JP2012046592A - Oriented film - Google Patents
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- JP2012046592A JP2012046592A JP2010188304A JP2010188304A JP2012046592A JP 2012046592 A JP2012046592 A JP 2012046592A JP 2010188304 A JP2010188304 A JP 2010188304A JP 2010188304 A JP2010188304 A JP 2010188304A JP 2012046592 A JP2012046592 A JP 2012046592A
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- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 20
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 20
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 6
- 239000011342 resin composition Substances 0.000 abstract description 8
- 229920006267 polyester film Polymers 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 32
- 239000010410 layer Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
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- 238000005266 casting Methods 0.000 description 8
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- 125000003118 aryl group Chemical group 0.000 description 7
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- 229920000728 polyester Polymers 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 125000005487 naphthalate group Chemical group 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical group OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- 230000002040 relaxant effect Effects 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 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 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- IUJMPBDJRAXYCK-UHFFFAOYSA-N 6-[2-(6-carboxynaphthalen-2-yl)oxyethoxy]naphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OCCOC3=CC4=CC=C(C=C4C=C3)C(=O)O)=CC=C21 IUJMPBDJRAXYCK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 230000005288 electromagnetic effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000009864 tensile test Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Chemical & Material Sciences (AREA)
- Magnetic Record Carriers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
Description
本発明は、環境変化、特に湿度変化に対して優れた寸法安定性を発現するポリエステルフィルムに関し、特にデジタルデータなどの高密度記録メディアのベースフィルムに適したポリエステルフィルムに関する。 The present invention relates to a polyester film that exhibits excellent dimensional stability against environmental changes, particularly humidity changes, and more particularly to a polyester film suitable for a base film for high-density recording media such as digital data.
ポリエステルフィルムは、優れた機械的特性、熱的特性および化学的特性とを有することから、各種用途に用いられており、特に寸法安定に優れることからデジタルビデオ用テープやコンピュータのバックアップ用テープ（以後、データテープという）など磁気記録媒体のベースフィルムとして用いられている。 Polyester film has excellent mechanical properties, thermal properties, and chemical properties, so it is used in various applications. Especially, it has excellent dimensional stability. Used as a base film for magnetic recording media.
このデータテープは、近年記録密度の高密度化が進み、トラックの幅が非常に狭くになってきている。その結果、データテープの走行または保存の間に生じるわずかな熱的・力学的寸法変化や、データを記録する際と読み取る際の温湿度環境の違いにより、データを読み取る磁気ヘッドとトラックの位置とがずれてしまい、データの再生不良を引き起こす問題点が生じてきた。従って、高密度記録に対応するデータテープには、湿度変化に対して高い寸法安定性が要求されている。特に記録方式がリニア記録方式のデータテープでは、データテープの幅方向により高い寸法安定性が要求されている。 In recent years, the recording density of this data tape has been increased, and the track width has become very narrow. As a result, due to slight thermal and mechanical dimensional changes that occur during the running or storage of data tape and the difference in temperature and humidity environment when recording and reading data, This causes a problem that causes data reproduction failure. Therefore, a data tape corresponding to high-density recording is required to have high dimensional stability against humidity changes. In particular, in a data tape in which the recording method is a linear recording method, higher dimensional stability is required in the width direction of the data tape.
このような、データテープのベースフィルムに用いるフィルムの素材としては、ポリエチレンテレフタレート（以下、ＰＥＴと称することがある。）やポリエチレン−２，６−ナフタレンジカルボキシレート（以下、ＰＥＮと称することがある。）が用いられてきた。しかし、高密度記録のデータテープに求められる寸法安定性の要求はますます厳しくなっており、それだけでは不十分となってきている。 Such a film material used for the base film of the data tape is sometimes referred to as polyethylene terephthalate (hereinafter sometimes referred to as PET) or polyethylene-2,6-naphthalenedicarboxylate (hereinafter referred to as PEN). .) Have been used. However, the demand for dimensional stability required for high-density recording data tapes is becoming stricter and it is not enough.
一方で、ＰＥＴやＰＥＮのほかに、ポリエステル素材として、ポリトリメチレン−２，６−ナフタレンジカルボキシレート（以下、ＰＴＮと称することがある）が知られている。例えば、特許文献１では、ＰＴＮの配向フィルムを感熱孔版用途に用いることが提案されている。また、特許文献２および３では、ＰＴＮの配向フィルムが良好なガスバリア性および耐光性を持つことが提案されている。しかしながら、これら特許文献１〜３の実施例に具体的に開示されたフィルムを追試してみると、湿度膨張係数が従来のＰＥＴやＰＥＮと同等程度のものでしかなかった。 On the other hand, in addition to PET and PEN, polytrimethylene-2,6-naphthalenedicarboxylate (hereinafter sometimes referred to as PTN) is known as a polyester material. For example, Patent Document 1 proposes to use an oriented film of PTN for heat-sensitive stencil applications. Patent Documents 2 and 3 propose that the oriented film of PTN has good gas barrier properties and light resistance. However, when the films specifically disclosed in the examples of Patent Documents 1 to 3 were reexamined, the humidity expansion coefficient was only comparable to that of conventional PET and PEN.
また、特許文献４では、２，６−ポリトリメチレンナフタレート、２，６−ポリテトラメチレンナフタレート、２，６−ポリペンタメチレンナフタレート、及び２，６−ポリヘキサメチレンナフタレートのいずれかからなるフィルムを磁気記録媒体のベースフィルムに用いることが提案されている。また、その実施例の湿度膨張係数を見ると、幅方向のヤング率が９ＧＰａのＰＥＮを用いた場合が６．８ｐｐｍ／％ＲＨで、幅方向のヤング率を１１ＧＰａまで高めた２，６−ポリテトラメチレンナフタレートや２，６−ポリヘキサメチレンナフタレートを用いた場合が５．９〜６．４ｐｐｍ／％ＲＨとある。そして、ポリエステルフィルムの場合、その方向のヤング率が高いほど、分子鎖がその方向に揃っていて湿度膨張係数が低くなる傾向にあることを勘案すると、特許文献４の実施例からは、同程度のヤング率ならＰＥＮと、そのグリコール成分の炭素数を変更したものとでは湿度膨張係数はほとんど変わらないことが理解される。なお、特許文献４は、具体的に２，６−ポリトリメチレンナフタレートでの確認はされていない。 In Patent Document 4, any one of 2,6-polytrimethylene naphthalate, 2,6-polytetramethylene naphthalate, 2,6-polypentamethylene naphthalate, and 2,6-polyhexamethylene naphthalate is used. It has been proposed to use a film made of the above as a base film of a magnetic recording medium. Further, when the humidity expansion coefficient of the example is seen, it is 6.8 ppm /% RH in the case where PEN having a Young's modulus in the width direction of 9 GPa is used, and 2,6-poly which has increased the Young's modulus in the width direction to 11 GPa. The case where tetramethylene naphthalate or 2,6-polyhexamethylene naphthalate is used is 5.9 to 6.4 ppm /% RH. In the case of a polyester film, considering that the higher the Young's modulus in that direction, the molecular chains are aligned in that direction and the humidity expansion coefficient tends to be lower. It is understood that the coefficient of humidity expansion hardly changes between the PEN and the glycol component whose carbon number is changed. In addition, Patent Document 4 does not specifically confirm 2,6-polytrimethylene naphthalate.
本発明の課題は、ＰＥＴやＰＥＮからなるフィルムに比べ、優れた湿度変化に対する寸法安定性と、ＰＴＮからなるフィルムに比べ、優れた機械的強度とを兼備するポリエステルフィルムを提供することにある。 The subject of this invention is providing the polyester film which combines the dimensional stability with respect to the humidity change which was excellent compared with the film which consists of PET and PEN, and the outstanding mechanical strength compared with the film which consists of PTN.
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、ＰＥＴやＰＥＮとほとんど湿度膨張係数について変わらないと思われていたポリトリメチレン−２，６−ナフタレンジカルボキシレートを、特許文献１−３に記載されたフィルムよりもさらに面内方向に高屈折率となる方向を有するフィルムとすると、驚くべきことにＰＥＴやＰＥＮに比べて極めて小さな湿度膨張係数を有するフィルムを得ることができ、しかも、ＰＥＴやＰＥＮを特定の割合でブレンドすることで、湿度膨張係数を低くしつつヤング率などの機械的特性も向上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-mentioned problems, the inventors of the present invention disclosed polytrimethylene-2,6-naphthalenedicarboxylate, which was considered to be almost the same as PET and PEN in terms of humidity expansion coefficient. If the film has a direction having a higher refractive index in the in-plane direction than the film described in -3, it is surprisingly possible to obtain a film having a very small humidity expansion coefficient compared to PET and PEN, In addition, by blending PET and PEN at a specific ratio, it was found that mechanical properties such as Young's modulus can be improved while lowering the coefficient of humidity expansion, and the present invention has been achieved.
かくして本発明によれば、ポリトリメチレン−２，６−ナフタレンジカルボキシレートからなる樹脂Ａと、ポリエチレンテレフタレートまたはポリエチレン−２，６−ナフタレンジカルボキシレートからなる群より選ばれる樹脂Ｂとを、重量比（樹脂Ａ：樹脂Ｂ）で４：６〜８：２の割合で含有する樹脂組成物からなる配向フィルムが提供される。 Thus, according to the present invention, the resin A composed of polytrimethylene-2,6-naphthalenedicarboxylate and the resin B selected from the group consisting of polyethylene terephthalate or polyethylene-2,6-naphthalenedicarboxylate are weighted. An oriented film comprising a resin composition contained in a ratio (resin A: resin B) in a ratio of 4: 6 to 8: 2 is provided.
また、本発明の配向フィルムの好ましい態様として、幅方向の湿度膨張係数が７．５ｐｐｍ／％ＲＨ以下であること、磁気記録媒体のベースフィルムとして用いられることの少なくともいずれかを具備する配向フィルムも提供される。 Further, as a preferred embodiment of the oriented film of the present invention, there is also an oriented film having at least one of having a humidity expansion coefficient in the width direction of 7.5 ppm /% RH or less and being used as a base film of a magnetic recording medium. Provided.
従来のＰＥＴやＰＥＮからなるフィルムに比べ、ヤング率などの機械的特性を維持しつつ、より湿度膨張係数が低い方向を有する配向フィルムが得られる。したがって、本発明の配向フィルムを、例えば磁気記録媒体などのベースフィルムに用いれば、目的とする方向により湿度変化に対して優れた寸法安定性と実用に耐えうるヤング率などの機械的特性とを有するデータテープなどの製品を得ることができる。 Compared to a conventional film made of PET or PEN, an oriented film having a lower humidity expansion coefficient can be obtained while maintaining mechanical properties such as Young's modulus. Therefore, when the oriented film of the present invention is used for a base film such as a magnetic recording medium, for example, it has excellent dimensional stability against humidity change depending on the intended direction and mechanical properties such as Young's modulus that can withstand practical use. A product such as a data tape can be obtained.
本発明における樹脂ＡはＰＴＮであり、このＰＴＮとは、主たる芳香族ジカルボン酸成分が２，６−ナフタレンジカルボン酸成分で、主たるグリコール成分がトリメチレングリコール成分である芳香族ポリエステルである。もちろん、本発明の目的を損なわない範囲で、それ自体公知の共重合成分を共重合しても良い。なお、共重合する場合は、通常全酸性分のモル数を基準として、２０モル％以下、更に１０モル％以下が好ましい。 The resin A in the present invention is PTN, which is an aromatic polyester in which the main aromatic dicarboxylic acid component is a 2,6-naphthalenedicarboxylic acid component and the main glycol component is a trimethylene glycol component. Of course, a copolymer component known per se may be copolymerized as long as the object of the present invention is not impaired. In the case of copolymerization, it is usually preferably 20 mol% or less, more preferably 10 mol% or less, based on the total number of moles of acidic components.
つぎに、本発明における樹脂Ｂは、ポリエチレンテレフタレートおよびポリエチレン−２，６−ナフタレンジカルボキシレートからなる群より選ばれた少なくとも１種の樹脂である。なお、本発明におけるＰＥＴとは、主たる芳香族ジカルボン酸成分がテレフタル酸成分で、主たるグリコール成分がエチレングリコール成分である芳香族ポリエステルである。また、本発明におけるＰＥＮとは、主たる芳香族ジカルボン酸成分が２，６−ナフタレンジカルボン酸成分で、主たるグリコール成分がエチレングリコール成分である芳香族ポリエステルである。もちろん、本発明の目的を損なわない範囲で、これらＰＥＴやＰＥＮは、それ自体公知の共重合成分を共重合しても良い。特に、６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸成分などの６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸成分を共重合することは、さらに湿度膨張係数を低減しやすいことから好ましい態様である。なお、共重合する場合は、通常全酸成分のモル数を基準として、２０モル％以下、更に１０モル％以下が好ましい。 Next, the resin B in the present invention is at least one resin selected from the group consisting of polyethylene terephthalate and polyethylene-2,6-naphthalenedicarboxylate. The PET in the present invention is an aromatic polyester in which the main aromatic dicarboxylic acid component is a terephthalic acid component and the main glycol component is an ethylene glycol component. Further, PEN in the present invention is an aromatic polyester in which the main aromatic dicarboxylic acid component is a 2,6-naphthalenedicarboxylic acid component and the main glycol component is an ethylene glycol component. Of course, as long as the object of the present invention is not impaired, these PET and PEN may be copolymerized with publicly known copolymer components. In particular, copolymerizing 6,6 ′-(alkylenedioxy) di-2-naphthoic acid component such as 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component further increases the coefficient of humidity expansion. This is a preferred embodiment because it can be easily reduced. In the case of copolymerization, it is usually preferably 20 mol% or less, more preferably 10 mol% or less, based on the number of moles of all acid components.
本発明における樹脂Ａおよび樹脂Ｂの固有粘度（Ｉ．Ｖ．）の好ましい範囲は、０．５〜１．５ｄｌ／ｇ、さらに０．５５〜１．４ｄｌ／ｇである。この下限より下回るＩ．Ｖ．では、フィルム製膜において結晶化が問題になり、均一な延伸が困難になる。またこの上限を上回るＩ．Ｖ．では、高分子鎖の絡み合いにより延伸時の応力が大きすぎて、均一な延伸が困難になる。このような好ましい範囲のＩ．Ｖ．を有するＰＴＮは、溶融重合や固相重合法によるＩ．Ｖ．調整によって合成可能となる。 The preferable range of the intrinsic viscosity (IV) of Resin A and Resin B in the present invention is 0.5 to 1.5 dl / g, and more preferably 0.55 to 1.4 dl / g. I. below this lower limit. V. Then, crystallization becomes a problem in film formation, and uniform stretching becomes difficult. In addition, I. V. Then, due to the entanglement of polymer chains, the stress during stretching is too large, and uniform stretching becomes difficult. Such a preferred range of I.V. V. A PTN having an I.V. V. It can be synthesized by adjustment.
ところで、本発明の配向フィルムの特徴は、前述の樹脂Ａと樹脂Ｂとを、重量比（樹脂Ａ：樹脂Ｂ）４：６〜８：２の範囲でブレンドし、樹脂組成物の状態で用いたことにある。樹脂Ａの割合が下限未満だと、湿度膨張係数の低減効果が乏しくなり、他方樹脂Ｂの割合が下限未満だと、ヤング率などの機械的特性が低下しやすくなる。好ましい重量比（樹脂Ａ：樹脂Ｂ）は、５：５〜７．９：２．１、さらに６：４〜７．８：２．２の範囲である。 By the way, the feature of the oriented film of the present invention is that the above-mentioned resin A and resin B are blended in a weight ratio (resin A: resin B) in the range of 4: 6 to 8: 2, and used in a resin composition state. There is that. When the ratio of the resin A is less than the lower limit, the effect of reducing the humidity expansion coefficient is poor, and when the ratio of the resin B is less than the lower limit, mechanical characteristics such as Young's modulus are likely to be lowered. A preferred weight ratio (resin A: resin B) is in the range of 5: 5 to 7.9: 2.1, and further 6: 4 to 7.8: 2.2.
ところで、本発明の配向フィルムは、フィルムの製膜方向または幅方向の屈折率が１．７４以上であることが好ましい。もちろん、製膜方向と幅方向の両方向が、屈折率１．７４以上であっても良いし、それは好ましい態様である。屈折率の好ましい範囲は、１．７４〜１．８５、さらに１．７５〜１．８０、特に好ましくは１．７６〜１．８０の範囲である。このように極めて高度に分子鎖が配向された方向を存在させることで、フィルムの当該方向における湿度膨張係数を極めて低くできる。製膜方向および幅方向のいずれの方向も、屈折率が上記下限値よりも低い場合、従来のＰＥＴやＰＥＮと同程度の高い湿度膨張係数を有するフィルムしか得られず、本発明の湿度膨張係数の低減効果が奏されない。なお、製膜方向または幅方向の屈折率の上限は、使用する用途に適した湿度膨張係数になるように適宜設定すればよい。ただ、あまりにも屈折率を大きくすると、湿度膨張係数が負の値、すなわち収縮が過度に大きくなったり、製膜時にそれだけ高い延伸倍率で延伸することが必要になって、製膜が難しくなることから、１．８５以下であることが好ましい。もちろん、成形品としての湿度膨張係数が小さければよく、例えば湿度膨張係数の大きな層と貼り合せるような場合は、貼り合せた状態で湿度膨張係数が小さくなるように、本発明の配向フィルムは、その屈折率の最大値を１．８５以上にしてもよい。 By the way, the oriented film of the present invention preferably has a refractive index of 1.74 or more in the film forming direction or the width direction of the film. Of course, both the film forming direction and the width direction may have a refractive index of 1.74 or more, which is a preferable mode. A preferable range of the refractive index is 1.74 to 1.85, further 1.75 to 1.80, and particularly preferably 1.76 to 1.80. Thus, the presence of a direction in which molecular chains are extremely highly oriented makes it possible to extremely reduce the humidity expansion coefficient in the direction of the film. When the refractive index is lower than the lower limit in both the film forming direction and the width direction, only a film having a high humidity expansion coefficient comparable to that of conventional PET or PEN can be obtained, and the humidity expansion coefficient of the present invention is obtained. The reduction effect is not achieved. The upper limit of the refractive index in the film forming direction or the width direction may be appropriately set so as to have a humidity expansion coefficient suitable for the intended use. However, if the refractive index is increased too much, the humidity expansion coefficient is negative, that is, the shrinkage becomes excessively large, and it is necessary to stretch at a higher draw ratio at the time of film formation, which makes film formation difficult. Therefore, it is preferably 1.85 or less. Of course, it is sufficient that the humidity expansion coefficient as a molded product is small.For example, in the case where it is bonded to a layer having a large humidity expansion coefficient, the oriented film of the present invention has a low coefficient of humidity expansion in the bonded state. The maximum value of the refractive index may be 1.85 or more.
また、本発明の配向フィルムは、データテープなどテープ状で用いる場合は、テープの長手方向に進行させながら用いることが多く、前述の屈折率が１．７４以上である方向は幅方向であることが好ましい。特にデータトラックを幅方向に非常に狭い間隔で並べるリニア記録方式のデータテープの場合、少なくとも幅方向の屈折率が１．７４以上であることが好ましい。 In addition, when the oriented film of the present invention is used in the form of a tape such as a data tape, it is often used while being advanced in the longitudinal direction of the tape, and the direction in which the refractive index is 1.74 or more is the width direction. Is preferred. In particular, in the case of a linear recording type data tape in which data tracks are arranged at very narrow intervals in the width direction, it is preferable that at least the refractive index in the width direction is 1.74 or more.
そういった観点から、本発明の配向フィルムは、幅方向の湿度膨張係数が７．５ｐｐｍ／％ＲＨ以下であることが好ましく、さらに０ｐｐｍ／％ＲＨ以上７．５ｐｐｍ／％ＲＨ以下の範囲にあることが、製膜性と湿度変化に対する高度な寸法安定性とを得られることから好ましい。なお、前述のとおり、湿度膨張係数は、その方向の分子鎖の配向を高めるような延伸条件を採用することで、小さくすることができる。具体的には、その方向の延伸倍率を高めたり、より分子鎖が配向しやすいような温度条件を採用すればよい。 From such a point of view, the oriented film of the present invention preferably has a humidity expansion coefficient in the width direction of 7.5 ppm /% RH or less, and more preferably in the range of 0 ppm /% RH to 7.5 ppm /% RH. The film forming property and the high dimensional stability against humidity change are preferable. As described above, the humidity expansion coefficient can be reduced by adopting stretching conditions that enhance the orientation of molecular chains in that direction. Specifically, a temperature condition that increases the stretching ratio in that direction or that facilitates the orientation of molecular chains may be employed.
ところで、湿度膨張係数は、樹脂Ａと樹脂Ｂをブレンドする割合によっても変化する。そのような観点から、樹脂Ａ：樹脂Ｂが４：６〜４．９：５．１ときは、屈折率１．７４以上の方向の湿度膨張係数が７．５ｐｐｍ／％ＲＨ以下であることが好ましく、樹脂Ａ：樹脂Ｂが５．５〜６．５：３．５のときは、屈折率１．７４以上の方向の湿度膨張係数が６ｐｐｍ／％ＲＨ以下であることが好ましく、樹脂Ａ：樹脂Ｂが６．６：３．４〜８：２のときは、湿度膨張係数が５ｐｐｍ／％ＲＨ以下であることが好ましい。特に、湿度膨張係数が６ｐｐｍ／％ＲＨ以下から０ｐｐｍ／％ＲＨ以上、さらに５．２ｐｐｍ／％ＲＨ以下から０ｐｐｍ／％ＲＨ以上といった特性を有する場合、磁気記録媒体のベースフィルムに好適に用いることができ、特にその方向が幅方向である場合、トラックズレなどの幅方向における寸法変化の抑制が求められるリニア記録方式の磁気記録媒体支持体に好適に用いることができる。 By the way, a humidity expansion coefficient changes also with the ratio which blends resin A and resin B. FIG. From such a viewpoint, when the resin A: resin B is 4: 6 to 4.9: 5.1, the humidity expansion coefficient in the direction with a refractive index of 1.74 or more may be 7.5 ppm /% RH or less. Preferably, when the resin A: resin B is 5.5 to 6.5: 3.5, the humidity expansion coefficient in the direction with a refractive index of 1.74 or more is preferably 6 ppm /% RH or less, and the resin A: When the resin B is 6.6: 3.4 to 8: 2, the humidity expansion coefficient is preferably 5 ppm /% RH or less. In particular, when the coefficient of humidity expansion is from 6 ppm /% RH or less to 0 ppm /% RH or more, and further from 5.2 ppm /% RH or less to 0 ppm /% RH or more, it is preferably used for a base film of a magnetic recording medium. In particular, when the direction is the width direction, it can be suitably used for a linear recording type magnetic recording medium support in which suppression of dimensional change in the width direction such as track deviation is required.
本発明の配向フィルムは、それ自体で単層フィルムとして用いてもよいし、さらに別のフィルム層と積層した積層配向フィルムとして用いても良い。すなわち、少なくとも１つの層として、本発明の配向フィルムを有していれば良い。 The oriented film of the present invention may be used as a single-layer film by itself or as a laminated oriented film laminated with another film layer. That is, it is only necessary to have the oriented film of the present invention as at least one layer.
また、本発明の配向フィルムは、本発明の効果を損なわない範囲、例えば配向フィルムの重量を基準として、２０重量％以下、さらに１０重量％以下の範囲で、樹脂組成物に、それ自体公知の機能剤や他の樹脂を含有させて組成物として用いたものでも良い。具体的な機能剤としては、他の熱可塑性ポリマー、紫外線吸収剤等の安定剤、酸化防止剤、可塑剤、滑剤（ワックスや不活性粒子など）、難燃剤、離型剤、顔料、核剤、充填剤あるいはガラス繊維、炭素繊維、層状ケイ酸塩などが挙げられ、他の熱可塑性ポリマーとしては、脂肪族ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート、ＡＢＳ樹脂、ポリメチルメタクリレート、ポリアミド系エラストマー、ポリエステル系エラストマー、ポリエーテルイミド、ポリイミドなどが挙げられる。特に、磁気記録媒体支持体として使用されてきたＰＥＮに比べ、ＰＴＮはガラス転移温度（以下Ｔｇと称する場合がある）が低くなりやすいので、例えばポリエーテルイミドなどガラス転移温度を高められるような成分を共重合したり、ブレンドすることは好ましい態様である。 Further, the oriented film of the present invention is known per se to the resin composition in a range not impairing the effects of the present invention, for example, in a range of 20% by weight or less, further 10% by weight or less based on the weight of the oriented film. It may be used as a composition containing a functional agent or other resin. Specific functional agents include other thermoplastic polymers, stabilizers such as UV absorbers, antioxidants, plasticizers, lubricants (such as waxes and inert particles), flame retardants, mold release agents, pigments, and nucleating agents. , Fillers or glass fibers, carbon fibers, layered silicates, etc., and other thermoplastic polymers include aliphatic polyester resins, polyamide resins, polycarbonates, ABS resins, polymethyl methacrylates, polyamide elastomers, Examples thereof include polyester elastomers, polyether imides, polyimides and the like. In particular, since PTN tends to have a low glass transition temperature (hereinafter sometimes referred to as Tg) as compared with PEN that has been used as a magnetic recording medium support, for example, a component that can increase the glass transition temperature, such as polyetherimide. Copolymerizing or blending is a preferred embodiment.
つぎに、本発明の配向フィルムの好ましい態様について、さらに詳述する。
本発明における樹脂組成物は、ＤＳＣで測定したガラス転移温度が、７０℃以上、さらに７５℃以上であることが、耐熱性や寸法安定性の点から好ましい。このようなガラス転移温度は、ガラス転移温度を下げるような成分の割合を制御することで調整できる。一方、ガラス転移温度の上限については、特に制限されないが、製膜性の点から、１５０℃以下、さらに１３０℃以下が好ましい。なお、通常副生物の少ないホモのＰＴＮであれば、ガラス転移温度は９０℃程度であり、よりガラス転移温度の高いものとするには、前述のようにポリエーテルイミドなど、Ｔｇをあげる目的でそれ自体公知の他の共重合成分を共重合したり、ブレンドしても良い。
Next, a preferred embodiment of the oriented film of the present invention will be further described in detail.
The resin composition in the present invention preferably has a glass transition temperature measured by DSC of 70 ° C. or higher, more preferably 75 ° C. or higher from the viewpoint of heat resistance and dimensional stability. Such a glass transition temperature can be adjusted by controlling the ratio of components that lower the glass transition temperature. On the other hand, the upper limit of the glass transition temperature is not particularly limited, but is preferably 150 ° C. or lower and more preferably 130 ° C. or lower from the viewpoint of film forming property. In addition, in the case of homo PTN with usually few by-products, the glass transition temperature is about 90 ° C. For higher glass transition temperature, as described above, for the purpose of increasing Tg such as polyetherimide. Other copolymer components known per se may be copolymerized or blended.
また、本発明における樹脂組成物は、ＤＳＣで測定した融点が、１９０〜２３０℃の範囲、さらに１９０〜２２５℃の範囲、特に１９５〜２２５℃の範囲にあることが製膜性の点から好ましい。融点が上記上限を越えると、溶融押出して成形する際に、流動性が劣り、吐出などが不均一化しやすくなるため生産性は悪化する。一方で、上記下限未満になると、製膜性は優れるものの、芳香族ポリエステルの持つ機械的特性などは損なわれやすくなる。 In addition, the resin composition in the present invention preferably has a melting point measured by DSC in the range of 190 to 230 ° C., more preferably in the range of 190 to 225 ° C., particularly in the range of 195 to 225 ° C. from the viewpoint of film forming properties. . When the melting point exceeds the above upper limit, when melt extrusion is performed, the fluidity is inferior, and the discharge tends to be non-uniform, so that the productivity is deteriorated. On the other hand, when it is less than the above lower limit, although the film-forming property is excellent, the mechanical properties and the like of the aromatic polyester are easily impaired.
本発明の配向フィルムは、前述のとおり、単層フィルムでもよいが、データテープのベースフィルムとして用いる場合には、平滑性と走行性とをより高度に両立させやすいことから、少なくとも２層以上の積層フィルムであることが好ましい。また、配向フィルム表面に、厚み１〜５０ｎｍの水溶性または水分散性高分子、あるいは溶剤可溶性高分子などからなる易滑性を向上させるようなそれ自体公知のコーティング層を積層しても良い。 As described above, the oriented film of the present invention may be a single layer film. However, when used as a base film of a data tape, it is easy to achieve both a smoothness and a running property at a higher level. A laminated film is preferred. Moreover, you may laminate | stack a well-known coating layer which improves the slipperiness | lubricity which consists of a 1-50 nm-thick water-soluble or water-dispersible polymer or a solvent-soluble polymer on the surface of an oriented film.
本発明の配向フィルムは、走行性や巻取り性などを向上させるために、不活性粒子を含有させてもよい。なお、本発明でいう不活性粒子とは、無機または有機の粒子で、フィルムを形成するポリマー中で、本発明の効果を損なうような化学的反応や、磁気記録テープとしたときに記録特性を損なうような電磁気的影響を与えないものをいう。不活性粒子としては、それ自体公知のものを好適に使用できる。 The oriented film of the present invention may contain inert particles in order to improve running properties and winding properties. The inert particles referred to in the present invention are inorganic or organic particles, and in a polymer forming a film, a chemical reaction that impairs the effects of the present invention, or recording characteristics when used as a magnetic recording tape. The one that does not cause electromagnetic effects that may be damaged. As the inert particles, those known per se can be preferably used.
本発明の配向フィルムが不活性粒子を含有する場合、その好ましい平均粒径および含有量は、配向フィルムの用途や積層構成によって異なるが、例えばデータテープのベースフィルムに用いる場合、以下のような範囲が好ましい。 When the oriented film of the present invention contains inert particles, the preferred average particle size and content vary depending on the use of the oriented film and the laminated structure, but for example, when used for a base film of a data tape, the following ranges: Is preferred.
２層以上の積層構成を有する磁性層を形成する側のフィルム層に用いられている場合、含有する不活性粒子の平均粒径は、０．００５〜０．５μｍが好ましく、より好ましくは、０．０１〜０．３μｍ、さらに好ましくは０．０３〜０．２μｍ、最も好ましくは０．０５〜０．１５μｍである。また、その不活性粒子の含有量は、該不活性粒子を含有するフィルム層の重量を基準として、０．００１〜１重量％が好ましく、より好ましくは０．００５〜０．５重量％、さらに好ましくは０．０１〜０．３重量％、最も好ましくは０．０１〜０．２重量％である。一方、磁性層を形成しない側（非磁性層側）のフィルム層に用いられる場合、含有する不活性粒子は、２種類以上のサイズの異なる不活性粒子を用いることが好ましい。平均粒径の大きな不活性粒子の平均粒径は、０．０５〜２μｍが好ましく、より好ましくは、０．１〜１μｍ、さらに好ましくは０．２〜０．６μｍである。また、平均粒径の小さな不活性粒子の平均粒経は、０．０１〜０．３μｍが好ましく、さらに好ましくは０．０３〜０．２μｍ、最も好ましくは０．０５〜０．１５μｍである。なお、平均粒径の大きな不活性粒子と平均粒径の小さな不活性粒子との平均粒径の差は０．０４μｍ以上あることが好ましい。平均粒径の大きな不活性粒子の含有量は、該不活性粒子を含有するフィルム層の重量を基準として、０．００１〜１重量％が好ましく、より好ましくは０．００５〜０．５重量％、さらに好ましくは０．０１〜０．３重量％、最も好ましくは０．０２〜０．２重量％である。また、平均粒径の小さな不活性粒子の含有量は、該不活性粒子を含有するフィルム層の重量を基準として、０．００１〜１重量％が好ましく、より好ましくは０．００５〜０．５重量％、さらに好ましくは０．０１〜０．３重量％、最も好ましくは０．０２〜０．２重量％である。 When used in a film layer on the side of forming a magnetic layer having a laminate structure of two or more layers, the average particle size of the inert particles contained is preferably 0.005 to 0.5 μm, more preferably 0. 0.01 to 0.3 μm, more preferably 0.03 to 0.2 μm, and most preferably 0.05 to 0.15 μm. Further, the content of the inert particles is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.5% by weight, based on the weight of the film layer containing the inert particles. Preferably it is 0.01 to 0.3 weight%, Most preferably, it is 0.01 to 0.2 weight%. On the other hand, when used for the film layer on the side where the magnetic layer is not formed (non-magnetic layer side), it is preferable to use two or more kinds of inert particles having different sizes as the contained inert particles. The average particle size of the inert particles having a large average particle size is preferably 0.05 to 2 μm, more preferably 0.1 to 1 μm, and still more preferably 0.2 to 0.6 μm. The average particle diameter of the inert particles having a small average particle diameter is preferably 0.01 to 0.3 μm, more preferably 0.03 to 0.2 μm, and most preferably 0.05 to 0.15 μm. The difference in average particle diameter between the inert particles having a large average particle diameter and the inert particles having a small average particle diameter is preferably 0.04 μm or more. The content of the inert particles having a large average particle diameter is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.5% by weight, based on the weight of the film layer containing the inert particles. More preferably, it is 0.01 to 0.3% by weight, and most preferably 0.02 to 0.2% by weight. The content of inert particles having a small average particle diameter is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.5%, based on the weight of the film layer containing the inert particles. % By weight, more preferably 0.01 to 0.3% by weight, most preferably 0.02 to 0.2% by weight.
本発明の配向フィルムが、２層以上のフィルム層を積層した積層フィルムの少なくとも一つの層に用いられている場合、本発明の配向フィルムの厚みは、積層フィルムの厚みに対して、２０％以上、さらに３０％以上、特に４０％以上であることが、得られる積層フィルムに優れた湿度膨張係数を発現させられることから好ましい。 When the oriented film of the present invention is used in at least one layer of a laminated film in which two or more film layers are laminated, the thickness of the oriented film of the present invention is 20% or more with respect to the thickness of the laminated film. Further, it is preferably 30% or more, particularly 40% or more, since an excellent humidity expansion coefficient can be expressed in the obtained laminated film.
なお、本発明の配向フィルムが、単層フィルムとしてデータテープのベースフィルムに用いられる場合には、含有する不活性粒子の平均粒径は、０．０１〜１μｍが好ましく、より好ましくは、０．０５〜０．５μｍである。また、含有する不活性粒子の含有量は、配向フィルムの重量を基準として、０．０１〜１重量％が好ましく、より好ましくは０．０５〜０．５重量％である。 In addition, when the oriented film of this invention is used for the base film of a data tape as a single layer film, 0.01 to 1 micrometer is preferable and, as for the average particle diameter of containing inert particle | grains, 0. It is 05-0.5 micrometer. Moreover, 0.01 to 1 weight% is preferable based on the weight of an oriented film, and, as for content of the inert particle to contain, More preferably, it is 0.05 to 0.5 weight%.
つづいて、本発明の配向フィルムの製造方法の一例について、説明する。
まず、本発明の配向フィルムを製造するためのＰＴＮ、ＰＥＴ、ＰＥＮは、それ自体公知の方法で製造できる。具体的には、ＰＴＮの場合、２，６−ナフタレンジカルボン酸もしくはその低級アルキルエステルとトリメチレングリコールとを、エステル化反応もしくはエステル交換反応させて、さらに所望の固有粘度になるまで重縮合反応させればよい。この際、エステル化反応、エステル交換反応または重縮合反応の反応速度を高めるために、それ自体公知の触媒を好適に使用できる。
このようにして得られたＰＴＮ、ＰＥＴ、ＰＥＮを溶融状態で所望の割合にブレンドしてダイからシート状に回転している冷却ドラム上に押出し、未延伸シートを作成する。
It continues and demonstrates an example of the manufacturing method of the oriented film of this invention.
First, PTN, PET, and PEN for producing the oriented film of the present invention can be produced by a method known per se. Specifically, in the case of PTN, 2,6-naphthalenedicarboxylic acid or its lower alkyl ester and trimethylene glycol are subjected to an esterification reaction or a transesterification reaction, and a polycondensation reaction is performed until a desired intrinsic viscosity is obtained. Just do it. In this case, a catalyst known per se can be suitably used in order to increase the reaction rate of the esterification reaction, transesterification reaction or polycondensation reaction.
The PTN, PET, and PEN thus obtained are blended at a desired ratio in a molten state and extruded from a die onto a cooling drum that is rotating into a sheet shape, thereby producing an unstretched sheet.
このようにして得られた未延伸シートを、樹脂組成物のガラス転移温度（Ｔｇ）以上からＴｇ＋３０℃以下の範囲で、製膜方向または幅方向に３．０倍以上延伸すればよい。なお、屈折率が１．７４以上の方向を発現させるための延伸条件は、その方向の延伸倍率のほかに、延伸温度や延伸方向と直交する方向の延伸条件などが影響する。例えば、一方向にしか延伸処理を行わない一軸配向フィルムの場合は、Ｔｇ＋２０℃で延伸する場合は、延伸倍率を２．５倍以上にすることで屈折率１．７４以上とすることができ、より延伸倍率を高めたり、延伸温度を低くすることで、より屈折率を高くできる。また、直交する２方向に延伸する場合、例えばフィルムの製膜方向に延伸倍率１．５倍で延伸し、幅方向の屈折率を１．７４以上にしたいときは、幅方向の延伸倍率を４．２倍以上にすることが望ましい。なお、詳細な延伸条件は、実際に目的とする屈折率およびその方向が決まれば、それに応じてその方向により高い延伸倍率の条件で延伸をして、目的とする屈折率に足らなければ、その方向の延伸倍率を高めたり、延伸温度を低くすること、またはそれと直交する方向の延伸倍率を低くしたり、延伸温度を低くするなどして、調整すればよい。 The unstretched sheet thus obtained may be stretched 3.0 times or more in the film forming direction or the width direction in the range from the glass transition temperature (Tg) of the resin composition to Tg + 30 ° C. or less. The stretching conditions for expressing the direction having a refractive index of 1.74 or more are affected by the stretching temperature, the stretching conditions in the direction orthogonal to the stretching direction, and the like in addition to the stretching ratio in that direction. For example, in the case of a uniaxially oriented film that is stretched only in one direction, when stretched at Tg + 20 ° C., the refractive index can be set to 1.74 or more by increasing the stretch ratio to 2.5 times or more. The refractive index can be further increased by increasing the stretching ratio or decreasing the stretching temperature. Also, when stretching in two orthogonal directions, for example, when stretching in the film forming direction at a stretch ratio of 1.5 times and a refractive index in the width direction of 1.74 or more is desired, the stretch ratio in the width direction is set to 4 It is desirable to make it twice or more. In addition, if the detailed refractive conditions are actually determined as the target refractive index and its direction, the film is stretched under the conditions of a higher draw ratio in the direction accordingly, and if the target refractive index is not sufficient, Adjustment may be made by increasing the stretching ratio in the direction, decreasing the stretching temperature, decreasing the stretching ratio in the direction orthogonal thereto, or decreasing the stretching temperature.
もちろん、本発明の配向フィルムは、上述のような延伸工程を経た後、弛緩、定長もしくは緊張化で、１５０〜１８０℃の温度で熱固定処理を行うことが、その後の寸法安定性をより高められることから好ましい。
なお、前述の説明は、単層フィルムについて説明したが、積層フィルムの場合は、それ自体公知の共押出や貼り合せなどによって積層フィルムとすればよい。
Of course, the oriented film of the present invention is subjected to a heat fixing treatment at a temperature of 150 to 180 ° C. by relaxation, constant length or tension after passing through the stretching process as described above. It is preferable because it is enhanced.
In addition, although the above-mentioned description demonstrated the single layer film, in the case of a laminated | multilayer film, what is necessary is just to make it into a laminated | multilayer film by co-extrusion or bonding known per se.
このようにして得られた本発明の配向フィルムは、目的とする方向の湿度膨張係数を極めて低いものとすることができ、例えば幅方向の屈折率を１．７４以上にしてリニア記録方式のデータテープのベースフィルムに用いれば、磁気ヘッドとの湿度変化による幅方向のトラックの位置がずれる、いわゆるトラックズレによるエラーが極めて低いデータテープとすることができる。 The oriented film of the present invention thus obtained can have a very low humidity expansion coefficient in the intended direction. For example, the linear recording type data with a refractive index in the width direction of 1.74 or more. When used as a base film of a tape, a data tape can be obtained in which an error due to a so-called track shift, in which a track position in the width direction is shifted due to a change in humidity with the magnetic head, is extremely low.
なお、このようなデータテープは、本発明の配向フィルムの一方の面に、磁性層を形成するための磁性層用塗液を塗布および乾燥することで製造できる。もちろん、必要に応じて、ベースフィルムと磁性層との間に、磁性層の厚みを薄くするための非磁性層を形成したり、磁性層を形成しない側に、データテープとしたときの走行性を向上させるためのバックコート層を形成しても良い。 In addition, such a data tape can be manufactured by apply | coating and drying the coating liquid for magnetic layers for forming a magnetic layer in one side of the oriented film of this invention. Of course, if necessary, a non-magnetic layer for reducing the thickness of the magnetic layer is formed between the base film and the magnetic layer, or the running property when a data tape is formed on the side where the magnetic layer is not formed. A back coat layer may be formed to improve the resistance.
次の実施例に基づき、本発明の実施形態を説明する。
＜測定方法＞
（１）固有粘度（Ｉ．Ｖ．）
得られたポリエステルの固有粘度は、３５℃でのオルソクロロフェノールを溶媒として用いて測定した。
Based on the following examples, embodiments of the present invention will be described.
<Measurement method>
(1) Intrinsic viscosity (IV)
The intrinsic viscosity of the obtained polyester was measured using orthochlorophenol at 35 ° C. as a solvent.
（２）ガラス転移温度および融点
ガラス転移温度および融点はＤＳＣ（ＴＡインスツルメンツ株式会社製、商品名：Ｔｈｅｒｍａｌ ａｎａｌｙｓｔ２１００）により試料量１０ｍｇ、昇温速度２０℃／ｍｉｎで測定した。
(2) Glass transition temperature and melting point The glass transition temperature and melting point were measured by DSC (TA Instruments Co., Ltd., trade name: Thermal analyst 2100) at a sample amount of 10 mg and a heating rate of 20 ° C./min.
（３）ヤング率
得られた配向フィルムを、測定方向がそれぞれ製膜方向および幅方向になるように、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）にて引っ張って測定する。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。なお、ヤング率は、製膜方向および幅方向にそれぞれ５回繰り返し、それらの平均値とした。
(3) Young's modulus The obtained oriented film was cut with a sample width of 10 mm and a length of 15 cm so that the measurement directions were the film forming direction and the width direction, respectively, and the chuck speed was 100 mm, the tensile speed was 10 mm / min, and the chart speed was 500 mm. It is measured by pulling with a universal tensile testing device (trade name: Tensilon, manufactured by Toyo Baldwin) under the conditions of / min. The Young's modulus is calculated from the tangent of the rising portion of the obtained load-elongation curve. The Young's modulus was repeated 5 times in the film forming direction and the width direction, and the average value thereof was used.
（４）屈折率
メトリコン社製レーザー屈折計（商品名：プリズムカプラ）を用い、フィルムの製膜方向と幅方向の屈折率を測定した。
(4) Refractive index The refractive index of the film forming direction and the width direction of the film was measured using a laser refractometer (trade name: prism coupler) manufactured by Metricon.
（５）湿度膨張係数（αｈ）
前述の（４）の測定で屈折率が１．７４以上であった方向が測定方向となるように長さ１２ｍｍ、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で３０分間静置したときのサンプルの長さを測定し、それをＬ２０とし、その後１２分かけて湿度を８０％ＲＨに変更し、３０分間静置してから湿度８０％ＲＨにおけるそれぞれのサンプルの長さを測定し、それをＬ８０とした。そして、次式にて湿度膨張係数を算出した。なお、測定方向が切り出した試料の長手方向であり、５回測定し、その平均値をαｈとした。また、前述の（４）の測定で屈折率がいずれの方向も１．７４未満であった場合は、その最も屈折率が高い方向について、測定した。
αｈ＝（Ｌ８０−Ｌ２０）／（Ｌ８０×△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。
(5) Humidity expansion coefficient (αh)
Cut out into a length of 12 mm and a width of 5 mm so that the direction in which the refractive index was 1.74 or more in the measurement of (4) described above becomes the measurement direction, set in a vacuum Riko TMA3000, and under a nitrogen atmosphere at 30 ° C. the length of the sample when allowed to stand for 30 minutes at humidity of 20% RH was measured, it was the L 20, and change the humidity RH 80% over the next 12 minutes, humidity 80 after standing for 30 minutes % the length of each sample was measured in the RH, which was as L 80. And the humidity expansion coefficient was computed by following Formula. In addition, the measurement direction is the longitudinal direction of the cut out sample, the measurement was performed 5 times, and the average value was αh. Moreover, when the refractive index was less than 1.74 in any direction in the measurement of (4), the measurement was performed in the direction with the highest refractive index.
αh = (L 80 −L 20 ) / (L 80 × 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.
［実施例１］
２，６−ナフタレンジカルボン酸ジメチル１００重量部と１，３−プロパンジオール６０重量部およびテトラブチルチタネート０．０８重量部を使用し、エステル交換反応を行った。次いで高真空下で重縮合反応を行ない、固有粘度が０．６２ｄｌ／ｇのポリトリメチレン−２，６−ナフタレンジカルボキシレート（樹脂Ａ１）を得た。
また２，６−ナフタレンジカルボン酸ジメチル１００重量部とエチレングリコール６０重量部およびテトラブチルチタネート０．０８重量部を使用し、エステル交換反応を行った。次いで高真空下で重縮合反応を行ない、固有粘度が０．６２ｄｌ／ｇのポリエチレン−２，６−ナフタレンジカルボキシレート（樹脂Ｂ１）を得た。
上記原料を重量比で樹脂Ａ１：樹脂Ｂ１＝７．８：２．２の割合でブレンドして乾燥した後、押出機に供給し、温度を３００℃で溶融押出し、静電印加キャスト法を用いて表面温度５０℃のキャスティングドラムにて冷却固化し、未延伸フィルムを作製した。この未延伸フィルムを、製膜方向に延伸せず、製膜方向に直交する方向（幅方向に）に延伸温度１２０℃で４．８倍の倍率で延伸をした後、一旦冷却し、１６０℃で１．５％幅方向に弛緩しつつ熱処理を施した。こうして延伸された厚み１０μｍの配向フィルムをワインダーで巻き取り、配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Example 1]
Transesterification was carried out using 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 60 parts by weight of 1,3-propanediol and 0.08 parts by weight of tetrabutyl titanate. Subsequently, polycondensation reaction was performed under high vacuum to obtain polytrimethylene-2,6-naphthalenedicarboxylate (resin A1) having an intrinsic viscosity of 0.62 dl / g.
Further, 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 60 parts by weight of ethylene glycol, and 0.08 part by weight of tetrabutyl titanate were used for transesterification. Subsequently, a polycondensation reaction was performed under high vacuum to obtain polyethylene-2,6-naphthalenedicarboxylate (resin B1) having an intrinsic viscosity of 0.62 dl / g.
The above raw materials are blended in a weight ratio of resin A1: resin B1 = 7.8: 2.2, dried, then supplied to an extruder, melt extruded at 300 ° C., and an electrostatic application casting method is used. Then, it was cooled and solidified with a casting drum having a surface temperature of 50 ° C. to produce an unstretched film. This unstretched film was not stretched in the film forming direction, and was stretched at a stretching temperature of 120 ° C. at a stretching ratio of 4.8 times in the direction perpendicular to the film forming direction (in the width direction), and then cooled to 160 ° C. Then, heat treatment was performed while relaxing in the width direction of 1.5%. The oriented film having a thickness of 10 μm thus stretched was wound up with a winder to obtain an oriented film.
The properties of the obtained oriented film are shown in Table 1.
［実施例２］
実施例１において、樹脂Ａ１：樹脂Ｂ１を７．８：２．２から６：４に変更したほかは、実施例１と同様にして配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Example 2]
An oriented film was obtained in the same manner as in Example 1, except that the resin A1: resin B1 was changed from 7.8: 2.2 to 6: 4 in Example 1.
The properties of the obtained oriented film are shown in Table 1.
［実施例３］
実施例１において、樹脂Ａ１：樹脂Ｂ１を７．８：２．２から４：６に変更し、製膜方向に１３５℃にて延伸倍率２．９倍で延伸を行うように変更し、また幅方向の延伸温度を１２０℃から１３５℃に、また延伸倍率を５．３倍に変更し、厚みを１０μｍになるように調整したほかは、実施例１と同様にして配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Example 3]
In Example 1, the resin A1: resin B1 was changed from 7.8: 2.2 to 4: 6, and the film was formed to be stretched at 135 ° C. at a stretching ratio of 2.9 times in the film forming direction. An oriented film was obtained in the same manner as in Example 1, except that the stretching temperature in the width direction was changed from 120 ° C. to 135 ° C., the stretching ratio was changed to 5.3 times, and the thickness was adjusted to 10 μm.
The properties of the obtained oriented film are shown in Table 1.
［実施例４］
テレフタル酸ジメチル１００重量部とエチレングリコール６０重量部およびテトラブチルチタネート０．０８重量部を使用し、エステル交換反応を行った。次いで高真空下で重縮合反応を行ない、固有粘度が０．６３ｄｌ／ｇのポリエチレンテレフタレート（樹脂Ｂ２）を得た。
そして、実施例１における樹脂Ｂ１の代わりに樹脂Ｂ２を、樹脂Ａ１：樹脂Ｂ２の重量比が７．８：２．２となるように用い、溶融押出の温度を２８０℃に変更したほかは、実施例１と同様な操作を繰り返した。こうして延伸された厚み１０μｍの配向フィルムをワインダーで巻き取り、配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Example 4]
Transesterification was carried out using 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol and 0.08 parts by weight of tetrabutyl titanate. Subsequently, polycondensation reaction was performed under high vacuum to obtain polyethylene terephthalate (resin B2) having an intrinsic viscosity of 0.63 dl / g.
Then, instead of resin B1 in Example 1, resin B2 was used so that the weight ratio of resin A1: resin B2 was 7.8: 2.2, and the melt extrusion temperature was changed to 280 ° C. The same operation as in Example 1 was repeated. The oriented film having a thickness of 10 μm thus stretched was wound up with a winder to obtain an oriented film.
The properties of the obtained oriented film are shown in Table 1.
［実施例５］
実施例１において、未延伸フィルムを製膜方向に温度１２０℃で、延伸倍率１．７倍で延伸してから、幅方向に延伸するように変更し、さらに幅方向の延伸倍率を４．７倍に変更し、厚みが１０μｍになるように調整したほかは、実施例１と同様にして配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Example 5]
In Example 1, the unstretched film was stretched in the film-forming direction at a temperature of 120 ° C. and a stretch ratio of 1.7 times, and then changed to be stretched in the width direction, and the stretch ratio in the width direction was 4.7. An oriented film was obtained in the same manner as in Example 1 except that the thickness was changed to double and the thickness was adjusted to 10 μm.
The properties of the obtained oriented film are shown in Table 1.
［実施例６］
実施例２において、製膜方向の延伸倍率を２．１倍に変更し、幅方向の延伸倍率を４．９倍に変更し、厚みを１０μｍになるように調整したほかは、実施例２と同様にして配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Example 6]
In Example 2, the stretch ratio in the film forming direction was changed to 2.1 times, the stretch ratio in the width direction was changed to 4.9 times, and the thickness was adjusted to 10 μm. An oriented film was obtained in the same manner.
The properties of the obtained oriented film are shown in Table 1.
［比較例１］
２，６−ナフタレンジカルボン酸ジメチル１００重量部と１，３−プロパンジオール６０重量部およびテトラブチルチタネート０．０８重量部を使用し、エステル交換反応を行った。次いで高真空下で重縮合反応を行ない、固相重合をさらに行い固有粘度が０．７０ｄｌ／ｇのポリトリメチレン−２，６−ナフタレンジカルボキシレート（樹脂Ａ２）を得た。
上記原料を十分乾燥した後、押出機に供給し、温度を２８０℃で溶融押出し、静電印加キャスト法を用いて表面温度３０℃のキャスティングドラムにて冷却固化し、未延伸フィルムを作製した。この未延伸フィルムを、９０℃の予熱ロールを通して、延伸温度を１１０℃で製膜方向に１．５倍延伸し、つづいて製膜方向に直交する方向（幅方向に）に延伸温度１２０℃で４．２倍の倍率で逐次二軸延伸をした後、一旦冷却し、１６０℃で１．５％幅方向に弛緩しつつ熱処理を施した。こうして延伸された厚み１０μｍの配向フィルムをワインダーで巻き取り、ＰＴＮの二軸配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 1]
Transesterification was carried out using 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 60 parts by weight of 1,3-propanediol and 0.08 parts by weight of tetrabutyl titanate. Subsequently, polycondensation reaction was performed under high vacuum, and solid phase polymerization was further performed to obtain polytrimethylene-2,6-naphthalenedicarboxylate (resin A2) having an intrinsic viscosity of 0.70 dl / g.
After sufficiently drying the raw material, the raw material was supplied to an extruder, melt-extruded at a temperature of 280 ° C., and cooled and solidified with a casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method to produce an unstretched film. This unstretched film is stretched 1.5 times in the film forming direction at a stretching temperature of 110 ° C. through a 90 ° C. preheating roll, and subsequently stretched at 120 ° C. in the direction perpendicular to the film forming direction (in the width direction). After sequentially biaxial stretching at a magnification of 4.2, the film was once cooled and heat-treated while relaxing at 160 ° C. in the 1.5% width direction. The oriented film having a thickness of 10 μm thus stretched was wound with a winder to obtain a biaxially oriented film of PTN.
The properties of the obtained oriented film are shown in Table 1.
［比較例２］
製膜方向の延伸倍率を４．０倍に、また幅方向の延伸倍率を３．０倍に変更し、厚みが１０μｍになるように未延伸フィルムの厚みを変更したほかは比較例１と同様な操作を繰り返した。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 2]
Same as Comparative Example 1 except that the draw ratio in the film forming direction was changed to 4.0 times, the draw ratio in the width direction was changed to 3.0 times, and the thickness of the unstretched film was changed so that the thickness became 10 μm. Repeated operations.
The properties of the obtained oriented film are shown in Table 1.
［比較例３］
製膜方向の延伸を行わなかったことと、幅方向の延伸倍率を４．２倍から２．０倍に変更したことと、厚みが１０μｍになるように未延伸フィルムの厚みを調整したほかは、比較例１と同様にしてＰＴＮの配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 3]
Except that the stretching in the film forming direction was not performed, the stretching ratio in the width direction was changed from 4.2 times to 2.0 times, and the thickness of the unstretched film was adjusted to 10 μm. In the same manner as in Comparative Example 1, an oriented film of PTN was obtained.
The properties of the obtained oriented film are shown in Table 1.
［比較例４］
前記樹脂Ｂ２（ＰＥＴ）を十分乾燥した後、押出機に供給し、温度を２８０℃で溶融押出し、静電印加キャスト法を用いて表面温度３０℃のキャスティングドラムにて冷却固化し、未延伸フィルムを作製した。この未延伸フィルムを、延伸温度１００℃で幅方向に６．０倍の倍率で延伸をした後、一旦冷却し、２００℃で１．５％幅方向に弛緩しつつ熱処理を施した。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 4]
After sufficiently drying the resin B2 (PET), it is supplied to an extruder, melt-extruded at a temperature of 280 ° C., cooled and solidified by a casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method, and an unstretched film Was made. This unstretched film was stretched at a stretching temperature of 100 ° C. in the width direction at a magnification of 6.0 times, then cooled once, and heat treated while relaxing at 200 ° C. in the width direction of 1.5%.
The properties of the obtained oriented film are shown in Table 1.
［比較例５］
前記樹脂Ｂ１（ＰＥＮ）を十分乾燥した後、押出機に供給し、温度を３００℃で溶融押出し、静電印加キャスト法を用いて表面温度５０℃のキャスティングドラムにて冷却固化し、未延伸フィルムを作製した。この未延伸フィルムを、延伸温度１３５℃で幅方向に５．７倍の倍率で延伸をした後、一旦冷却し、２００℃で１．５％幅方向に弛緩しつつ熱処理を施した。こうして延伸されたＰＥＮ配向フィルムをワインダーで巻き取り、フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 5]
After sufficiently drying the resin B1 (PEN), it is supplied to an extruder, melt-extruded at a temperature of 300 ° C., cooled and solidified with a casting drum having a surface temperature of 50 ° C. using an electrostatic application casting method, and an unstretched film Was made. The unstretched film was stretched at a stretching temperature of 135 ° C. in the width direction at a magnification of 5.7 times, then cooled once and subjected to heat treatment while relaxing at 200 ° C. in the width direction of 1.5%. The stretched PEN-oriented film was wound up with a winder to obtain a film.
The properties of the obtained oriented film are shown in Table 1.
［比較例６］
前記樹脂Ａ２とＢ１とを、重量比９．５：０．５になるように加え、製膜方向の延伸倍率を３倍に、幅方向の延伸温度を１２０℃から１３５℃に変更し、幅方向の延伸倍率を４．２倍から４．２５倍に変更し、厚みが１０μｍになるように未延伸フィルムの厚みを調整したほかは、比較例１と同様にして配向フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 6]
The resins A2 and B1 are added so that the weight ratio is 9.5: 0.5, the draw ratio in the film forming direction is tripled, and the stretching temperature in the width direction is changed from 120 ° C. to 135 ° C. An oriented film was obtained in the same manner as in Comparative Example 1, except that the stretching ratio in the direction was changed from 4.2 times to 4.25 times and the thickness of the unstretched film was adjusted so that the thickness became 10 μm.
The properties of the obtained oriented film are shown in Table 1.
［比較例７］
前記樹脂Ａ２とＢ２とを、重量比１．０：９．０になるように加え、２８０℃で溶融押出し、未延伸フィルムを作成した。この未延伸フィルムを１００℃で製膜方向の延伸倍率を３倍に延伸し、続いて幅方向に１１０℃で４．５倍延伸し、１８０℃で１．５％幅方向に弛緩しつつ熱処理を施した。こうして延伸された配向フィルムをワインダーで巻き取り、フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 7]
The resins A2 and B2 were added at a weight ratio of 1.0: 9.0 and melt extruded at 280 ° C. to prepare an unstretched film. This unstretched film was stretched at 100 ° C. in the film forming direction at a stretch ratio of 3 times, subsequently stretched 4.5 times at 110 ° C. in the width direction, and heat-treated while relaxing at 180 ° C. in the width direction at 1.5%. Was given. The oriented film thus stretched was wound up with a winder to obtain a film.
The properties of the obtained oriented film are shown in Table 1.
［比較例８］
前記樹脂Ａ２とＢ１とを、重量比１．０：９．０になるように加え、３００℃で溶融押出し、未延伸フィルムを作成した。この未延伸フィルムを１３５℃で製膜方向の延伸倍率を３倍に延伸し、続いて幅方向に１４５℃で４．５倍延伸し、１８０℃で１．５％幅方向に弛緩しつつ熱処理を施した。こうして延伸された配向フィルムをワインダーで巻き取り、フィルムを得た。
得られた配向フィルムの特性を表１に示す。
[Comparative Example 8]
The resins A2 and B1 were added at a weight ratio of 1.0: 9.0, and melt-extruded at 300 ° C. to prepare an unstretched film. This unstretched film was stretched at 135 ° C. in the film forming direction at a stretch ratio of 3 times, subsequently stretched 4.5 times at 145 ° C. in the width direction, and heat-treated while relaxing at 180 ° C. in the width direction at 1.5%. Was given. The oriented film thus stretched was wound up with a winder to obtain a film.
The properties of the obtained oriented film are shown in Table 1.
本発明の配向フィルムは、ヤング率などの機械的特性を実用上問題のない範囲に維持しつつ、湿度膨張係数が小さな方向を有し、例えばデータテープなどのベースフィルムなど、湿度変化に対する寸法安定性と機械的特性とが求められる用途に好ましく用いられる。 The oriented film of the present invention has a direction in which the coefficient of humidity expansion is small while maintaining mechanical properties such as Young's modulus in a range that does not cause any practical problems. For example, a base film such as a data tape is dimensionally stable against humidity changes. It is preferably used for applications where properties and mechanical properties are required.
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| JP2011241316A (en) * | 2010-05-19 | 2011-12-01 | Teijin Dupont Films Japan Ltd | Oriented film |
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| JP2000017159A (en) * | 1998-07-03 | 2000-01-18 | Teijin Ltd | Polyester composition and polyester film therefrom |
| JP2002523604A (en) * | 1998-09-01 | 2002-07-30 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Blend of poly (1,3-propylene 2,6-naphthalate) |
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