JP5710938B2 - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester film Download PDFInfo
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- JP5710938B2 JP5710938B2 JP2010242194A JP2010242194A JP5710938B2 JP 5710938 B2 JP5710938 B2 JP 5710938B2 JP 2010242194 A JP2010242194 A JP 2010242194A JP 2010242194 A JP2010242194 A JP 2010242194A JP 5710938 B2 JP5710938 B2 JP 5710938B2
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- 229920006267 polyester film Polymers 0.000 title claims description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 83
- 229920000728 polyester Polymers 0.000 claims description 33
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- -1 phosphorus compound Chemical class 0.000 claims description 17
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 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 3
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KDRBAEZRIDZKRP-UHFFFAOYSA-N 2,2-bis[3-(aziridin-1-yl)propanoyloxymethyl]butyl 3-(aziridin-1-yl)propanoate Chemical compound C1CN1CCC(=O)OCC(COC(=O)CCN1CC1)(CC)COC(=O)CCN1CC1 KDRBAEZRIDZKRP-UHFFFAOYSA-N 0.000 description 1
- MFJDFPRQTMQVHI-UHFFFAOYSA-N 3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound O=C1OCOC(=O)C2=CC=C1C=C2 MFJDFPRQTMQVHI-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-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
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- CTSAXXHOGZNKJR-UHFFFAOYSA-N methyl 2-diethoxyphosphorylacetate Chemical compound CCOP(=O)(OCC)CC(=O)OC CTSAXXHOGZNKJR-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Description
本発明は二軸配向ポリエステルフィルムに関する。 The present invention relates to a biaxially oriented polyester film.
ポリエチレンテレフタレートやポリエチレン−２，６−ナフタレートに代表される芳香族ポリエステルは優れた機械的特性、寸法安定性および耐熱性を有することから、フィルムなどに幅広く使用されている。特にポリエチレン−２，６−ナフタレートは、ポリエチレンテレフタレートよりも優れた機械的特性、寸法安定性および耐熱性を有することから、それらの要求の厳しい用途、例えば高密度磁気記録テープなどのベースフィルムなどに使用されている。しかしながら、近年の高密度磁気記録テープなどでの寸法安定性の要求はますます高くなってきており、さらなる特性の向上、例えば温度や湿度などの環境変化に対する高度の寸法安定性が求められている。 Aromatic polyesters typified by polyethylene terephthalate and polyethylene-2,6-naphthalate have excellent mechanical properties, dimensional stability and heat resistance, and thus are widely used for films and the like. In particular, polyethylene-2,6-naphthalate has mechanical properties, dimensional stability and heat resistance superior to those of polyethylene terephthalate, so that it is used in demanding applications such as a base film such as a high-density magnetic recording tape. It is used. However, demands for dimensional stability in high-density magnetic recording tapes and the like in recent years are increasing, and further improvement of characteristics, for example, high dimensional stability against environmental changes such as temperature and humidity is required. .
ところで、特許文献１には、ポリ（１，４−シクロヘキサンジメチレンテレフタレート）（以下ＰＣＴと略す）を用いることで、湿度膨張係数の小さな二軸配向ポリエステルフィルムを得られることが、また、特許文献２には、ＰＣＴとポリエチレンテレフタレートとをブレンドすることで引裂強度を向上できることが開示されている。
しかしながら、これらに記載された二軸配向ポリエステルフィルムは、湿度膨張係数は低いものの、温度膨張係数がいずれの方向も１０ｐｐｍ／℃以上という温度変化に対する寸法変化が大きなものでしかなかった。
By the way, in Patent Document 1, it is possible to obtain a biaxially oriented polyester film having a low humidity expansion coefficient by using poly (1,4-cyclohexanedimethylene terephthalate) (hereinafter abbreviated as PCT). 2 discloses that the tear strength can be improved by blending PCT and polyethylene terephthalate.
However, although the biaxially oriented polyester films described therein have a low humidity expansion coefficient, the temperature expansion coefficient has only a large dimensional change with respect to a temperature change of 10 ppm / ° C. or more in any direction.
本発明の課題は、少なくとも一方向に極めて優れた環境変化に対する寸法安定性と高温での張力を負荷しても伸びにくい加工性とを具備させることができる、特に高密度磁気記録テープのベースフィルムに適した二軸配向ポリエステルフィルムを提供することにある。 An object of the present invention is to provide a base film for a high-density magnetic recording tape, in particular, which can be provided with dimensional stability against an environmental change that is extremely excellent in at least one direction and workability that is difficult to stretch even when a high-temperature tension is applied. It is in providing the biaxially-oriented polyester film suitable for.
本発明者らは、上記課題を解決しようと鋭意研究した結果、前述のエチレングリコール成分を共重合した共重合１，４−シクロヘキサンジメチレンテレフタレートを用い、かつ触媒金属化合物と安定剤としてのリン化合物とを特定の比となるように用いたとき、特定の方向に極めて小さな温度膨張係数と湿度膨張係数とを具備できることを見出し、本発明に到達した。 As a result of diligent research to solve the above problems, the present inventors have used a copolymerized 1,4-cyclohexanedimethylene terephthalate copolymerized with the aforementioned ethylene glycol component, and a catalytic metal compound and a phosphorus compound as a stabilizer. Has been found to be able to have an extremely small temperature expansion coefficient and humidity expansion coefficient in a specific direction, and the present invention has been achieved.
かくして、本発明によれば、以下の１〜６の二軸配向ポリエステルフィルムが提供される。
１．以下の（１）〜（３）
（１）全酸成分の９５モル％以上が、テレフタル酸成分であること、
（２）全グリコール成分の９５モル％以上が、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分で、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、９５：５〜６５：３５の範囲にあること、そして
（３）触媒として用いた金属化合物の金属元素量（Ｍ：ｍｍｏｌ％）が１０〜８０ｍｍｏｌ％でかつ安定剤として用いたリン化合物のリン元素量（Ｐ：ｍｍｏｌ％）とのモル比（Ｍ／Ｐ）が１〜３の範囲にあること
を満足する固有粘度が、０．５〜０．８ｄｌ／ｇの範囲にある芳香族ポリエステルからなり、
フィルムの長手方向に直交する方向（幅方向）における温度膨張係数が８ｐｐｍ／℃以下である二軸配向ポリエステルフィルム。
２．リン化合物のリン元素量（Ｐ）が、３〜７０ｍｍｏｌ％の範囲である上記１記載の二軸配向ポリエステルフィルム。
３．共重合成分が、イソフタル酸成分とエチレングリコール成分である上記１記載の二軸配向ポリエステルフィルム。
４．厚みが３〜８μｍの範囲である上記１記載の二軸配向ポリエステルフィルム。
５．芳香族ポリエステルが、１，４−シクロヘキサンジメタチレンテレフタレートを主たる繰り返し単位とするポリエステルＡと、エチレンテレフタレートを主たる繰り返し単位とするポリエステルＢを溶融混練したものである上記１記載の二軸配向ポリエステルフィルム。
６．磁気テープのベースフィルムに用いる上記１〜５のいずれかに記載の二軸配向ポリエステルフィルム。
Thus, according to the present invention, the following biaxially oriented polyester films 1 to 6 are provided.
1. The following (1) to (3)
(1) 95 mol% or more of all acid components are terephthalic acid components,
(2) 95 mol% or more of the total glycol component is 1,4-cyclohexanedimethanol component and ethylene glycol component, and the molar ratio of 1,4-cyclohexanedimethanol component to ethylene glycol component is 95: 5-65: 35 and (3) the amount of metal element (M: mmol%) of the metal compound used as the catalyst is 10 to 80 mmol% and the amount of phosphorus element of the phosphorus compound used as the stabilizer (P: mmol%) ) molar ratio of (M / P) is the intrinsic viscosity which satisfies that is in the range from 1 to 3 Ri Do aromatic polyester in the range of 0.5~0.8dl / g,
The biaxially oriented polyester film temperature expansion coefficient of Ru der following 8 ppm / ° C. in a direction (width direction) perpendicular to the longitudinal direction of the film.
2. 2. The biaxially oriented polyester film according to 1 above, wherein the phosphorus element amount (P) of the phosphorus compound is in the range of 3 to 70 mmol%.
3. 2. The biaxially oriented polyester film as described in 1 above, wherein the copolymer components are an isophthalic acid component and an ethylene glycol component.
4 . 2. The biaxially oriented polyester film according to 1 above, wherein the thickness is in the range of 3 to 8 μm.
5 . 2. The biaxially oriented polyester film as described in 1 above, wherein the aromatic polyester is a melt-kneaded polyester A having 1,4-cyclohexanedimethylene terephthalate as a main repeating unit and polyester B having ethylene terephthalate as a main repeating unit. .
6 . The biaxially oriented polyester film according to any one of 1 to 5 above, which is used for a base film of a magnetic tape.
本発明によれば、ＰＣＴにエチレングリコール成分とを特定の割合で存在させつつ、触媒金属化合物と安定剤としてのリン化合物とを特定の比となるように用いており、環境変化に対する寸法安定性が求められる方向に高度に分子鎖を配向させる高度の延伸を行うことができる。
したがって、本発明の二軸配向ポリエステルフィルムは、例えば幅方向の温度膨張係数を１０ｐｐｍ／℃以下、さらに８ｐｐｍ／℃以下とすることで、磁気テープのベースフィルムとして好適に用いることができ、その工業的価値はきわめて高い。
According to the present invention, the catalyst metal compound and the phosphorus compound as the stabilizer are used at a specific ratio while the ethylene glycol component is present in the PCT at a specific ratio, and the dimensional stability against environmental changes is achieved. It is possible to carry out a high degree of stretching that highly orients the molecular chain in the direction in which it is required.
Therefore, the biaxially oriented polyester film of the present invention can be suitably used as a base film of a magnetic tape, for example, by setting the temperature expansion coefficient in the width direction to 10 ppm / ° C. or less, further 8 ppm / ° C. or less. Target value is extremely high.
本発明における芳香族ポリエステルについて、詳述する。
本発明におけるポリエステルは、全酸成分の９５モル％以上が、テレフタル酸成分であること、全グリコール成分の９５モル％以上が、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分で、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、９５：５〜６５：３５の範囲にあること、そして、触媒として用いた触媒金属化合物の金属元素量（Ｍ：ｍｍｏｌ％）が１０〜８０ｍｍｏｌ％でかつ安定剤として用いたリン化合物のリン元素量（Ｐ：ｍｍｏｌ％）とのモル比（Ｍ／Ｐ）が１〜４の範囲にある。
The aromatic polyester in the present invention will be described in detail.
In the polyester of the present invention, 95 mol% or more of all acid components are terephthalic acid components, and 95 mol% or more of all glycol components are 1,4-cyclohexanedimethanol component and ethylene glycol component, and 1,4 -The molar ratio of cyclohexanedimethanol component and ethylene glycol component is in the range of 95: 5 to 65:35, and the amount of metal element (M: mmol%) of the catalyst metal compound used as the catalyst is 10 to 80 mmol. % And the molar ratio (M / P) of the phosphorus compound used as a stabilizer to the amount of phosphorus element (P: mmol%) is in the range of 1-4.
全酸成分の９５モル％以上が、テレフタル酸成分にあることで、環境変化に対する寸法安定性が求められる方向に高度に分子鎖を配向させる高度の延伸を行うことができ、しかもその高度に延伸を行った方向と直交する方向にも加工性などに必要な十分な機械特性を具備させることができる。 Since 95 mol% or more of the total acid component is in the terephthalic acid component, it can be highly stretched to highly orient molecular chains in the direction where dimensional stability against environmental changes is required. Sufficient mechanical properties necessary for workability and the like can also be provided in a direction orthogonal to the direction in which the process is performed.
また、本発明におけるポリエステルは、全グリコール成分の９５モル％以上が、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分で、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、９５：５〜６５：３５の範囲、好ましくは９４：６〜６７：３３、さらに好ましくは８６：１４〜７０：３０の範囲にあることで、環境変化に対する寸法安定性が求められる方向に高度に分子鎖を配向させる高度の延伸を行うことができ、しかもその高度に延伸を行った方向と直交する方向にも加工性などに必要な十分な機械特性を具備させることができる。すなわち、エチレングリコール成分の存在によって延伸性をより高めることができるが、エチレングリコール成分が過剰に多くなると、湿度膨張係数などを低下させにくくなる。 In the polyester of the present invention, 95 mol% or more of the total glycol component is 1,4-cyclohexanedimethanol component and ethylene glycol component, and the molar ratio of 1,4-cyclohexanedimethanol component to ethylene glycol component is 95. : In the range of 5 to 65:35, preferably in the range of 94: 6 to 67:33, more preferably in the range of 86:14 to 70:30. It is possible to perform a high degree of stretching for orienting the chain, and also to provide sufficient mechanical properties necessary for processability and the like in a direction orthogonal to the direction of the high degree of stretching. That is, the stretchability can be further enhanced by the presence of the ethylene glycol component, but when the amount of the ethylene glycol component is excessive, it is difficult to reduce the humidity expansion coefficient and the like.
また、本発明におけるポリエステルは、全酸成分のモル数を基準として、テレフタル酸成分と１，４−シクロヘキサンジメタノール成分以外の共重合成分の合計が、１０モル％以上、さらに１５モル％以上であることで、環境変化に対する寸法安定性が求められる方向に高度の延伸を行えるような延伸性を発現させるために好ましい。なお、上限は、前述の組成の関係から自ずと決まることは容易に理解されるであろう。このような共重合成分としては、イソフタル酸成分、２，６−ナフタレンジカルボン酸成分、２，７−ナフタレンジカルボン酸成分が好ましく挙げられ、グリコール成分としては、エチレングリコール成分、トリメチレングリコール成分、テトラメチレングリコール成分などが挙げられる。これらの中でも、ヤング率の観点から、イソフタル酸成分およびエチレングリコール成分からなる群より選ばれる少なくとも１種を共重合したものが好ましい。 In the polyester of the present invention, the total of copolymer components other than the terephthalic acid component and the 1,4-cyclohexanedimethanol component is 10 mol% or more, and further 15 mol% or more, based on the number of moles of all acid components. It is preferable in order to develop stretchability that enables high-stretching in a direction that requires dimensional stability against environmental changes. It will be easily understood that the upper limit is naturally determined from the above-described compositional relationship. Preferred examples of such a copolymer component include an isophthalic acid component, a 2,6-naphthalenedicarboxylic acid component, and a 2,7-naphthalenedicarboxylic acid component. Examples of the glycol component include an ethylene glycol component, a trimethylene glycol component, a tetramethylene glycol component, and a tetramethylene glycol component. Examples include a methylene glycol component. Among these, from the viewpoint of Young's modulus, a copolymer obtained by copolymerizing at least one selected from the group consisting of an isophthalic acid component and an ethylene glycol component is preferable.
ところで、本発明におけるポリエステルは、触媒として用いた触媒金属化合物の金属元素量（Ｍ：ｍｏｌ％）と、安定剤として用いたリン化合物のリン元素量（Ｐ：ｍｍｏｌ％）とのモル比（Ｍ／Ｐ）が１〜４、好ましくは１〜３、さらに好ましくは１〜２．５の範囲にあることが必要である。上記範囲にあることで、製膜する際の溶融押出工程などでの熱劣化が抑制でき、その後の延伸性を高度に維持することができる。 By the way, the polyester of the present invention has a molar ratio (M) of the amount of metal element (M: mol%) of the catalyst metal compound used as the catalyst and the amount of phosphorus element (P: mmol%) of the phosphorus compound used as the stabilizer. / P) must be in the range of 1-4, preferably 1-3, more preferably 1-2.5. By being in the said range, the thermal deterioration in the melt-extrusion process at the time of forming into a film can be suppressed, and the subsequent drawability can be maintained highly.
また、上記触媒金属化合物の含有量は、ポリエステルの全酸成分のモル数を基準としたときの金属元素量で、１０〜８０ｍｍｏｌ％の範囲、好ましくは３０〜７５ｍｍｏｌ％、さらに好ましくは５０〜７０ｍｍｏｌ％の範囲にあることが、より熱劣化などを抑制しつつ、重合反応性を高度維持できる。 Further, the content of the catalytic metal compound is a metal element amount based on the number of moles of the total acid component of the polyester, in the range of 10 to 80 mmol%, preferably 30 to 75 mmol%, more preferably 50 to 70 mmol. %, It is possible to maintain a high degree of polymerization reactivity while further suppressing thermal degradation.
なお、本発明における触媒金属化合物としては、それ自体公知のものを挙げることができ、Ｔｉ、Ａｌ、Ｓｂ、Ｇｅなどの金属成分を有する金属化合物や、エステル交換反応を経由する場合は、Ｌｉ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｍｎ、Ｃｏ、Ｔｉなどの金属成分を有する金属化合物が好ましく挙げられる。これらの中でも、反応活性が高く、異物などの析出を押さえやすいことから、Ｔｉを金属成分として有する触媒金属化合物を触媒として用いたものが好ましい。もちろん、これらの触媒は１種に限らず、２種以上を併用しても良い。 In addition, as a catalyst metal compound in this invention, a publicly known thing can be mentioned, and when passing through transesterification, the metal compound which has metal components, such as Ti, Al, Sb, Ge, Li, Preferable examples are metal compounds having metal components such as Na, K, Mg, Ca, Mn, Co, and Ti. Among these, those using a catalytic metal compound having Ti as a metal component as a catalyst are preferable because they have high reaction activity and easily suppress the precipitation of foreign substances. Of course, these catalysts are not limited to one type, and two or more types may be used in combination.
また、上記リン化合物の含有量は、ポリエステルの全酸成分のモル数を基準としたときのリン元素量で、３〜７０ｍｍｏｌ％の範囲、さらに１０〜６５ｍｍｏｌ％、特に４０〜５０ｍｍｏｌ％の範囲にあることが、より熱劣化などを抑制しつつ、重合反応性を高度維持できることから好ましい。 The content of the phosphorus compound is the amount of phosphorus element based on the number of moles of all acid components of the polyester, in the range of 3 to 70 mmol%, more preferably in the range of 10 to 65 mmol%, particularly in the range of 40 to 50 mmol%. It is preferable that the polymerization reactivity can be maintained at a high level while further suppressing thermal degradation.
なお、本発明におけるリン化合物としては、それ自体公知のものを挙げることができ、化合物中にリン元素を有するものであれば特に限定されず、例えば、リン酸、亜リン酸、リン酸トリメチルエステル、リン酸トリブチルエステル、リン酸トリフェニルエステル、リン酸モノメチルエステル、リン酸ジメチルエステル、フェニルホスホン酸、フェニルホスホン酸ジメチルエステル、フェニルホスホン酸ジエチルエステル、リン酸アンモニウム、トリエチルホスホノアセテート、メチルジエチルホスホノアセテートなどを挙げることができ、これらのリン化合物は二種以上を併用してもよい。また、リン化合物の添加時期は、エステル化反応やエステル交換反応が実質的に終了してから重縮合反応初期の間に行なうことが好ましく、添加は一度に行ってもよいし、２回以上に分割して行ってもよい。 In addition, as a phosphorus compound in this invention, a publicly known thing can be mentioned, if it has a phosphorus element in a compound, it will not specifically limit, For example, phosphoric acid, phosphorous acid, phosphoric acid trimethyl ester , Phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phenylphosphonic acid, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, ammonium phosphate, triethylphosphonoacetate, methyldiethylphospho Noacetate and the like can be mentioned, and two or more of these phosphorus compounds may be used in combination. Moreover, it is preferable to add the phosphorus compound during the initial stage of the polycondensation reaction after the esterification reaction or transesterification reaction is substantially completed. The addition may be performed once or more than once. You may divide and go.
ところで、このようなポリエステルは、それ自体公知の方法で製造でき、所望の組成になるように原料を仕込み、エステル交換反応またはエステル化反応を経由して重縮合反応させてもよいし、シクロヘキサンジメチレンテレフタレートを主たる繰り返し単位とするポリエステルと、エチレンテレフタレートを主たる繰り返し単位とするポリエステルとを用意し、これらを溶融混練させて所望の組成のポリエステルとしてもよい。特に本発明の効果の点からは、その理由は不明だが、後者の溶融混練させるほうが、ヤング率などの機械的物性をより高めやすいことから好ましい。 By the way, such a polyester can be produced by a method known per se, and raw materials are charged so as to have a desired composition, and a polycondensation reaction may be carried out via an ester exchange reaction or an esterification reaction. A polyester having methylene terephthalate as a main repeating unit and a polyester having ethylene terephthalate as a main repeating unit are prepared, and these may be melt-kneaded to obtain a polyester having a desired composition. In particular, from the viewpoint of the effect of the present invention, the reason is unclear, but the latter melting and kneading is preferable because mechanical properties such as Young's modulus are more easily improved.
つぎに、本発明の二軸配向ポリエステルフィルムについて説明する。
本発明の二軸配向ポリエステルフィルムは、前述のポリエステルを製膜方向と幅方向とに延伸したものである。積層構造は特に制限されず、単層フィルムでも、２層以上の積層フィルムでもよい。また、積層フィルムの場合は、少なくとも１層が本発明の二軸配向ポリエステルフィルムであればよい。また、本発明の二軸配向積層ポリエステルフィルムは、前述のポリエステル樹脂からなり、本発明の効果を阻害しない範囲で、それ自体公知の樹脂や機能剤などを含有していてもよい。ブレンドする樹脂としては、ポリエーテルイミドや液晶性樹脂などは、得られるフィルムの耐熱性などを向上させやすいことから好ましい。
Next, the biaxially oriented polyester film of the present invention will be described.
The biaxially oriented polyester film of the present invention is obtained by stretching the aforementioned polyester in the film forming direction and the width direction. The laminated structure is not particularly limited, and may be a single layer film or a laminated film having two or more layers. In the case of a laminated film, at least one layer may be the biaxially oriented polyester film of the present invention. Moreover, the biaxially oriented laminated polyester film of the present invention is made of the above-described polyester resin, and may contain a resin or a functional agent known per se as long as the effects of the present invention are not impaired. As the resin to be blended, polyetherimide, liquid crystalline resin, and the like are preferable because the heat resistance and the like of the obtained film are easily improved.
以下、本発明の二軸配向ポリエステルフィルムの好ましい態様について説明する。
本発明の二軸配向ポリエステルフィルムは、フィルムの製膜方向または幅方向のいずれかの方向は、ヤング率が４ＧＰａ以上、さらに４．５ＧＰａ以上、特に５ＧＰａ以上であることが好ましい。いずれの方向もヤング率が４ＧＰａ未満である場合、温度膨張係数を低減することが困難となりやすい。また、特に、磁気記録テープにベースフィルムに用いる場合、ヤング率を高める方向が二軸配向ポリエステルフィルムの幅方向であることが、トラックずれなどを抑制できることから好ましい。なお、ヤング率の上限は特に制限されないが、延伸時の破断などを抑制する点から、１１ＧＰａ以下、さらに１０ＧＰａ以下が好ましい。
Hereinafter, the preferable aspect of the biaxially-oriented polyester film of this invention is demonstrated.
The biaxially oriented polyester film of the present invention preferably has a Young's modulus of 4 GPa or more, more preferably 4.5 GPa or more, and particularly preferably 5 GPa or more in either the film forming direction or the width direction. If the Young's modulus is less than 4 GPa in any direction, it is difficult to reduce the temperature expansion coefficient. In particular, when used as a base film for a magnetic recording tape, the direction in which the Young's modulus is increased is preferably the width direction of the biaxially oriented polyester film because track deviation and the like can be suppressed. The upper limit of Young's modulus is not particularly limited, but is preferably 11 GPa or less, more preferably 10 GPa or less, from the viewpoint of suppressing breakage during stretching.
また、磁気テープ用として使用する場合、使用時の伸びを少なくする観点から、フィルムの製膜方向および幅方向ヤング率は、いずれも２．４ＧＰａ以上であることが好ましい。 Moreover, when using it for magnetic tapes, it is preferable that both the film forming direction and the width direction Young's modulus of a film are 2.4 GPa or more from a viewpoint of reducing the elongation at the time of use.
このような特定の方向に高いヤング率といずれの方向にも実用上必要なヤング率を有するフィルムを得るには、前述の特定量の１，４−シクロヘキサンジメチレンテレフタレート成分を含むポリエステル樹脂を用いること、ヤング率を高めたい方向に高度に延伸すること、さらにより特定方向のヤング率を高めたい場合は、ヤング率を高めたい方向と直交する方向の延伸を緩和すること、また共重合芳香族ポリエステルとして、前述のような１，４−シクロヘキサンジメチレンテレフタレート成分の割合が異なる２種以上のポリエステルを用意し、これらをブレンドすることなどが挙げられる。 In order to obtain a film having such a high Young's modulus in a specific direction and a practically necessary Young's modulus in any direction, a polyester resin containing the above-mentioned specific amount of 1,4-cyclohexanedimethylene terephthalate component is used. In order to increase the Young's modulus in a direction highly desired, and to further increase the Young's modulus in a specific direction, the stretching in the direction orthogonal to the direction in which the Young's modulus is desired to be relaxed, and the copolymer aromatic Examples of the polyester include preparing two or more kinds of polyesters having different proportions of the 1,4-cyclohexanedimethylene terephthalate component as described above, and blending them.
ところで、本発明の二軸配向ポリエステルフィルムは、優れた寸法安定性を発現する点から、少なくとも１方向、好ましくはフィルムの幅方向の温度膨張係数（αｔ）が１０ｐｐｍ／℃以下であることが好ましい。フィルムの少なくとも一方向における温度膨張係数が１０ｐｐｍ／℃以下であることで環境変化に対する優れた寸法安定性を発現することが出来る。温度膨張係数の下限は制限されないが、通常−１５ｐｐｍ／℃である。好ましい温度膨張係数（αｔ）は−１０〜１０ｐｐｍ／℃、さらに−７〜７ｐｐｍ／℃、特に−５〜６ｐｐｍ／℃の範囲であることが、例えば磁気記録テープとしたとき、雰囲気の温度変化による寸法変化に対して優れた寸法安定性を発現できることから好ましい。 By the way, the biaxially oriented polyester film of the present invention preferably has a temperature expansion coefficient (αt) of at least 10 ppm / ° C. in at least one direction, preferably the width direction of the film, from the viewpoint of exhibiting excellent dimensional stability. . When the temperature expansion coefficient in at least one direction of the film is 10 ppm / ° C. or less, excellent dimensional stability against environmental changes can be exhibited. The lower limit of the temperature expansion coefficient is not limited, but is usually −15 ppm / ° C. The preferred temperature expansion coefficient (αt) is in the range of −10 to 10 ppm / ° C., more preferably −7 to 7 ppm / ° C., particularly preferably −5 to 6 ppm / ° C. It is preferable because it can exhibit excellent dimensional stability against dimensional changes.
また、本発明の二軸配向ポリエステルフィルムは、少なくとも一方向、好ましくはフィルムの幅方向の湿度膨張係数が１〜７ｐｐｍ／％ＲＨ、好ましくは３〜５ｐｐｍ／％ＲＨの範囲にあることが、例えば磁気記録テープとしたとき、雰囲気の湿度変化による寸法変化に対して優れた寸法安定性を発現できることから好ましい。 Further, the biaxially oriented polyester film of the present invention has a humidity expansion coefficient of at least one direction, preferably the film width direction, in the range of 1 to 7 ppm /% RH, preferably 3 to 5 ppm /% RH. When a magnetic recording tape is used, it is preferable because it can exhibit excellent dimensional stability against dimensional changes due to changes in atmospheric humidity.
本発明の二軸配向ポリエステルフィルムの厚みは特に制限されないが、磁気テープに用いる場合は、フィルム全体の厚みで２〜１５μｍの範囲、さらに３〜８μｍの範囲、特に３．５〜５μｍの範囲にあることが好ましい。この厚みが上限を超えると、フィルム厚みが厚くなりすぎ、例えば磁気記録媒体に用いた場合はカセットに入れるテープ長さが短くなり、十分な磁気記録容量が得られない。 The thickness of the biaxially oriented polyester film of the present invention is not particularly limited, but when used for a magnetic tape, the total film thickness is in the range of 2 to 15 μm, more preferably in the range of 3 to 8 μm, particularly in the range of 3.5 to 5 μm. Preferably there is. If this thickness exceeds the upper limit, the film thickness becomes too thick. For example, when used for a magnetic recording medium, the tape length to be put in the cassette is shortened and a sufficient magnetic recording capacity cannot be obtained.
ところで、本発明の二軸配向ポリエステルフィルムは、Ｐ−クロロフェノール／１，１，２，２−テトラクロロエタン（重量比４０／６０）の混合溶媒を用いて３５℃で測定した固有粘度が０．５〜０．８ｄｌ／ｇ、さらに０．５〜０．７ｄｌ／ｇの範囲にあることが、高度の延伸に耐えられることから好ましい。このような固有粘度は、製膜などのときの溶融混練時に低下する固有粘度の低下を勘案して、あらかじめ用いるポリエステルの固有粘度を高めておけばよいが、本発明におけるポリエステルは通常のポリエチレンテレフタレートに比べ、非常に溶融混練時に低下する固有粘度が大きく、これだけでは調整が困難であり、さらに、触媒金属化合物量とリン化合物量とを前述の範囲に調整して固有粘度の低下を少なくしておくことや、溶融混練の時間を短くしたり、温度を低くすることなどが好ましく挙げられる。 By the way, the biaxially oriented polyester film of the present invention has an intrinsic viscosity measured at 35 ° C. using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (weight ratio 40/60) of 0. A range of 5 to 0.8 dl / g, and more preferably 0.5 to 0.7 dl / g is preferable because it can withstand a high degree of stretching. The intrinsic viscosity of the polyester used in the present invention may be increased by taking into account the decrease in intrinsic viscosity that is reduced during melt-kneading at the time of film formation. In comparison, the intrinsic viscosity that decreases during melt-kneading is very large, and it is difficult to adjust by itself.Furthermore, the amount of catalytic metal compound and the amount of phosphorus compound are adjusted to the above-mentioned ranges to reduce the decrease in intrinsic viscosity. For example, it is preferable to shorten the melt kneading time or to lower the temperature.
つぎに、本発明の二軸配向ポリエステルフィルムを製造する方法について説明するが、本発明はこれに限定されるものではない。
まず、本発明の二軸配向ポリエステルフィルムは、前述のポリエステルを溶融製膜して、シート状に押出し、製膜方向と幅方向に延伸することで得られる。
Next, a method for producing the biaxially oriented polyester film of the present invention will be described, but the present invention is not limited thereto.
First, the biaxially oriented polyester film of the present invention is obtained by melt-forming the above-mentioned polyester, extruding it into a sheet, and stretching it in the film forming direction and the width direction.
用いるポリエステル樹脂のＰ−クロロフェノール／１，１，２，２−テトラクロロエタン（重量比４０／６０）の混合溶媒を用いて３５℃で測定した固有粘度は、０．５〜１．１ｄｌ／ｇ、さらに０．６〜１．１ｄｌ／ｇの範囲にあることが本発明の効果の点から好ましい。固有粘度が上限以上だと、粘度が高くなりすぎ、製膜時の押出機からの樹脂の押出が困難になる。また、固有粘度が下限以下だと、フィルムが脆化し、延伸が困難になる。 The intrinsic viscosity measured at 35 ° C. using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (weight ratio 40/60) of the polyester resin used is 0.5 to 1.1 dl / g. Further, it is preferably in the range of 0.6 to 1.1 dl / g from the viewpoint of the effect of the present invention. If the intrinsic viscosity is equal to or higher than the upper limit, the viscosity becomes too high, and it becomes difficult to extrude the resin from the extruder during film formation. On the other hand, if the intrinsic viscosity is less than the lower limit, the film becomes brittle and stretching becomes difficult.
本発明の二軸配向ポリエステルフィルムは、製膜方向と幅方向に延伸してそれぞれの方向の分子配向を高めたものであることが好ましく、例えば以下のような方法で製造することが、製膜性を維持しつつ、ヤング率を向上させやすいことから好ましい。 The biaxially oriented polyester film of the present invention is preferably one in which the molecular orientation in each direction is enhanced by stretching in the film forming direction and the width direction. For example, it can be produced by the following method. It is preferable because the Young's modulus is easily improved while maintaining the properties.
まず、前述のポリエステルもしくは溶融混練によって前述のポリエステルの組成となる複数のポリエステル樹脂を原料とし、これを乾燥後、フィルムにしたときのポリエステル樹脂の融点ないし（Ｔｍ＋５０）℃の温度に加熱された押出機に供給して、例えばＴダイなどのダイよりシート状に押出す。この押出されたシート状物を回転している冷却ドラムなどで急冷固化して未延伸フィルムとし、さらに該未延伸フィルムを二軸延伸する。このとき、溶融混練の間に前述のエステル交換反応が進んでしまわないように注意することが必要である。 First, the above-described polyester or a plurality of polyester resins having the above-mentioned polyester composition by melt-kneading are used as raw materials, and this is dried and then extruded at a temperature from the melting point of the polyester resin to a temperature of (Tm + 50) ° C. It is fed to a machine and extruded into a sheet form from a die such as a T die. The extruded sheet is rapidly cooled and solidified with a rotating cooling drum or the like to form an unstretched film, and the unstretched film is further biaxially stretched. At this time, care must be taken so that the above-described transesterification reaction does not proceed during melt-kneading.
なお、前述のヤング率、αｔおよびαｈを好ましい範囲にするには、その後の延伸を進行させやすくすることが必要であり、そのような観点から冷却ドラムによる冷却は非常に速やかに行うことが好ましい。そのような観点から、２０〜６０℃という低温で行なうことが好ましい。このような低温で行うことで、未延伸フィルムの状態での結晶化が抑制され、その後の延伸をよりスムーズに行うことが可能となる。 In order to make the aforementioned Young's modulus, αt, and αh within the preferable ranges, it is necessary to facilitate the subsequent stretching. From such a viewpoint, it is preferable to perform cooling with a cooling drum very quickly. . From such a viewpoint, it is preferable to carry out at a low temperature of 20 to 60 ° C. By performing at such a low temperature, crystallization in the state of an unstretched film is suppressed, and subsequent stretching can be performed more smoothly.
二軸延伸としては、逐次二軸延伸でも同時二軸延伸でもよい。
ここでは、逐次二軸延伸について、製膜方向および幅方向に延伸し、熱処理をこの順で行う製造方法を一例として挙げて説明する。まず、最初の製膜方向の延伸はポリエステルのガラス転移温度（Ｔｇ：℃）ないし（Ｔｇ＋４０）℃の温度で、２〜８倍に延伸し、次いで幅方向に先の製膜方向の延伸と同等かそれよりも高温の（Ｔｇ＋１０）〜（Ｔｇ＋５０）℃の温度で３〜１０倍に延伸し、さらに熱処理としてポリマーの融点以下の温度でかつ（Ｔｇ＋５０）〜（Ｔｇ＋１５０）℃の温度で１〜２０秒、さらに１〜１５秒熱固定処理するのが好ましい。熱処理は、所望に応じて、製膜方向または幅方向に、弛緩させたり、延伸させたりしてもよいが、その範囲は熱処理前の長さを基準として、−５〜５％の範囲が好ましい。
Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching.
Here, the sequential biaxial stretching will be described by taking, as an example, a manufacturing method in which stretching is performed in the film forming direction and the width direction and heat treatment is performed in this order. First, stretching in the first film forming direction is performed at a glass transition temperature (Tg: ° C.) to (Tg + 40) ° C. of the polyester at 2 to 8 times, and then in the width direction is the same as the previous film forming direction. It is stretched 3 to 10 times at a temperature of (Tg + 10) to (Tg + 50) ° C., which is higher than that, and further treated as a heat treatment at a temperature below the melting point of the polymer and at a temperature of (Tg + 50) to (Tg + 150) ° C. It is preferable to perform heat setting treatment for 1 second, and further for 1 to 15 seconds. The heat treatment may be relaxed or stretched in the film forming direction or the width direction as desired, but the range is preferably -5 to 5% based on the length before the heat treatment. .
前述の説明は逐次二軸延伸について説明したが、本発明の二軸配向ポリエステルフィルムは縦延伸と横延伸とを同時に行う同時二軸延伸でも製造でき、例えば先で説明した延伸倍率や延伸温度などを参考にすればよい。 Although the above description has been described for sequential biaxial stretching, the biaxially oriented polyester film of the present invention can be produced by simultaneous biaxial stretching in which longitudinal stretching and lateral stretching are simultaneously performed, for example, the stretching ratio and stretching temperature described above, etc. Should be referred to.
また、本発明の二軸配向ポリエステルフィルムは、前述のとおり、単層フィルムに限られず、積層フィルムであってもよく、その場合は、少なくとも一つのフィルム層が本発明の二軸配向ポリエステルフィルムであれば良い。このような積層フィルムの作り方としては、例えば２種以上の溶融ポリエステルをダイ内で積層してからフィルム状に押出し、好ましくはそれぞれのポリエステルの融点（Ｔｍ：℃）ないし（Ｔｍ＋７０）℃の温度で押出すか、２種以上の溶融ポリエステルをダイから押出した後に積層し、急冷固化して積層未延伸フィルムとし、ついで前述の単層フィルムの場合と同様な方法で二軸延伸および熱処理を行うとよい。 Further, as described above, the biaxially oriented polyester film of the present invention is not limited to a single layer film and may be a laminated film. In that case, at least one film layer is the biaxially oriented polyester film of the present invention. I need it. As a method of making such a laminated film, for example, two or more types of molten polyester are laminated in a die and then extruded into a film, preferably at a temperature of the melting point (Tm: ° C.) to (Tm + 70) ° C. of each polyester. Extrude or laminate after extruding two or more types of molten polyester from a die, quench and solidify to make a laminated unstretched film, then biaxially stretch and heat treatment in the same manner as in the case of the above-mentioned single layer film .
また、本発明二軸配向ポリエステルフィルムは、接着性や滑り性を向上させるために、それ自体公知の塗布層を設けても良い。塗布層を設ける場合は、前記した未延伸フィルムまたは一軸延伸フィルムの片面または両面に所望の塗布液を塗布し、後は前述の単層フィルムの場合と同様な方法で二軸延伸および熱処理を行えばよい。
このようにして得られた本発明の二軸配向ポリエステルフィルムは、その一方の面に非磁性層および磁性層をこの順で形成し、他方の面にバックコート層を形成することで、ＬＴＯなどのリニア記録方式の磁気記録テープとすることができる。
In addition, the biaxially oriented polyester film of the present invention may be provided with a coating layer known per se in order to improve adhesion and slipperiness. When providing a coating layer, apply the desired coating solution on one or both sides of the unstretched film or uniaxially stretched film, and then perform biaxial stretching and heat treatment in the same manner as in the case of the single-layer film described above. Just do it.
In the biaxially oriented polyester film of the present invention thus obtained, a nonmagnetic layer and a magnetic layer are formed in this order on one surface, and a backcoat layer is formed on the other surface, so that LTO or the like is formed. The linear recording type magnetic recording tape can be obtained.
以下に実施例及び比較例を挙げ、本発明をより具体的に説明する。なお、本発明では、以下の方法により、その特性を測定および評価した。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the present invention, the characteristics were measured and evaluated by the following methods.
（１）固有粘度
得られたポリエステルの固有粘度はＰ−クロロフェノール／１，１，２，２−テトラクロロエタン（４０／６０重量比）の混合溶媒を用いてポリマーを溶解して３５℃で測定して求めた。
(1) Intrinsic viscosity The intrinsic viscosity of the obtained polyester was measured at 35 ° C by dissolving the polymer using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (40/60 weight ratio). And asked.
（２）ヤング率
得られたフィルムを試料巾１０ｍｍ、長さ１５ｃｍで切り取り、チャック間１００ｍｍ、引張速度１０ｍｍ／分、チャート速度５００ｍｍ／分の条件で万能引張試験装置（東洋ボールドウィン製、商品名：テンシロン）にて引っ張る。得られた荷重―伸び曲線の立ち上がり部の接線よりヤング率を計算する。
(2) Young's modulus The obtained film was cut out with a sample width of 10 mm and a length of 15 cm, and a universal tensile testing device (product name: manufactured by Toyo Baldwin, trade name: 100 mm between chucks, tensile speed 10 mm / min, chart speed 500 mm / min). Pull with Tensilon). The Young's modulus is calculated from the tangent of the rising portion of the obtained load-elongation curve.
（３）温度膨張係数（αｔ）
得られたフィルムを、フィルムの製膜方向または幅方向が測定方向となるようにそれぞれ長さ１５ｍｍ、幅５ｍｍに切り出し、真空理工製ＴＭＡ３０００にセットし、窒素雰囲気下（０％ＲＨ）、６０℃で３０分前処理し、その後室温まで降温させる。その後２５℃から７０℃まで２℃／ｍｉｎで昇温して、各温度でのサンプル長を測定し、次式より温度膨張係数（αｔ）を算出する。なお、測定方向が切り出した試料の長手方向である。
αｔ＝｛（Ｌ６０−Ｌ４０）｝／（Ｌ４０×△Ｔ）｝＋０．５
ここで、上記式中のＬ４０は４０℃のときのサンプル長（ｍｍ）、Ｌ６０は６０℃のときのサンプル長（ｍｍ）、△Ｔは２０（＝６０−４０）℃、０．５は石英ガラスの温度膨張係数（ｐｐｍ／℃）である。
(3) Temperature expansion coefficient (αt)
The obtained film was cut into a length of 15 mm and a width of 5 mm so that the film forming direction or the width direction of the film would be the measurement direction, set in TMA3000 manufactured by Vacuum Riko, and under a nitrogen atmosphere (0% RH) at 60 ° C. For 30 minutes and then let it cool to room temperature. Thereafter, the temperature is raised from 25 ° C. to 70 ° C. at 2 ° C./min, the sample length at each temperature is measured, and the temperature expansion coefficient (αt) is calculated from the following equation. The measurement direction is the longitudinal direction of the cut sample.
αt = {(L 60 −L 40 )} / (L 40 × ΔT)} + 0.5
Here, L 40 in the above formula is the sample length (mm) at 40 ° C., L 60 is the sample length (mm) at 60 ° C., ΔT is 20 (= 60-40) ° C., 0.5 Is the temperature expansion coefficient (ppm / ° C.) of quartz glass.
（４）湿度膨張係数（αｈ）
得られたフィルムを、フィルムの製膜方向または幅方向が測定方向となるように長さ１５ｍｍ、幅５ｍｍに切り出し、真空理工製ＴＭＡ３０００にセットし、３０℃の窒素雰囲気下で、湿度２０％ＲＨと湿度８０％ＲＨにおけるそれぞれのサンプルの長さを測定し、次式にて湿度膨張係数を算出する。なお、測定方向が切り出した試料の長手方向である。
αｈ＝（Ｌ８０−Ｌ２０）／（Ｌ２０×△Ｈ）
ここで、上記式中のＬ２０は２０％ＲＨのときのサンプル長（ｍｍ）、Ｌ８０は８０％ＲＨのときのサンプル長（ｍｍ）、△Ｈ：６０（＝８０−２０）％ＲＨである。
(4) Humidity expansion coefficient (αh)
The obtained film was cut into a length of 15 mm and a width of 5 mm so that the film forming direction or the width direction of the film would be the measurement direction, set in TMA3000 manufactured by Vacuum Riko, and a humidity of 20% RH in a nitrogen atmosphere at 30 ° C. The length of each sample at a humidity of 80% RH is measured, and the humidity expansion coefficient is calculated by the following equation. The measurement direction is the longitudinal direction of the cut sample.
αh = (L 80 −L 20 ) / (L 20 × ΔH)
Here, L 20 in the above formula is a sample length (mm) when 20% RH, L 80 is a sample length (mm) when 80% RH, ΔH: 60 (= 80-20)% RH is there.
（５）最大延伸倍率（ＭＤＲ）
フィルム製膜時に、幅方向の倍率をあげていき、フィルムの切断がおきる直前の倍率を最大延伸倍率とした。
(5) Maximum draw ratio (MDR)
During film formation, the magnification in the width direction was increased, and the magnification immediately before the film was cut was defined as the maximum draw ratio.
（６）共重合量
グリコール成分については、試料１０ｍｇをｐ−クロロフェノール：１，１，２，２−テトラクロロエタン＝３：１（容積比）混合溶液０．５ｍｌに８０℃で溶解した。イソプロピルアミンを加えて、十分に混合した後に６００Ｍの１Ｈ−ＮＭＲ（日本電子製 ＪＥＯＬ Ａ６００）にて８０℃で測定し、それぞれのグリコール成分量を測定した。
また、芳香族ジカルボン酸成分については、試料５０ｍｇをｐ−クロロフェノール：１，１，２，２−テトラクロロエタン＝３：１混合溶液０．５ｍｌに１４０℃で溶解し、１００Ｍ １３Ｃ−ＮＭＲ（日本電子 ＪＥＯＬ Ａ６００）にて１４０℃で測定し、それぞれの酸成分量を測定した。
(6) Copolymerization amount As for the glycol component, 10 mg of a sample was dissolved at 80 ° C. in 0.5 ml of a mixed solution of p-chlorophenol: 1,1,2,2-tetrachloroethane = 3: 1 (volume ratio). Added isopropylamine, measured at 80 ° C. at 1 600M after thorough mixing H-NMR (JEOL JEOL A600), were measured each glycol component amount.
As for the aromatic dicarboxylic acid component, 50 mg of a sample was dissolved at 140 ° C. in 0.5 ml of a mixed solution of p-chlorophenol: 1,1,2,2-tetrachloroethane = 3: 1, and 100 M 13 C-NMR ( JEOL JEOL A600) was measured at 140 ° C., and the amount of each acid component was measured.
（７）触媒、安定剤の元素量
フィルム５ｇをホットプレート上で３１０℃にまで加熱して融解し、平板状のディスクを作成する。そして該ディスクを理学電気（株）製の蛍光Ｘ線３２７０Ｅ型を用いて測定し、該ディスクに含有される各元素量を測定した。
得られた元素量から、ポリマー中の全酸成分のモル数に対する各元素のモル数の割合を求めた。
(7) Element amounts of catalyst and stabilizer 5 g of a film is heated to 310 ° C. on a hot plate and melted to prepare a flat disk. The disk was measured using a fluorescent X-ray 3270E type manufactured by Rigaku Denki Co., Ltd., and the amount of each element contained in the disk was measured.
From the obtained element amount, the ratio of the number of moles of each element to the number of moles of all acid components in the polymer was determined.
［参考例１］ＰＣＴ−Ａの作成
テレフタル酸ジメチル（ＴＡ）、イソフタル酸ジメチル（ＩＡ）、１，４−シクロヘキサンジメタノール（ＣＨＤＭ）を、それぞれのモル比（ＤＭＴ：ＤＭＩ：ＣＨＤＭ）が９６：４：２００となるように仕込み、そこに触媒として、トリメット酸チタンを表１に示す含有量となるように加えてオートクレーブにいれ、攪拌下で加熱してエステル交換した。ついで、トリエチルホスホノアセテートを表１に示す含有量となるように添加して、重縮合し、固有粘度１．１ｄｌ／ｇのポリ−１，４−シクロヘキサンジメチレンテレフタレート（以下、ＰＣＴ―Ａと称する）を得た。
[Reference Example 1] Preparation of PCT-A Dimethyl terephthalate (TA), dimethyl isophthalate (IA), and 1,4-cyclohexanedimethanol (CHDM) in a molar ratio (DMT: DMI: CHDM) of 96: 4: 200 was charged, and titanium trimetate was added as a catalyst so as to have the content shown in Table 1 and placed in an autoclave, and the mixture was transesterified by heating with stirring. Next, triethylphosphonoacetate was added so as to have the content shown in Table 1, polycondensed, and poly-1,4-cyclohexanedimethylene terephthalate (hereinafter referred to as PCT-A) having an intrinsic viscosity of 1.1 dl / g. Obtained).
［参考例２］ＰＥＮ―Ｂの作成
２，６−ナフタレンジカルボン酸ジメチル（ＮＡ）、エチレングリコールを、それぞれのモル比（ＮＡ：ＥＧ）が１００：２００となるように仕込み、そこに触媒として、酢酸マンガンを含有量が４１ｍｍoｌ％となるようにオートクレーブにいれ、攪拌下で加熱してエステル交換した。ついで、三酸化アンチモンを含有量が４１ｍｍｏｌ％とリン酸トリメチルを表１に示す含有量となるように添加して、重縮合し、表１に示すポリエチレン−２，６−ナフタレンジカルボキシレート（以下、ＰＥＮ―Ｂと称する）を得た。
[Reference Example 2] Preparation of PEN-B Dimethyl 2,6-naphthalenedicarboxylate (NA) and ethylene glycol were charged so that each molar ratio (NA: EG) would be 100: 200, and there as a catalyst, Manganese acetate was placed in an autoclave so that the content was 41 mmol%, and transesterification was performed by heating with stirring. Subsequently, antimony trioxide was added to a content of 41 mmol% and trimethyl phosphate so as to have the content shown in Table 1, polycondensed, and polyethylene-2,6-naphthalenedicarboxylate (hereinafter referred to as Table 1). , Referred to as PEN-B).
［参考例３］ＰＥＴ―Ｃの作成
テレフタル酸ジメチル（ＴＡ）、エチレングリコールを、それぞれのモル比（ＴＡ：ＥＧ）が１００：２００となるように仕込み、そこに触媒として、酢酸マンガンを含有量がが３４ｍｍoｌ％となるように加えてオートクレーブにいれ、攪拌下で加熱してエステル交換した。ついで、三酸化アンチモンを含有量が４３ｍｍｏｌ％となるように加え、さらにリン酸トリメチルを表１に示す含有量となるように添加して、重縮合し、表１に示すポリエチレンテレフタレート（以下、ＰＥＴ−Ｃと称する）を得た。
[Reference Example 3] Preparation of PET-C Dimethyl terephthalate (TA) and ethylene glycol were charged so that each molar ratio (TA: EG) would be 100: 200, and the content of manganese acetate as a catalyst there. Was added to an amount of 34 mmol%, and the mixture was placed in an autoclave and transesterified by heating with stirring. Next, antimony trioxide was added to a content of 43 mmol%, trimethyl phosphate was further added to the content shown in Table 1, polycondensation, and polyethylene terephthalate (hereinafter referred to as PET) shown in Table 1. -C)).
［参考例４］ＰＣＴ−Ｄの作成
テレフタル酸ジメチル（ＴＡ）、１，４−シクロヘキサンジメタノール（ＣＨＤＭ）を、それぞれのモル比（ＴＡ：ＣＨＤＭ）が１００：２００となるように仕込み、そこに触媒として、トリメット酸チタンを表１に示す含有量となるように加えてオートクレーブにいれ、攪拌下で加熱してエステル交換した。ついで、トリエチルホスホノアセテートを表１に示す含有量となるように添加して、重縮合し、表１に示すポリ−１，４−シクロヘキサンジメチレンテレフタレート（以下、ＰＣＴ―Ｄと称する）を得た。
[Reference Example 4] Preparation of PCT-D Dimethyl terephthalate (TA) and 1,4-cyclohexanedimethanol (CHDM) were charged so that the respective molar ratios (TA: CHDM) were 100: 200. As a catalyst, titanium trimetate was added so as to have a content shown in Table 1, and the mixture was placed in an autoclave, and transesterified by heating with stirring. Next, triethylphosphonoacetate was added so as to have the content shown in Table 1 and polycondensed to obtain poly-1,4-cyclohexanedimethylene terephthalate (hereinafter referred to as PCT-D) shown in Table 1. It was.
［参考例５］ＰＣＴ−Ｅ〜Ｉ、Ｌの作成
参考例４において、トリメット酸チタンおよびトリエチルホスホノアセテートを表１に示す含有量となるように変更した以外は同様にして、表１に示すポリ−１，４−シクロヘキサンジメチレンテレフタレート（以下、ＰＣＴ―Ｅ〜Ｉ、Ｌと称する）を得た。
[Reference Example 5] Preparation of PCT-E to I and L In Reference Example 4, except that titanium trimetate and triethylphosphonoacetate were changed to the contents shown in Table 1, the same is shown in Table 1. Poly-1,4-cyclohexanedimethylene terephthalate (hereinafter referred to as PCT-E to I, L) was obtained.
［参考例６］ＰＣＴ−Ｊの作成
テレフタル酸ジメチル（ＴＡ）、２，６−ナフタレンジカルボン酸ジメチル（ＮＤＣ）、１，４−シクロヘキサンジメタノール（ＣＨＤＭ）を、それぞれのモル比（ＴＡ：ＮＤＣ：ＣＨＤＭ）が９０：１０：２００となるように仕込み、そこに触媒として、トリメット酸チタンを表１に示す含有量となるように加えてオートクレーブにいれ、攪拌下で加熱してエステル交換した。ついで、トリエチルホスホノアセテートを表１に示す含有量となるように添加して、重縮合し、表１に示すポリ−１，４−シクロヘキサンジメチレンテレフタレート（以下、ＰＣＴ―Ｊと称する）を得た。
Reference Example 6 Preparation of PCT-J Dimethyl terephthalate (TA), dimethyl 2,6-naphthalenedicarboxylate (NDC), and 1,4-cyclohexanedimethanol (CHDM) were each in a molar ratio (TA: NDC: CHDM) was charged at 90: 10: 200, and titanium trimetate was added as a catalyst so as to have the content shown in Table 1, and the mixture was placed in an autoclave, and the mixture was transesterified by heating with stirring. Next, triethylphosphonoacetate was added so as to have the content shown in Table 1 and polycondensed to obtain poly-1,4-cyclohexanedimethylene terephthalate (hereinafter referred to as PCT-J) shown in Table 1. It was.
［参考例７］ＰＣＴ−Ｋの作成
テレフタル酸ジメチル（ＴＡ）、２，６−ナフタレンジカルボン酸ジメチル（ＮＤＣ）、１，４−シクロヘキサンジメタノール（ＣＨＤＭ）、エチレングリコール（ＥＧ）を、それぞれのモル比（ＴＡ：ＮＤＣ：ＣＨＤＭ：ＥＧ）が９０：１０：１８０：２０となるように仕込み、そこに触媒として、トリメット酸チタンを表１に示す含有量となるように加えてオートクレーブにいれ、攪拌下で加熱してエステル交換した。ついで、トリエチルホスホノアセテートを表１に示す含有量となるように添加して、重縮合し、表１に示すポリ−１，４−シクロヘキサンジメチレンテレフタレート（以下、ＰＣＴ―Ｋと称する）を得た。
[Reference Example 7] Preparation of PCT-K Dimethyl terephthalate (TA), dimethyl 2,6-naphthalenedicarboxylate (NDC), 1,4-cyclohexanedimethanol (CHDM), and ethylene glycol (EG) were added to respective moles. The ratio (TA: NDC: CHDM: EG) was charged so as to be 90: 10: 180: 20, and titanium trimetate was added as a catalyst so as to have the content shown in Table 1, and the mixture was stirred. Transesterification by heating under. Next, triethylphosphonoacetate was added so as to have the content shown in Table 1 and polycondensed to obtain poly-1,4-cyclohexanedimethylene terephthalate (hereinafter referred to as PCT-K) shown in Table 1. It was.
［参考例８］ＰＥＴ−Ｍの作成
参考例３において、トリメリット酸チタンとトリエチルホスホノアセテートを表１に示す含有量となるように調整したほかは、同様な操作を繰り返して、表１に示すポリエチレン−２，６−ナフタレンジカルボキシレート（ＰＥＴ−Ｍ）を得た。
[Reference Example 8] Preparation of PET-M In Reference Example 3, the same procedure was repeated except that titanium trimellitic acid and triethylphosphonoacetate were adjusted so as to have the contents shown in Table 1. Table 1 The polyethylene-2,6-naphthalenedicarboxylate (PET-M) shown was obtained.
［実施例１］
表１に示したＰＣＴ−Ａ９５重量％とＰＥＴ−Ｃ５重量％とを混合し、乾燥した後、３００℃で溶融押し出しし、２５℃に保持した急冷ドラム上で冷却した未延伸フィルムを得た。そして、製膜方向に沿って回転速度の異なる二組のローラー間で、フィルム表面温度が１１０℃になるように加熱して縦方向（製膜方向）の延伸を、延伸倍率３．０倍で行い、一軸延伸フィルムを得た。そして、この一軸延伸フィルムをステンターに導き、横延伸温度１１５℃で横延伸倍率５．５倍、熱固定処理（１８０℃で１０秒間）および冷却を行い、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 1]
PCT-A 95% by weight shown in Table 1 and PET-C 5% by weight were mixed, dried, melt extruded at 300 ° C., and cooled on a quenching drum maintained at 25 ° C. to obtain an unstretched film. Then, between two sets of rollers having different rotation speeds along the film forming direction, the film surface temperature is heated to 110 ° C., and stretching in the longitudinal direction (film forming direction) is performed at a draw ratio of 3.0 times. And a uniaxially stretched film was obtained. And this uniaxially stretched film is led to a stenter, a transverse stretching temperature of 115 ° C., a transverse stretching ratio of 5.5 times, heat setting treatment (180 ° C. for 10 seconds) and cooling, and a biaxially stretched film having a thickness of 6.5 μm Got.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例２］
実施例１において、ＰＣＴ−ＡとＰＥＴ−Ｃの重量比を９０：１０とした。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 2]
In Example 1, the weight ratio of PCT-A and PET-C was 90:10. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例３］
実施例１においてＰＣＴ−ＡとＰＥＴ−Ｃの重量比を８０：２０とし、横延伸倍率を６倍とした。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 3]
In Example 1, the weight ratio of PCT-A and PET-C was 80:20, and the transverse draw ratio was 6 times. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例４］
実施例１において、ＰＣＴ−ＡとＰＥＴ−Ｃの重量比を８０：２０とし、溶融押出温度を３１０℃に変更した以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 4]
A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner as in Example 1, except that the weight ratio of PCT-A and PET-C was 80:20 and the melt extrusion temperature was changed to 310 ° C. It was.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例５］
実施例１において、ＰＣＴ−ＡとＰＥＴ−Ｃの重量比を７５：２５とし、横延伸倍率を６倍とした。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 5]
In Example 1, the weight ratio of PCT-A and PET-C was 75:25, and the transverse draw ratio was 6 times. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例６］
実施例１において、ＰＣＴ−Ａの代わりに表１に示すＰＣＴ−Ｄを用い、ＰＣＴ−ＤとＰＥＴ−Ｃの重量比を８０：２０とし、横延伸倍率を５．３倍とした。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 6]
In Example 1, PCT-D shown in Table 1 was used instead of PCT-A, the weight ratio of PCT-D and PET-C was 80:20, and the transverse stretch ratio was 5.3 times. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例７］
実施例６において、ＰＣＴ−Ｄの代わりに表１に示すＰＣＴ−Ｆを用いた。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 7]
In Example 6, PCT-F shown in Table 1 was used instead of PCT-D. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例８］
実施例６において、ＰＣＴ−Ｄの代わりに表１に示すＰＣＴ−Ｉを用いた。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 8]
In Example 6, PCT-I shown in Table 1 was used instead of PCT-D. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［実施例９］
実施例６において、ＰＣＴ−Ｄの代わりに表１に示すＰＣＴ−Ｌ、ＰＥＴ−Ｃの代わりに表１に示すＰＥＴ−Ｍを用いた。それ以外の条件は同様にして、厚さ６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Example 9]
In Example 6, PCT-L shown in Table 1 was used instead of PCT-D, and PET-M shown in Table 1 was used instead of PET-C. A biaxially stretched film having a thickness of 6.5 μm was obtained in the same manner under other conditions.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例１］
ＰＣＴ−Ａを用いず、ＰＥＴ−Ｃのみを用い、溶融押出温度を２８０℃、延伸倍率を縦倍率３．２倍、横倍率４．３倍にし、それ以外は同様にして厚さ４．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 1]
PCT-A is not used, only PET-C is used, the melt extrusion temperature is 280 ° C., the draw ratio is 3.2 times in the longitudinal direction, and 4.3 times in the transverse direction. Otherwise, the thickness is 4.5 μm. A biaxially stretched film was obtained.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例２］
ＰＥＮ−Ｂを乾燥後、３００℃で溶融押し出しし、６０℃に保持した急冷ドラム上で冷却した未延伸フィルムを得た。そして、製膜方向に沿って回転速度の異なる二組のローラー間で、フィルム表面温度が１３０℃になるように加熱して縦方向（製膜方向）の延伸を、延伸倍率５．１倍で行い、一軸延伸フィルムを得た。そして、この一軸延伸フィルムをステンターに導き、横延伸温度１２５℃で横延伸倍率４．６倍、熱固定処理（１８０℃で１０秒間）および冷却を行い、厚さ４．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 2]
PEN-B was dried, melted and extruded at 300 ° C., and an unstretched film cooled on a quenching drum maintained at 60 ° C. was obtained. And between two sets of rollers having different rotational speeds along the film forming direction, the film surface temperature is heated to 130 ° C., and stretching in the longitudinal direction (film forming direction) is performed at a draw ratio of 5.1 times. And a uniaxially stretched film was obtained. Then, this uniaxially stretched film is led to a stenter, a transverse stretch temperature of 125 ° C., a transverse stretch ratio of 4.6 times, heat setting treatment (180 ° C. for 10 seconds) and cooling, and a biaxially stretched film having a thickness of 4.5 μm. Got.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例３］
実施例１において、ＰＥＴ−Ｃを用いず、ＰＣＴ−Ａのみを用いて、延伸倍率を縦倍率３．０倍、横倍率５．０倍にし、それ以外は同様にして厚さ１１μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 3]
In Example 1, using only PCT-A without using PET-C, the stretching magnification was set to 3.0 times in the longitudinal direction and 5.0 times in the lateral direction. A stretched film was obtained.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例４］
実施例１においてＰＣＴ−ＡとＰＥＴ−Ｄの重量比を７０：３０とし、縦方向の延伸倍率を３倍、横方向の延伸倍率を５．３倍とした。それ以外の条件は同様にして、１５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 4]
In Example 1, the weight ratio of PCT-A and PET-D was 70:30, the stretching ratio in the longitudinal direction was 3 times, and the stretching ratio in the lateral direction was 5.3 times. Other conditions were similarly obtained to obtain a 15 μm biaxially stretched film.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例５］
実施例１において、ＰＣＴ−Ａの代わりに表１に示すＰＣＴ−Ｅを用い、ＰＣＴ−ＥとＰＥＴ−Ｃの重量比を８０：２０とし、溶融押出温度を３１０℃、横延伸倍率を４．２倍とした。それ以外の条件は同様にして、６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 5]
In Example 1, PCT-E shown in Table 1 was used instead of PCT-A, the weight ratio of PCT-E and PET-C was 80:20, the melt extrusion temperature was 310 ° C., and the transverse draw ratio was 4. Doubled. Other conditions were similarly obtained to obtain a 6.5 μm biaxially stretched film.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例６］
比較例５において、ＰＣＴ−Ｅの代わりに表１に示すＰＣＴ−Ｈを用いた。それ以外の条件は同様にして、６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 6]
In Comparative Example 5, PCT-H shown in Table 1 was used instead of PCT-E. Other conditions were similarly obtained to obtain a 6.5 μm biaxially stretched film.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例７］
表１に示したＰＣＴ−Ｊを乾燥した後、３００℃で溶融押し出しし、２５℃に保持した急冷ドラム上で冷却した未延伸フィルムを得た。そして、製膜方向に沿って回転速度の異なる二組のローラー間で、フィルム表面温度が１１０℃になるように加熱して縦方向（製膜方向）の延伸を、延伸倍率３．０倍で行い、一軸延伸フィルムを得た。そして、この一軸延伸フィルムをステンターに導き、横延伸温度１１５℃で横延伸倍率４．０倍、熱固定処理（１８０℃で１０秒間）および冷却を行い、厚さ１５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 7]
After drying PCT-J shown in Table 1, it was melt extruded at 300 ° C., and an unstretched film cooled on a quenching drum maintained at 25 ° C. was obtained. Then, between two sets of rollers having different rotation speeds along the film forming direction, the film surface temperature is heated to 110 ° C., and stretching in the longitudinal direction (film forming direction) is performed at a draw ratio of 3.0 times. And a uniaxially stretched film was obtained. Then, this uniaxially stretched film is guided to a stenter, and a transverse stretch temperature of 115 ° C. and a transverse stretch ratio of 4.0 times, heat setting treatment (180 ° C. for 10 seconds) and cooling are performed to obtain a biaxially stretched film having a thickness of 15 μm. It was.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例８］
比較例７において、ＰＣＴ−Ｊの代わりに、表１に示したＰＣＴ−Ｋを用い、横延伸倍率を５．０倍とした。それ以外の条件は同様にして、厚さ１４μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 8]
In Comparative Example 7, PCT-K shown in Table 1 was used instead of PCT-J, and the transverse draw ratio was 5.0 times. Other conditions were similarly obtained to obtain a biaxially stretched film having a thickness of 14 μm.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
［比較例９］
比較例５において、ＰＣＴ−Ｅの代わりに表１に示すＰＣＴ−Ｇを用いた。それ以外の条件は同様にして、６．５μｍの二軸延伸フィルムを得た。
得られた二軸配向ポリエステルフィルムの特性を表２に示す。
[Comparative Example 9]
In Comparative Example 5, PCT-G shown in Table 1 was used instead of PCT-E. Other conditions were similarly obtained to obtain a 6.5 μm biaxially stretched film.
The properties of the obtained biaxially oriented polyester film are shown in Table 2.
本発明の二軸配向ポリエステルフィルムは、従来のポリエチレンテレフタレート、ポリエチレン−２，６−ナフタレートやでは達成できなかったような優れた寸法安定性を有し、寸法安定性が求められる用途、特に高密度磁気記録媒体のベースフィルムとして、好適に使用することができる。 The biaxially oriented polyester film of the present invention has excellent dimensional stability that cannot be achieved by conventional polyethylene terephthalate, polyethylene-2,6-naphthalate, and the like, particularly high density. It can be suitably used as a base film for magnetic recording media.
Claims (6)
（１）全酸成分の９５モル％以上が、テレフタル酸成分であること、
（２）全グリコール成分の９５モル％以上が、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分で、１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、９５：５〜６５：３５の範囲にあること、そして
（３）触媒として用いた金属化合物の金属元素量（Ｍ：ｍｍｏｌ％）が１０〜８０ｍｍｏｌ％でかつ安定剤として用いたリン化合物のリン元素量（Ｐ：ｍｍｏｌ％）とのモル比（Ｍ／Ｐ）が１〜３の範囲にあること
を満足する固有粘度が、０．５〜０．８ｄｌ／ｇの範囲にある芳香族ポリエステルからなり、
フィルムの長手方向に直交する方向（幅方向）における温度膨張係数が８ｐｐｍ／℃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。 The following (1) to (3)
(1) 95 mol% or more of all acid components are terephthalic acid components,
(2) 95 mol% or more of the total glycol component is 1,4-cyclohexanedimethanol component and ethylene glycol component, and the molar ratio of 1,4-cyclohexanedimethanol component to ethylene glycol component is 95: 5-65: 35 and (3) the amount of metal element (M: mmol%) of the metal compound used as the catalyst is 10 to 80 mmol% and the amount of phosphorus element of the phosphorus compound used as the stabilizer (P: mmol%) ) molar ratio of (M / P) is the intrinsic viscosity which satisfies that is in the range from 1 to 3 Ri Do aromatic polyester in the range of 0.5~0.8dl / g,
The biaxially oriented polyester film temperature expansion coefficient, wherein the der Rukoto below 8 ppm / ° C. in a direction (width direction) perpendicular to the longitudinal direction of the film.
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| JPS60203422A (en) * | 1984-03-28 | 1985-10-15 | Teijin Ltd | Biaxially oriented polyester film |
| JPS61278022A (en) * | 1985-06-04 | 1986-12-08 | Teijin Ltd | Magnetic recording flexible disk |
| JP3799211B2 (en) * | 1999-06-04 | 2006-07-19 | 帝人株式会社 | Method for producing polyester composition for film |
| JP2003132523A (en) * | 2001-10-22 | 2003-05-09 | Teijin Dupont Films Japan Ltd | Biaxially oriented polyester film for magnetic recording medium |
| JP4893190B2 (en) * | 2006-09-26 | 2012-03-07 | 東レ株式会社 | Biaxially oriented polyester film |
| JP2010031175A (en) * | 2008-07-30 | 2010-02-12 | Teijin Ltd | Copolyester and production method thereof |
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2010
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