標準偏差が大きい粒子を使用すると、粗大粒子の頻度が多くなり、光学的な欠陥を生ずる場合がある。ここで、不活性粒子の平均粒径と粒径比は、まず粒子表面に導電性付与のための金属を極く薄くスパッターし、電子顕微鏡にて、1万〜3万倍に拡大した像から、長径、短径および面積円相当径を求め、次いでこれらを次式に当てはめることで算出される。
平均粒径=測定粒子の面積円相当径の総和/測定粒子数
粒径比=粒子の平均長径/粒子の平均短径
さらにその結果をもとに相対標準偏差が算出される。
Examples of the inert particles contained in the biaxially stretched multilayer laminated film include inorganic inert particles such as silica, alumina, calcium carbonate, calcium phosphate, kaolin, and talc, silicone, crosslinked polystyrene, and styrene-divinylbenzene copolymer. Such organic inert particles can be mentioned. These inert particles are spherical particles whose ratio of major axis to minor axis is 1.2 or less, and further 1.1 or less (hereinafter sometimes referred to as true spherical particles). And optical properties can be maintained at a high level. Further, these inert particles preferably have a sharp particle size distribution. For example, those having a relative standard deviation of less than 0.3, more preferably less than 0.2 are preferable. When particles having a large relative standard deviation are used, the frequency of coarse particles increases, which may cause optical defects. Here, the average particle size and the particle size ratio of the inert particles are based on an image obtained by first sputtering a metal for imparting conductivity on the particle surface very thinly and expanding 10,000 to 30,000 times with an electron microscope. The major axis, the minor axis, and the area equivalent circle diameter are obtained, and then these are applied to the following equation.
Average particle diameter = total sum of area equivalent circle diameters of measured particles / measured particle number particle diameter ratio = average long diameter of particles / average short diameter of particles The relative standard deviation is calculated based on the result.
本発明の二軸延伸多層積層フィルムは、ヘーズが10%以下であることが好ましい。不活性粒子による光の散乱などでヘーズが10%以下になると、フィルム自体が白っぽくなり、光沢が失われる。 The biaxially stretched multilayer laminated film of the present invention preferably has a haze of 10% or less. If the haze is 10% or less due to light scattering by inert particles, the film itself becomes whitish and loses gloss.
[二軸延伸多層積層フィルムの製造方法]
つぎに、本発明の二軸延伸多層積層フィルムの製造方法について、詳述する。
[Method for producing biaxially stretched multilayer laminated film]
Below, the manufacturing method of the biaxially stretched multilayer laminated film of this invention is explained in full detail.
本発明の二軸延伸多層積層フィルムは、融点が250〜260℃のエチレンテレフタレート成分を主たる繰返し単位とするポリエステル(第1の層用)と、該第1の層を構成するポリエステルよりも、延伸処理後の融点が少なくとも10℃以上低い、エチレンテレフタレ−ト成分を主たる繰返し単位とするポリエステル(第2の層用)とを、溶融状態で交互に少なくとも11層以上重ね合わせた状態で、押出し、多層未延伸フィルム(シート状物とする工程)とする。なお、第1の層および第2の層を構成するポリエステルは、前述の第1の層および第2の層で説明したのと、同様である。第1の層用ポリエステルの融点が250℃未満だと、第2の層用ポリエステルとの融点差が十分につかず、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。一方、ホモポリエチレンテレフタレートの融点が256℃近傍であることから、第1の層用ポリエステルの融点の上限は高々260℃程度である。また、第2の層用ポリエステルの融点が、第1の層用ポリエステルよりも15℃以上低くないときは、第2の層用ポリエステルとの融点差が十分につかず、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の層用ポリエステルの融点と第2の層用ポリエステルの融点差の上限は、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。 The biaxially stretched multilayer laminated film of the present invention is stretched more than polyester (for the first layer) having an ethylene terephthalate component having a melting point of 250 to 260 ° C. as a main repeating unit and the polyester constituting the first layer. Extruded in a molten state with a polyester (for the second layer) having a melting point of at least 10 ° C. lower than that of the ethylene terephthalate component as a main repeating unit, and alternately superposed at least 11 layers in a molten state And a multilayer unstretched film (a step of forming a sheet-like material). The polyester constituting the first layer and the second layer is the same as that described for the first layer and the second layer. When the melting point of the first layer polyester is less than 250 ° C., the difference in melting point from the second layer polyester is not sufficiently applied, and as a result, a sufficient refractive index difference cannot be imparted between the layers of the resulting multilayer stretched film. On the other hand, since the melting point of homopolyethylene terephthalate is around 256 ° C., the upper limit of the melting point of the first layer polyester is about 260 ° C. at most. In addition, when the melting point of the second layer polyester is not lower by 15 ° C. or more than the first layer polyester, the difference in melting point from the second layer polyester is not sufficient, and as a result, the resulting multilayer stretch A sufficient refractive index difference cannot be imparted between the layers of the film. The upper limit of the melting point difference between the first layer polyester and the second layer polyester is preferably at most 50 ° C. from the viewpoint of maintaining the adhesion between the two layers.
このようにして得られた多層未延伸フィルムは、製膜方向とそれに直交する幅方向の2軸方向(フィルム面に沿った方向)に延伸される。延伸温度は、第1の層のポリエステルのガラス転移点の温度(Tg)〜Tg+50℃の範囲が好ましい。このときの面積倍率は5〜50倍であることが好ましい。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る、すなわち、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。2方向に延伸する際の延伸方法は、逐次2軸延伸でも同時2軸延伸であってもよい。 The multilayer unstretched film thus obtained is stretched in the biaxial direction (the direction along the film surface) in the film forming direction and the width direction perpendicular thereto. The stretching temperature is preferably in the range of the glass transition temperature (Tg) to Tg + 50 ° C. of the polyester of the first layer. The area magnification at this time 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 is reduced by thinning by stretching, that is, the optical interference of the multilayer stretched film becomes uniform in the plane direction. Therefore, it is preferable. The stretching method for stretching in two directions may be sequential biaxial stretching or simultaneous biaxial stretching.
このようにして延伸された多層フィルムを、第2の層用ポリエステルの融点よりも10℃低い温度から、第1の層用ポリエステルの融点よりも15℃低い温度の範囲で熱処理して、第2の層内の分子鎖の配向を緩和させ、第2の層の屈折率を低下させることにある。熱処理の温度が、第2の層用ポリエステルの融点よりも10℃を超えて低いと、第2の層内の分子鎖の配向を緩和させて屈折率を低下させる効果が不十分となり、得られる多層延伸フィルムに十分な屈折率差を付与できない。一方、熱処理の温度が、第1の層用ポリエステルの融点よりも10℃以上低い温度でないと、第1の層内の分子鎖の配向も緩和されて屈折率が低下し、得られる多層延伸フィルムに十分な屈折率差を付与できない。好ましい熱処理の温度は、第2の層用ポリエステルの融点よりも6℃低い温度から、第1の層用ポリエステルの融点よりも16℃低い温度、さらには第2の層用ポリエステルの融点よりも2℃低い温度から、第1の層用ポリエステルの融点よりも18℃低い温度である。なお、熱処理の時間は、1〜60秒が好ましい。 The multilayer film thus stretched is heat-treated at a temperature in the range from 10 ° C. lower than the melting point of the second layer polyester to 15 ° C. lower than the melting point of the first layer polyester. The purpose is to relax the orientation of the molecular chains in the layer and to lower the refractive index of the second layer. When the temperature of the heat treatment is lower than the melting point of the polyester for the second layer by more than 10 ° C., the effect of reducing the refractive index by relaxing the molecular chain orientation in the second layer is obtained and obtained. A sufficient refractive index difference cannot be imparted to the multilayer stretched film. On the other hand, if the temperature of the heat treatment is not lower by 10 ° C. or more than the melting point of the polyester for the first layer, the orientation of molecular chains in the first layer is relaxed and the refractive index is lowered, and the resulting multilayer stretched film Cannot provide a sufficient difference in refractive index. A preferable heat treatment temperature is 6 ° C. lower than the melting point of the second layer polyester, 16 ° C. lower than the melting point of the first layer polyester, and 2 more than the melting point of the second layer polyester. The temperature is lower by 18 ° C. than the melting point of the first layer polyester. The heat treatment time is preferably 1 to 60 seconds.
また、この熱処理の温度や時間を変化させることにより、樹脂の組成を変化させることなく、第2の層の屈折率を調整することができる、すなわち樹脂の組成を変化させることなく、多層延伸フィルムの反射特性を変化させることができる。 Further, by changing the temperature and time of this heat treatment, the refractive index of the second layer can be adjusted without changing the resin composition, that is, the multilayer stretched film without changing the resin composition. The reflection characteristics can be changed.
[評価方法]
後述の実施例と比較例において、フィルムの物性や特性は下記の方法にて測定または評価した。
[Evaluation methods]
In Examples and Comparative Examples described later, the physical properties and characteristics of the films were measured or evaluated by the following methods.
(1)ポリエステル樹脂の融点およびガラス転移点(Tg)
ポリエステル樹脂試料を10mgサンプリングし、DSC(TAインスツルメンツ社製、商品名:DSC2920)を用い、20℃/分の昇温速度で、融点を測定する。
(1) Melting point and glass transition point (Tg) of polyester resin
10 mg of a polyester resin sample is sampled, and the melting point is measured at a temperature increase rate of 20 ° C./min using DSC (trade name: DSC2920, manufactured by TA Instruments).
(2)各層の厚み
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する。そして、包埋されたサンプルをミクロト−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) Thickness of each layer A sample is cut into a triangle, fixed to an embedding capsule, and then embedded with 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)光学特性(反射率、反射波長)
分光光度計(島津製作所製、MPC−3100)を用い、各波長でのアルミ蒸着したミラーとの相対鏡面反射率を波長350nmから2000nmの範囲で測定する。その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波長とする。
(3) Optical characteristics (reflectance, reflection wavelength)
Using a spectrophotometer (manufactured by Shimadzu Corp., MPC-3100), the relative specular reflectance with the aluminum-deposited mirror at each wavelength is measured in the wavelength range of 350 nm to 2000 nm. Among the measured reflectivities, the maximum reflectivity is set as the maximum reflectivity, and the wavelength is set as the maximum reflectivity wavelength.
(4)光学特性(全光線透過率及びヘーズ)
JIS K7105−1981に準じて、ヘーズ測定機(日本電色工業(株)製、NDH−20)を使用して全光線透過率Tt(%)と散乱光透過率Td(%)とを測定し、「H=(Td/Tt)×100」との式からヘーズH(%)を算出する。
(4) Optical characteristics (total light transmittance and haze)
According to JIS K7105-1981, a total light transmittance Tt (%) and a scattered light transmittance Td (%) were measured using a haze measuring machine (NDH-20, manufactured by Nippon Denshoku Industries Co., Ltd.). The haze H (%) is calculated from the equation “H = (Td / Tt) × 100”.
(5)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/分で、チャート速度500m/分の条件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っ張る。そして得られた荷重−伸び曲線から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。
(5) Breaking strength The breaking strength in the film forming direction is that the sample film is cut into a sample width (width direction) of 10 mm and length (film forming direction) of 150 mm, the chuck is 100 mm, the pulling speed is 100 mm / min, and the chart speed is 500 m / Pull the sample with an Instron type universal tensile tester under the conditions of minutes. And the breaking strength was measured from the obtained load-elongation curve.
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.
(6)熱収縮率
150℃で30分間処理したときの熱収縮率は、150℃に温度設定されたオーブンの中に無緊張状態で30分間フィルムを保持し、加熱処理前後での寸法変化を熱収縮率として下記式により算出する。また200℃で10分間処理したときの熱収縮率は、200℃に温度設定されたオーブンの中に無緊張状態で10分間フィルムを保持し、加熱処理前後での寸法変化を熱収縮率として下記式により算出する。
熱収縮率(%)={(L0−L)/L0}×100
ここでL0は熱処理前の標点間距離で、Lは熱処理後の漂点間距離である。
(6) Heat Shrinkage The heat shrinkage when treated at 150 ° C. for 30 minutes is such that the film is held in an unstrained state for 30 minutes in an oven set at 150 ° C., and the dimensional change before and after the heat treatment is observed. The heat shrinkage is calculated by the following formula. The heat shrinkage rate when treated at 200 ° C. for 10 minutes is as follows: the film is held in an oven set at 200 ° C. without tension for 10 minutes, and the dimensional change before and after the heat treatment is defined as the heat shrinkage rate. Calculate by the formula.
Thermal contraction rate (%) = {(L0−L) / L0} × 100
Here, L0 is the distance between the gauge points before the heat treatment, and L is the distance between the floating points after the heat treatment.
(7)厚み変動率
製膜方向および幅方向にそれぞれ1m×1mとなるように切り出したフィルムサンプルを縦方向及び幅方向に沿ってそれぞれ2cm幅で25本に切り出し、各サンプルの厚みを電子マイクロメ−タ及びレコーダー(K−312A,K310B、安立電気(株)製)を使用して連続的に測定する。全測定値から平均厚みを算出し、さらに測定値を200mmごとに細分化し、その中での最大値と最小値を読み取り、下式により平均厚みに対する厚み変動率を算出する。
厚みの変動率(%)={(Tmax−Tmin)/Tave}×100
ここで、上記式中のTmaxは厚みの最大値、Tminは厚みの最小値、Taveは厚みの平均値である。
(7) Thickness variation rate A film sample cut to 1 m × 1 m in the film forming direction and the width direction was cut into 25 pieces each having a width of 2 cm along the vertical direction and the width direction, and the thickness of each sample was measured with an electronic micrometer. -Continuous measurement using a recorder and a recorder (K-312A, K310B, manufactured by Anritsu Electric Co., Ltd.). The average thickness is calculated from all the measured values, and the measured values are further subdivided every 200 mm, the maximum value and the minimum value are read, and the thickness variation rate with respect to the average thickness is calculated by the following equation.
Variation rate of thickness (%) = {(T max −T min ) / T ave } × 100
Here, T max in the above formula is the maximum thickness, T min is the minimum thickness, and T ave is the average thickness.
(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−プ(ニチバン社製、商品名:セロテープ)を100mm貼り付け、185度の剥離角度で剥がした後、剥離面を観察する。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集計した。
(8) Interlayer adhesion A 24 mm wide adhesive tape (manufactured by Nichiban Co., Ltd., trade name: cello tape) is attached to both sides of a sample film (10 mm × 50 mm), peeled at a peeling angle of 185 degrees, and then peeled Observe the surface. This was performed for each 10 samples, and the number of delaminations was counted.
(9)色の斑
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、サンプルフィルムを通しての白色普通紙の色斑を目視にて観測することでフィルム透過光の色斑を評価した。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、サンプルフィルム表面を目視にて観測することでフィルム反射光の色斑を評価した。透過色および反射色の色斑を総合して、以下の評価基準で判断した。
○:サンプル内に視認できる色斑がない。
△:サンプル内に一部、色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斑が確認できる。
(9) Color spots Prepare 10 A4-size sample films, overlay each sample film on white plain paper, and visually observe the color spots on white plain paper through the sample film under 30 lux illumination. The color spots of the film transmitted light were evaluated by observing. In addition, 10 A4-sized sample films were prepared, and the back surface of each sample film was colored with a black spray, and then the surface of the sample film was visually observed under 30 lux illumination. The color spots were evaluated. The transmitted and reflected color spots were combined and judged according to the following evaluation criteria.
○: There is no visible color spot in the sample.
Δ: Part of the sample with a different color is observed.
X: Color spots that clearly appear as spots or streaks can be confirmed.
[実施例1]
固有粘度0.62(オルトクロロフェノール、35℃)のポリエチレンテレフタレート(PET)を第1の層用ポリエステルとし、第2の層用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0.65(オルトクロロフェノール、35℃)の共重合ポリエチレンテレフタレート(IA12PET)に真球状シリカ粒子(平均粒径:1.5μm、長径と短径の比:1.02、粒径の平均偏差:0.1。表中では種類「ア」と表記)を0.10重量%添加したものを準備した。そして、第1の層用ポリエステルおよび第2の層用ポリエステルを、それぞれ170℃で3時間乾燥後、押出し機に供給し、280℃まで加熱して溶融状態とし、第1の層用ポリエステルを101層、第2の層用ポリエステルを100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、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の層と第2の層が交互に積層された総数201層の未延伸多層積層フィルムを作成した。このとき第1の層と第2の層の押出し量が1.5:1.0になるように調整し、かつ、両端層が第1の層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、更に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特性を表2に示す。
[Example 1]
Polyethylene terephthalate (PET) having an intrinsic viscosity of 0.62 (orthochlorophenol, 35 ° C.) is used as the first layer polyester, and 12 mol% of isophthalic acid is copolymerized as the second layer polyester. Copolymerized polyethylene terephthalate (IA12PET) of orthochlorophenol (35 ° C.) and true spherical silica particles (average particle size: 1.5 μm, ratio of major axis to minor axis: 1.02, average deviation of particle size: 0.1. In the table, 0.10% by weight of type “A” was added. The first layer polyester and the second layer 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, and the first layer polyester is 101. After the polyester for the second layer and the second layer are branched into 100 layers, a multilayer feedblock device in which the first layer and the second layer are alternately stacked is used, and the die is maintained while maintaining the stacked state. Then, the film was cast on a casting drum to produce a total of 201 unstretched multilayer laminated films in which the first layer and the second layer were alternately laminated so that the thickness of each layer was equal. At this time, the extrusion amount of the first layer and the second layer was adjusted to be 1.5: 1.0, and the both end layers were laminated so as to be the first layer. 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-fixed at 230 ° C. for 3 seconds. . Table 2 shows the properties of the obtained biaxially stretched multilayer laminated film.
[実施例2〜3]
各層の厚みの条件を表1に示すように変更する以外は、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。得られた多層延伸フィルムの特性を表2に示す。
[Examples 2-3]
A biaxially stretched multilayer laminated film was produced in the same manner as in Example 1 except that the thickness conditions of each layer were changed as shown in Table 1. The properties of the obtained multilayer stretched film are shown in Table 2.
[比較例1]
固有粘度0.62(オルトクロロフェノール、35℃)のポリエチレン2、6−ナフタレンジカルボキシレート(PEN)を第1の層用ポリエステルとし、第2の層用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0.65(オルトクロロフェノール、35℃)の共重合ポリエチレンテレフタレート(IA12PET)に真球状シリカ粒子(平均粒径:0.2μm、長径と短径の比:1.02、粒径の平均偏差:0.1。表中では種類「イ」と表記)を0.10重量%添加したものを準備した。そして、第1の層用ポリエステルおよび第2の層用ポリエステルを、それぞれ170℃で3時間乾燥後、押出し機に供給し、280℃まで加熱して溶融状態とし、第1の層用ポリエステルを101層、第2の層用ポリエステルを100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、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の層と第2の層が交互に積層された総数201層の未延伸多層積層フィルムを作成した。このとき第1の層と第2の層の押出し量が1.0:1.0になるように調整し、かつ、両端層が第1の層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4.0倍延伸し、更に95℃の温度で幅方向に4.3倍に延伸し、230℃で3秒間熱固定処理を行った。
[Comparative Example 1]
Polyethylene 2,6-naphthalenedicarboxylate (PEN) with an intrinsic viscosity of 0.62 (orthochlorophenol, 35 ° C.) is used as the first layer polyester, and 12 mol% of isophthalic acid is copolymerized as the second layer polyester. Copolymerized polyethylene terephthalate (IA12PET) having an intrinsic viscosity of 0.65 (orthochlorophenol, 35 ° C.) and spherical silica particles (average particle size: 0.2 μm, ratio of major axis to minor axis: 1.02; Average deviation: 0.1 (indicated in the table as type “I”) was prepared by adding 0.10 wt%. The first layer polyester and the second layer 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, and the first layer polyester is 101. After the polyester for the second layer and the second layer are branched into 100 layers, a multilayer feedblock device in which the first layer and the second layer are alternately stacked is used, and the die is maintained while maintaining the stacked state. Then, the film was cast on a casting drum to produce a total of 201 unstretched multilayer laminated films in which the first layer and the second layer were alternately laminated so that the thickness of each layer was equal. At this time, the extrusion amount of the first layer and the second layer was adjusted to be 1.0: 1.0, and the both end layers were laminated so as to be the first layer. This multilayer unstretched film was stretched 4.0 times in the film forming direction at a temperature of 90 ° C., further stretched 4.3 times in the width direction at a temperature of 95 ° C., and heat-set at 230 ° C. for 3 seconds. .
得られた二軸延伸多層積層フィルムの特性を表2に示す。比較例1で得られたフィルムは、色斑、層間密着性などは優れるものの強度が不十分なフィルムであった。 Table 2 shows the properties of the obtained biaxially stretched multilayer laminated film. The film obtained in Comparative Example 1 was a film having excellent color spots and interlayer adhesion, but insufficient strength.
[比較例2〜4]
製造条件を表1に示すように変更した以外は、比較例1と同様にして二軸延伸多層積層フィルムを製造した。得られたフィルムの特性を表2に示す。比較例2、3で得られたフィルムは、反射性能に劣るフィルムであった。比較例4で得られたフィルムは比較例1同様、色相斑がひどく、層間の剥離特性の劣るフィルムであった。
[Comparative Examples 2 to 4]
A biaxially stretched multilayer laminated film was produced in the same manner as in Comparative Example 1 except that the production conditions were changed as shown in Table 1. The properties of the obtained film are shown in Table 2. The films obtained in Comparative Examples 2 and 3 were inferior in reflection performance. As in Comparative Example 1, the film obtained in Comparative Example 4 was a film having severe hue spots and inferior peeling properties between layers.
なお表中で樹脂種類を示す「IA3PET」は、イソフタル酸を3モル%共重合した固有粘度0.65(オルトクロロフェノール、35℃)のポリエチレンテレフタレートである。また「NDC10PET」は、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0.70(オルトクロロフェノール、35℃)のポリエチレンテレフタレートである。 “IA3PET” indicating the resin type in the table is polyethylene terephthalate having an intrinsic viscosity of 0.65 (orthochlorophenol, 35 ° C.) obtained by copolymerizing 3 mol% of isophthalic acid. “NDC10PET” is polyethylene terephthalate having an intrinsic viscosity of 0.70 (orthochlorophenol, 35 ° C.) obtained by copolymerization of 10 mol% of 2,6-naphthalenedicarboxylic acid.
本発明のフィルムは、構造的な発色により意匠性に優れたものであるため、衣料や包装等の装飾用途に好ましく適用できる。 Since the film of the present invention is excellent in design due to structural color development, it can be preferably applied to decorative uses such as clothing and packaging.
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
Claims (7)
伸を施した多層積層フィルムであって、波長350〜2000nmの範囲での光の最大反
射率は、波長350〜2000nmの範囲での光反射率曲線から得られる反射率のベース
ラインよりも20%以上高く、第1の層はポリエステル組成物から構成され、第2の層は
第1の層とは組成の異なるポリエステル組成物から構成され、第1の層は第2の層よりも
屈折率が高く、第1の層と第2の層は厚みが0.05〜0.5μmの範囲内であり、なお
かつ第1の層の厚みと第2の層の厚み比(第1の層/第2の層)が1.2以上5.0以下
である二軸延伸多層積層フィルムであって、該二軸延伸多層積層フィルムを1mm角以下に粉砕して装飾用粉末とする用途に用いることを特徴とする、装飾用粉末用二軸延伸多層積層フィルム。 A multilayer laminated film in which the first layer and the second layer are alternately laminated so that the total number of layers is 11 or more, and biaxially stretched, and has a wavelength of 350 to 2000 nm. The maximum reflectance is 20% or more higher than the reflectance baseline obtained from the light reflectance curve in the wavelength range of 350 to 2000 nm, the first layer is composed of the polyester composition, and the second layer is the second layer. The first layer is composed of a polyester composition having a different composition, the first layer has a higher refractive index than the second layer, and the first layer and the second layer have a thickness of 0.05 to 0.5 μm. of in the range, yet the first thickness ratio of the thickness and the second layer of the layer (the first layer / second layer) is biaxially oriented multi-layer laminate film is 1.2 to 5.0 The biaxially stretched multilayer laminated film is pulverized to 1 mm square or less to make a decorative powder. It characterized that, biaxially oriented multi-layer laminated film for decorative powder be used.
いても、単位断面積あたり150MPa以上である請求項1または2に記載の装飾用粉末用二軸延伸多層積層フィルム。 The biaxially oriented multilayer laminate for decorative powder according to claim 1 or 2, wherein the breaking strength is 150 MPa or more per unit cross-sectional area in both the continuous film-forming direction and the width direction perpendicular to the continuous film-forming direction. the film.
0モル%以上である請求項1〜3のいずれかに記載の装飾用粉末用二軸延伸多層積層フィルム。 The proportion of ethylene terephthalate component is 8 based on the total repeating units of the polyester.
The biaxially stretched multilayer laminated film for decorative powder according to any one of claims 1 to 3 , which is 0 mol% or more .
ボン酸成分である請求項1〜4のいずれかに記載の装飾用粉末用二軸延伸多層積層フィルム。 The biaxially stretched multilayer laminated film for decorative powder according to any one of claims 1 to 4 , wherein 1.5 to 20 mol% of all repeating units are isophthalic acid or a 2,6-naphthalenedicarboxylic acid component .
モル%以上がエチレンテレフタレート成分であって、第2の層を構成するポリエステルが
、結晶性ポリエステルであり、全繰返し単位の75〜97モル%がエチレンテレフタレー
ト成分である請求項1〜5のいずれかに記載の装飾用粉末用二軸延伸多層積層フィルム。 The polyester constituting the first layer is a crystalline polyester, and 90% of all repeating units.
Mol% or more is an ethylene terephthalate component, the polyester constituting the second layer is a crystalline polyester, claim 1-5 75 to 97 mole% of the total repeating units is ethylene terephthalate component A biaxially oriented multilayer laminated film for decorative powder as described in 1 .
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