JP2013129079A - Laminated film - Google Patents
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- JP2013129079A JP2013129079A JP2011278514A JP2011278514A JP2013129079A JP 2013129079 A JP2013129079 A JP 2013129079A JP 2011278514 A JP2011278514 A JP 2011278514A JP 2011278514 A JP2011278514 A JP 2011278514A JP 2013129079 A JP2013129079 A JP 2013129079A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 71
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 38
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 38
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 25
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 238000010030 laminating Methods 0.000 abstract description 6
- 238000004898 kneading Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 90
- 239000002245 particle Substances 0.000 description 20
- 230000003746 surface roughness Effects 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000006073 displacement reaction 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
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Abstract
Description
本発明は積層フィルムに関する。 The present invention relates to a laminated film.
ポリエチレンテレフタレート（以下ＰＥＴと略す。）やポリエチレン−２，６−ナフタレート（以下ＰＥＮと略す。）に代表される芳香族ポリエステルは優れた機械的特性、寸法安定性および耐熱性を有することから、フィルムなどに幅広く使用されている。特にポリエチレン−２，６−ナフタレートは、ポリエチレンテレフタレートよりも優れた機械的特性、寸法安定性および耐熱性を有することから、それらの要求の厳しい用途、例えば高密度磁気記録テープなどのベースフィルムなどに使用されている。しかしながら、近年の高密度磁気記録テープなどでの寸法安定性の要求はますます高くなってきており、さらなる特性の向上、例えば温度や湿度などの環境変化に対する高度の寸法安定性が求められている。 Aromatic polyesters typified by polyethylene terephthalate (hereinafter abbreviated as PET) and polyethylene-2,6-naphthalate (hereinafter abbreviated as PEN) have excellent mechanical properties, dimensional stability and heat resistance. Widely used in In particular, polyethylene-2,6-naphthalate has mechanical properties, dimensional stability and heat resistance superior to those of polyethylene terephthalate, so that it is used in demanding applications such as a base film such as a high-density magnetic recording tape. It is used. However, demands for dimensional stability in high-density magnetic recording tapes and the like in recent years are increasing, and further improvement of characteristics, for example, high dimensional stability against environmental changes such as temperature and humidity is required. .
ところで、特許文献１〜３には、ポリ（１，４−シクロヘキサンジメチレンテレフタレート）（以下ＰＣＴと略す。）からなるフィルムが、また、特許文献４には、ＰＣＴとＰＥＴとをブレンドすることが開示され、湿度膨張係数が小さく寸法安定性に優れた二軸配向ポリエステルフィルムを得られることが記載されている。
しかしながら、これらに記載された二軸配向ポリエステルフィルムは、湿度膨張係数は低いものの、温度膨張係数がいずれの方向も１０ｐｐｍ／℃以上ある温度変化に対する寸法変化が大きなものでしかなかった。
By the way, in Patent Documents 1 to 3, a film made of poly (1,4-cyclohexanedimethylene terephthalate) (hereinafter abbreviated as PCT) is used. In Patent Document 4, PCT and PET are blended. It is disclosed that a biaxially oriented polyester film having a small humidity expansion coefficient and excellent dimensional stability can be obtained.
However, although the biaxially oriented polyester films described in these documents have a low coefficient of humidity expansion, they have only a large dimensional change with respect to a temperature change in which the temperature expansion coefficient is 10 ppm / ° C. or more in any direction.
本発明者らは、上記従来技術の有する問題を解決しようと、ＰＣＴの温度膨張係数を低減するためにＰＥＴやＰＥＮとの積層を研究したが、温度膨張係数を低減しようと高度に延伸しようとすると工程が不安定になってしまう問題があることが判明した。そこで、ＰＣＴとＰＥＮとをブレンドしたものについてさらに研究をしたが、こちらでは両者は相溶性が乏しく、また延伸性も異なることから、延伸されたフィルムは表面平坦性やカールなどの問題があることが判明した。そこで、さらにＰＣＴとＰＥＮとの共重合についても研究したが、ＰＣＴによる湿度膨張係数の低減を十分に発現できるだけ加えると、高温で加工する際の加工性が乏しくなるという問題があることが判明した。 In order to solve the above-described problems of the prior art, the present inventors have studied the lamination with PET or PEN in order to reduce the temperature expansion coefficient of PCT, but have tried to highly stretch to reduce the temperature expansion coefficient. Then, it became clear that there was a problem that the process became unstable. Therefore, further research was conducted on blends of PCT and PEN, but here they are poorly compatible and have different stretchability, so the stretched film has problems such as surface flatness and curl. There was found. Therefore, we also studied the copolymerization of PCT and PEN, but it was found that there was a problem that the workability at the time of processing at high temperature would be poor if the reduction of the humidity expansion coefficient by PCT was fully expressed. .
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、特定の共重合芳香族ポリエステルをＰＥＴとブレンドしたものと、ＰＥＴとを積層することで、上記課題を具備する積層フィルムが得られることを見出し、本発明に到達した。 As a result of diligent research to solve the above-mentioned problems, the present inventors can obtain a laminated film having the above-mentioned problems by laminating a specific copolymerized aromatic polyester blended with PET and PET. The present invention has been found.
かくして本発明によれば、以下の１〜５の積層フィルムが提供される。
１．フィルム層Ａとポリエチレンテレフタレートからなるフィルム層Ｂを積層した積層フィルムであって、
フィルム層Ａを構成する樹脂成分Ａが、
全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、７５：２５〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、４０：６０〜９０：１０の範囲である樹脂Ａ´とポリエチレンテレフタレートとを
全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、９０：１０〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、１２：８８〜４０：６０となるように溶融混練したものである積層フィルム。
２．フィルム層Ａを構成する樹脂成分Ａにおける樹脂Ａ´とテレフタレートとの重量比が１０：９０〜９０：１０の範囲である上記１記載の積層フィルム。
３．積層フィルムの厚み方向において、フィルム層Ａが占める厚みとフィルム層Ｂが占める厚みとの比が、１０：９０〜８０：２０の範囲である上記１または２に記載の積層フィルム。
４．積層フィルム全体における、全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、９２：８〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、３：９７〜３０：７０の範囲である上記１〜３のいずれかに記載の積層フィルム。
５．製膜方向および幅方向のヤング率がともに４．５ＧＰａ以上である上記１〜４のいずれかに記載の積層フィルム。
Thus, according to the present invention, the following laminated films 1 to 5 are provided.
1. A laminated film in which a film layer A and a film layer B made of polyethylene terephthalate are laminated,
The resin component A constituting the film layer A is
The molar ratio of the terephthalic acid component of the total acid component to the 2,6-naphthalenedicarboxylic acid component is in the range of 75:25 to 100: 0, and the moles of the 1,4-cyclohexanedimethanol component of the total glycol component and the ethylene glycol component Resin A ′ having a ratio in the range of 40:60 to 90:10 and polyethylene terephthalate. The molar ratio of the total terephthalic acid component to the 2,6-naphthalenedicarboxylic acid component is 90:10 to 100: 0. In this range, the laminated film is melt-kneaded so that the molar ratio of the 1,4-cyclohexanedimethanol component and the ethylene glycol component of the total glycol component is 12:88 to 40:60.
2. 2. The laminated film according to 1 above, wherein the weight ratio of the resin A ′ and terephthalate in the resin component A constituting the film layer A is in the range of 10:90 to 90:10.
3. The laminated film according to 1 or 2 above, wherein the ratio of the thickness occupied by the film layer A to the thickness occupied by the film layer B is in the range of 10:90 to 80:20 in the thickness direction of the laminated film.
4). In the entire laminated film, the molar ratio of the terephthalic acid component of the total acid component to the 2,6-naphthalenedicarboxylic acid component is in the range of 92: 8 to 100: 0, and the 1,4-cyclohexanedimethanol component of the total glycol component The laminated film according to any one of 1 to 3, wherein the molar ratio of the ethylene glycol component is in the range of 3:97 to 30:70.
5. The laminated film according to any one of 1 to 4 above, wherein Young's modulus in the film forming direction and the width direction are both 4.5 GPa or more.
本発明によれば、特定の共重合芳香族ポリエステルをＰＥＴとブレンドしたフィルム層と、ＰＥＴからなるフィルム層とを積層することで、温度や湿度変化に対する寸法安定性と表面の平坦性とに優れ、フィルムのカールが小さく、しかも高温での加工性にも優れた積層フィルムが提供される。 According to the present invention, by laminating a film layer obtained by blending a specific copolymerized aromatic polyester with PET and a film layer made of PET, it is excellent in dimensional stability against temperature and humidity changes and surface flatness. A laminated film having a small film curl and excellent workability at high temperatures is provided.
本発明の積層フィルムは、フィルム層Ａとポリエチレンテレフタレートからなるフィルム層Ｂを積層した積層フィルムである。以下、フィルム層Ａとフィルム層Ｂ、積層フィルムおよびその製造方法に分けて説明する。 The laminated film of the present invention is a laminated film in which a film layer A and a film layer B made of polyethylene terephthalate are laminated. Hereinafter, the film layer A, the film layer B, the laminated film, and the manufacturing method thereof will be described separately.
＜フィルム層Ｂ＞
本発明におけるフィルム層Ｂは、ポリエチレンテレフタレート（以下、ＰＥＴと称する。）からなることが、後述のフィルム層Ａと積層したときの延伸性を揃え、表面の平坦性やカールを抑制し、さらに温度膨張係数を低減する上で必要である。
<Film layer B>
The film layer B in the present invention is made of polyethylene terephthalate (hereinafter referred to as PET), which has uniform stretchability when laminated with the film layer A described later, suppresses surface flatness and curling, and further increases the temperature. Necessary for reducing the expansion coefficient.
本発明におけるＰＥＴは、全繰り返し単位の９０モル％以上、好ましくは９５モル％以上、さらに好ましくは９８モル％以上がエチレンテレフタレートであるＰＥＴである。したがって、本発明におけるＰＥＴは、ホモポリマーであっても良いし、本発明の効果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たものであっても良い。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、２，６−ナフタレンジカルボン酸、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。 The PET in the present invention is PET in which 90% by mole or more, preferably 95% by mole or more, and more preferably 98% by mole or more of all repeating units is ethylene terephthalate. Therefore, the PET in the present invention may be a homopolymer or may be a copolymer obtained by copolymerizing a known copolymer component as long as the effects of the present invention are not impaired. Examples of copolymer components include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 5-sodium sulfoisophthalic acid. Ingredients.
本発明におけるＰＥＴのＰ−クロロフェノール／１，１，２，２−テトラクロロエタン（重量比４０／６０）の混合溶媒を用いて３５℃で測定した固有粘度は、０．５〜１．１ｄｌ／ｇ、さらに０．６〜１．１ｄｌ／ｇの範囲にあることが本発明の効果の点から好ましい。固有粘度が上限以上だと、粘度が高くなりすぎ、製膜時の押出機からの樹脂の押出が困難になる。また、固有粘度が下限以下だと、フィルムが脆化し、延伸が困難になる。 The intrinsic viscosity measured at 35 ° C. using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (weight ratio 40/60) of PET in the present invention is 0.5 to 1.1 dl / g, and more preferably in the range of 0.6 to 1.1 dl / g from the viewpoint of the effect of the present invention. When the intrinsic viscosity is equal to or higher than the upper limit, the viscosity becomes too high and it becomes difficult to extrude the resin from the extruder during film formation. On the other hand, if the intrinsic viscosity is less than the lower limit, the film becomes brittle and stretching becomes difficult.
また、本発明におけるフィルム層Ｂは、本発明の効果を損なわない範囲で、必要に応じて、他の熱可塑性ポリマー、不活性粒子やワックスなどの滑剤、紫外線吸収剤等の安定剤、滑剤、酸化防止剤、可塑剤、滑剤、難燃剤、離型剤、核剤を必要に応じて配合しても良い。なお、表面の平坦性をより高度に発現させる観点から、表面欠点を形成しやすいＰＥＴに対して非相溶の他の熱可塑性ポリマー、顔料、充填剤、ガラス繊維、炭素繊維、層状ケイ酸塩などは含有させないことが好ましい。また、積層フィルムにしたときの走行性や巻取り性を確保しつつ、表面の平坦性を確保する観点から、平均粒径が０．０１〜０．５μｍの不活性粒子を、０．００１〜１．０質量％の範囲で含有させるのが好ましい。含好ましい不活性粒子の平均粒径は、０．０２〜０．４μｍ、さらに０．０５〜０．３５μｍの範囲である。また、好ましい含有量は０．００５〜０．５質量％、さらに０．０１〜０．４質量％である。含有させる不活性粒子としては、シリコーン樹脂、架橋アクリル樹脂、架橋ポリエステル、架橋ポリスチレンなどの有機高分子粒子および球状シリカからなる群から選ばれる少なくとも１種の粒子であることが好ましく、特にシリコーン樹脂、架橋ポリスチレンおよび球状シリカからなる群から選ばれる少なくとも１種の粒子であることが好ましい。 Further, the film layer B in the present invention is within the range not impairing the effects of the present invention, if necessary, other thermoplastic polymers, lubricants such as inert particles and wax, stabilizers such as ultraviolet absorbers, lubricants, You may mix | blend antioxidant, a plasticizer, a lubricant, a flame retardant, a mold release agent, and a nucleating agent as needed. In addition, from the viewpoint of expressing surface flatness to a higher degree, other thermoplastic polymers, pigments, fillers, glass fibers, carbon fibers, layered silicates that are incompatible with PET, which easily forms surface defects. Etc. are preferably not contained. In addition, from the viewpoint of ensuring the flatness of the surface while ensuring the runnability and winding property when the laminated film is formed, the inert particles having an average particle diameter of 0.01 to 0.5 μm are added to 0.001 to 0.001. It is preferable to make it contain in 1.0 mass%. The average particle diameter of the preferable inert particles is preferably 0.02 to 0.4 μm, more preferably 0.05 to 0.35 μm. Moreover, preferable content is 0.005-0.5 mass%, Furthermore, 0.01-0.4 mass%. The inert particles to be contained are preferably at least one kind of particles selected from the group consisting of organic polymer particles such as silicone resin, crosslinked acrylic resin, crosslinked polyester, crosslinked polystyrene, and spherical silica. It is preferably at least one particle selected from the group consisting of crosslinked polystyrene and spherical silica.
＜フィルム層Ａ＞
本発明におけるフィルム層Ａは、全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、７５：２５〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、４０：６０〜９０：１０の範囲である樹脂Ａ´とポリエチレンテレフタレートとを、全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、９０：１０〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、１２：８０〜４０：６０となるように溶融混練したものである。
<Film layer A>
Film layer A in the present invention has a molar ratio of terephthalic acid component of the total acid component to 2,6-naphthalenedicarboxylic acid component in the range of 75:25 to 100: 0, and 1,4-cyclohexanedi of the total glycol component. Resin A ′ and polyethylene terephthalate in which the molar ratio of the methanol component to the ethylene glycol component is in the range of 40:60 to 90:10, the molar ratio of the terephthalic acid component of the total acid component to the 2,6-naphthalenedicarboxylic acid component However, in the range of 90:10 to 100: 0, melt-kneaded so that the molar ratio of 1,4-cyclohexanedimethanol component of all glycol components and ethylene glycol component is 12:80 to 40:60. is there.
樹脂Ａ´中のテレフタル酸成分が過度に少ないか、２，６−ナフタレンジカルボン酸成分の割合が過度に多いと、ポリエチレンテレフタレートと溶融混練する際の相溶性が悪化し表面荒れを起こす。好ましい樹脂Ａ´中のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比は、９１：９〜１００：０、さらに９２：８〜１００：０の範囲である。 If the terephthalic acid component in the resin A ′ is excessively small or the proportion of the 2,6-naphthalenedicarboxylic acid component is excessively large, compatibility when melt kneaded with polyethylene terephthalate is deteriorated and surface roughness is caused. The molar ratio of the terephthalic acid component to the 2,6-naphthalenedicarboxylic acid component in the preferred resin A ′ is in the range of 91: 9 to 100: 0, and further 92: 8 to 100: 0.
また、樹脂Ａ´中の１，４−シクロヘキサンジメタノール成分が過度に少ないか、エチレングリコール成分の割合が過度に多いと、十分な湿度膨張係数低減効果が得られなくなる。他方、樹脂Ａ´中の１，４−シクロヘキサンジメタノール成分が過度に多いか、エチレングリコール成分の割合が過度に少ないと、フィルムにした場合のヤング率が増加させにくくなる。好ましい樹脂Ａ´中の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比は、４２：５８〜８６：１４、さらに４４：５６〜８３：１７の範囲である。 If the 1,4-cyclohexanedimethanol component in the resin A ′ is excessively small or the proportion of the ethylene glycol component is excessively large, a sufficient humidity expansion coefficient reducing effect cannot be obtained. On the other hand, if the 1,4-cyclohexanedimethanol component in the resin A ′ is excessively large or the proportion of the ethylene glycol component is excessively small, the Young's modulus in the case of forming a film is difficult to increase. The molar ratio of the 1,4-cyclohexanedimethanol component and the ethylene glycol component in the preferred resin A ′ is in the range of 42:58 to 86:14, and further 44:56 to 83:17.
なお、上記樹脂Ａ´と溶融混練するポリエチレンテレフタレートは、前述のフィルム層Ｂで説明したのと同様なことが言え、生産性の観点からは、フィルム層Ｂに用いるＰＥＴと同じものを用いることが好ましい。 The polyethylene terephthalate that is melt-kneaded with the resin A ′ can be said to be the same as that described for the film layer B described above. From the viewpoint of productivity, the same PET as that used for the film layer B can be used. preferable.
そして、本発明におけるフィルム層Ａは、前述の樹脂Ａ´とＰＥＴとを溶融混練した樹脂Ａからなり、この樹脂Ａは、前述の通り、全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、９０：１０〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、１２：８８〜４０：６０となるように溶融混練したものである。 The film layer A in the present invention comprises a resin A obtained by melt-kneading the above-described resin A ′ and PET. As described above, the resin A is composed of the terephthalic acid component of the total acid component and 2,6-naphthalene dicarboxylic acid. The molar ratio of the acid component is in the range of 90:10 to 100: 0, and the molar ratio of the 1,4-cyclohexanedimethanol component to the ethylene glycol component of all glycol components is 12:88 to 40:60. It is melt-kneaded.
樹脂Ａ中のテレフタル酸成分が過度に少ないか、２，６−ナフタレンジカルボン酸成分の割合が過度に多いと、ＰＥＴとの相溶性が悪化し表面荒れが起こる。好ましい樹脂Ａ中のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比は、９１：９〜１００：０、さらに９２：８〜１００：０の範囲である。 When the terephthalic acid component in the resin A is excessively small or the proportion of the 2,6-naphthalenedicarboxylic acid component is excessively large, compatibility with PET deteriorates and surface roughness occurs. The molar ratio of the terephthalic acid component and the 2,6-naphthalenedicarboxylic acid component in the preferred resin A is in the range of 91: 9 to 100: 0, and further 92: 8 to 100: 0.
また、樹脂Ａ中の１，４−シクロヘキサンジメタノール成分が過度に少ないか、エチレングリコール成分の割合が過度に多いと、十分な湿度膨張係数の低減効果が得られなくなる。他方、樹脂Ａ中の１，４−シクロヘキサンジメタノール成分が過度に多いか、エチレングリコール成分の割合が過度に少ないと、フィルム表面が荒れやすくなる。好ましい樹脂Ａ中の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比は、１４：８６〜３６：６４、さらに１６：８４〜３３：６７の範囲である。 Further, if the 1,4-cyclohexanedimethanol component in the resin A is excessively small or the proportion of the ethylene glycol component is excessively large, a sufficient effect of reducing the coefficient of humidity expansion cannot be obtained. On the other hand, if the 1,4-cyclohexanedimethanol component in the resin A is excessively large or the proportion of the ethylene glycol component is excessively small, the film surface tends to be rough. The molar ratio of the 1,4-cyclohexanedimethanol component and the ethylene glycol component in the preferred resin A is in the range of 14:86 to 36:64, and further 16:84 to 33:67.
ところで、樹脂Ａ´とＰＥＴとを溶融混練するのではなく、重合の段階で上記組成になるように初めから共重合した場合、塗布などの加工性が乏しく、ヤング率などの機械的物性も乏しいものとなりやすい。そのような観点から、溶融混練する樹脂Ａ´とＰＥＴとの重量比は、１５：８５〜９０：１０の範囲、さらに２０：８０〜９０：１０の範囲であることが好ましい。 By the way, when resin A ′ and PET are not melt-kneaded but copolymerized from the beginning so as to have the above composition at the stage of polymerization, workability such as coating is poor and mechanical properties such as Young's modulus are also poor. It is easy to become a thing. From such a viewpoint, the weight ratio of the resin A ′ to be melt kneaded and PET is preferably in the range of 15:85 to 90:10, and more preferably in the range of 20:80 to 90:10.
なお、本発明における樹脂Ａ´および樹脂Ａは、本発明の効果を損なわない範囲で、それ自体公知の他の共重合成分を共重合したものであっても良い。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、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。 The resin A ′ and the resin A in the present invention may be those obtained by copolymerizing other copolymerization components known per se within a range not impairing the effects of the present invention. Examples of the copolymer component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid.
本発明における樹脂Ａ´および樹脂ＡのＰ−クロロフェノール／１，１，２，２−テトラクロロエタン（重量比４０／６０）の混合溶媒を用いて３５℃で測定した固有粘度は、０．５〜１．１ｄｌ／ｇ、さらに０．６〜１．１ｄｌ／ｇの範囲にあることが本発明の効果の点から好ましい。固有粘度が上限以上だと、粘度が高くなりすぎ、製膜時の押出機からの樹脂の押出が困難になる。また、固有粘度が下限以下だと、フィルムが脆化し、延伸が困難になる。 The intrinsic viscosity measured at 35 ° C. using a mixed solvent of Resin A ′ and Resin A P-chlorophenol / 1,1,2,2-tetrachloroethane (weight ratio 40/60) is 0.5. From the viewpoint of the effect of the present invention, it is preferably in the range of -1.1 dl / g, more preferably in the range of 0.6-1.1 dl / g. If the intrinsic viscosity is equal to or higher than the upper limit, the viscosity becomes too high, and it becomes difficult to extrude the resin from the extruder during film formation. On the other hand, if the intrinsic viscosity is less than the lower limit, the film becomes brittle and stretching becomes difficult.
また、本発明におけるフィルム層Ａは、本発明の効果を損なわない範囲で、必要に応じて、他の熱可塑性ポリマー、不活性粒子やワックスなどの滑剤、紫外線吸収剤等の安定剤、滑剤、酸化防止剤、可塑剤、滑剤、難燃剤、離型剤、核剤を必要に応じて配合しても良い。なお、表面の平坦性をより高度に発現させる観点から、表面欠点を形成しやすい樹脂Ａに対して非相溶の他の熱可塑性ポリマー、顔料、充填剤、ガラス繊維、炭素繊維、層状ケイ酸塩などは含有させないことが好ましい。また、積層フィルムにしたときの走行性や巻取り性を確保しつつ、表面の平坦性を確保する観点から、平均粒径が０．０１〜０．５μｍの不活性粒子を、０．００１〜１．０質量％の範囲で含有させるのが好ましい。好ましい不活性粒子の平均粒径は、０．０２〜０．４μｍ、さらに０．０５〜０．３５μｍの範囲である。また、好ましい含有量は０．００５〜０．５質量％、さらに０．０１〜０．４質量％である。含有させる不活性粒子としては、シリコーン樹脂、架橋アクリル樹脂、架橋ポリエステル、架橋ポリスチレンなどの有機高分子粒子および球状シリカからなる群から選ばれる少なくとも１種の粒子であることが好ましく、特にシリコーン樹脂、架橋ポリスチレンおよび球状シリカからなる群から選ばれる少なくとも１種の粒子であることが好ましい。 Further, the film layer A in the present invention is within a range not impairing the effects of the present invention, if necessary, other thermoplastic polymers, lubricants such as inert particles and wax, stabilizers such as ultraviolet absorbers, lubricants, You may mix | blend antioxidant, a plasticizer, a lubricant, a flame retardant, a mold release agent, and a nucleating agent as needed. In addition, from the viewpoint of expressing surface flatness to a higher degree, other thermoplastic polymers, pigments, fillers, glass fibers, carbon fibers, layered silicic acid that are incompatible with the resin A that easily forms surface defects. It is preferable not to contain a salt or the like. In addition, from the viewpoint of ensuring the flatness of the surface while ensuring the runnability and winding property when the laminated film is formed, the inert particles having an average particle diameter of 0.01 to 0.5 μm are added to 0.001 to 0.001. It is preferable to make it contain in 1.0 mass%. A preferable average particle diameter of the inert particles is in the range of 0.02 to 0.4 μm, and further 0.05 to 0.35 μm. Moreover, preferable content is 0.005-0.5 mass%, Furthermore, 0.01-0.4 mass%. The inert particles to be contained are preferably at least one kind of particles selected from the group consisting of organic polymer particles such as silicone resin, crosslinked acrylic resin, crosslinked polyester, crosslinked polystyrene, and spherical silica. It is preferably at least one particle selected from the group consisting of crosslinked polystyrene and spherical silica.
＜積層フィルム＞
本発明の積層フィルムは、前述のフィルム層Ａとフィルム層Ｂとを積層したものであり、積層構造は、フィルム層Ａとフィルム層Ｂの２層積層フィルム、フィルム層Ａの両面にフィルム層Ｂやフィルム層Ｂの両面にフィルム層Ａを積層した３層積層フィルム、フィルム層Ａとフィルム層Ｂとを交互に積層した多層積層フィルムであっても良い。多層積層フィルムの場合、フィルム層Ａとフィルム層Ｂの合計層数は、カールなどを抑制し、また延伸性をより高めやすいことから、８層以上、さらに１０層以上、特に１５層以上が好ましく、他方上限は特に制限されないが、生産工程の煩雑化を抑制する観点から、１０００層以下、さらに５００層以下、特に２００層以下であることが好ましい。
<Laminated film>
The laminated film of the present invention is obtained by laminating the above-described film layer A and film layer B. The laminated structure is a two-layer laminated film of film layer A and film layer B, and film layer B on both sides of film layer A. Alternatively, it may be a three-layer laminated film in which the film layer A is laminated on both surfaces of the film layer B, or a multilayer laminated film in which the film layer A and the film layer B are alternately laminated. In the case of a multilayer laminated film, the total number of layers of the film layer A and the film layer B is preferably 8 layers or more, more preferably 10 layers or more, and particularly preferably 15 layers or more because curling and the like are easily suppressed and stretchability is more easily improved. The other upper limit is not particularly limited, but is preferably 1000 layers or less, more preferably 500 layers or less, and particularly preferably 200 layers or less, from the viewpoint of suppressing complication of the production process.
また、本発明の積層フィルムは、その厚み方向に見たとき、フィルム層Ａが占める厚みとフィルム層Ｂが占める厚みとが、１０：９０〜８０：２０の範囲であることが、温度膨張係数と湿度膨張係数とをより高度に低減させやすいことから好ましい。好ましいフィルム層Ａが占める厚みとフィルム層Ｂが占める厚みとは、１０：９０〜７５：２５の範囲であること、さらに１０：９０〜７０：３０の範囲であることが好ましい。 Moreover, when the laminated film of this invention is seen in the thickness direction, it is the temperature expansion coefficient that the thickness which the film layer A occupies and the thickness which the film layer B occupies is the range of 10: 90-80: 20. And the humidity expansion coefficient are preferred because they can be easily reduced to a higher degree. The thickness occupied by the preferred film layer A and the thickness occupied by the film layer B are preferably in the range of 10:90 to 75:25, and more preferably in the range of 10:90 to 70:30.
そのような観点から、本発明の積層フィルムは、積層フィルム全体で見たとき、全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、９０：１０〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、３：９７〜３０：７０の範囲であることが好ましい。積層フィルム全体で見たときの、テレフタル酸成分が過度に少ないか、２，６−ナフタレンジカルボン酸成分の割合が過度に多いと、湿度膨張係数が低下しにくい。好ましい積層フィルム全体で見たときの、テレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比は、１００：０〜９０：１０、さらに１００：０〜９５：５の範囲である。 From such a viewpoint, when the laminated film of the present invention is viewed in the whole laminated film, the molar ratio of the terephthalic acid component of the total acid component and the 2,6-naphthalenedicarboxylic acid component is 90:10 to 100: 0. Preferably, the molar ratio of the 1,4-cyclohexanedimethanol component to the ethylene glycol component of the total glycol component is in the range of 3:97 to 30:70. If the terephthalic acid component is excessively small or the proportion of the 2,6-naphthalenedicarboxylic acid component is excessively large when viewed from the whole laminated film, the humidity expansion coefficient is difficult to decrease. The molar ratio of the terephthalic acid component to the 2,6-naphthalenedicarboxylic acid component when viewed from the entire preferred laminated film is in the range of 100: 0 to 90:10, and further 100: 0 to 95: 5.
また、積層フィルム全体で見たときの、１，４−シクロヘキサンジメタノール成分が過度に少ないか、エチレングリコール成分の割合が過度に多いと、十分な湿度膨張係数の低減効果が得られにくい。他方、積層フィルム全体での１，４−シクロヘキサンジメタノール成分が過度に多いか、エチレングリコール成分の割合が過度に少ないと、フィルムとしてのヤング率が得られにくく、また温度膨張係数が増加しやすくなる。好ましい樹脂Ａ中の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比は、５：９５〜２５：７５、さらに１０：９０〜２５：７５の範囲である。 Further, when the 1,4-cyclohexanedimethanol component is excessively small or the proportion of the ethylene glycol component is excessively large when viewed from the entire laminated film, it is difficult to obtain a sufficient effect of reducing the humidity expansion coefficient. On the other hand, if the 1,4-cyclohexanedimethanol component in the entire laminated film is excessively large or the proportion of the ethylene glycol component is excessively small, it is difficult to obtain the Young's modulus as a film, and the temperature expansion coefficient tends to increase. Become. The molar ratio of the 1,4-cyclohexanedimethanol component and the ethylene glycol component in the preferred resin A is in the range of 5:95 to 25:75, more preferably 10:90 to 25:75.
ところで、本発明の積層フィルムは、表裏の表面粗さ（Ｒａ）の差が１ｎｍ以上、さらに２ｎｍ以上異なることが、一方の表面で走行性や巻取り性を具備させつつ、他方の表面の平坦性をより高度に発現できるため好ましい。なお、表裏の表面粗さ（Ｒａ）の差の上限は特に制限されないが、過度に差を持たせると、平坦な側の表面に平坦でない側の表面の形状が転写しやすくなるので、１０ｎｍ以下であることが好ましい。そして、このような表面粗さに差を持たせる観点から、本発明の積層フィルムは、その厚み方向に非対称なフィルム層ＡとＢとが非対象な層構成であることが好ましく、例えばフィルム層Ａの厚み割合で見たとき、一方の表面からフィルムの中心部分までの割合と、他方の表面からフィルムの中心部分までの割合とが、厚み比で１０％以上異なることが好ましい。 By the way, in the laminated film of the present invention, the difference in surface roughness (Ra) between the front and back surfaces is different by 1 nm or more, and further by 2 nm or more. It is preferable because sex can be expressed to a higher degree. The upper limit of the difference in surface roughness (Ra) between the front and back surfaces is not particularly limited. However, if the difference is excessive, the shape of the surface on the non-flat side is easily transferred to the surface on the flat side. It is preferable that And from the viewpoint of giving such a difference in surface roughness, the laminated film of the present invention preferably has a layer structure in which the film layers A and B that are asymmetric in the thickness direction are untargeted, for example, a film layer When viewed in terms of the thickness ratio of A, the ratio from one surface to the central portion of the film and the ratio from the other surface to the central portion of the film are preferably different by 10% or more in thickness ratio.
つぎに、本発明の積層フィルムの好ましい態様について、以下に説明する。
本発明の積層フィルムは、製膜方向（縦方向またはＭＤ方向と称することもある。）および幅方向（フィルム面方向における製膜方向に直交する方向で、横方向またはＴＤ方向と称することもある。）に延伸された二軸配向フィルムであることが好ましく、製膜方向及び幅方向におけるヤング率が、４．５ＧＰａ以上であることが、温度膨張係数を小さくし、高温での加工特性を高度に発現できることから好ましい。特に、磁気記録テープにベースフィルムに用いる場合、ヤング率を高める方向が積層フィルムの幅方向であることが、トラックずれなどを抑制できることから好ましい。
Below, the preferable aspect of the laminated | multilayer film of this invention is demonstrated below.
The laminated film of the present invention has a film forming direction (also referred to as a longitudinal direction or an MD direction) and a width direction (a direction perpendicular to the film forming direction in the film surface direction, sometimes referred to as a transverse direction or a TD direction). .) Is preferably a biaxially oriented film, and the Young's modulus in the film forming direction and the width direction is 4.5 GPa or more, so that the temperature expansion coefficient is reduced and the processing characteristics at high temperature are high. It is preferable because it can be expressed. In particular, when used as a base film for a magnetic recording tape, it is preferable that the direction in which the Young's modulus is increased is the width direction of the laminated film because track misalignment can be suppressed.
このような高いヤング率を有するフィルムを得るには、共重合芳香族ポリエステルとして、前述の特定量の１，４−シクロヘキサンジメチレンテレフタレート成分となるように重合されたものを直接用いるのではなく、１，４−シクロヘキサンジメチレンテレフタレート成分の割合が異なる２種以上のポリエステルを用意し、これらをブレンドし、さらにＰＥＴと積層すること、ヤング率を高めたい方向に高度に延伸すること、さらにより特定方向のヤング率を高めたい場合は、ヤング率を高めたい方向と直交する方向の延伸を緩和することなどが挙げられる。 In order to obtain a film having such a high Young's modulus, instead of directly using a copolymerized aromatic polyester polymerized to become the above-mentioned specific amount of 1,4-cyclohexanedimethylene terephthalate component, Prepare two or more kinds of polyesters with different proportions of 1,4-cyclohexanedimethylene terephthalate component, blend them, laminate with PET, highly stretch in the direction you want to increase Young's modulus, even more specific When it is desired to increase the Young's modulus in the direction, for example, the stretching in the direction perpendicular to the direction in which the Young's modulus is desired to be relaxed.
本発明の積層フィルムは、少なくとも一方向、好ましくはフィルムの幅方向における温度膨張係数の関係を満足する方向の温度膨張係数が−５〜１０ｐｐｍ／℃、好ましくは−２〜１０ｐｐｍ／℃、さらに好ましくは−２〜７．５ｐｐｍ／℃の範囲にあることが、特に磁気記録テープにしたときの寸法安定性の点で好ましい。上記上限を上回ると磁気テープにした場合に、温度条件によってトラックずれが起こり好ましくない。また上記下限を下回ると磁気テープとそれを読み取るヘッドの温度膨張係数の差が大きくなるため、これも読み取り誤差を大きくするため好ましくない。 The laminated film of the present invention has a temperature expansion coefficient of −5 to 10 ppm / ° C., preferably −2 to 10 ppm / ° C., more preferably in a direction satisfying the relationship of the temperature expansion coefficient in at least one direction, preferably the width direction of the film. Is preferably in the range of −2 to 7.5 ppm / ° C., particularly in terms of dimensional stability when a magnetic recording tape is formed. When the above upper limit is exceeded, when a magnetic tape is used, track deviation occurs due to temperature conditions, which is not preferable. Also, if the lower limit is not reached, the difference between the temperature expansion coefficients of the magnetic tape and the head for reading it becomes large, which is also not preferable because it increases the reading error.
本発明の積層フィルムは、少なくとも一方向、好ましくはフィルムの幅方向における温度膨張係数の関係を満足する方向の湿度膨張係数が１〜７ｐｐｍ／％ＲＨ、好ましくは３〜７ｐｐｍ／％ＲＨ、さらに好ましくは３〜６．５ｐｐｍ／％ＲＨの範囲にあることが、特に磁気記録テープにしたときの寸法安定性の点で好ましい。上記上限を上回ると磁気テープにした場合に、温度条件によってトラックずれが起こり好ましくない。 The laminated film of the present invention has a humidity expansion coefficient of 1 to 7 ppm /% RH, preferably 3 to 7 ppm /% RH, more preferably in a direction satisfying the relationship of the temperature expansion coefficient in at least one direction, preferably the width direction of the film. Is preferably in the range of 3 to 6.5 ppm /% RH, particularly in terms of dimensional stability when used as a magnetic recording tape. When the above upper limit is exceeded, when a magnetic tape is used, track deviation occurs due to temperature conditions, which is not preferable.
本発明の積層フィルムは、用いる用途に応じて適宜採用すればよいが、本発明の効果を発現しやすいことから、フィルム厚みが２〜１５μｍの範囲にあることが好ましい。特に、磁気記録テープのベースフィルムに用いる場合、２〜１０μｍ、さらに２．５〜５μｍ、特に３〜４．７μｍの範囲にあることが、カセットに入れるテープ長さを十分に確保して記憶容量を高める点と、フィルム製膜時の生産性の点から好ましい。 The laminated film of the present invention may be appropriately employed depending on the application to be used, but the film thickness is preferably in the range of 2 to 15 μm because the effects of the present invention are easily exhibited. In particular, when used as a base film for magnetic recording tape, it is in the range of 2 to 10 μm, more preferably 2.5 to 5 μm, especially 3 to 4.7 μm, so that a sufficient tape length can be secured in the cassette and a storage capacity can be obtained. It is preferable from the point of raising the point and the productivity at the time of film forming.
本発明の積層フィルムは、表面の平坦性に優れることから、少なくとも一方の表面は、表面粗さＲａが１０ｎｍ以下、さらに８ｎｍ以下であることが好ましい。また、磁気記録テープのベースフィルムに用いる場合、磁性層を形成する側の表面は、表面粗さＲａが０．５〜４ｎｍの範囲にあることが好ましく、走行性と巻取り性を高度に具備させるために、磁性層を形成しない側の表面は、表面粗さＲａが３〜１０ｎｍの範囲にあることが好ましい。磁性層を形成しない側の表面粗さＲａが上記上限を超えると、製膜時のハンドリング性は優れるものの、フィルムを巻き取った際に磁性層を形成する側の表面の平坦性が損なわれることがある。他方、上記下限を下回ると、フィルムのハンドリングが非常に問題になりえる。 Since the laminated film of the present invention is excellent in surface flatness, at least one surface preferably has a surface roughness Ra of 10 nm or less, and more preferably 8 nm or less. Further, when used for a base film of a magnetic recording tape, the surface on the side on which the magnetic layer is formed preferably has a surface roughness Ra in the range of 0.5 to 4 nm, and has a high running property and winding property. Therefore, the surface on the side where the magnetic layer is not formed preferably has a surface roughness Ra in the range of 3 to 10 nm. If the surface roughness Ra on the side where the magnetic layer is not formed exceeds the above upper limit, the handleability during film formation is excellent, but the flatness of the surface on the side where the magnetic layer is formed is impaired when the film is wound. There is. On the other hand, below the lower limit, film handling can be very problematic.
本発明の積層フィルムは、後述の測定方法によって測定されるフィルムカールが−１〜１ｍｍ、さらに−０．５〜０．５ｍｍ、特に−０．３〜０．３ｍｍであることが好ましい。カールが上限または下限を外れると、フィルムカールがきつくなりすぎ、例えばフィルム製膜工程上で切断などが起き、生産性が悪化する。また磁気テープを作成する際のハンドリング性も悪化する。このようなカールは、前述の特定の共重合芳香族ポリエステルをＰＥＮとブレンドしたフィルム層Ａと、ＰＥＮからなるフィルム層Ａとを積層することで抑えることができる。 In the laminated film of the present invention, the film curl measured by the measurement method described later is preferably −1 to 1 mm, more preferably −0.5 to 0.5 mm, and particularly preferably −0.3 to 0.3 mm. When the curl deviates from the upper limit or the lower limit, the film curl becomes too tight, for example, cutting occurs in the film forming process, and productivity is deteriorated. In addition, the handling property when producing a magnetic tape also deteriorates. Such curling can be suppressed by laminating the film layer A obtained by blending the above-mentioned specific copolymerized aromatic polyester with PEN and the film layer A made of PEN.
本発明の積層フィルムは、後述の測定方法で測定される１１０℃でのＭＤ方向の塗布適性が、１．５％以下であることが好ましい。塗布適性が１．５％以下、さらに１．０％以下であることで、磁性層を塗布する工程など、高温で張力がかかる状態での加工において、フィルムにシワが入るのを抑制できる。また、より高温の条件やより高張力の条件で加工できるようにもなるので、より高速での加工が可能になり、生産性を向上することもできる。このような塗布適性は、前述の特定の共重合芳香族ポリエステルをＰＥＮとブレンドしたフィルム層Ａと、ＰＥＮからなるフィルム層Ａとを積層し、製膜方向の延伸などを強化することで抑えることができる。 The laminated film of the present invention preferably has a coating suitability in the MD direction at 110 ° C. of 1.5% or less as measured by a measurement method described later. When the coating suitability is 1.5% or less, and further 1.0% or less, wrinkles can be prevented from entering the film in processing in a state where tension is applied at a high temperature such as a step of applying a magnetic layer. In addition, since processing can be performed under higher temperature conditions and higher tension conditions, processing at higher speeds is possible, and productivity can be improved. Such coating suitability is suppressed by laminating the film layer A in which the above-mentioned specific copolymerized aromatic polyester is blended with PEN and the film layer A made of PEN, and strengthening stretching in the film forming direction. Can do.
＜積層フィルムの製造方法＞
本発明の積層フィルムの好ましい製造方法について、以下説明する。
まず、前述の樹脂Ａ´とＰＥＴとを用意し、これらを必要に応じて乾燥処理をした後、２台の押出機に供給する。具体的には、第１の押出機には、樹脂Ａ´とＰＥＴとを目的の樹脂Ａの組成になるように供給し、第２の押出機にはＰＥＮを供給し、溶融混練する。この際、エステル交換反応や分子量低下が過度に進行しないように、第１の押出機の溶融混練は得られる樹脂Ａの融点（ＴｍＡ：℃）以上ＴｍＡ＋５０℃以下、好ましくはＴｍＡ＋１０℃以上ＴｍＡ＋３０℃以下の温度で、第２の押出機の溶融混練はＰＥＴの融点（ＴｍＢ：℃）以上ＴｍＢ＋５０℃以下、好ましくはＴｍＢ＋１０℃以上ＴｍＢ＋３０℃以下の温度で行い、比較的短時間、例えば２０分以下で行うことが好ましい。
そして、このようにして溶融状態になった樹脂ＡとＰＥＴとを、例えばフィードブロックにて所望の層構成になるように溶融状態で積層し、ダイから回転している冷却ドラムの上に押出し、急冷して未延伸積層フィルムを製造する。
<Method for producing laminated film>
A preferred method for producing the laminated film of the present invention will be described below.
First, the above-described resin A ′ and PET are prepared, dried as necessary, and then supplied to two extruders. Specifically, resin A ′ and PET are supplied to the first extruder so as to have the composition of the target resin A, PEN is supplied to the second extruder, and melt-kneaded. At this time, the melt-kneading of the first extruder is not less than the melting point (TmA: ° C.) of the obtained resin A and not more than TmA + 50 ° C., preferably not less than TmA + 10 ° C. and not more than TmA + 30 ° C., so that transesterification and molecular weight reduction do not proceed excessively. The melting and kneading of the second extruder is performed at a temperature of PET melting point (TmB: ° C.) or higher and TmB + 50 ° C. or lower, preferably TmB + 10 ° C. or higher and TmB + 30 ° C. or lower, for a relatively short time, for example, 20 minutes or shorter. It is preferable.
Then, the resin A and PET in a molten state in this way are laminated in a molten state so as to have a desired layer structure, for example, in a feed block, and are extruded onto a cooling drum rotating from a die, Quenched to produce an unstretched laminated film.
なお、前述のヤング率、温度膨張係数（αｔ）および湿度膨張係数（αｈ）を好ましい範囲にするには、その後の延伸を進行させやすくすることが必要であり、そのような観点から冷却ドラムによる冷却は非常に速やかに行うことが好ましい。そのような観点から、２０〜６０℃という低温で行うことが好ましい。このような低温にすることで、未延伸フィルムの状態での結晶化が抑制され、その後の延伸をよりスムーズに行える。 In order to make the aforementioned Young's modulus, temperature expansion coefficient (αt), and humidity expansion coefficient (αh) within the preferable ranges, it is necessary to facilitate the subsequent stretching. Cooling is preferably performed very quickly. From such a viewpoint, it is preferable to carry out at a low temperature of 20 to 60 ° C. By setting it as such low temperature, crystallization in the state of an unstretched film is suppressed and subsequent stretching can be performed more smoothly.
二軸延伸としては、逐次二軸延伸でも同時二軸延伸でもよい。ここでは、逐次二軸延伸で、縦延伸、横延伸および熱処理をこの順で行う製造方法を一例として挙げて説明する。まず、最初の縦延伸はフィルム層Ａの樹脂Ａのガラス転移温度（ＴｇＡ：℃）ないし（ＴｇＡ＋４０）℃の温度で、２〜８倍に延伸し、次いで横方向に先の縦延伸と同様の温度で３〜１０倍に延伸し、さらに熱処理として樹脂Ａの融点（ＴｍＡ：℃）以下の温度でかつ（ＴｇＡ＋５０）〜（ＴｇＡ＋１５０）℃の温度で１〜２０秒、さらに１〜１５秒熱固定処理するのが好ましい。なお、ヤング率を高めたい場合、温度膨張係数や湿度膨張係数を小さくしたい場合、その方向の延伸倍率を高くすること、その方向の延伸時の温度を低くすること、その方向に直交する方向の延伸倍率を小さくすることなどが有効である。 Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching. Here, a manufacturing method in which longitudinal stretching, lateral stretching, and heat treatment are performed in this order by sequential biaxial stretching will be described as an example. First, the first longitudinal stretching is performed at a temperature of glass transition temperature (TgA: ° C.) to (TgA + 40) ° C. of the resin A of the film layer A, and then stretched 2 to 8 times, and then the same as the previous longitudinal stretching in the transverse direction. Stretched 3 to 10 times at a temperature, and further heat-treated as a heat treatment at a temperature below the melting point (TmA: ° C.) of resin A and at a temperature of (TgA + 50) to (TgA + 150) ° C. for 1 to 20 seconds, and further for 1 to 15 seconds It is preferable to process. If you want to increase the Young's modulus, if you want to reduce the temperature expansion coefficient or humidity expansion coefficient, increase the stretching ratio in that direction, decrease the temperature during stretching in that direction, or in the direction orthogonal to that direction. It is effective to reduce the draw ratio.
なお、前述の説明は逐次二軸延伸について説明したが、本発明の積層フィルムは縦延伸と横延伸とを同時に行う同時二軸延伸でも製造でき、例えば先で説明した延伸倍率や延伸温度などを参考にすればよい。
本発明によれば、本発明の積層フィルムをベースフィルムとし、その一方の面に非磁性層および磁性層がこの順で形成され、他方の面にバックコート層が形成することなどで高密度磁気記録テープとすることができる。
In addition, although the above description explained sequential biaxial stretching, the laminated film of the present invention can be manufactured by simultaneous biaxial stretching in which longitudinal stretching and lateral stretching are simultaneously performed. For example, the stretching ratio and the stretching temperature described above are set. You can refer to it.
According to the present invention, the laminated film of the present invention is used as a base film, a nonmagnetic layer and a magnetic layer are formed in this order on one side, and a backcoat layer is formed on the other side. It can be a recording tape.
以下に実施例及び比較例を挙げ、本発明をより具体的に説明する。なお、本発明では、以下の方法により、その特性を測定および評価した。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the present invention, the characteristics were measured and evaluated by the following methods.
（１）固有粘度
得られたポリエステルの固有粘度はＰ−クロロフェノール／１，１，２，２−テトラクロロエタン（４０／６０重量比）の混合溶媒を用いてポリマーを溶解して３５℃で測定して求めた。
(1) Intrinsic viscosity The intrinsic viscosity of the obtained polyester was measured at 35 ° C by dissolving the polymer using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (40/60 weight ratio). And asked.
（２）ガラス転移点および融点
ガラス転移点、融点はＤＳＣ（ＴＡインスツルメンツ株式会社製、商品名：Ｔｈｅｒｍａｌ ｌｙｓｔ２１００）によりサンプル重量１０ｍｇ、昇温速度１０℃／ｍｉｎで測定した。
(2) Glass transition point and melting point The glass transition point and melting point were measured by DSC (TA Instruments Co., Ltd., trade name: Thermal lyst 2100) at a sample weight of 10 mg and a heating rate of 10 ° C / min.
（３）密度
得られたフィルムを一辺が３〜５ｍｍの任意の形に切り出し、密度勾配管法で測定した。
(3) Density The obtained film was cut into an arbitrary shape having a side of 3 to 5 mm and measured by a density gradient tube method.
（４）ヤング率
得られたフィルムを試料巾１０ｍｍ、長さ１５ｃｍで切り取り、チャック間１００ｍｍ、引張速度１０ｍｍ／分、チャート速度５００ｍｍ／分の条件で万能引張試験装置（東洋ボールドウィン製、商品名：テンシロン）にて引っ張る。得られた荷重―伸び曲線の立ち上がり部の接線よりヤング率を計算する。なお、測定は５回行い、その平均値をヤング率とした。
(4) Young's modulus The obtained film was cut out with a sample width of 10 mm and a length of 15 cm, and a universal tensile testing device (product name: Toyo Baldwin, trade name: 100 mm between chucks, tensile speed 10 mm / min, chart speed 500 mm / min). Pull with Tensilon). The Young's modulus is calculated from the tangent of the rising portion of the obtained load-elongation curve. In addition, the measurement was performed 5 times and the average value was made into the Young's modulus.
（５）温度膨張係数（αｔ）
得られたフィルムを、フィルムの幅方向が測定方向となるように長さ２０ｍｍ、幅４ｍｍに切り出し、ＳＩＩ製ＥＸＳＴＡＲ６０００にセットし、窒素雰囲気下（０％ＲＨ）、８０℃で３０分前処理し、その後室温まで降温させる。その後３０℃から７０℃まで２℃／ｍｉｎで昇温して、各温度でのサンプル長を測定し、次式より温度膨張係数（αｔ）を算出する。なお、測定方向が切り出した試料の長手方向であり、５回測定し、その平均値を用いた。
αｔ＝｛（Ｌ６０−Ｌ４０）｝／（Ｌ４０×△Ｔ）｝＋０．５
ここで、上記式中のＬ４０は４０℃のときのサンプル長（ｍｍ）、Ｌ６０は６０℃のときのサンプル長（ｍｍ）、△Ｔは２０（＝６０−４０）℃、０．５は石英ガラスの温度膨張係数（×１０−６ｐｐｍ／℃）である。
(5) Temperature expansion coefficient (αt)
The obtained film was cut into a length of 20 mm and a width of 4 mm so that the width direction of the film would be the measurement direction, set in EXSTAR6000 manufactured by SII, and pretreated at 80 ° C. for 30 minutes in a nitrogen atmosphere (0% RH). Then, the temperature is lowered to room temperature. Thereafter, the temperature is raised from 30 ° C. to 70 ° C. at 2 ° C./min, the sample length at each temperature is measured, and the temperature expansion coefficient (αt) is calculated from the following equation. In addition, the measurement direction is the longitudinal direction of the sample cut out, the measurement was performed 5 times, and the average value was used.
αt = {(L 60 −L 40 )} / (L 40 × ΔT)} + 0.5
Here, L 40 in the above formula is the sample length (mm) at 40 ° C., L 60 is the sample length (mm) at 60 ° C., ΔT is 20 (= 60-40) ° C., 0.5 Is the temperature expansion coefficient of quartz glass (× 10 −6 ppm / ° C.).
（６）湿度膨張係数（αｈ）
得られたフィルムを、フィルムの幅方向が測定方向となるように長さ１５ｍｍ、幅５ｍｍに切り出し、ＢＲＵＫＥＲ製ＴＭＡ４０００ＳＡにセットし、３０℃の窒素雰囲気下で、湿度２０％ＲＨと湿度８０％ＲＨにおけるそれぞれのサンプルの長さを測定し、次式にて湿度膨張係数を算出する。なお、測定方向が切り出した試料の長手方向であり、５回測定し、その平均値をαｈ（ｐｐｍ／％ＲＨ）とした。
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。
(6) Humidity expansion coefficient (αh)
The obtained film was cut into a length of 15 mm and a width of 5 mm so that the width direction of the film would be the measurement direction, set in BRUKER TMA4000SA, and in a nitrogen atmosphere at 30 ° C., humidity 20% RH and humidity 80% RH. The length of each sample is measured, and the humidity expansion coefficient is calculated by the following equation. 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 (ppm /% RH).
αh = (L 80 −L 20 ) / (L 80 × ΔH)
Here, L 20 in the above formula is a sample length (mm) at 20% RH, and L 80 is 80%.
Sample length at RH (mm), ΔH: 60 (= 80-20)% RH.
（７）共重合量
グリコール成分については、試料１０ｍｇをｐ−クロロフェノール：１，１，２，２−テトラクロロエタン＝３：１（容積比）混合溶液０．５ｍｌに８０℃で溶解した。イソプロピルアミンを加えて、十分に混合した後に１Ｈ−ＮＭＲ（日立電子製 ＪＥＯＬ Ａ６００）にて８０℃で測定し、それぞれのグリコール成分量を測定した。
また、芳香族ジカルボン酸成分については、試料５０ｍｇをｐ−クロロフェノール：１，１，２，２−テトラクロロエタン＝３：１混合溶液０．５ｍｌに１４０℃で溶解し、１３Ｃ−ＮＭＲ（日立電子 ＪＥＯＬ Ａ６００）にて１４０℃で測定し、それぞれの酸成分量を測定した。
(7) Copolymerization amount As for the glycol component, 10 mg of a sample was dissolved at 80 ° C. in 0.5 ml of a mixed solution of p-chlorophenol: 1,1,2,2-tetrachloroethane = 3: 1 (volume ratio). Added isopropylamine, measured at 80 ° C. in 1 H-NMR (Hitachi Denshi Ltd. JEOL A600) after thorough mixing, was measured each glycol component amount.
As for the aromatic dicarboxylic acid component, 50 mg of a sample was dissolved at 140 ° C. in 0.5 ml of a mixed solution of p-chlorophenol: 1,1,2,2-tetrachloroethane = 3: 1, and 13 C-NMR (Hitachi). Electronic JEOL A600) was measured at 140 ° C., and the amount of each acid component was measured.
（８）表面粗さ
非接触式三次元表面粗さ計（ＺＹＧＯ社製：Ｎｅｗ Ｖｉｅｗ５０２２）を用いて測定倍率１０倍、測定面積２８３μｍ×２１３μｍ（＝０．０６０３ｍｍ２）の条件にて測定し、該粗さ計に内蔵された表面解析ソフトＭｅｔｒｏＰｒｏにより中心面平均粗さ（Ｒａ：ｎｍ）を求める。
(8) Surface roughness Measured using a non-contact type three-dimensional surface roughness meter (manufactured by ZYGO: New View 5022) at a measurement magnification of 10 times and a measurement area of 283 μm × 213 μm (= 0.0603 mm 2 ). The center surface average roughness (Ra: nm) is obtained by the surface analysis software MetroPro built in the roughness meter.
（９）カール
まず、フィルムを長手方向に１７０ｍｍ、幅方向に１／２インチ幅に切り出す。そして、水平方向に配置された2つのフリーロールにフィルムの表面粗さが平坦な側の表面を下にしてセットする。なお、フリーロールはフィルムと接する部分の外経が１０ｍｍ、フリーロールの中心軸間の距離は１０ｃｍとし、フィルムの両端には、１７．５ｇ／ｍｍ２の荷重をかける。次に、発光部と受光部を兼ね備えたキーエンス製レーザー変位計ＬＫ−Ｇ３０を、フィルムの上方に配置し、レーザー光をフィルムの面方向に斜めに照射した。そして、フィルムの幅方向に沿って、フィルムの変位（距離）を計測する。
計測された変位について、フィルムの幅方向における両端の変位の平均値と、フィルム幅方向における中央部分で観測される極大値または極小値とを用い、前述の平均値と極大値または極小値との差異をカールの値とする。なお、表面粗さが平坦な側の表面を内側にしてカールしている場合はプラスの値とし、表面粗さが平坦な側の表面を外側にしてカールしている場合はマイナスの値とした。上記測定を、３つのサンプルについて行い、それらの平均値を算出してカールの値とした。
(9) Curl First, the film is cut to 170 mm in the longitudinal direction and ½ inch in the width direction. Then, the film is set on two free rolls arranged in the horizontal direction with the surface having the flat surface facing down. In the free roll, the outer diameter of the portion in contact with the film is 10 mm, the distance between the central axes of the free roll is 10 cm, and a load of 17.5 g / mm 2 is applied to both ends of the film. Next, a KEYENCE laser displacement meter LK-G30 having both a light emitting part and a light receiving part was arranged above the film, and laser light was irradiated obliquely in the surface direction of the film. Then, the displacement (distance) of the film is measured along the width direction of the film.
About the measured displacement, using the average value of the displacement at both ends in the width direction of the film and the maximum value or the minimum value observed in the central portion in the film width direction, the above average value and the maximum value or the minimum value The difference is the curl value. In addition, when curling with the surface of the flat surface side facing inward, it is a positive value, and when curling with the surface roughness of the flat surface side facing out, it is a negative value. . The above measurement was performed on three samples, and an average value thereof was calculated as a curl value.
（１０）塗布適性
得られたフィルムを、フィルムの製膜方向が測定方向となるように長さ２０ｍｍ、幅４ｍｍに切り出し、ＳＩＩ製ＥＸＳＴＡＲ６０００にセットし、窒素雰囲気下（０％ＲＨ）、３０℃で保持した後、２℃／ｍｉｎで１５０℃まで昇温して、各温度でのサンプル長を測定し、３０℃で保持した後の昇温する前のフィルム長（Ｌ３０）に対し、１１０℃におけるフィルム長（Ｌ１１０）から、以下の式にて、いてどの程度長さ方向に膨張したかを計算した。
塗布適性（％）＝（Ｌ１１０−Ｌ３０）／Ｌ３０×１００
(10) Application suitability The obtained film was cut into a length of 20 mm and a width of 4 mm so that the film-forming direction of the film would be the measurement direction, set in EXSTAR6000 made of SII, and in a nitrogen atmosphere (0% RH), 30 ° C. After being held at 110 ° C., the sample length at each temperature was measured by raising the temperature to 150 ° C. at 2 ° C./min, and the film length (L30) before being heated after being held at 30 ° C. was 110 ° C. From the film length (L110), the degree of expansion in the length direction was calculated according to the following formula.
Application suitability (%) = (L110−L30) / L30 × 100
［実施例１］
ジカルボン酸成分としてテレフタル酸ジメチルと２，６−ナフタレンジカルボン酸ジメチル、ジオール成分としてエチレングリコールと１，４−シクロヘキサンジメタノールをチタンテトラブトキシドの存在下でエステル交換反応を行い、さらに引き続いて重縮合反応を行って、固有粘度０．６２ｄｌ／ｇのシクロヘキサンジメタノールを共重合せしめた共重合ポリエステルを得て、これを樹脂Ａ´−１とした。
樹脂Ａ’の各成分はモル比は、テレフタル酸成分：ナフタレンジカルボン酸成分が８０：２０、シクロヘキサンジメタノール成分：エチレングリコール成分が８０：２０であった。
一方、ジカルボン酸成分としてテレフタル酸ジメチルとジオール成分としてエチレングリコールとをチタンテトラブトキシドの存在下でエステル交換反応を行い、さらに引き続いて重縮合反応を行って、固有粘度０．６２ｄｌ／ｇのポリエチレンテレフタレートを得て、これを樹脂Ｂ−１とした。
このようにして得られた樹脂Ａ´−１と樹脂Ｂ−１を、重量比２９：７１になるようにブレンドし、樹脂Ａ−１を得た。
このようにして得られた樹脂Ａ−１と樹脂Ｂ−１を、押出機に供給して、樹脂Ａと樹脂Ｂの吐出量の比が２：１になるように、２８０℃でダイから溶融状態でフィードブロックを用いて表１に示す厚みの層構成になるように２層に積層せしめ、回転中の温度３０℃の冷却ドラム上にシート状に押し出し積層未延伸フィルムとした。なお、フィルム層Ａには、平均粒径０．３μｍの球状シリカ粒子を、フィルム層Ａの質量を基準としたとき、０．１５質量％となるように含有させ、フィルム層Ｂには、平均粒径０．１μｍの球状シリカ粒子を、フィルム層Ｂの質量を基準としたとき、０．１０質量％となるように含有させた。
そして、積層未延伸フィルムを、製膜方向に沿って回転速度の異なる二組のローラー間で、上方よりＩＲヒーターにてフィルム表面温度が９５℃になるように加熱して、縦方向（製膜方向）の延伸を、延伸倍率４．５倍で行い、一軸延伸フィルムを得た。そして、この一軸延伸フィルムをステンターに導き、１０５℃で横方向（幅方向）に延伸倍率５．２倍で延伸し、その後２００℃で３秒間熱固定処理を行い、厚さ４．５μｍの積層二軸配向フィルムを得た。
得られた積層二軸配向フィルムの特性を表１に示す。
[Example 1]
Transesterification of dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate as the dicarboxylic acid component, ethylene glycol and 1,4-cyclohexanedimethanol as the diol component in the presence of titanium tetrabutoxide, followed by polycondensation reaction To obtain a copolymerized polyester copolymerized with cyclohexanedimethanol having an intrinsic viscosity of 0.62 dl / g, and this was designated as resin A′-1.
The molar ratio of each component of the resin A ′ was 80:20 for the terephthalic acid component: naphthalenedicarboxylic acid component, and 80:20 for the cyclohexanedimethanol component: ethylene glycol component.
On the other hand, dimethyl terephthalate as a dicarboxylic acid component and ethylene glycol as a diol component are transesterified in the presence of titanium tetrabutoxide, followed by a polycondensation reaction to give polyethylene terephthalate having an intrinsic viscosity of 0.62 dl / g. This was designated as Resin B-1.
The resin A′-1 and the resin B-1 thus obtained were blended so as to have a weight ratio of 29:71 to obtain a resin A-1.
Resin A-1 and Resin B-1 thus obtained are supplied to an extruder and melted from a die at 280 ° C. so that the ratio of the discharge amount of Resin A and Resin B is 2: 1. In the state, it was laminated | stacked on 2 layers so that it might become the layer structure of the thickness shown in Table 1 using the feed block, and it extruded on the cooling drum of the temperature of 30 degreeC in rotation, and was set as the laminated unstretched film. In addition, the film layer A contains spherical silica particles having an average particle diameter of 0.3 μm so as to be 0.15% by mass, based on the mass of the film layer A, and the film layer B has an average Spherical silica particles having a particle size of 0.1 μm were contained so as to be 0.10% by mass, based on the mass of the film layer B.
Then, the laminated unstretched film is heated between two sets of rollers having different rotation speeds along the film forming direction from above with an IR heater so that the film surface temperature becomes 95 ° C. Direction) was performed at a draw ratio of 4.5 times to obtain a uniaxially stretched film. Then, this uniaxially stretched film is guided to a stenter, stretched at 105 ° C. in the transverse direction (width direction) at a stretch ratio of 5.2 times, and then heat-set at 200 ° C. for 3 seconds to form a laminate having a thickness of 4.5 μm. A biaxially oriented film was obtained.
Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
［実施例２］
表１に示すように、積層構成を２層から、フィルム層Ａとフィルム層Ｂとを交互に積層した５０層に変更した以外は実施例１と同様にして積層二軸配向フィルムを得た。得られた積層二軸配向フィルムの特性を表１に示す。
[Example 2]
As shown in Table 1, a laminated biaxially oriented film was obtained in the same manner as in Example 1 except that the laminated structure was changed from 2 layers to 50 layers in which film layers A and B were alternately laminated. Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
［実施例３］
ジカルボン酸成分としてテレフタル酸ジメチル、ジオール成分としてエチレングリコールと１，４−シクロヘキサンジメタノールをチタンテトラブトキシドの存在下でエステル交換反応を行い、さらに引き続いて重縮合反応を行って、固有粘度０．６２ｄｌ／ｇのシクロヘキサンジメタノールを共重合せしめた共重合ポリエステルを得て、これを樹脂Ａ´−３とした。樹脂Ａ´−２の各成分は、モル比で、テレフタル酸成分：ナフタレンジカルボン酸成分が１００：０、シクロヘキサンジメタノール成分：エチレングリコール成分が４５：５５である。
こうして得られた樹脂Ａ´−２を用いて、樹脂Ａ´−２と樹脂Ｂ−１とを重量比４５：５５になるようにブレンドし、樹脂Ａ−２を作成し、この樹脂Ａ−２を樹脂Ａ−１の代わりに用いた以外は、実施例２と同様にして二軸配向フィルムを得た。得られた積層二軸配向フィルムの特性を表１に示す。
[Example 3]
A transesterification reaction of dimethyl terephthalate as the dicarboxylic acid component and ethylene glycol and 1,4-cyclohexanedimethanol as the diol component in the presence of titanium tetrabutoxide, followed by a polycondensation reaction, an intrinsic viscosity of 0.62 dl / G of cyclohexanedimethanol was obtained, and this was designated as Resin A′-3. The components of the resin A′-2 are in a molar ratio of terephthalic acid component: naphthalenedicarboxylic acid component of 100: 0 and cyclohexanedimethanol component: ethylene glycol component of 45:55.
Using the resin A′-2 thus obtained, the resin A′-2 and the resin B-1 are blended so as to have a weight ratio of 45:55 to prepare a resin A-2. A biaxially oriented film was obtained in the same manner as in Example 2 except that was used instead of Resin A-1. Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
［実施例４］
樹脂Ａ´−２と樹脂Ｂ−１とを重量比７３：２７になるようにブレンドし、樹脂Ａ−３を作成し、樹脂Ａ−１の代わりに樹脂Ａ−３を用いた以外は、実施例２と同様にして二軸配向フィルムを得た。得られた積層二軸配向フィルムの特性を表１に示す。
[Example 4]
Resin A′-2 and resin B-1 were blended in a weight ratio of 73:27 to prepare resin A-3, except that resin A-3 was used instead of resin A-1. A biaxially oriented film was obtained in the same manner as in Example 2. Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
［実施例５］
樹脂Ａ´−１と樹脂Ｂ−１とを重量比５８：４２になるようにブレンドし、樹脂Ａ−４を作成し、樹脂Ａ−１の代わりに樹脂Ａ−４を用い、吐出量の比を樹脂Ａ：樹脂Ｂが表１に示す厚み比になるようにした以外は、実施例２と同様にして二軸配向フィルムを得た。得られた積層二軸配向フィルムの特性を表１に示す。
[Example 5]
The resin A′-1 and the resin B-1 are blended so as to have a weight ratio of 58:42, a resin A-4 is prepared, and the resin A-4 is used instead of the resin A-1, and the ratio of the discharge amount A biaxially oriented film was obtained in the same manner as in Example 2 except that resin A: resin B had a thickness ratio shown in Table 1. Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
［比較例１］
ジカルボン酸成分としてテレフタル酸ジメチル、ジオール成分としてエチレングリコールと１，４−シクロヘキサンジメタノールをチタンテトラブトキシドの存在下でエステル交換反応を行い、さらに引き続いて重縮合反応を行って、固有粘度０．６２ｄｌ／ｇのシクロヘキサンジメタノールを共重合せしめた共重合ポリエステルを得て、これを樹脂Ａ´−５とした。樹脂Ａ´−５の各成分は、モル比で、テレフタル酸成分：ナフタレンジカルボン酸成分が１００：０、シクロヘキサンジメタノール成分：エチレングリコール成分が５５：４５である。
こうして得られた樹脂Ａ´−５を用いて、樹脂Ａ´−５と樹脂Ｂ−１とを重量比８４：１６になるようにブレンドし、樹脂Ａ−５を作成し、この樹脂Ａ−５を樹脂Ａ−１の代わりに用いた以外は、実施例２と同様にして二軸配向フィルムを得た。得られた積層二軸配向フィルムの特性を表１に示す。
[Comparative Example 1]
A transesterification reaction of dimethyl terephthalate as the dicarboxylic acid component and ethylene glycol and 1,4-cyclohexanedimethanol as the diol component in the presence of titanium tetrabutoxide, followed by a polycondensation reaction, an intrinsic viscosity of 0.62 dl / G cyclohexane dimethanol copolymerized polyester was obtained, and this was designated as resin A′-5. The components of the resin A′-5 are molar ratios of terephthalic acid component: naphthalenedicarboxylic acid component 100: 0, cyclohexanedimethanol component: ethylene glycol component 55:45.
Using the resin A′-5 thus obtained, the resin A′-5 and the resin B-1 were blended so as to have a weight ratio of 84:16 to prepare a resin A-5. This resin A-5 A biaxially oriented film was obtained in the same manner as in Example 2 except that was used instead of Resin A-1. Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
［比較例２］
樹脂Ａ´−１と樹脂Ｂ−１とを重量比９６：４になるようにブレンドし、樹脂Ａ−６を作成し、樹脂Ａ−１の代わりに樹脂Ａ−６を用い、吐出量の比を表1に示す厚み比になるようにした以外は、実施例２と同様にして二軸配向フィルムを得た。得られた積層二軸配向フィルムの特性を表１に示す。
[Comparative Example 2]
The resin A′-1 and the resin B-1 are blended so as to have a weight ratio of 96: 4 to prepare a resin A-6, and the resin A-6 is used instead of the resin A-1, and the ratio of the discharge amount A biaxially oriented film was obtained in the same manner as in Example 2 except that the thickness ratio was as shown in Table 1. Table 1 shows the characteristics of the obtained laminated biaxially oriented film.
表１中の表層Ａ層は樹脂Ａからなる最表層に位置するフィルム層Ａの厚み、内層Ａ層は最表層に位置しない各フィルム層Ａの厚みを測定し、それから算出した厚みの平均値、内層Ｂ層は最表層に位置しない各フィルム層Ｂの厚みを測定し、それから算出した厚みの平均値、表層Ｂ層は樹脂Ｂからなる最表層に位置するフィルム層Ｂの厚みを示す。また、表１中のＴＡはテレフタル酸成分、ＮＤＣはナフタレンジカルボン酸成分、ＣＨＤＭはシクロヘキサンジメタノール成分、ＥＧはエチレングリコール成分、ＲａＢは最表層に位置するフィルム層Ｂの表面粗さ、ＲａＡは最表層に位置するフィルム層Ａの表面粗さ、ＣＴＥは温度膨張係数、ＣＨＥは湿度膨張係数を意味する。 In Table 1, the surface layer A layer is the thickness of the film layer A located on the outermost layer made of the resin A, the inner layer A layer is the thickness of each film layer A that is not located on the outermost layer, and the average value of the thicknesses calculated therefrom, The inner layer B layer measures the thickness of each film layer B that is not positioned on the outermost layer, and the average value of the thicknesses calculated therefrom, and the surface layer B layer indicates the thickness of the film layer B that is positioned on the outermost layer made of the resin B. In Table 1, TA is the terephthalic acid component, NDC is the naphthalene dicarboxylic acid component, CHDM is the cyclohexanedimethanol component, EG is the ethylene glycol component, RaB is the surface roughness of the film layer B located on the outermost layer, and RaA is the highest. The surface roughness of the film layer A located in the surface layer, CTE means a temperature expansion coefficient, and CHE means a humidity expansion coefficient.
本発明の積層フィルムは、優れた寸法安定性と表面平坦性とを有し、カールが小さく高温での加工性にも優れることから、高密度磁気記録テープのベースフィルムなどに、好適に使用することができる。 The laminated film of the present invention has excellent dimensional stability and surface flatness, is small in curl and excellent in workability at high temperatures, and therefore is suitably used for a base film of a high-density magnetic recording tape. be able to.
Claims (5)
フィルム層Ａを構成する樹脂成分Ａが、
全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、７５：２５〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、４０：６０〜９０：１０の範囲である樹脂Ａ´とポリエチレンテレフタレートとを
全酸成分のテレフタル酸成分と２，６−ナフタレンジカルボン酸成分のモル比が、９０：１０〜１００：０の範囲で、全グリコール成分の１，４−シクロヘキサンジメタノール成分とエチレングリコール成分のモル比が、１２：８８〜４０：６０となるように溶融混練したものである積層フィルム。 A laminated film in which a film layer A and a film layer B made of polyethylene terephthalate are laminated,
The resin component A constituting the film layer A is
The molar ratio of the terephthalic acid component of the total acid component to the 2,6-naphthalenedicarboxylic acid component is in the range of 75:25 to 100: 0, and the moles of the 1,4-cyclohexanedimethanol component of the total glycol component and the ethylene glycol component. Resin A ′ having a ratio in the range of 40:60 to 90:10 and polyethylene terephthalate. The molar ratio of the total terephthalic acid component to the 2,6-naphthalenedicarboxylic acid component is 90:10 to 100: 0. In this range, the laminated film is melt-kneaded so that the molar ratio of the 1,4-cyclohexanedimethanol component and the ethylene glycol component of the total glycol component is 12:88 to 40:60.
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