JP2012229368A - Biaxially oriented film - Google Patents
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- JP2012229368A JP2012229368A JP2011099788A JP2011099788A JP2012229368A JP 2012229368 A JP2012229368 A JP 2012229368A JP 2011099788 A JP2011099788 A JP 2011099788A JP 2011099788 A JP2011099788 A JP 2011099788A JP 2012229368 A JP2012229368 A JP 2012229368A
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- 229920000728 polyester Polymers 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- -1 naphthalene-diyl group Chemical group 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000013500 data storage Methods 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 91
- 239000010410 layer Substances 0.000 description 18
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 13
- 239000011112 polyethylene naphthalate Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
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- 239000000463 material Substances 0.000 description 3
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical group C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZYZYQCACSQDPSB-UHFFFAOYSA-N 12,15-dioxatricyclo[8.6.0.02,7]hexadeca-1(10),2,4,6,8-pentaene-11,16-dione Chemical compound O=C1OCCOC(=O)C2=C1C=CC1=CC=CC=C21 ZYZYQCACSQDPSB-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer 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
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、寸法安定性に優れる二軸配向フィルムに関し、さらに詳しくは、寸法安定性に優れた磁気記録媒体用、特にデジタルデータストレージテープに適した二軸配向フィルムに関する。 The present invention relates to a biaxially oriented film having excellent dimensional stability, and more particularly to a biaxially oriented film suitable for magnetic recording media, particularly digital data storage tape, having excellent dimensional stability.
ポリエステルフィルムは優れた熱、機械特性を有することから磁気記録媒体用など広い分野で用いられている。磁気記録媒体、特にデータストレージ用磁気記録媒体においては、テープの高容量化、高密度化が進み、それに伴ってベースフィルムへの特性要求も厳しいものとなっている。ＱＩＣ、ＤＬＴ、さらに高容量のスーパーＤＬＴ、ＬＴＯのごとき、リニアトラック方式を採用するデータストレージ用磁気記録媒体では、テープの高容量化を実現するために、トラックピッチを非常に狭くしており、そのためテープ幅方向の寸法変化が起こると、トラックずれを引き起こし、エラーが発生するという問題をかかえている。これらの寸法変化には、走行時にかかる張力の変化によるもの、高張力で巻き取られた状態で保管中に生じる経時変化によるものとがある。この寸法変化を小さくするにはフィルムのヤング率を高めることが有効ではある。 Polyester films are used in a wide range of fields such as magnetic recording media because they have excellent heat and mechanical properties. In magnetic recording media, in particular, magnetic recording media for data storage, the capacity and density of tapes are increasing, and accordingly, the characteristic requirements for base films are becoming strict. In magnetic recording media for data storage that employs a linear track system, such as QIC, DLT, and higher capacity Super DLT, LTO, the track pitch is very narrow in order to realize high capacity tape. For this reason, when a dimensional change in the tape width direction occurs, there is a problem that a track shift occurs and an error occurs. These dimensional changes include a change in tension applied during traveling and a change over time that occurs during storage in a state of being wound with high tension. In order to reduce this dimensional change, it is effective to increase the Young's modulus of the film.
そこで、このような寸法変化を解決するために、特開平５−２１２７８７号公報には、縦方向のヤング率（ＥＭ）および横方向のヤング率（ＥＴ）がそれぞれ５５０ｋｇ／ｍｍ２以上および７００ｋｇ／ｍｍ２以上であり、両ヤング率の比（ＥＴ／ＥＭ）が１．１〜２．０である二軸配向ポリエチレン−２，６−ナフタレンジカルボキシレートフィルムが開示されている。また、国際公開第９９／２９４８８号パンフレットには、縦方向に荷重を負荷したとき該荷重に対する横方向の収縮率Ｐ（ｐｐｍ／ｇ）とを特定の範囲にした二軸配向ポリエステルフィルムが開示されている。さらにまた、国際公開第００／７６７４９号パンフレットには、縦方向に荷重を負荷して放置したときの幅方向の寸法変化、幅方向の温度膨張係数αｔ（×１０−６／℃）、幅方向の湿度膨張係数αｈ（×１０−６／％ＲＨ）および縦方向に荷重を負荷したとき該荷重に対する幅方向の収縮率Ｐ（ｐｐｍ／ｇ）とを特定の範囲にした二軸配向ポリエステルフィルムが開示されている。 Therefore, in order to solve such a dimensional change, Japanese Patent Laid-Open No. 5-212787 discloses a longitudinal Young's modulus (EM) and a lateral Young's modulus (ET) of 550 kg / mm 2 or more and 700 kg / mm, respectively. mm 2 or more, the ratio of both Young's modulus (ET / EM) is biaxially oriented polyethylene-2,6-naphthalene dicarboxylate film is 1.1 to 2.0 is disclosed. In addition, International Publication No. 99/29488 pamphlet discloses a biaxially oriented polyester film having a specific range of shrinkage rate P (ppm / g) in the lateral direction with respect to the load when a load is applied in the longitudinal direction. ing. Furthermore, in the pamphlet of International Publication No. 00/76749, a dimensional change in the width direction when left standing with a load in the vertical direction, a temperature expansion coefficient αt (× 10 −6 / ° C.) in the width direction, A biaxially oriented polyester film having a specific range of a humidity expansion coefficient αh (× 10 −6 /% RH) and a shrinkage rate P (ppm / g) in the width direction with respect to the load when a load is applied in the longitudinal direction. It is disclosed.
しかしながら、これらの公報で提案されている方法は、延伸条件やその後の熱固定処理条件を特定の範囲にすることで達成するものであり、例えば、縦方向に荷重をかけたときの幅方向の経時収縮は、ベースフィルムの縦方向ヤング率を大きくすることで改善することができるが、他方ではポリマー特性と製膜性の点から、縦方向のヤング率を大きくすればする程、横方向のヤング率の上限は小さくなり、根本的な解決には至っていなかった。 However, the methods proposed in these publications are achieved by setting stretching conditions and subsequent heat setting treatment conditions within a specific range, for example, in the width direction when a load is applied in the longitudinal direction. Shrinkage with time can be improved by increasing the longitudinal Young's modulus of the base film. On the other hand, the larger the Young's modulus in the longitudinal direction, the greater the Young's modulus in the lateral direction, in terms of polymer properties and film-forming properties. The upper limit of the Young's modulus has become smaller and has not led to a fundamental solution.
本発明の目的は、寸法安定性に優れ、磁気記録媒体、特にデジタルデータストレージなどに用いられるベースフィルムに適した二軸配向フィルムの提供にある。 An object of the present invention is to provide a biaxially oriented film which is excellent in dimensional stability and suitable for a magnetic recording medium, particularly a base film used for digital data storage and the like.
本発明者らは上記従来技術に鑑み鋭意検討を重ねた結果、従来の二軸配向フィルムを、特定のポリエーテルエステルを特定割合含有した芳香族ポリエステル組成物からなる二軸配向フィルムとすることで、機械特性に優れ、張力に対する寸法安定性が大きく向上することを見出し、本発明に至った。 As a result of intensive studies in view of the prior art, the present inventors have made a conventional biaxially oriented film a biaxially oriented film made of an aromatic polyester composition containing a specific proportion of a specific polyetherester. The present inventors have found that the mechanical properties are excellent and the dimensional stability against tension is greatly improved, leading to the present invention.
かくして、本発明によれば、芳香族ポリエステル（Ａ）に、下記式（Ｂ）で表されるジカルボン酸成分および下記式（Ｃ）で表されるジオール成分からなるポリエーテルエステル（Ｄ）を０．１〜７重量％含有する芳香族ポリエステル組成物（Ｅ）からなる二軸配向フィルムが提供される。 Thus, according to the present invention, the aromatic polyester (A) is converted to a polyether ester (D) comprising a dicarboxylic acid component represented by the following formula (B) and a diol component represented by the following formula (C). A biaxially oriented film comprising the aromatic polyester composition (E) containing from 1 to 7% by weight is provided.
また、本発明によれば、本発明の好ましい態様として、二軸配向フィルムの面方向における少なくとも一方向のヤング率が５ＧＰａ以上であること、二軸配向フィルムの厚みが２〜１０μｍの範囲にあること、磁気記録媒体のベースフィルム材料として用いられることの少なくともいずれかひとつを具備する二軸配向フィルムも提供される。 Moreover, according to this invention, as a preferable aspect of this invention, the Young's modulus of at least one direction in the surface direction of a biaxially oriented film is 5 GPa or more, and the thickness of a biaxially oriented film exists in the range of 2-10 micrometers. Also provided is a biaxially oriented film comprising at least one of the base film materials for magnetic recording media.
本発明によれば、特定のポリエーテルエステルを特定割合含有する芳香族ポリエステル組成物からなる二軸配向フィルムであることから、従来の二軸配向フィルムに比べ、湿度変化に対する寸法安定性は維持しつつ、ヤング率に基づく張力に対する寸法変化を小さくすることができ、磁気記録媒体のベースフィルム材料に好適な二軸配向フィルムを提供することができる。 According to the present invention, since it is a biaxially oriented film composed of an aromatic polyester composition containing a specific proportion of a specific polyether ester, the dimensional stability against humidity change is maintained as compared with the conventional biaxially oriented film. However, the dimensional change with respect to the tension based on the Young's modulus can be reduced, and a biaxially oriented film suitable for the base film material of the magnetic recording medium can be provided.
以下、本発明を詳しく説明する。
本発明の二軸配向フィルムは、芳香族ポリエステル（Ａ）に、前記式（Ｂ）で表されるジカルボン酸成分および前記式（Ｃ）で表されるジオール成分からなるポリエーテルエステル（Ｄ）を、０．１〜７重量％含有する芳香族ポリエステル組成物（Ｅ）からなる。
ポリエーテルエステル（Ｄ）を上記範囲の割合で含有することで、二軸配向フィルムのヤング率を向上させることができる。ポリエーテルエステル（Ｄ）の割合は、好ましくは１重量％以上６重量％以下、さらに好ましくは２重量％以上５重量％以下である。ポリエーテルエステル（Ｄ）の割合が下限より少なくても、多くてもヤング率向上効果が不十分となる。
The present invention will be described in detail below.
The biaxially oriented film of the present invention comprises a polyetherester (D) comprising a dicarboxylic acid component represented by the formula (B) and a diol component represented by the formula (C) on the aromatic polyester (A). The aromatic polyester composition (E) is contained in an amount of 0.1 to 7% by weight.
By containing the polyether ester (D) in the above range, the Young's modulus of the biaxially oriented film can be improved. The proportion of the polyether ester (D) is preferably 1% by weight to 6% by weight, more preferably 2% by weight to 5% by weight. Even if the proportion of the polyether ester (D) is less than the lower limit or at most, the Young's modulus improvement effect is insufficient.
＜ポリエーテルエステル（Ｄ）＞
本発明におけるポリエーテルエステル（Ｄ）は、前記式（Ｂ）のジカルボン酸成分と前記式（Ｃ）のジオール成分からなるポリエーテルエステルである。前記式（Ｂ）中、Ｐｈはフェニレン基またはナフタレンジイル基であり、１，４−フェニレン基と２，６−ナフタレンジイル基が好ましく、特に製膜性などの観点から、１，４−フェニレン基が好ましい。また、前記式（Ｃ）中、ＲＣは炭素数２〜１０のアルキレン基もしくは炭素数８〜１０のシクロアルキレン基を表す。二軸配向フィルムとするときの製膜性からは、エチレン基、１，４−ブチレン基、１，４−シクロヘキサンジメチレン基が好ましく、特に炭素数２のエチレン基が好ましい。
<Polyetherester (D)>
The polyether ester (D) in the present invention is a polyether ester comprising the dicarboxylic acid component of the formula (B) and the diol component of the formula (C). In the formula (B), Ph is a phenylene group or a naphthalenediyl group, and a 1,4-phenylene group and a 2,6-naphthalenediyl group are preferable. In particular, from the viewpoint of film forming property, a 1,4-phenylene group Is preferred. In the formula (C), R C represents an alkylene group having 2 to 10 carbon atoms or a cycloalkylene group having 8 to 10 carbon atoms. From the viewpoint of film forming property when a biaxially oriented film is used, an ethylene group, 1,4-butylene group, and 1,4-cyclohexanedimethylene group are preferable, and an ethylene group having 2 carbon atoms is particularly preferable.
＜芳香族ポリエステル（Ａ）＞
本発明における芳香族ポリエステル組成物（Ｅ）のポリエーテルエステル（Ｄ）以外の主成分である芳香族ポリエステル（Ａ）は、ジオールと芳香族ジカルボン酸との重縮合によって得られるポリマーである。かかる芳香族ジカルボン酸として、例えばテレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸が挙げられ、またジオールとして、例えばエチレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノール、１，６−ヘキサンジオールが挙げられる。これらの中でも、力学特性の観点から、エチレンテレフタレートとエチレンナフタレンジカルボキシレートを主たる繰り返し単位とするものが好ましく、特にエチレン−２，６−ナフタレンジカルボキシレートを主たる繰り返し単位とするポリエチレン−２，６−ナフタレンジカルボキシレートが好ましい。
<Aromatic polyester (A)>
The aromatic polyester (A), which is a main component other than the polyether ester (D) of the aromatic polyester composition (E) in the present invention, is a polymer obtained by polycondensation of a diol and an aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid. Examples of the diol include ethylene glycol, 1,4-butanediol, , 4-cyclohexanedimethanol and 1,6-hexanediol. Among these, from the viewpoint of mechanical properties, those having ethylene terephthalate and ethylene naphthalene dicarboxylate as main repeating units are preferred, and polyethylene-2,6 having ethylene-2,6-naphthalenedicarboxylate as the main repeating unit is particularly preferable. -Naphthalene dicarboxylate is preferred.
また、本発明における芳香族ポリエステル（Ａ）は、単独でも他のポリエステルとの共重合体、２種以上の芳香族ポリエステルからなる混合体のいずれであってもかまわないが、力学特性の観点からは、単独の方が好ましい。共重合成分としては、ジエチレングリコール、ネオペンチルグリコール、ポリアルキレングリコール等のジオール成分、アジピン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸（主たる酸成分がナフタレンジカルボキシレートの場合）、ナフタレンジカルボン酸（主たる酸成分がテレフタル酸の場合）、５−ナトリウムスルホイソフタル酸等のジカルボン酸成分が挙げられる。 In addition, the aromatic polyester (A) in the present invention may be either a single copolymer or a copolymer with another polyester, or a mixture of two or more aromatic polyesters, from the viewpoint of mechanical properties. Is preferably alone. Copolymerization components include diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid (when the main acid component is naphthalene dicarboxylate), naphthalene dicarboxylic acid (When the main acid component is terephthalic acid), dicarboxylic acid components such as 5-sodium sulfoisophthalic acid can be mentioned.
本発明における芳香族ポリエステル（Ａ）の固有粘度は、ο−クロロフェノール中、３５℃において、０．４０以上であることが好ましく、０．４０〜０．８０であることがさらに好ましい。固有粘度が０．４未満ではフィルム製膜時に切断が多発したり、成形加工後の製品の強度が不足することがある。一方固有粘度が０．８を超える場合は重合時の生産性が低下する。 The intrinsic viscosity of the aromatic polyester (A) in the present invention is preferably 0.40 or more, more preferably 0.40 to 0.80 at 35 ° C. in o-chlorophenol. If the intrinsic viscosity is less than 0.4, cutting may occur frequently during film formation, or the strength of the product after forming may be insufficient. On the other hand, when the intrinsic viscosity exceeds 0.8, the productivity during polymerization decreases.
本発明における芳香族ポリエステル（Ａ）の融点は、２００〜３００℃であることが好ましく、更には２６０〜２９０℃であることが好ましい。融点が下限に満たないとポリエステルフィルムの耐熱性が不十分な場合がある。また融点が上限を超える場合はポリエーテルエステル（Ｄ）を含有させて溶融押出しすることが困難となることがある。 The melting point of the aromatic polyester (A) in the present invention is preferably 200 to 300 ° C, more preferably 260 to 290 ° C. If the melting point is less than the lower limit, the heat resistance of the polyester film may be insufficient. Moreover, when melting | fusing point exceeds an upper limit, it may become difficult to contain polyether ester (D) and to melt-extrude.
なお、本発明におけるポリエステル組成物（Ｅ）は前記の通り、芳香族ポリエステル（Ａ）とポリエーテルエステル（Ｄ）とからなるが、それ自体公知の機能剤を含有させても良い。具体的には、不活性粒子、ワックスなどの潤滑剤、酸化防止剤、紫外線吸収剤などが挙げられ、またポリエーテルイミドなどの他の樹脂などを含有させることも好ましい。 In addition, as above-mentioned, although the polyester composition (E) in this invention consists of aromatic polyester (A) and polyether ester (D), you may contain a well-known functional agent in itself. Specific examples include lubricants such as inert particles and waxes, antioxidants, ultraviolet absorbers, and the like, and it is also preferable to contain other resins such as polyetherimide.
＜ヤング率＞
本発明の二軸配向フィルムは、その面方向の少なくとも一方向のヤング率は５ＧＰａ以上とすることが好ましい。製膜方向（以下ＭＤ方向、縦方向、長手方向と称することがある。）のヤング率がこの範囲以上であると、磁気記録媒体としたときに長手方向にかかる張力に対する寸法安定性がさらに向上する。一方、製膜方向に直交する方向（以下ＴＤ方向、横方向、幅方向と称することがある。）のヤング率がこの範囲以上であると、磁気記録媒体としたときの幅方向の湿度寸法安定性や、温度寸法安定性も向上させることができる。ヤング率の範囲は、好ましくは、５．５ＧＰａ以上であり、さらに好ましくは６ＧＰａ以上である。また、製膜方向と幅方向のヤング率の和は、２２ＧＰａ以下であることが好ましい。製膜方向のヤング率と幅方向のヤング率の和が、上限を超えると、フィルム製膜時、延伸倍率が過度に高くなり、フィルム破断が多発し、製品歩留りが著しく悪くなる。好ましい製膜方向と幅方向のヤング率は、その和の上限が、２０ＧＰａ以下、さらに１８ＧＰａ以下である。
<Young's modulus>
The biaxially oriented film of the present invention preferably has a Young's modulus of at least one direction in the plane direction of 5 GPa or more. When the Young's modulus in the film forming direction (hereinafter sometimes referred to as MD direction, longitudinal direction, and longitudinal direction) is within this range, the dimensional stability against tension applied in the longitudinal direction is further improved when a magnetic recording medium is obtained. To do. On the other hand, if the Young's modulus in the direction perpendicular to the film forming direction (hereinafter sometimes referred to as the TD direction, the lateral direction, and the width direction) is within this range, the humidity dimension stability in the width direction when the magnetic recording medium is obtained. And temperature dimensional stability can also be improved. The range of Young's modulus is preferably 5.5 GPa or more, and more preferably 6 GPa or more. The sum of Young's moduli in the film forming direction and the width direction is preferably 22 GPa or less. When the sum of the Young's modulus in the film forming direction and the Young's modulus in the width direction exceeds the upper limit, the draw ratio becomes excessively high during film formation, the film breaks frequently, and the product yield is remarkably deteriorated. The upper limit of the sum of Young's moduli in the preferred film forming direction and width direction is 20 GPa or less, and further 18 GPa or less.
＜湿度膨張係数＞
本発明の二軸配向フィルムは、フィルムの幅方向の湿度膨張係数αｈが０．１×１０−６〜１３×１０−６／％ＲＨの範囲にあることが好ましい。好ましいαｈは、０．５×１０−６〜１０×１０−６／％ＲＨ、特に１×１０−６〜８×１０−６／％ＲＨの範囲である。αｈを下限よりも小さくするには、二軸配向フィルムとするときの幅方向の延伸倍率を過度に高くしたりすることになり、製膜性が低下し、一方上限を超えると、湿度変化によってフィルムが伸びてしまい、トラックずれなどを惹起することがある。このようなαｈは、測定方向のヤング率を延伸により適度に向上させることによって達成される。
<Humidity expansion coefficient>
The biaxially oriented film of the present invention preferably has a humidity expansion coefficient αh in the width direction of the film in the range of 0.1 × 10 −6 to 13 × 10 −6 /% RH. Preferred αh is in the range of 0.5 × 10 −6 to 10 × 10 −6 /% RH, particularly 1 × 10 −6 to 8 × 10 −6 /% RH. In order to make αh smaller than the lower limit, the stretching ratio in the width direction when making a biaxially oriented film will be excessively increased, and the film-forming property will decrease, whereas if the upper limit is exceeded, the humidity will change. The film may stretch and cause track misalignment. Such αh is achieved by appropriately increasing the Young's modulus in the measurement direction by stretching.
＜温度膨張係数＞
本発明の二軸配向フィルムは、フィルムの幅方向の温度膨張係数αｔが−１０×１０−６〜＋１５×１０−６／℃の範囲にあることが好ましい。より好ましいαｔは、−８×１０−６〜＋１０×１０−６／℃、特に−５×１０−６〜＋５×１０−６／℃の範囲である。αｔが下限よりも小さいと、磁気記録媒体としたときの温度変化に対する寸法変化が、磁気ヘッドに対し相対的に収縮方向に大きくずれてしまい、一方上限を超えると、逆に磁気ヘッドに対し相対的に膨張方向に大きくずれてしまうため、いずれの場合もトラックずれなどを惹起することがある。このようなαｔは、測定方向のヤング率を延伸により適度に向上させることによって達成される。
<Temperature expansion coefficient>
The biaxially oriented film of the present invention preferably has a temperature expansion coefficient αt in the width direction of the film in the range of −10 × 10 −6 to + 15 × 10 −6 / ° C. More preferable αt is in the range of −8 × 10 −6 to + 10 × 10 −6 / ° C., particularly −5 × 10 −6 to + 5 × 10 −6 / ° C. If αt is smaller than the lower limit, the dimensional change with respect to the temperature change when the magnetic recording medium is used is greatly shifted in the shrinking direction relative to the magnetic head, whereas if the upper limit is exceeded, the dimensional change is relative to the magnetic head. Therefore, in any case, a track shift or the like may be caused. Such αt is achieved by appropriately increasing the Young's modulus in the measurement direction by stretching.
＜フィルム厚み＞
本発明の二軸配向フィルムは、フィルム全体の厚みが２〜１０μｍ、さらに３〜７μｍ、特に３．５〜６μｍであることが好ましい。この厚みが上限を超えると、テープ厚みが厚くなりすぎ、例えばカセットに入れるテープ長さが短くなったりして、十分な磁気記録容量が得られないことがある。一方、下限未満ではフィルム厚みが薄すぎて、フィルム製膜時にフィルム破断が多発したり、またフィルムの巻取性が不良となったりすることがある。
<Film thickness>
The biaxially oriented film of the present invention preferably has a total film thickness of 2 to 10 μm, further 3 to 7 μm, particularly 3.5 to 6 μm. When this thickness exceeds the upper limit, the tape thickness becomes too thick, for example, the tape length to be put in the cassette is shortened, and a sufficient magnetic recording capacity may not be obtained. On the other hand, if it is less than the lower limit, the film thickness is too thin, and film breakage may occur frequently during film formation, or the film winding property may be poor.
本発明の二軸配向フィルムは、他のフィルム層と積層した二軸配向積層フィルムとすることができる。特に表面性を改良するために、含有する不活性粒子の組成や、含有するポリエーテルエステル（Ｄ）の含有量や種類を変えることで、それぞれの表面の表面性を個々に変化させることが出来る。もちろん、ヤング率の観点からは、全てのフィルム層が前記ポリエーテルエステル（Ｄ）を含有することが好ましい。 The biaxially oriented film of the present invention can be a biaxially oriented laminated film laminated with another film layer. In particular, in order to improve the surface properties, the surface properties of each surface can be individually changed by changing the composition of the inert particles contained and the content and type of the polyether ester (D) contained. . Of course, from the viewpoint of Young's modulus, it is preferable that all the film layers contain the polyether ester (D).
＜製膜方法＞
本発明の二軸配向フィルムは、以下の方法にて製造するのが好ましい。
上述の芳香族ポリエステル（Ａ）に、ポリエーテルエステル（Ｄ）を含有させた芳香族ポリエステル組成物（Ｅ）を乾燥後、３００℃程度に加熱された押出機に供給し、ダイに展開して押し出す。そして、ダイから押し出されたシート状物を、テンター法、インフレーション法など公知の製膜方法を用いて製造することができる。具体的には、芳香族ポリエステル（Ａ）の融点（Ｔｍ：℃）ないし（Ｔｍ＋７０）℃の温度で押出し、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一軸方向（縦方向または横方向）に（Ｔｇ−１０）〜（Ｔｇ＋７０）℃の温度（但し、Ｔｇ：芳香族ポリエステルのガラス転移温度）で所定の倍率に延伸し、次いで上記延伸方向と直角方向（一段目が縦方向の場合には二段目は横方向となる）にＴｇ〜（Ｔｇ＋７０）℃の温度で所定の倍率に延伸し、さらに熱処理する方法を用いて製造することができる。その際延伸倍率、延伸温度、熱処理条件等は上記フィルムの特性から選択、決定される。面積延伸倍率は１５〜４０倍、さらには２０〜３５倍にするのが好ましい。熱固定温度は１９０〜２５０℃の範囲内から、また処理時間は１〜６０秒の範囲内から決めるとよい。
<Film forming method>
The biaxially oriented film of the present invention is preferably produced by the following method.
The aromatic polyester composition (E) containing the polyether ester (D) in the aromatic polyester (A) described above is dried, then supplied to an extruder heated to about 300 ° C., and developed on a die. Extrude. And the sheet-like material extruded from die | dye can be manufactured using well-known film forming methods, such as a tenter method and an inflation method. Specifically, the aromatic polyester (A) is extruded at a temperature of the melting point (Tm: ° C.) to (Tm + 70) ° C., rapidly cooled and solidified to obtain an unstretched film, and the unstretched film is further uniaxially (longitudinal or transverse). Direction) at a temperature of (Tg-10) to (Tg + 70) ° C. (where Tg is the glass transition temperature of the aromatic polyester) and then stretched at a predetermined magnification, and then perpendicular to the stretching direction (the first stage is the longitudinal direction). In some cases, the second stage is in the transverse direction), and the film can be produced by a method of stretching at a predetermined magnification at a temperature of Tg to (Tg + 70) ° C. and further heat-treating. At that time, the stretching ratio, stretching temperature, heat treatment conditions, etc. are selected and determined from the characteristics of the film. The area stretch ratio is preferably 15 to 40 times, more preferably 20 to 35 times. The heat setting temperature may be determined from the range of 190 to 250 ° C., and the treatment time may be determined from the range of 1 to 60 seconds.
かかる逐次二軸延伸法のほかに、同時二軸延伸法を用いることもできる。また逐次二軸延伸法において縦方向、横方向の延伸回数は１回に限られるものではなく、縦−横延伸を数回の延伸処理により行うことができ、その回数に限定されるものではない。例えば、さらに機械特性を上げたい場合には、熱固定処理前の上記二軸延伸フィルムについて、（Ｔｇ＋２０）〜（Ｔｇ＋７０）℃の温度で熱処理し、さらにこの熱処理温度より１０〜４０℃高い温度で縦方向または横方向に延伸し、続いてさらにこの延伸温度より２０〜５０℃高い温度で横方向または縦方向に延伸し、縦方向の場合総合延伸倍率を３．０〜７．０倍、横方向の場合総合延伸倍率を３．０〜８．０倍にとすることが好ましい。 In addition to the sequential biaxial stretching method, a simultaneous biaxial stretching method can also be used. Further, in the sequential biaxial stretching method, the number of stretching in the longitudinal direction and the transverse direction is not limited to one, and the longitudinal-lateral stretching can be performed by several stretching processes, and the number of stretching is not limited thereto. . For example, when it is desired to further improve the mechanical properties, the biaxially stretched film before the heat setting treatment is heat-treated at a temperature of (Tg + 20) to (Tg + 70) ° C., and further 10 to 40 ° C. higher than the heat treatment temperature. The film is stretched in the machine direction or the transverse direction, and then further stretched in the transverse direction or the longitudinal direction at a temperature 20 to 50 ° C. higher than the stretching temperature. In the case of the machine direction, the overall stretching ratio is 3.0 to 7.0 times, In the case of the direction, the overall draw ratio is preferably 3.0 to 8.0 times.
また、塗布層を設ける場合、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するのが好ましい。また、本発明の二軸配向フィルムを積層フィルムとする場合、それ自体公知の方法で、２種以上の原料を用意し、マルチマニホールドダイやフィードブロックで積層して、共押出すればよい。 Moreover, when providing a coating layer, it is preferable to apply | coat a desired coating liquid to the one or both surfaces of an above-mentioned unstretched film or a uniaxially stretched film. When the biaxially oriented film of the present invention is used as a laminated film, two or more kinds of raw materials may be prepared by a method known per se, laminated with a multi-manifold die or a feed block, and coextruded.
＜磁気記録媒体＞
本発明の二軸配向フィルムは、その片面に磁性層を設けることにより、磁気記録媒体のベースフィルムとして好ましく用いられる。なお、磁性層を形成する面は、二軸配向フィルムが積層フィルムの場合、より平坦な方の表面であることが好ましい。
磁気記録媒体としては、特に限定されないが、例えば、ＱＩＣやＤＬＴさらには高容量タイプであるＳ−ＤＬＴやＬＴＯ等のリニアトラック方式のデータストレージテープが挙げられる。なお、ベースフィルムが張力に対する寸法変化が極めて小さいので、テープの高容量化を確保するためにトラックピッチを狭くしてもトラックずれを引起こし難く、高密度高容量に好適な磁気記録媒体となる。
<Magnetic recording medium>
The biaxially oriented film of the present invention is preferably used as a base film of a magnetic recording medium by providing a magnetic layer on one side. In addition, when the biaxially oriented film is a laminated film, the surface on which the magnetic layer is formed is preferably a flatter surface.
The magnetic recording medium is not particularly limited, and examples thereof include QIC and DLT, and linear track type data storage tapes such as S-DLT and LTO which are high capacity types. In addition, since the dimensional change with respect to the tension of the base film is extremely small, even if the track pitch is narrowed in order to ensure a high capacity of the tape, it is difficult to cause a track shift, and the magnetic recording medium is suitable for high density and high capacity .
以下、実施例に基づいて本発明をさらに説明する。なお、本発明における種々の物性値および特性は、以下のようにして測定されたものであり、かつ定義される。 Hereinafter, the present invention will be further described based on examples. Various physical property values and characteristics in the present invention are measured and defined as follows.
（１）ヤング率
フイルムを試料幅１０ｍｍ、長さ１５ｃｍに切り、チャック間１００ｍｍにして引張速度１０ｍｍ／ｍｉｎ、チャート速度５００ｍｍ／ｍｉｎでインストロンタイプの万能引張試験装置にて引張り、得られる荷重−伸び曲線の立上り部の接線よりヤング率を計算する。ヤング率は１０回測定し、その平均値を用いた。
(1) Young's modulus The film is cut into a sample width of 10 mm and a length of 15 cm, the chuck is 100 mm, the tensile speed is 10 mm / min, and the chart speed is 500 mm / min. The Young's modulus is calculated from the tangent of the rising part of the elongation curve. The Young's modulus was measured 10 times and the average value was used.
（２）ガラス転移点および融点
芳香族ポリエステルまたはポリエーテルエステル１０ｍｇを、測定用のアルミニウム製パンに封入し、ＤＳＣ（ＴＡインスツルメンツ社製、Ｑ１００）を用いて２５℃から３００℃まで２０℃／ｍｉｎの昇温速度で測定し、それぞれの融点およびそれぞれのガラス転移点を求めた。
(2) Glass transition point and melting point 10 mg of aromatic polyester or polyether ester was enclosed in an aluminum pan for measurement, and 20 ° C./min from 25 ° C. to 300 ° C. using DSC (TA Instruments, Q100). The respective melting points and respective glass transition points were determined.
（３）各層の厚み
積層フィルムを３角形に切り出し、包埋カプセルに固定後、エポキシ樹脂にて包埋する。ミクロトーム（ＵＬＴＲＡＣＵＴ−Ｓ）で、製膜方向と厚み方向とに平行な方向にカットして、厚み５０ｎｍ薄膜切片にする。そして、透過型電子顕微鏡を用い、加速電圧１０００ｋｖにて観察し、倍率１万倍〜１０万倍で撮影し、写真より各層の厚みを測定した。
(3) Thickness of each layer A laminated film is cut into a triangle, fixed to an embedded capsule, and then embedded with an epoxy resin. Using a microtome (ULTRACUT-S), the film is cut in a direction parallel to the film forming direction and the thickness direction to form a thin film slice having a thickness of 50 nm. And using the transmission electron microscope, it observed at the acceleration voltage of 1000 kv, image | photographed by the magnification of 10,000 times-100,000 times, and measured the thickness of each layer from the photograph.
［実施例１］
２，６−ナフタレンジカルボン酸ジメチルエステルとエチレングリコールとを、テトラブトキシチタンを触媒として用いて反応させ、固有粘度（ｏ−クロロフェノール、３５℃）が０．６２ｄｌ／ｇで融点（Ｔｍ）が２６９℃のポリエチレンナフタレート（ＰＥＮ−１）を作成した。また、平均粒径０．１μｍの球状シリカ粒子を１．０質量％となるように添加した以外は同様な操作を行い、固有粘度（ｏ−クロロフェノール、３５℃）が０．６２ｄｌ／ｇで融点（Ｔｍ）が２６９℃のポリエチレンナフタレート（ＰＥＮ−２）を作成した。
一方、シクロヘキサンジメタノールをピリジンの溶媒化で塩化トシル（p-CH3C6H4SO2Cl）と反応させて、シクロヘキサンジメタノールの水酸基の水素をトシル基で置換したものを作成し、これをジメチルホルムアミド（(CH3)2CHO）の溶媒下で、炭酸カリウムを触媒として用い、ｐ−ヒドロキシ安息香酸メチルと反応させ、下記式で表されるジカルボン酸のジメチルエステルを作成した。
[Example 1]
2,6-Naphthalenedicarboxylic acid dimethyl ester and ethylene glycol are reacted using tetrabutoxytitanium as a catalyst, the intrinsic viscosity (o-chlorophenol, 35 ° C.) is 0.62 dl / g, and the melting point (Tm) is 269. Polyethylene naphthalate (PEN-1) at 0 ° C. was prepared. Further, the same operation was performed except that spherical silica particles having an average particle size of 0.1 μm were added so as to be 1.0% by mass, and the intrinsic viscosity (o-chlorophenol, 35 ° C.) was 0.62 dl / g. Polyethylene naphthalate (PEN-2) having a melting point (Tm) of 269 ° C. was prepared.
On the other hand, cyclohexanedimethanol was reacted with tosyl chloride (p-CH 3 C 6 H 4 SO 2 Cl) by solvation of pyridine to prepare a compound in which the hydrogen of the hydroxyl group of cyclohexanedimethanol was replaced with a tosyl group. Was reacted with methyl p-hydroxybenzoate using potassium carbonate as a catalyst in a solvent of dimethylformamide ((CH 3 ) 2 CHO) to prepare a dimethyl ester of dicarboxylic acid represented by the following formula.
そして、このジカルボン酸のジメチルエステルとエチレングリコールとをテトラブトキシチタンを触媒として用い、エステル交換反応および重縮合反応を行い、固有粘度（Ｐ−クロロフェノール／テトラクロロエタン（４０／６０重量比）の混合溶媒にて３５℃で測定）が０．７５ｄｌ／ｇ、融点が２８０℃のポリエーテルエステル（Ｄ）を作成した。なお、ポリエーテルエステル（Ｄ）中のシクロヘキサンジメタノールのCisとTransの割合は、モル比で１６対８４であった。
そして、得られる樹脂組成物の重量を基準として、球状シリカ粒子の含有量が０．３質量％となるように、またポリエチレン−２，６−ナフタレート（ＰＥＮ）とポリエーテルエステル（Ｄ）との重量比が９５：５となるように、ＰＥＮ−１とＰＥＮ−２とポリエーテルエステルＤをブレンドして樹脂組成物１を作成した。そして、１６０℃で５時間乾燥後、押し出し機に供給して３００℃にて溶融し、ダイへと導き、キャスティングドラム上にキャストして未延伸シートを作成した。なお、ダイから押し出された未延伸シートは、表面仕上げ０．３Ｓ、表面温度６０℃に保持したキャスティングドラム上で急冷固化せしめて、未延伸フィルムとされた。
この未延伸フイルムを、１３０℃で製膜方向および幅方向にそれぞれ４倍と６倍に延伸し、さらに引き続いて２００℃で１０秒間熱固定した後、１２０℃にて横方向に１．０％弛緩処理をし、厚み５．０μｍの二軸配向フィルムを得た。得られた二軸配向フィルムの特性を表１に示す。
Then, the dimethyl ester of dicarboxylic acid and ethylene glycol are used as a catalyst for tetrabutoxytitanium to perform an ester exchange reaction and a polycondensation reaction, thereby mixing intrinsic viscosity (P-chlorophenol / tetrachloroethane (40/60 weight ratio)). A polyether ester (D) having a 0.75 dl / g (measured with a solvent at 35 ° C.) and a melting point of 280 ° C. was prepared. In addition, the ratio of Cis and Trans of cyclohexane dimethanol in polyether ester (D) was 16 to 84 by molar ratio.
And based on the weight of the resin composition to be obtained, the content of spherical silica particles is 0.3% by mass, and polyethylene-2,6-naphthalate (PEN) and polyether ester (D) PEN-1, PEN-2, and polyether ester D were blended so that the weight ratio was 95: 5 to prepare a resin composition 1. And after drying at 160 degreeC for 5 hours, it supplied to the extruder and fuse | melted at 300 degreeC, it led to the die | dye, and it casted on the casting drum, and produced the unstretched sheet | seat. The unstretched sheet extruded from the die was rapidly cooled and solidified on a casting drum maintained at a surface finish of 0.3 S and a surface temperature of 60 ° C. to obtain an unstretched film.
This unstretched film was stretched by 4 times and 6 times in the film forming direction and the width direction at 130 ° C., respectively, and then heat-fixed at 200 ° C. for 10 seconds and then 1.0% in the lateral direction at 120 ° C. A relaxation treatment was performed to obtain a biaxially oriented film having a thickness of 5.0 μm. The characteristics of the obtained biaxially oriented film are shown in Table 1.
［実施例２〜４］
ポリエーテルエステル（Ｄ）の割合を、表１に示すように変更した以外は、実施例１と同様にして二軸配向フィルムを得た。得られた二軸配向フィルムの特性を表１に示す。
[Examples 2 to 4]
A biaxially oriented film was obtained in the same manner as in Example 1 except that the ratio of the polyether ester (D) was changed as shown in Table 1. The characteristics of the obtained biaxially oriented film are shown in Table 1.
［実施例５］
実施例１において作成した樹脂組成物１と、ＰＥＮ−１とを用意し、それぞれを１６０℃で５時間乾燥後、押し出し機に供給して３００℃にて溶融し、ダイへと導き、共押出により、キャスティングドラム上にキャストして未延伸積層シートを作成した。なお、未延伸積層シートは、樹脂組成物１の層とＰＥＮ−１の層との２層からなり、樹脂組成物１の層とＰＥＮ−１の層との厚みの比は７：３であった。このようにして得られた未延伸積層シートを、実施例１と同様な操作を繰り返して、二軸配向積層フィルムを得た。得られた二軸配向積層フィルムの特性を表１に示す。
[Example 5]
Resin composition 1 prepared in Example 1 and PEN-1 were prepared, each was dried at 160 ° C. for 5 hours, then supplied to an extruder, melted at 300 ° C., led to a die, and co-extruded. Thus, an unstretched laminated sheet was prepared by casting on a casting drum. The unstretched laminated sheet is composed of two layers of a resin composition 1 layer and a PEN-1 layer, and the ratio of the thickness of the resin composition 1 layer and the PEN-1 layer is 7: 3. It was. The unstretched laminated sheet thus obtained was subjected to the same operation as in Example 1 to obtain a biaxially oriented laminated film. The characteristics of the obtained biaxially oriented laminated film are shown in Table 1.
［実施例６］
実施例５において、未延伸積層シートを、樹脂組成物１の層とＰＥＮ−１の層との厚みの比を７：３となるように維持しつつ、樹脂組成物１の層とＰＥＮ−１の層とが交互に２５層ずつ積層された合計５０層の多層未延伸積層シートとなるように各フィルム層の厚みを変更した以外は、実施例５と同様な操作を繰り返して、二軸配向積層フィルムを得た。得られた二軸配向積層フィルムの特性を表１に示す。
[Example 6]
In Example 5, while maintaining the unstretched laminated sheet so that the ratio of the thickness of the resin composition 1 layer to the PEN-1 layer is 7: 3, the resin composition 1 layer and the PEN-1 Biaxial orientation was repeated by repeating the same operation as in Example 5 except that the thickness of each film layer was changed so that a total of 50 layers of multi-layer unstretched laminated sheets were laminated with 25 layers alternately. A laminated film was obtained. The characteristics of the obtained biaxially oriented laminated film are shown in Table 1.
［比較例１］
実施例１で用いたＰＥＮ−１とＰＥＮ−２とを球状シリカ粒子の含有量が０．３質量％となるようにブレンドして樹脂組成物２を作成した。そして、樹脂組成物１の代わりに樹脂組成物２を用いたほかは、実施例１と同様な操作を繰り返した。得られた二軸配向フィルムの特性を表１に示す。
[Comparative Example 1]
A resin composition 2 was prepared by blending PEN-1 and PEN-2 used in Example 1 so that the content of spherical silica particles was 0.3% by mass. And operation similar to Example 1 was repeated except having used the resin composition 2 instead of the resin composition 1. FIG. The characteristics of the obtained biaxially oriented film are shown in Table 1.
［比較例２］
ポリエーテルエステル（Ｄ）の割合を、表１に示すように変更した以外は、実施例１と同様にして二軸配向フィルムを得た。得られた二軸配向フィルムの特性を表１に示す。
[Comparative Example 2]
A biaxially oriented film was obtained in the same manner as in Example 1 except that the ratio of the polyether ester (D) was changed as shown in Table 1. The characteristics of the obtained biaxially oriented film are shown in Table 1.
表１中のＰＥＮはポリエチレン−２，６−ナフタレンジカルボキシレート、ＰＥＣＰは実施例１で作成したポリエステル（Ｄ）を意味する。 PEN in Table 1 means polyethylene-2,6-naphthalene dicarboxylate, and PECP means the polyester (D) prepared in Example 1.
本発明の二軸配向フィルムは、従来の二軸配向フィルムに比べ、ヤング率などに基づく張力に対する寸法変化を小さくすることができ、磁気記録媒体のベースフィルムとして好適に使用でき、特にＱＩＣやＤＬＴさらに高容量タイプであるＳ−ＤＬＴやＬＴＯ等のリニアトラック方式のデータストレージテープのベースフィルムとして好適に利用できる。 Compared with the conventional biaxially oriented film, the biaxially oriented film of the present invention can reduce the dimensional change with respect to tension based on Young's modulus and the like, and can be suitably used as a base film of a magnetic recording medium, particularly QIC and DLT. Furthermore, it can be suitably used as a base film for a linear storage type data storage tape such as S-DLT or LTO which is a high capacity type.
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