JP2007138183A - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester film Download PDFInfo
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- JP2007138183A JP2007138183A JP2006349063A JP2006349063A JP2007138183A JP 2007138183 A JP2007138183 A JP 2007138183A JP 2006349063 A JP2006349063 A JP 2006349063A JP 2006349063 A JP2006349063 A JP 2006349063A JP 2007138183 A JP2007138183 A JP 2007138183A
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- polyester film
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- oriented polyester
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 61
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 238000002844 melting Methods 0.000 claims abstract description 38
- 230000008018 melting Effects 0.000 claims abstract description 36
- 150000002009 diols Chemical class 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 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 abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000012916 structural analysis Methods 0.000 claims abstract description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 description 24
- 238000005452 bending Methods 0.000 description 16
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000011146 organic particle Substances 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000005388 cross polarization Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000004202 carbamide Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012948 isocyanate Substances 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
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、包装用あるいは工業用分野において好適に使用することができる強靱な二軸配向ポリエステルフィルムに関する。 The present invention relates to a tough biaxially oriented polyester film that can be suitably used in packaging or industrial fields.
ポリエステルフィルム、特にポリエチレンテレフタレートを主成分とするポリエステルフィルムは、優れた機械的特性、熱的特性、電気的特性、表面特性、光学特性、また、耐熱性、耐薬品性などの性質を利用して、磁気記録媒体用、工業材料用、包装用など種々の用途に幅広く用いられている。しかしながら、包装材料などで特に求められる耐衝撃性、耐屈曲ピンホール性に劣るため、このような用途においてはナイロン二軸延伸フイルムが多く使用されている。一方、ナイロンフイルムにも吸湿率および湿度膨張係数が大きく、保存時や加工時の取り扱いに注意を要し、蒸着加工が困難である。また、耐熱性や印刷適性、腰の強さ、寸法安定性を補うため、ポリエステルフィルムと貼り合わせた形態で用いられる場合が多い。また、ポリエステルフィルム単体での耐衝撃性を与える方法として、ＰＥＴにダイマー酸を共重合する方法（例えば特開平６−７９７７６号公報）が提案されているが、耐熱性が低く、粘着しやすいため製膜工程や加工工程で巻き付きなどのトラブルが起こりやすいという問題があった。
本発明は、かかる従来技術の背景に鑑み、強靱で耐衝撃性に優れたポリエステルフィルムを提供せんとするものである。 In view of the background of such prior art, the present invention intends to provide a polyester film that is tough and excellent in impact resistance.
本発明の二軸配向ポリエステルフィルムはかかる課題を解決するために、主として次の構成を有する。すなわち、密度が１．３７〜１．４１ｇ／ｃｍ3であり、固体高分解能ＮＭＲによる構造解析におけるジオール炭素の緩和時間Ｔ１ρが５０ミリ秒以上１００ミリ秒以下であることを特徴とする二軸配向ポリエステルフィルムである。 In order to solve this problem, the biaxially oriented polyester film of the present invention mainly has the following configuration. That is, the biaxial orientation is characterized in that the density is 1.37 to 1.41 g / cm 3 and the relaxation time T1ρ of diol carbon in the structural analysis by solid high-resolution NMR is 50 milliseconds or more and 100 milliseconds or less. It is a polyester film.
本発明によれば、包装材料や、耐屈曲性や耐衝撃性が要求される建材用などの用途に好適に用いられる二軸配向ポリエステルフィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the biaxially-oriented polyester film used suitably for uses, such as a packaging material and the use for building materials in which bending resistance and impact resistance are requested | required can be provided.
本発明は、前記課題、つまり強靱で耐衝撃性に優れたポリエステルフィルムについて、鋭意検討し、特定な密度で、かつ、ジオール炭素の緩和時間Ｔ１ρが特定な二軸配向ポリエステルフィルムとしてみたところ、かかる課題を一挙に解決することを究明したものである。 The present invention has been intensively studied on the above-mentioned problem, that is, a tough and excellent impact resistance polyester film. As a biaxially oriented polyester film having a specific density and a specific relaxation time T1ρ of diol carbon, It was clarified to solve the problem at once.
本発明の二軸配向ポリエステルフィルムを構成するポリエステルとしては、ジオール成分としてエチレングリコール、トリメチレングリコール、テトラメチレングリコールなどから選ばれる直鎖骨格を有するジオールと、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸などから選ばれるジカルボン酸からなるポリエステルが好ましいが、２種類以上のグリコール成分を有する共重合ポリエステルや、２種類以上のポリエステルを混合したものでもよいが、中でも全繰り返し単位の４０％以上がエチレンテレフタレートであるポリエステルが、高い弾性率と耐屈曲性、耐衝撃性のバランスの良いフィルムを提供しやすいので好ましい。 The polyester constituting the biaxially oriented polyester film of the present invention includes a diol having a linear skeleton selected from ethylene glycol, trimethylene glycol, tetramethylene glycol and the like as a diol component, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc. A polyester comprising a dicarboxylic acid selected from is preferable, but a copolymer polyester having two or more types of glycol components or a mixture of two or more types of polyesters may be used. Among them, 40% or more of all repeating units are ethylene terephthalate. A certain polyester is preferable because it easily provides a film having a high balance of elasticity, flex resistance, and impact resistance.
かかるポリエステルフィルムの密度は、１．３７〜１．４１ｇ／ｃｍ3 であることが必要である。かかる密度が１．３７ｇ／ｃｍ3より小さい場合、弾性率が小さくなったり、熱収縮率が大きくなってしまうため、ポリエステルフィルム本来のメリットである弾性率が高く、寸法安定性に優れたフィルムを得ることができず、他のポリエステルフィルムなどの、弾性率が高く寸、法安定性に優れたフィルムと貼り合わせて使用する必要があるなど、使用方法が制限されてしまう。また、かかる密度が１．４１ｇ／ｃｍ3より大きいと、脆くて、耐衝撃性の劣ったフィルムを提供することができなくなってしまう。 The density of such a polyester film needs to be 1.37 to 1.41 g / cm 3 . When the density is less than 1.37 g / cm 3 , the elastic modulus is decreased or the heat shrinkage rate is increased. Therefore, a film having a high elastic modulus, which is an original merit of the polyester film, and excellent in dimensional stability. It cannot be obtained, and the usage method is limited, for example, it is necessary to use the polyester film with another film such as a polyester film having a high elastic modulus and dimensions and excellent method stability. On the other hand, when the density is higher than 1.41 g / cm 3 , it is not possible to provide a film that is brittle and inferior in impact resistance.
上記のようなポリエステルフィルムは、一般に耐屈曲性、耐衝撃性が非常に悪く、包装材料として用いる場合は、これらの特性の優れたナイロンフィルムと貼り合わせて使用されることが多い。 The polyester film as described above generally has very poor bending resistance and impact resistance, and when used as a packaging material, it is often used by being bonded to a nylon film having excellent properties.
我々は種々の検討を行った結果、固体高分解能ＮＭＲによる構造解析におけるジオール炭素の緩和時間Ｔ１ρを５０ミリ秒以上１００ミリ秒以下とすることにより、弾性率、寸法安定性といった、ポリエステルフィルム本来の利点を損なうことなく、耐屈曲性、耐衝撃性に優れたフィルムを得ることが出来ることを見出した。 As a result of various investigations, the relaxation time T1ρ of diol carbon in the structural analysis by solid-state high-resolution NMR is set to 50 milliseconds or more and 100 milliseconds or less. It has been found that a film excellent in bending resistance and impact resistance can be obtained without impairing the advantages.
ここで、ジオール炭素の緩和時間Ｔ１ρとは、ポリエステル分子鎖中のジオール部分の運動性を示すものであり、一般に、結晶化して密度が１．３７ｇ／ｃｍ3以上であるような二軸配向ポリエステルフィルムでは、１２０ミリ秒以上となる。かかるジオール炭素の緩和時間Ｔ１ρを５０ミリ秒以上１００ミリ秒以下と特定な範囲に制御すると、非晶部の運動性を高めることができ、かくすることにより、繰り返し屈曲を行っても、ピンホールが発生しにくく、かつ、衝撃を受けた場合にも、劈開が起こりにくいフィルムを提供することができる。なお、かかるジオール炭素の緩和時間Ｔ１ρが１００ミリ秒より大きいと、耐屈曲性、耐衝撃性が悪くなる。 Here, the relaxation time T1ρ of the diol carbon indicates the mobility of the diol portion in the polyester molecular chain, and is generally a biaxially oriented polyester that crystallizes and has a density of 1.37 g / cm 3 or more. For films, it is 120 milliseconds or more. When the relaxation time T1ρ of the diol carbon is controlled within a specific range of 50 milliseconds or more and 100 milliseconds or less, the mobility of the amorphous part can be increased. It is possible to provide a film that is less likely to cause cleaving and that is less likely to cleave when subjected to an impact. When the relaxation time T1ρ of the diol carbon is longer than 100 milliseconds, the bending resistance and the impact resistance are deteriorated.
また、ポリエステルフィルムの密度が１．３７ｇ／ｃｍ3以上のポリエステルフィルムの場合では、かかるジオール炭素の緩和時間Ｔ１ρを５０ミリ秒より小さくすることは困難であり、たとえ出来たとしても、弾性率が小さく、腰の弱いフィルムとなってしまう。特に耐屈曲性、耐衝撃性の高いフィルムを得るためには、かかるジオール炭素の緩和時間Ｔ１ρを６０〜８５ミリ秒の範囲に制御することが好ましい。 In the case of a polyester film having a polyester film density of 1.37 g / cm 3 or more, it is difficult to make the relaxation time T1ρ of the diol carbon smaller than 50 milliseconds. It becomes a small and weak film. In particular, in order to obtain a film having high bending resistance and impact resistance, it is preferable to control the relaxation time T1ρ of the diol carbon in the range of 60 to 85 milliseconds.
このような密度と固体高分解能ＮＭＲによるジオール炭素の緩和時間Ｔ１ρが上述の範囲にあるようなポリエステルフィルムを得るための手段としては、融点が２４６〜２７０℃のエチレンテレフタレートを主な繰り返し単位とするポリエステルを好ましくは５０〜９５重量％、より好ましくは７０〜９０重量％配合し、融点が１５０〜２４０℃の熱可塑性樹脂を好ましくは５〜５０重量％、より好ましくは１０〜３０重量％を配合、混合してなるブレンドポリマーを用いることが好ましく採用される。 As a means for obtaining a polyester film having such a density and a relaxation time T1ρ of diol carbon by solid high-resolution NMR in the above-mentioned range, ethylene terephthalate having a melting point of 246 to 270 ° C. is a main repeating unit. Polyester is preferably blended in an amount of 50 to 95% by weight, more preferably 70 to 90% by weight, and a thermoplastic resin having a melting point of 150 to 240 ° C. is preferably blended in an amount of 5 to 50% by weight, more preferably 10 to 30% by weight. It is preferable to use a blend polymer obtained by mixing.
かかる融点が２４６〜２７０℃のエチレンテレフタレートを主な繰り返し単位とするポリエステルとしては、ポリエチレンテレフタレートのホモポリエステルや、ポリエチレンテレフタレートにイソフタル酸、１，４シクロヘキサンジカルボン酸、トリメチレングリコール、テトラメチレングリコールを好ましくは２０重量％以下、より好ましくは１０重量％の範囲で共重合したコポリエステルが使用される。 As the polyester having ethylene terephthalate having a melting point of 246 to 270 ° C. as a main repeating unit, polyethylene terephthalate homopolyester, polyethylene terephthalate, isophthalic acid, 1,4 cyclohexanedicarboxylic acid, trimethylene glycol, tetramethylene glycol are preferable. Is a copolyester copolymerized in an amount of 20% by weight or less, more preferably 10% by weight.
また、これに混合する融点が１５０〜２４０℃の熱可塑性樹脂としては、結晶性の熱可塑性樹脂が好ましく用いられるが、中でも融点が１５０〜２３０℃のポリマーが好ましく用いられる。かかる熱可塑性樹脂の種類は特に問わないが、混合するエチレンテレフタレートを主な繰り返し単位とするポリエステルと相溶性が良い熱可塑性樹脂が好ましく採用される。かかる熱可塑性樹脂の中でも、特にポリトリメチレンテレフタレート、ポリブチレンテレフタレートやこれらにイソフタル酸を１〜２０重量％共重合したコポリエステル、これらポリエステルとポリエーテルのブロック共重合体等が好ましく用いられる。 Further, as the thermoplastic resin having a melting point of 150 to 240 ° C. mixed with this, a crystalline thermoplastic resin is preferably used, and a polymer having a melting point of 150 to 230 ° C. is preferably used. The type of the thermoplastic resin is not particularly limited, but a thermoplastic resin having good compatibility with the polyester having ethylene terephthalate to be mixed as a main repeating unit is preferably used. Among such thermoplastic resins, polytrimethylene terephthalate, polybutylene terephthalate, a copolyester obtained by copolymerizing 1 to 20% by weight of isophthalic acid with these, a block copolymer of these polyesters and polyether, and the like are preferably used.
かかる低融点熱可塑性樹脂としては、要するに、該高融点熱可塑性樹脂との相溶性に優れたポリマーが選択して用いられる。具体的には、これらのブレンドポリマーからなるフィルムのヘイズが好ましくは０．１〜１０％、より好ましくは０．５〜７％の範囲内にあれば、これらのポリマーの相溶性がよいことを意味するものであり、かかるヘイズを満足するものは、前記本発明の課題を好ましく達成する。 As such a low-melting point thermoplastic resin, in short, a polymer having excellent compatibility with the high-melting point thermoplastic resin is selected and used. Specifically, if the haze of the film comprising these blended polymers is preferably in the range of 0.1 to 10%, more preferably 0.5 to 7%, the compatibility of these polymers is good. Meaning and satisfying such haze preferably achieve the above-mentioned object of the present invention.
さらに、これらの樹脂に、ガラス転移温度が０℃以下、好ましくは−２０℃以下の熱可塑性樹脂を０．３〜５重量％、好ましくは０．５〜３重量％添加すると、耐屈曲性をさらに向上できるため好ましい。このようにガラス転移温度が０℃以下の熱可塑性樹脂を０．３〜５重量％添加する場合には、融点が２４６〜２７０℃のエチレンテレフタレートを主な繰り返し単位とするポリエステルの割合は４７．５〜９４．７重量％、融点が１５０〜２４０℃の熱可塑性樹脂の割合は４．７５〜４９．９重量％とするのが好ましい。 Further, when a thermoplastic resin having a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower is added to these resins in an amount of 0.3 to 5% by weight, preferably 0.5 to 3% by weight, the bending resistance is improved. Further improvement is preferable. Thus, when 0.3 to 5% by weight of a thermoplastic resin having a glass transition temperature of 0 ° C. or lower is added, the proportion of the polyester mainly composed of ethylene terephthalate having a melting point of 246 to 270 ° C. is 47. The proportion of the thermoplastic resin having 5 to 94.7% by weight and a melting point of 150 to 240 ° C. is preferably 4.75 to 49.9% by weight.
ガラス転移温度が０℃以下の熱可塑性樹脂の添加量が５重量％より多い場合、ガラス転移点の低い熱可塑性樹脂が相分離して大きなドメインを形成し、フィルムヘイズの大きなフィルムとなったり、逆に耐屈曲性に劣ったフィルムとなりやすいため好ましくない。このようなガラス転移温度が０℃以下の樹脂は特に問わないが、フィルムを構成する他の樹脂との相溶性の面からポリエステルが好ましく、ポリエチレンテレフタレートやポリトリメチレンテレフタレート、ポリブチレンテレフタレートに長鎖の柔軟性成分、例えばポリオキシメチレングリコールなどを共重合したポリエステルが好ましく用いられる。 When the addition amount of the thermoplastic resin having a glass transition temperature of 0 ° C. or less is more than 5% by weight, a thermoplastic resin having a low glass transition point is phase-separated to form a large domain, and a film having a large film haze is obtained. On the contrary, it is not preferable because the film tends to be inferior in bending resistance. Such a resin having a glass transition temperature of 0 ° C. or lower is not particularly limited, but polyester is preferable from the viewpoint of compatibility with other resins constituting the film, and polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate have long chains. Polyesters obtained by copolymerizing such flexible components such as polyoxymethylene glycol are preferably used.
さらに、耐屈曲性に優れたポリエステルフィルムを得るためには、フィルムを溶融、急冷した後再昇温した際に１５０℃〜２３５℃の範囲に融点が観察されないことが好ましい。ここで、融点が観察されるかどうかについては、以下の方法で判断することができる。フィルムを３００℃、５分間溶融した後急冷したサンプルを示差走査熱量計（ＤＳＣ）を用いて２０℃／分で昇温した際に、１５０〜２３５℃の範囲にポリマーの融解に起因する２Ｊ／ｇ以上の吸熱ピークが存在しない場合、この温度範囲に融点が観察されないと判断できる。この範囲に融点が観測される場合は、エチレンテレフタレートを主な繰り返し単位とするポリエステルに添加した低融点樹脂の融点が独立して存在することを意味し、低融点樹脂の大きなドメインが存在し、耐熱性、熱収縮率や耐屈曲性の悪いフィルムとなりやすいため好ましくない。 Furthermore, in order to obtain a polyester film having excellent bending resistance, it is preferable that no melting point is observed in the range of 150 ° C. to 235 ° C. when the film is melted, rapidly cooled and then heated again. Here, whether or not the melting point is observed can be determined by the following method. When a film was melted at 300 ° C. for 5 minutes and then rapidly cooled, the sample was heated at 20 ° C./minute using a differential scanning calorimeter (DSC), and in the range of 150 to 235 ° C., 2J / When no endothermic peak of g or more exists, it can be determined that no melting point is observed in this temperature range. When the melting point is observed in this range, it means that the melting point of the low melting point resin added to the polyester having ethylene terephthalate as the main repeating unit exists independently, and there is a large domain of the low melting point resin, It is not preferable because it tends to be a film having poor heat resistance, heat shrinkage rate and bending resistance.
また、密度と固体高分解能ＮＭＲによるジオール単層の緩和時間Ｔ１ρが、前記のごときポリエステルフィルムを得るためには、上記のようなポリエステルを用いるだけではなく、二軸延伸を行った後に、特定のエネルギーを与えることにより、ポリエステルの非晶部分の運動性を高める処理を行うことが好ましい。 In addition, in order to obtain the polyester film as described above, the relaxation time T1ρ of the diol monolayer by density and solid high-resolution NMR is not limited to using the polyester as described above. It is preferable to perform a treatment to increase the mobility of the amorphous portion of the polyester by applying energy.
かかるエネルギーを付与する方法としては、赤外線、紫外線などの特定波長の電磁波を吸収する添加剤をあらかじめ添加して、電磁波を照射する方法、電子線を照射する方法、特定条件で加熱する方法や、これらの組み合わせなどを採用することができるが、中でも特に上記のような融点のエチレンテレフタレートを主な繰り返し単位とするポリエステルと、これと相溶性の良い特定融点の熱可塑性樹脂とを混合して用い、かつ、添加する熱可塑性樹脂の融点近傍での熱処理を行うことが有効である。 As a method of imparting such energy, an additive that absorbs electromagnetic waves of a specific wavelength such as infrared rays and ultraviolet rays is added in advance, a method of irradiating electromagnetic waves, a method of irradiating electron beams, a method of heating under specific conditions, A combination of these may be employed, but in particular, a polyester mainly composed of ethylene terephthalate having a melting point as described above is mixed with a thermoplastic resin having a specific melting point that is compatible with the polyester. In addition, it is effective to perform a heat treatment near the melting point of the thermoplastic resin to be added.
かかる熱処理度としては、添加する熱可塑性樹脂の融点より１５℃低い温度〜融点までの温度範囲で、５秒以上行う条件で行うことが好ましいが、この熱処理温度は、エチレンテレフタレートを主な繰り返し単位とするポリエステルの非晶部の運動性が高くなる温度域である１８０〜２４０℃である場合に、特に有効である。 As the degree of heat treatment, it is preferable that the heat treatment is performed for 5 seconds or more in a temperature range from 15 ° C. to the melting point lower than the melting point of the thermoplastic resin to be added. This is particularly effective when the temperature is 180 to 240 ° C., which is a temperature range in which the mobility of the amorphous part of the polyester is high.
また、かかる熱処理や電磁波照射、電子線照射などで、非晶部分の運動性を高める処理を行った後の冷却過程では、運動性が高められた非晶部が再結晶化しやすい１２０〜１８０℃の温度域で、１０秒以上保持しないように注意することが好ましい。ただし、上記のようなポリエステルと熱可塑性樹脂の組み合わせで用いる場合は、１２０℃以上で、かつ、添加する熱可塑性樹脂の融点より２０℃低い温度との間に、１０秒以上保持しないことが好ましい。このような温度域に、１０秒以上保持すると、非晶部の結晶化が進むため、ジオール炭素の緩和時間Ｔ１ρが１００ミリ秒より大きなフィルムとなりやすい。 In addition, in the cooling process after performing the treatment for increasing the mobility of the amorphous part by such heat treatment, electromagnetic wave irradiation, electron beam irradiation, etc., the amorphous part with increased mobility is easily recrystallized at 120 to 180 ° C. It is preferable to be careful not to hold for 10 seconds or more in this temperature range. However, in the case of using a combination of the polyester and the thermoplastic resin as described above, it is preferable not to hold for 10 seconds or more between the temperature of 120 ° C. or higher and 20 ° C. lower than the melting point of the thermoplastic resin to be added. . If the temperature is maintained in such a temperature range for 10 seconds or longer, crystallization of the amorphous portion proceeds, and thus a film having a relaxation time T1ρ of diol carbon larger than 100 milliseconds is likely to be obtained.
本発明の二軸配向ポリエステルフィルムは、取扱い性、成形性の点から、フィルム厚みが、５〜５０μｍであることが好ましい。さらに好ましくは１０〜３０μｍである。 The biaxially oriented polyester film of the present invention preferably has a film thickness of 5 to 50 μm from the viewpoint of handleability and moldability. More preferably, it is 10-30 micrometers.
また、本発明の二軸配向ポリエステルフィルムの面配向係数は、好ましくは０．５０〜０．１７、さらに好ましくは０．８０〜０．１６であるものがよい。ここで面配向係数とは、フィルム長手方向の屈折率とフィルム幅方向の屈折率の平均値とフィルム厚さ方向の差である。各方向の屈折率は、例えば偏光子付き接眼レンズを備えたアッベ式屈折率計などで測定することができる。かかる面配向係数が０．５０より小さいと、弾性率の大きなフィルムを得ることが困難となり、また０．１７より大きいと、ジオール炭素の緩和時間Ｔ１ρが１００より大きくなりやすいため好ましくない。 The plane orientation coefficient of the biaxially oriented polyester film of the present invention is preferably 0.50 to 0.17, more preferably 0.80 to 0.16. Here, the plane orientation coefficient is the difference between the average value of the refractive index in the film longitudinal direction and the refractive index in the film width direction and the film thickness direction. The refractive index in each direction can be measured by, for example, an Abbe refractometer equipped with an eyepiece with a polarizer. If the plane orientation coefficient is less than 0.50, it is difficult to obtain a film having a large elastic modulus, and if it is more than 0.17, the relaxation time T1ρ of diol carbon tends to be greater than 100, such being undesirable.
本発明の二軸配向ポリエステルフィルムは、単層で用いてもよいが、高温の工程での粘着などの問題を防止するため、少なくとも片面に融点が２５０〜２７０℃のエチレンテレフタレートを主な繰り返し単位とするポリエステルからなる層をフィルム全体の厚みに対して３０％以下の厚みの範囲で積層するのが好ましい。かかる積層ポリエステル層の厚さが、フィルム全体の厚みに対して３０％より大きい場合は、耐屈曲性や耐衝撃性の劣るフィルムとなってしまう。 The biaxially oriented polyester film of the present invention may be used in a single layer, but in order to prevent problems such as adhesion in a high temperature process, ethylene terephthalate having a melting point of 250 to 270 ° C. on at least one side is a main repeating unit. It is preferable to laminate | stack the layer which consists of said polyester in the range of 30% or less of thickness with respect to the thickness of the whole film. When the thickness of the laminated polyester layer is larger than 30% with respect to the thickness of the whole film, the film is inferior in flex resistance and impact resistance.
本発明の二軸配向ポリエステルフィルムは、取り扱い性、加工性を向上させるために、平均粒子径０．０１〜１０μｍの公知の内部粒子、無機粒子および／または有機粒子を０．０１〜３重量％含有することが好ましい。内部粒子の析出方法としては、公知の技術を用いることができるが、たとえば特開昭４８−６１５５６号公報、特開昭５１−１２８６０号公報、特開昭５３−４１３５５号公報、特開昭５４−９０３９７号公報などに記載の技術を採用することができる。さらに、特公昭５５−２０４９６号公報、特開昭５９−２０４６１７号公報などの粒子を併用することもできる。なお、１０μｍを越える平均粒子径を有する粒子を使用すると、フィルムに欠陥が生じることがあるので注意を要する。 The biaxially oriented polyester film of the present invention contains 0.01 to 3 wt% of known internal particles, inorganic particles and / or organic particles having an average particle diameter of 0.01 to 10 μm in order to improve handleability and processability. It is preferable to contain. As a method for precipitating the internal particles, known techniques can be used. For example, JP-A-48-61556, JP-A-51-12860, JP-A-53-41355, JP-A-54. The technology described in Japanese Patent No. -90397 can be employed. In addition, particles such as JP-B-55-20496 and JP-A-59-204617 can be used in combination. Note that if particles having an average particle diameter exceeding 10 μm are used, defects may occur in the film.
かかる無機粒子としては、たとえば湿式および乾式シリカ、コロイダルシリカ、ケイ酸アルミ、酸化チタン、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、酸化アルミ、マイカ、カオリン、クレーなど、有機粒子としてはスチレン、シリコーン、アクリル酸類、メタクリル酸類、ポリエステル類、ジビニル化合物などを構成成分とする粒子を使用することができる。なかでも、湿式および乾式シリカ、アルミナなどの無機粒子およびスチレン、シリコーン、アクリル酸、メタクリル酸、ポリエステル、ジビニルベンゼンなどを構成成分とする粒子を使用することが好ましい。さらに、これらの内部粒子、無機粒子および有機粒子は二種以上を併用してもよい。 Examples of such inorganic particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, aluminum oxide, mica, kaolin, and clay, and examples of organic particles include styrene, silicone, and acrylic acids. Particles containing methacrylic acids, polyesters, divinyl compounds and the like as constituent components can be used. Among them, it is preferable to use inorganic particles such as wet and dry silica and alumina, and particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components. Furthermore, these internal particles, inorganic particles, and organic particles may be used in combination of two or more.
また、本発明の二軸配向ポリエステルフィルム中には、本発明の効果を阻害しない範囲内で、各種の添加剤や樹脂組成物、架橋剤などを含有してもよい。例えば酸化防止剤、耐熱安定剤、紫外線吸収剤、有機、無機の粒子、顔料、染料、帯電防止剤、核剤、難燃剤、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、ポリオレフィン樹脂、ポリカーボネート樹脂、アルキッド樹脂、エポキシ樹脂、尿素樹脂、フェノール樹脂、シリコーン樹脂、ゴム系樹脂、ワックス組成物、メラミン系架橋剤、オキサゾリン系架橋剤、メチロール化、アルキロール化された尿素系架橋剤、アクリルアミド、ポリアミド、エポキシ樹脂、イソシアネート化合物、アジリジン化合物、各種シランカップリング剤、各種チタネート系カップリング剤などを含有させることができる。 In addition, the biaxially oriented polyester film of the present invention may contain various additives, resin compositions, cross-linking agents and the like within a range that does not impair the effects of the present invention. For example, antioxidants, heat stabilizers, UV absorbers, organic and inorganic particles, pigments, dyes, antistatic agents, nucleating agents, flame retardants, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyd resins , Epoxy resin, urea resin, phenol resin, silicone resin, rubber resin, wax composition, melamine crosslinking agent, oxazoline crosslinking agent, methylolated, alkylolized urea crosslinking agent, acrylamide, polyamide, epoxy resin , Isocyanate compounds, aziridine compounds, various silane coupling agents, various titanate coupling agents, and the like.
かかる二軸配向ポリエステルを構成するポリエステルの極限粘度（２５℃のｏ−クロロフェノール中で測定）としては、０．４〜１．２ｄｌ／ｇが好ましく、０．５〜０．８ｄｌ／ｇであるのがより好ましい。 The intrinsic viscosity (measured in o-chlorophenol at 25 ° C.) of the polyester constituting the biaxially oriented polyester is preferably 0.4 to 1.2 dl / g, and preferably 0.5 to 0.8 dl / g. Is more preferable.
次に、かかる二軸配向ポリエステルフィルムの製造方法としては、特に限定されるものではないが、たとえば、ポリエステルを、必要に応じて乾燥した後、公知の溶融押出機に供給、溶融しスリット状のダイからシート状に押出し、たとえばワイヤー状電極もしくはテープ状電極を使用して、静電印加する方法、キャスティングドラムと押出したポリマーシート間に、水膜を設けたキャスト法により、冷却固化し、未延伸フィルムを得る。 Next, the method for producing such a biaxially oriented polyester film is not particularly limited. For example, after drying the polyester as necessary, it is supplied to a known melt extruder and melted to form a slit. Extruded into a sheet form from a die, for example, a method of applying static electricity using a wire electrode or a tape-shaped electrode, and a method of cooling and solidifying by a casting method in which a water film is provided between a casting drum and an extruded polymer sheet. A stretched film is obtained.
かかる未延伸フィルムを、加熱ロールを用いて、長手方向に延伸した後、クリップに把持して、幅方向に延伸する、あるいは、幅方向に延伸した後、長手方向に延伸する逐次二軸延伸法、フィルムの長手方向、幅方向をほぼ同時に延伸していく同時二軸延伸法などにより延伸を行う。 Such an unstretched film is stretched in the longitudinal direction using a heating roll, and then gripped by a clip and stretched in the width direction, or stretched in the width direction and then stretched in the longitudinal direction. The film is stretched by a simultaneous biaxial stretching method in which the longitudinal direction and the width direction of the film are stretched almost simultaneously.
かかる延伸方法において、採用される延伸倍率としては、それぞれの方向に好ましくは１．６〜４．２倍、さらに好ましくは２．４〜４．０倍である。また、延伸速度は１０００〜２０００００％／分であることが望ましく、延伸温度はポリエステルのガラス転移点〜ガラス転移点より４０℃高い温度の間の温度範囲が好ましい。また、延伸は各方向に対して複数回行ってもよい。 In such a stretching method, the stretching ratio employed is preferably 1.6 to 4.2 times, more preferably 2.4 to 4.0 times in each direction. The stretching speed is desirably 1000 to 200000% / min, and the stretching temperature is preferably in the temperature range between the glass transition point of the polyester and a temperature 40 ° C. higher than the glass transition point. Moreover, you may perform extending | stretching in multiple times with respect to each direction.
さらにかかる二軸延伸の後に、フィルムの熱処理を行うが、この熱処理は、オーブン中で、定長もしくは順次収縮させながら１６０〜２３０℃の熱処理温度で１〜３０秒間熱処理を行う。ただし、非晶部の運動性を向上させる処理を加熱により行う場合は、上述の温度範囲で行うことが好ましい。熱処理を行った後、必要に応じて、紫外線照射、電子線照射などを行い、非晶部の運動性を向上させる。 Further, after the biaxial stretching, the film is subjected to heat treatment. This heat treatment is performed in an oven at a heat treatment temperature of 160 to 230 ° C. for 1 to 30 seconds while being contracted at a constant length or sequentially. However, when performing the process which improves the mobility of an amorphous part by heating, it is preferable to carry out in the above-mentioned temperature range. After performing the heat treatment, if necessary, ultraviolet irradiation, electron beam irradiation, or the like is performed to improve the mobility of the amorphous part.
本発明の二軸配向ポリエステルフィルムは、包装材料の好適であるが、耐屈曲性や耐衝撃性が要求される建材用などの用途にも用いることができる。 The biaxially oriented polyester film of the present invention is suitable as a packaging material, but can also be used for applications such as for building materials that require bending resistance and impact resistance.
（特性の測定方法および効果の評価方法）
本発明における特性の測定方法および効果の評価方法は次のとおりである。
(Characteristic measurement method and effect evaluation method)
The characteristic measurement method and effect evaluation method in the present invention are as follows.
（１）密度フィルムを一辺５ｍｍの正方形に切り取り、臭化ナトリウム水溶液を用いた密度勾配管により密度（ｇ／ｃｍ3）を測定した。 (1) The density film was cut into a square having a side of 5 mm, and the density (g / cm 3 ) was measured with a density gradient tube using an aqueous sodium bromide solution.
（２）ジオール炭素の緩和時間Ｔ１ρ高分解能固体ＮＭＲの測定装置は、ｃｈｅｍａｇｎｅｔｉｃｓ社製ＣＭＸＷ−３００を用いた。測定は13Ｃ核のＴ１ρ（回転座標における縦緩和）測定を実施した。 測定は、温度２４．５℃、湿度５０ＲＨ％、静磁場強度６．３４Ｔ（テスラ）下で、1Ｈ、13Ｃの共鳴周波数は、それぞれ２７０．２ＭＨｚ、６７．９ＭＨｚである。ケミカルシフトの異方性の影響を消すために、ＭＡＳ（マジック角度回転）法を採用した。回転数は、３．５〜３．７ｋＨｚで行った。パルス系列の条件は、1Ｈに対して９０℃、パルス幅４μｓｅｃ、ロッキング磁場強度６２．５ｋＨｚとした、1Ｈの分極を13Ｃに移すＣＰ（クロスポーラリゼーション）の接触時間は、１．５ｍｓｅｃである。
また、保持時間τとしては、０．００１，０．５，０．７，１，３，７，１０，２０，３０，４０，５０ｍｓｅｃを用いた。保持時間τ後の13Ｃの磁化ベクトルの自由誘導減衰（ＦＩＤ）を測定した（ＦＩＤ測定中1Ｈによる双極子相互作用の影響を除去するために高出力デカップリングを行った。なおＳ／Ｎ比を向上させるため５１２回の積算を行った）。また、パルス繰り返し時間としては、５ｓｅｃ〜１５ｓｅｃの間で行った。ジオール炭素のピークは６２ｐｐｍに観測される。
(2) Diol carbon relaxation time T1ρ High-resolution solid-state NMR was measured using a CMXW-300 manufactured by chemicals. The measurement was carried out by measuring T1ρ (longitudinal relaxation in rotating coordinates) of 13 C nucleus. In the measurement, the resonance frequency of 1 H and 13 C is 270.2 MHz and 67.9 MHz, respectively, under a temperature of 24.5 ° C., a humidity of 50 RH%, and a static magnetic field strength of 6.34 T (Tesla). In order to eliminate the influence of the anisotropy of the chemical shift, the MAS (magic angle rotation) method was adopted. The number of revolutions was 3.5 to 3.7 kHz. The conditions of the pulse sequence were 90 ° C. for 1 H, a pulse width of 4 μsec, a rocking magnetic field strength of 62.5 kHz, and the contact time of CP (cross polarization) for transferring the polarization of 1 H to 13 C was 1. 5 msec.
Further, 0.001, 0.5, 0.7, 1, 3, 7, 10, 20, 30, 40, 50 msec was used as the holding time τ. The free induction decay (FID) of the 13 C magnetization vector after the holding time τ was measured (high power decoupling was performed to eliminate the influence of dipole interaction due to 1 H during FID measurement. 512 integrations were performed to improve the ratio). The pulse repetition time was 5 sec to 15 sec. The diol carbon peak is observed at 62 ppm.
（３）融点、ガラス転移点、１５０℃〜２３５℃の範囲での融点有無セイコーインスツルメント社製のＤＳＣ（示差走査熱量計）ＲＤＣ２２０を用いて測定した。試料５ｍｇをＤＳＣ装置にセットし、−１００から１０℃／分で３００℃まで昇温し、ガラス転移点と、結晶融解に基づく吸熱ピーク温度から融点を求めた。また、１５０℃〜２３５℃の範囲での融点有無については、３００℃、５分間溶融した後液体窒素中で急冷したサンプルを示差走査熱量計（ＤＳＣ）を用いて２０℃／分で昇温した際に、１５０〜２３５℃の範囲にポリマーの融解に起因する２Ｊ／ｇ以上の吸熱ピークが存在する場合、この範囲に融点が存在すると判断し、２Ｊ／ｇ以上の吸熱ピークが存在しない場合はこの範囲に融点が存在しないと判断した。 (3) Melting point, glass transition point, melting point presence / absence in the range of 150 ° C. to 235 ° C. Measurement was performed using a DSC (Differential Scanning Calorimeter) RDC220 manufactured by Seiko Instruments Inc. 5 mg of a sample was set in a DSC apparatus, heated from −100 to 300 ° C. at 10 ° C./min, and the melting point was determined from the glass transition point and the endothermic peak temperature based on crystal melting. Further, regarding the presence or absence of a melting point in the range of 150 ° C. to 235 ° C., a sample which was melted at 300 ° C. for 5 minutes and then rapidly cooled in liquid nitrogen was heated at 20 ° C./min using a differential scanning calorimeter (DSC). In the case where an endothermic peak of 2 J / g or more resulting from the melting of the polymer is present in the range of 150 to 235 ° C., it is determined that a melting point exists in this range, and an endothermic peak of 2 J / g or more is not present. It was judged that there was no melting point in this range.
（４）ヘイズ一辺１０ｃｍのサンプルに切り出し、スガ試験機（株）製ヘーズメーターＨＧＭ−２ＤＰを用いて測定した。 (4) A haze was cut into a sample of 10 cm on a side and measured using a haze meter HGM-2DP manufactured by Suga Test Instruments Co., Ltd.
（５）面配向係数偏光子を備えたアタゴ（株）製アッベ屈折率計４Ｔを用いてフィルム各方向の屈折率を測定し、次式で面配向係数を求めた。光源はハロゲンランプ、浸液はヨウ化メチレン、上部プリズムには屈折率１．７４０のものを用いた。
面配向係数＝（ｎｘ＋ｎｙ）／２−ｎｚただし、ｎｘ：フィルム長手方向の屈折率、ｎｙ：フィルム幅方向の屈折率、ｎｙ：フィルム幅方向の屈折率である。
(5) Plane Orientation Coefficient The refractive index in each direction of the film was measured using an Abbe refractometer 4T manufactured by Atago Co., Ltd. equipped with a polarizer, and the plane orientation coefficient was determined by the following formula. The light source used was a halogen lamp, the immersion liquid was methylene iodide, and the upper prism had a refractive index of 1.740.
Planar orientation coefficient = (nx + ny) / 2−nz where nx: refractive index in the film longitudinal direction, ny: refractive index in the film width direction, and ny: refractive index in the film width direction.
（６）積層厚み積層フィルムから断面を切り出し、その断面を透過型電子顕微鏡で観察し、積層膜の厚みを測定した。 (6) Lamination thickness The cross section was cut out from the lamination film, the cross section was observed with the transmission electron microscope, and the thickness of the lamination film was measured.
（７）弾性率サンプルは、フィルム長手方向に長さ２００ｍｍ、幅１０ｍｍの短冊状に切り出して用いた。ＪＩＳ Ｋ ７１２７に規定された方法にしたがって、東洋精機製作所株式会社製の引張試験機を用いて、２５℃、６５％ＲＨにて測定した。
初期引張チャック間距離は、１００ｍｍとし、引張速度は、３００ｍｍ／分とした。測定は、サンプルを変更して２０回行い、平均値を用いた。
(7) The elastic modulus sample was cut into a strip shape having a length of 200 mm and a width of 10 mm in the longitudinal direction of the film. According to the method prescribed | regulated to JISK7127, it measured at 25 degreeC and 65% RH using the tensile tester by Toyo Seiki Seisakusho.
The distance between the initial tensile chucks was 100 mm, and the tensile speed was 300 mm / min. The measurement was performed 20 times by changing the sample, and the average value was used.
（８）熱収縮率ＪＩＳ Ｃ ２３１８に規定された方法にしたがって熱収縮率を測定した。ただし、オーブンの温度と保持時間は１００℃、３０分とし、それぞれサンプルを変え２０回の測定結果の平均を用いた。熱収縮率は小さいほど良いが、加工時のシワ抑制のためには２％以下であることが好ましい。 (8) Thermal contraction rate The thermal contraction rate was measured in accordance with the method prescribed in JIS C 2318. However, the temperature and holding time of the oven were 100 ° C. and 30 minutes, and the average of 20 measurement results was used for each sample. The smaller the heat shrinkage rate, the better, but it is preferably 2% or less in order to suppress wrinkles during processing.
（９）耐屈曲性（ゲルボテスト）
テスター産業（株）製恒温槽付ゲルボフレックステスターＢＥ−１００５を用いて、０℃、１０００回の繰り返し折り曲げテストを実施した後のピンホール個数を測定した。測定サンプルは１８０ｍｍ×２６０ｍｍである。
(9) Bending resistance (Gelbo test)
The number of pinholes after performing a repeated bending test at 0 ° C. and 1000 times was measured using a geloflex tester BE-1005 with a thermostatic bath manufactured by Tester Sangyo Co., Ltd. The measurement sample is 180 mm × 260 mm.
（１０）耐衝撃性（落袋試験）
厚さ６０μmのポリプロピレンシートをポリウレタン接着剤でラミネートし、インパルスシーラーを用いて４方をシールして水２５０ｍｌの入った２００ｍｍ×１５０ｍｍの袋を作成し、０℃で１２時間調温後１．２５ｍの高さから落下させ、破袋あるいは水漏れの有無を調べた。破袋および水漏れのない袋については再度１．２５ｍの高さから落下させ、破袋および水漏れを発生しない落下回数を調べた。２０サンプルについてこれを行い、平均落下回数を求め、２以上を合格とした。
(10) Impact resistance (drop bag test)
A polypropylene sheet with a thickness of 60 μm is laminated with a polyurethane adhesive and sealed on 4 sides using an impulse sealer to create a 200 mm × 150 mm bag containing 250 ml of water. After adjusting the temperature at 0 ° C. for 12 hours, 1.25 m It was dropped from the height and checked for bag breakage or water leakage. The bag without bag breakage and water leakage was dropped again from a height of 1.25 m, and the number of drops without causing bag breakage and water leakage was examined. This was done for 20 samples, the average number of drops was determined, and 2 or more were accepted.
以下、本発明を実施例により説明する。 Hereinafter, the present invention will be described with reference to examples.
実施例１
表１に記載のポリエステル１（ポリエチレンテレフタレート）とポリエステル２（ポリブチレンテレフタレート）を重量比で８０：２０で混合して用いた。混合したポリエステルチップを真空乾燥した後溶融押出を行い、口金から２０℃に冷却した金属ロール上に静電印加を行いながら吐出させ未延伸フィルムを得た。ついで外未延伸フィルムを８５℃に加熱してロール／ロール間で長手方向に３．２倍延伸した。その後、テンター式延伸機で、幅方向に、９５℃で、３．５倍延伸し、２２５℃で１０秒間熱処理を行った後、１００℃の冷却ゾーンを通過させて、厚さ１２μｍの二軸配向ポリエステルフィルムを得た。
Example 1
The polyester 1 (polyethylene terephthalate) and the polyester 2 (polybutylene terephthalate) shown in Table 1 were mixed at a weight ratio of 80:20. The mixed polyester chip was vacuum-dried and then melt-extruded, and discharged from a die on a metal roll cooled to 20 ° C. while applying an electrostatic force to obtain an unstretched film. The outer unstretched film was then heated to 85 ° C. and stretched 3.2 times in the longitudinal direction between rolls / rolls. Thereafter, the film was stretched 3.5 times at 95 ° C. in the width direction with a tenter type stretching machine, heat-treated at 225 ° C. for 10 seconds, passed through a cooling zone at 100 ° C., and biaxial with a thickness of 12 μm. An oriented polyester film was obtained.
この二軸配向ポリエステルフィルムは表２に示すとおり優れた特性を有していた。 This biaxially oriented polyester film had excellent properties as shown in Table 2.
実施例２
表１に記載のポリエステル１とポリエステル３（ポリトリメチレンテレフタレート）を、重量比で６０：４０で混合して用い、製膜条件を、表２に記載の条件に変更した以外は、実施例１と同様にして、厚さ１０μｍの二軸配向ポリエステルフィルムを得た。
この二軸配向ポリエステルフィルムは、表２に示すとおり優れた特性を有していた。
Example 2
Example 1 except that polyester 1 and polyester 3 (polytrimethylene terephthalate) shown in Table 1 were mixed at a weight ratio of 60:40 and the film forming conditions were changed to the conditions shown in Table 2. In the same manner as above, a biaxially oriented polyester film having a thickness of 10 μm was obtained.
This biaxially oriented polyester film had excellent characteristics as shown in Table 2.
実施例３
表１に記載のポリエステル１とポリエステル４（イソフタル酸を１０モル％共重合したポリブチレンテレフタレート）および紫外線吸収剤（シブロ化成（株）ＳＥＥＳＯＲＢ２０２）を、重量比で９０：８：２で混合して用い、製膜条件を、表２に記載の条件に変更して、延伸、熱処理を行った後、１６０Ｗ／ｃｍの紫外線ランプ１灯で、照射距離１０ｃｍで、紫外線照射処理を行い、厚さ３５μｍの二軸配向ポリエステルフィルムを得た。
この二軸配向ポリエステルフィルムは、ジオール部分の緩和時間Ｔ１ρがやや大きいため、耐屈曲性、耐衝撃性に若干劣るものの実用上十分な特性を有していた。
Example 3
Polyester 1 and polyester 4 shown in Table 1 (polybutylene terephthalate copolymerized with 10 mol% of isophthalic acid) and a UV absorber (Sibro Kasei Co., Ltd. SEESORB 202) were mixed at a weight ratio of 90: 8: 2. The film forming conditions were changed to the conditions shown in Table 2, and after stretching and heat treatment, an ultraviolet irradiation treatment was performed at an irradiation distance of 10 cm with one 160 W / cm ultraviolet lamp, and a thickness of 35 μm. A biaxially oriented polyester film was obtained.
This biaxially oriented polyester film had practically sufficient characteristics although it was slightly inferior in bending resistance and impact resistance because the relaxation time T1ρ of the diol portion was slightly large.
実施例４
表１に記載のポリエステル１とポリエステル２を、重量比で７５：２５で混合して、基層部原料として用い、ポリエステル５（イソフタル酸を１７モル％共重合したポリエチレンテレフタレート）を積層部原料として用い、それぞれ真空乾燥して、２台の押出機で溶融押出しを行い、口金上部の合流部で、糧面に積層するように合流させた後、口金から２０℃に冷却した金属ロール上に、静電印加を行いながら吐出させ、未延伸フィルムを得た。この未延伸フィルムについて、表２に記載の条件で、二軸延伸、熱処理を行い、厚さ１２μｍの二軸配向ポリエステルフィルムを得た。このポリエステル５の積層厚さは２μmであった。
この二軸配向ポリエステルフィルムは、耐屈曲性に若干劣るものの優れた特性を有していた。
Example 4
Polyester 1 and polyester 2 listed in Table 1 are mixed at a weight ratio of 75:25 and used as a base layer raw material, and polyester 5 (polyethylene terephthalate copolymerized with 17 mol% of isophthalic acid) is used as a laminated portion raw material. Each of these was vacuum dried, melt-extruded with two extruders, joined at the junction at the top of the die so as to be laminated on the food surface, and then statically placed on a metal roll cooled to 20 ° C. from the die. The film was discharged while applying electricity to obtain an unstretched film. The unstretched film was biaxially stretched and heat-treated under the conditions described in Table 2 to obtain a biaxially oriented polyester film having a thickness of 12 μm. The laminated thickness of this polyester 5 was 2 μm.
This biaxially oriented polyester film had excellent properties although slightly inferior in bending resistance.
比較例１〜３
表３に記載の原料を用い、表２の製膜条件で、実施例１と同様にして、比較例１〜３の二軸配向ポリエステルフィルムを得た。この二軸配向ポリエステルフィルムは、ジオール部分の緩和時間Ｔ１ρが好ましい範囲を外れるため、耐屈曲性、耐衝撃性に劣るフィルムであった。
Comparative Examples 1-3
Biaxially oriented polyester films of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 using the raw materials shown in Table 3 under the film forming conditions in Table 2. This biaxially oriented polyester film was inferior in bending resistance and impact resistance because the relaxation time T1ρ of the diol portion was outside the preferred range.
比較例４
積層厚さを６μmとした以外は、実施例４と同様にして、厚さ１２μｍの二軸配向ポリエステルフィルムを得た。
この二軸配向ポリエステルフィルムは、ジオール部分の緩和時間Ｔ１ρが大きく、耐屈曲性、耐衝撃性に劣るフィルムであった。
Comparative Example 4
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 4 except that the lamination thickness was 6 μm.
This biaxially oriented polyester film was a film in which the relaxation time T1ρ of the diol portion was large, and the flex resistance and impact resistance were inferior.
実施例５，比較例５
表１に記載のポリエステル１，ポリエステル２，ポリエステル３をそれぞれ表４に記載の重量比で混合して用いた以外は実施例１と同様にして厚さ１２μｍの２軸配向ポリエステルフィルムを得た。実施例５は優れた特性を有していたが、比較例５の二軸配向ポリエステルフィルムは、密度が低く、ジオール部分の緩和時間Ｔ１ρが小さすぎたため、熱収縮率が大きく、耐衝撃性に劣るフィルムであった。
Example 5, Comparative Example 5
A biaxially oriented polyester film having a thickness of 12 μm was obtained in the same manner as in Example 1 except that polyester 1, polyester 2, and polyester 3 listed in Table 1 were mixed and used at a weight ratio shown in Table 4, respectively. Although Example 5 had excellent characteristics, the biaxially oriented polyester film of Comparative Example 5 had a low density and a relaxation time T1ρ of the diol portion was too small, so that the heat shrinkage ratio was large and impact resistance was improved. It was an inferior film.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2006349063A JP2007138183A (en) | 2001-07-17 | 2006-12-26 | Biaxially oriented polyester film |
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| JP2001216328 | 2001-07-17 | ||
| JP2006349063A JP2007138183A (en) | 2001-07-17 | 2006-12-26 | Biaxially oriented polyester film |
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| JP2002207266A Division JP2003113258A (en) | 2001-07-17 | 2002-07-16 | Biaxially oriented polyester film |
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| JP2007138183A true JP2007138183A (en) | 2007-06-07 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009203353A (en) * | 2008-02-28 | 2009-09-10 | Riken Technos Corp | Decorative film |
| JP2014015233A (en) * | 2012-07-09 | 2014-01-30 | Kohjin Holdings Co Ltd | Packaging material for filling liquid including biaxially stretched polybutylene terephthalate film |
| JP2014133332A (en) * | 2013-01-09 | 2014-07-24 | Kohjin Film & Chemicals Co Ltd | Polybutylene terephthalate-based film for twist packaging |
| JPWO2021182191A1 (en) * | 2020-03-09 | 2021-09-16 | ||
| US12466926B2 (en) | 2020-04-22 | 2025-11-11 | Toyobo Co., Ltd. | Polyester film and use thereof |
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| JPH10324754A (en) * | 1997-03-21 | 1998-12-08 | Toray Ind Inc | Biaxially oriented polyester film for forming container |
| JPH1149874A (en) * | 1997-08-06 | 1999-02-23 | Kanebo Ltd | Polyester sheet and molded product comprising the same |
| JPH11302406A (en) * | 1998-04-22 | 1999-11-02 | Toray Ind Inc | Biaxially oriented polyester film and its preparation |
| JP2000129106A (en) * | 1998-10-29 | 2000-05-09 | Toppan Printing Co Ltd | Thermoplastic polyester resin composition and molded article using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10324754A (en) * | 1997-03-21 | 1998-12-08 | Toray Ind Inc | Biaxially oriented polyester film for forming container |
| JPH1149874A (en) * | 1997-08-06 | 1999-02-23 | Kanebo Ltd | Polyester sheet and molded product comprising the same |
| JPH11302406A (en) * | 1998-04-22 | 1999-11-02 | Toray Ind Inc | Biaxially oriented polyester film and its preparation |
| JP2000129106A (en) * | 1998-10-29 | 2000-05-09 | Toppan Printing Co Ltd | Thermoplastic polyester resin composition and molded article using the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009203353A (en) * | 2008-02-28 | 2009-09-10 | Riken Technos Corp | Decorative film |
| JP2014015233A (en) * | 2012-07-09 | 2014-01-30 | Kohjin Holdings Co Ltd | Packaging material for filling liquid including biaxially stretched polybutylene terephthalate film |
| JP2014133332A (en) * | 2013-01-09 | 2014-07-24 | Kohjin Film & Chemicals Co Ltd | Polybutylene terephthalate-based film for twist packaging |
| JPWO2021182191A1 (en) * | 2020-03-09 | 2021-09-16 | ||
| US12344778B2 (en) | 2020-03-09 | 2025-07-01 | Toyobo Co., Ltd. | Polyester film and use thereof |
| JP7708091B2 (en) | 2020-03-09 | 2025-07-15 | 東洋紡株式会社 | Polyester film and its uses |
| US12466926B2 (en) | 2020-04-22 | 2025-11-11 | Toyobo Co., Ltd. | Polyester film and use thereof |
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