JPH0367630A - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester filmInfo
- Publication number
- JPH0367630A JPH0367630A JP20529389A JP20529389A JPH0367630A JP H0367630 A JPH0367630 A JP H0367630A JP 20529389 A JP20529389 A JP 20529389A JP 20529389 A JP20529389 A JP 20529389A JP H0367630 A JPH0367630 A JP H0367630A
- Authority
- JP
- Japan
- Prior art keywords
- film
- stretching
- mol
- longitudinal direction
- stretched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 19
- 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 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 abstract description 14
- 239000004615 ingredient Substances 0.000 abstract 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 112
- 238000009998 heat setting Methods 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 210000001685 thyroid gland Anatomy 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱性、機械的強度および製膜連続性に優れ
た二軸配向ポリエステルフィルムに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a biaxially oriented polyester film that has excellent heat resistance, mechanical strength, and film formation continuity.
〔従来の技術および発明が解決しようとする課題〕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）は、ポリエチレンテレフタレート
（以下ＰＥＴと略す）と比べ融点（Ｔｍ）が５〜３５°
Ｃ高く、またガラス転移温度（Ｔｇ）も５〜２５°Ｃ高
いことが報告されている（Ｊ、Ｐｏｌｙｍｅｒ Ｓｃ
ｉ、Ｃ０６，１７、（１９６４））。すなわち、ＰＣＴ
フィルムはＰＥＴフィルムよりも耐熱性の点で優れたフ
ィルムである。[Prior art and problems to be solved by the invention] Poly(1,4-cyclohexane dimethylene terephthalate)
(hereinafter abbreviated as PCT) has a melting point (Tm) of 5 to 35° compared to polyethylene terephthalate (hereinafter abbreviated as PET).
It has been reported that the glass transition temperature (Tg) is 5 to 25°C higher (J, Polymer Sc
i, C06, 17, (1964)). That is, P.C.T.
The film has better heat resistance than PET film.
しかしながら強度に関しては、ＰＣＴフィルムはＰＥＴ
フィルムよりもかなり低く、例えばヤング率で比較する
と、ＰＥＴフィルムが６．８Ｘ１０５ｐｓｊ （＝ ４
８０ ｋｇ／ｍｍ” ）であるのに対し、ＰＣＴフィル
ムは４．ＯＸ １０’ ｐｓｉ（＞２８０ｋｇ／ｍｍ”
）であり、ＰＥＴの６割程度の強度であることが報告
されている（Ｓｏｃ、Ｐｌａｓｔｉｃｓ Ｅｎｇｒｓ
、Ｊ、ユ１０８３ （１９６１））。フィルムの強度、
特にヤング率は工業的にフィルムを連続加工する際には
非常に重要なファクターであり、ヤング率が小さい場合
には巻き出し、巻き取り、あるいは種々の加工時に加わ
る張力により、フィルムが不可逆的に伸びてしまうこと
もある。However, in terms of strength, PCT film is comparable to PET film.
It is much lower than that of film, for example, when comparing Young's modulus, PET film has 6.8X105 psj (= 4
80 kg/mm”), while PCT film has a 4.OX 10’ psi (>280 kg/mm”)
), and it is reported that the strength is about 60% that of PET (Soc, Plastics Engrs
, J. Yu 1083 (1961)). film strength,
In particular, Young's modulus is a very important factor when continuously processing films industrially, and if Young's modulus is small, the tension applied during unwinding, winding, or various processing may cause irreversible damage to the film. It may even stretch.
このため、特にフィルムの長平方向のヤング率は大きい
程好ましいが、ＰＣＴフィルムでは、従来２８０ ｋｇ
／ｎ＋＋ｉ”程度のヤング率のものしか知られていなか
った。For this reason, the Young's modulus in the longitudinal direction of the film is preferably as large as possible;
Only those having a Young's modulus of about /n++i'' were known.
本発明者らは、上記課題を解決すべく検討を行なった結
果、ある特定の密度及び複屈折率を有するフィルムが、
耐熱性に優れ、しかも従来知られているＰＣＴフィルム
よりも高強度であることを見出し、本発明を完成するに
至った。The present inventors conducted studies to solve the above problems, and found that a film having a certain density and birefringence index is
The present inventors have discovered that the film has excellent heat resistance and has higher strength than conventionally known PCT films, leading to the completion of the present invention.
すなわち本発明の要旨は、酸成分の８０モル％以上がテ
レフタル酸、グリコール成分の９０モル％以上が１，４
−シクロヘキサンジメタノールで構成されたポリエステ
ルフィルムであって、該フィルムの密度が１．２２０〜
１．２５０ ｇ／ｄ、複屈折率が０．０１０〜０．０４
０であり、かつフィルム長手方向のヤング率が３１０〜
４” ＯＯｋｇ／ ｍｓ”であることを特徴とする二軸
配向ポリエステルフィルムに存する。That is, the gist of the present invention is that 80 mol% or more of the acid component is terephthalic acid, and 90 mol% or more of the glycol component is 1,4
- A polyester film composed of cyclohexanedimethanol, the film having a density of 1.220 to
1.250 g/d, birefringence 0.010-0.04
0, and the Young's modulus in the longitudinal direction of the film is 310~
4"OOkg/ms".
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のポリエステルフィルムは、その酸成分の８０モ
ル％以上がテレフタル酸で構成されたフィルムであり、
好ましくは９０モル％以上、更に好ましくは９５モル％
以上がテレフタル酸で構成されたフィルムである。酸成
分中のテレフタル酸含有量が８０モル％未満である場合
にはポリマーの結晶性を低下させてしまい、耐熱性に悪
影響を及ぼす。なお、上記範囲を満せば、第３成分とし
て、イソフタル酸、２．６−あるいは２，７−ナフタレ
ンジカルボン酸、４，４′−ビフェニルジカルボン酸等
の芳香族ジカルボン酸、あるいはｐ−ヒドロキシ安息香
酸等の芳香族ヒドロキシ酸を共重合成分としてポリマー
中に含有していてもよい。The polyester film of the present invention is a film in which 80 mol% or more of the acid component is composed of terephthalic acid,
Preferably 90 mol% or more, more preferably 95 mol%
The above is a film made of terephthalic acid. If the terephthalic acid content in the acid component is less than 80 mol%, the crystallinity of the polymer will be reduced, which will have an adverse effect on heat resistance. In addition, as long as the above range is satisfied, aromatic dicarboxylic acids such as isophthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or p-hydroxybenzoic acid can be used as the third component. Aromatic hydroxy acids such as acids may be contained in the polymer as a copolymerization component.
また、本発明のポリエステルフィルムはそのグリコール
成分中の９０モル％以上がシクロヘキサンジメタノール
で構成されていることが必要であり、グリコール成分の
シクロヘキサンジメタノールの含有量は好ましくは９５
モル％以上、更に好ましくは９７モル％以上である。グ
リコール成分中のシクロヘキサンジメタノールの含有量
が９０モル％未満では、酸成分の場合と同様にポリマー
の結晶性が低下し、耐熱性に悪影響が及ぶ。Further, in the polyester film of the present invention, it is necessary that 90 mol% or more of the glycol component is composed of cyclohexanedimethanol, and the content of cyclohexanedimethanol in the glycol component is preferably 95% by mole.
It is mol% or more, more preferably 97 mol% or more. If the content of cyclohexanedimethanol in the glycol component is less than 90 mol %, the crystallinity of the polymer decreases, as in the case of the acid component, and the heat resistance is adversely affected.
本発明における１、４−シクロヘキサンジメタノールの
シス−トランス分率は、５０モル％以上がトランスであ
ることが好ましい、シス体が多い場合には、特に融点の
低下が著しく、高温での耐熱性が不足してしまう。The cis-trans fraction of 1,4-cyclohexanedimethanol in the present invention is preferably 50 mol% or more trans.If the cis-trans fraction is large, the melting point will be particularly low, and the heat resistance at high temperatures will be reduced. will be in short supply.
本発明におけるＰＣＴポリマーの重合方法は、公知のポ
リエステルの溶融重合方法を用いることができるが、熱
劣化を最小に抑えるため、溶融重合と固相重合を併用し
て所望の重合度とする方法も採用できる。また、本発明
のフィルムの重合度は、その極限粘度、すなわちフェノ
ール：テトラクロルエタン＝１：１（重量比）の溶液中
３０℃で測定しＨｉｉｇｇｉｎｓ定数を０．３３とした
値が０．４５以上好ましくは０．６０以上であることが
好ましい。極限粘度が０．４５未満である場合には、二
軸配向フィルムを得ようとする際に延伸性が劣るので好
ましくない。The method of polymerizing the PCT polymer in the present invention can be a known polyester melt polymerization method, but in order to minimize thermal deterioration, a method of combining melt polymerization and solid phase polymerization to achieve the desired degree of polymerization is also possible. Can be adopted. The degree of polymerization of the film of the present invention is determined by its intrinsic viscosity, which is 0.45 when measured at 30°C in a solution of phenol:tetrachloroethane=1:1 (weight ratio) and assuming Higgins' constant as 0.33. More preferably, it is 0.60 or more. If the intrinsic viscosity is less than 0.45, it is not preferable because the stretchability is poor when attempting to obtain a biaxially oriented film.
本発明のポリエステルフィルムには、ポリエステルに対
して不活性な微粒子を必要に応じて含有させることがで
きる。この微粒子には、無機あるいは有機の粒子、具体
的にはカオリン、タルク、二酸化ケイ素、炭酸カルシウ
ム、フッ化リチウム、二酸化チタン、ゼオライト、テレ
フタル酸カルシウム、架橋性高分子等から選択でき、ま
たその含有量、平均粒径も用途・必要に応じて適宜選択
できる。The polyester film of the present invention can contain fine particles that are inactive with respect to polyester, if necessary. These fine particles can be selected from inorganic or organic particles, specifically kaolin, talc, silicon dioxide, calcium carbonate, lithium fluoride, titanium dioxide, zeolite, calcium terephthalate, crosslinked polymers, etc. The amount and average particle size can also be selected as appropriate depending on the application and necessity.
本発明のポリエステルフィルムは、その密度が１．２２
０〜１．２５０ ｇ／ａＡの範囲であり、好ましくは１
．２２４〜１．２４０ｇ／ｃｊの範囲一である。密度が
１．２２０ｇ／ｄ未満である場合には、結晶化が不足し
て充分な耐熱性を得ることができない。The polyester film of the present invention has a density of 1.22
The range is 0 to 1.250 g/aA, preferably 1
．． The range is 224 to 1.240 g/cj. If the density is less than 1.220 g/d, sufficient heat resistance cannot be obtained due to insufficient crystallization.
また１、２５０ｇ／ｃ＋ａを超えることは通常困難では
あるが、製造したとしても結晶化が進行し過ぎ、フィル
ム自体が脆くなり、実用的でない。Although it is usually difficult to exceed 1,250 g/c+a, even if it is produced, crystallization will progress too much and the film itself will become brittle, making it impractical.
本発明のポリエステルフィルムの複屈折率（Δｎ）は０
．０１０〜０．０４０の範囲であることが必要である。The birefringence index (Δn) of the polyester film of the present invention is 0
．． It needs to be in the range of 0.010 to 0.040.
この複屈折率（Δｎ）は、ａｂｂｅの屈折計でフィルム
の長手方向及びそれと直角方向の屈折率を測定し、その
差を算出することで求めることができる。複屈折率（Δ
ｎ）が、０．０１０より小さい場合には、長平方向の強
度が不足であり、複屈折率（Δｎ）が０．０４０を超え
る場合には、フィルムの製膜時に、幅方向の延伸性が著
しるしく低下し、好ましくない。本発明のポリエステル
フィルムの複屈折率（Δｎ）は０．０１５〜０゜０３０
の範囲が更に好ましい。This birefringence (Δn) can be determined by measuring the refractive index of the film in the longitudinal direction and in the direction perpendicular thereto using an ABBE refractometer, and calculating the difference therebetween. Birefringence (Δ
When n) is smaller than 0.010, the strength in the longitudinal direction is insufficient, and when the birefringence index (Δn) exceeds 0.040, the stretchability in the width direction is insufficient during film formation. This is a significant decrease, which is not desirable. The birefringence (Δn) of the polyester film of the present invention is 0.015 to 0°030
The range is more preferable.
次に本発明の二軸配向ポリエステルの製造方法を詳述す
る。Next, the method for producing biaxially oriented polyester of the present invention will be described in detail.
本発明のポリエステルフィルムは、長平方向に充分に分
子配向させることが必要であるため、この方向の延伸は
、通常二段階で行われるが、更に多段で行うことも可能
である。例えば二段階で延伸する処方は、大別して２種
類の方法が可能である。まず１つの方法は、未延伸シー
トをロール延伸により長手方向に延伸する際に、二段延
伸を行う方法である。この場合、１段目の延伸を、フィ
ルムの実質温度が１００〜１２０°Ｃの範囲となるよう
に加熱し、１．５〜３．０倍に延伸する。次いで２段目
の延伸を、１段目より低温且つフィルムの実質温度が９
０〜１０５°Ｃの範囲となるように加熱し、１．４〜２
．５倍に延伸する。この際に長手方向の総合延伸倍率は
、３．３〜５．０倍に設定するのが好ましく、５．０倍
を超えると幅方向の延伸性が悪くなり、また３、３倍未
満では充分な分子配向が得られない。１段目と２段目の
延伸倍率の分配は、より低温で延伸を行う２段目の倍率
を大きくすると、フィルム内に微少なりランクやボイド
ができ易くなるため、２段目の倍率を総合延伸倍率の５
０％を超えて設定するのは好ましくない。また、延伸時
のフィルムの実質温度は、フィルムの厚み、ラインスピ
ード等によって最適温度が異るが、般的にフィルムが厚
く、ラインスピードが速い時は、やや高めに温度を設定
すると良い。さらに１段目の延伸が終了直後、フィルム
の実質温度がガラス転移点温度以下になるよう冷却し、
次いで２段目の延伸のための予熱を行うことが、温度制
御の容易さ及びフィルムの結晶化防止の点で好ましい。Since it is necessary for the polyester film of the present invention to have sufficient molecular orientation in the longitudinal direction, stretching in this direction is usually carried out in two stages, but it can also be carried out in more stages. For example, two-stage stretching formulations can be broadly classified into two types. First, one method is to perform two-stage stretching when stretching an unstretched sheet in the longitudinal direction by roll stretching. In this case, in the first stage of stretching, the film is heated so that the actual temperature of the film is in the range of 100 to 120°C, and the film is stretched 1.5 to 3.0 times. Next, the second stage of stretching is carried out at a temperature lower than that of the first stage and the actual temperature of the film is 9.
Heat to a temperature in the range of 0 to 105°C, 1.4 to 2
．． Stretch 5 times. At this time, it is preferable to set the overall stretching ratio in the longitudinal direction to 3.3 to 5.0 times; if it exceeds 5.0 times, the stretchability in the width direction will deteriorate, and if it is less than 3 times, it will be insufficient. molecular orientation cannot be obtained. The distribution of the stretching ratios in the first and second stages is such that if the stretching ratio in the second stage, which is stretched at a lower temperature, is increased, small ranks or voids are likely to be formed in the film, so the ratio in the second stage should be Stretching ratio of 5
It is not preferable to set it above 0%. Further, the optimum actual temperature of the film during stretching differs depending on the thickness of the film, line speed, etc., but in general, when the film is thick and the line speed is fast, it is better to set the temperature a little higher. Immediately after the first stage of stretching is completed, the film is cooled to a temperature below the glass transition temperature.
Next, it is preferable to perform preheating for the second stage of stretching in terms of ease of temperature control and prevention of crystallization of the film.
またこれらの延伸の際に、加熱ロールが高温であるとフ
ィルムがロールに粘着してしまうことがあるが、このよ
うな時には、ロールの材質を非粘着性のものに変えて延
伸することも可能である。Also, during stretching, if the heating roll is at a high temperature, the film may stick to the roll, but in such cases it is also possible to change the material of the roll to a non-adhesive material and stretch. It is.
非粘着ロールには、表面がマット加工された硬質クロム
メツキロールやセラミック製のロール及びエラストマー
ロール、フッ素樹脂ロール等が使用できる。As the non-adhesive roll, a hard chrome plated roll with a matte surface, a ceramic roll, an elastomer roll, a fluororesin roll, etc. can be used.
かくして得られた、長平方向に２段階で延伸した後のフ
ィルムは、その複屈折率（Δｎ）が０．０７０−０．１
００、かつ、フィルムの平均屈折率が１、５５５０〜１
．５６１０の範囲にあることが好ましい。この範囲にあ
るフィルムは、後述する幅方向の延伸を行った後に、強
度に優れたフィルムになる他、厚みの均一性に優れ、し
かも幅方向の延伸性も良好なものとなる。The thus obtained film after being stretched in two steps in the longitudinal direction has a birefringence index (Δn) of 0.070-0.1.
00, and the average refractive index of the film is 1,5550-1
．． It is preferably in the range of 5610. A film within this range, after being stretched in the width direction as described below, will not only have excellent strength but also excellent uniformity in thickness and good stretchability in the width direction.
幅方向の延伸は、通常いわゆるテンター法で行い、設定
倍率は３．５〜４．０倍の範囲から選択し、延伸後の実
質倍率ができるだけ設定倍率に近くなるように延伸温度
を決めると良い。この延伸温度は通常９５〜１１５°Ｃ
の範囲から選択できるが、一般的にフィルムが厚い程、
高い延伸温度が必要となる。Stretching in the width direction is usually carried out by the so-called tenter method, the set magnification is selected from the range of 3.5 to 4.0 times, and the stretching temperature is preferably determined so that the actual magnification after stretching is as close to the set magnification as possible. . This stretching temperature is usually 95-115°C
You can choose from a range of , but generally speaking, the thicker the film, the
High stretching temperatures are required.
このようにして得られた二軸配向ポリエステルフィルム
は、次に熱固定することで、耐熱性を飛躍的に向上させ
ることができる。熱固定には、幅方向の延伸と同様にテ
ンター法で行なうことが一般的であり、その条件は、１
８０〜２６０°Ｃ１好ましくは２２０〜２５０°Ｃの温
度で、１秒〜５分間熱風を当てて、フィルムの密度が１
．２２０〜１゜２５０ｇ／ｃ＋ａ、好ましくは１．２２
４〜１．２４０ ｇ／ ｃ＋ｌｌの範囲となるよう行う
。またこの際に幅方向の熱収縮率を改善する目的で、熱
固定をしながら、幅方向に３〜５％の弛緩処理を行うこ
とも可能である。熱固定温度については、ＰＣＴの融点
がＰＥＴと比べて高いことに関係して、ＰＣＴフィルム
では２５０″Ｃ程度までは後述するフィルムの面配向（
ΔＰ）を低下させずに熱固定することができる。ＰＥＴ
フィルムでは、２４０″Ｃの熱固定温度ではフィルム面
配向（ΔＰ）が低下し始めることが知られており、ＰＣ
Ｔフィルムの場合は上述のように熱固定温度を高く設定
できるため、良好な耐熱性が得られると考えられる。The biaxially oriented polyester film obtained in this manner can be then heat-set to dramatically improve its heat resistance. Heat setting is generally carried out by the tenter method, similar to the width direction stretching, and the conditions are 1.
Apply hot air at a temperature of 80 to 260°C, preferably 220 to 250°C, for 1 second to 5 minutes to reduce the density of the film to 1.
．． 220~1゜250g/c+a, preferably 1.22
It is carried out so that it is in the range of 4 to 1.240 g/c+ll. Further, at this time, for the purpose of improving the heat shrinkage rate in the width direction, it is also possible to perform a relaxation treatment of 3 to 5% in the width direction while heat setting. As for the heat setting temperature, since the melting point of PCT is higher than that of PET, PCT film can be heated up to about 250"C due to the film's planar orientation (described later).
Heat fixation can be performed without reducing ΔP). PET
It is known that film plane orientation (ΔP) begins to decrease at a heat setting temperature of 240″C, and PC
In the case of T film, the heat setting temperature can be set high as described above, so it is thought that good heat resistance can be obtained.
かくして得られる二軸配向ポリエステルフィルムは、長
手方向のヤング率が３１０〜３７０ｋｇ／ｍ−であり、
従来知られているＰＣＴフィルムよりも１０〜３０％程
度強度に優れるものとなる。The biaxially oriented polyester film thus obtained has a Young's modulus in the longitudinal direction of 310 to 370 kg/m,
The strength is about 10 to 30% better than conventionally known PCT films.
また、フィルムの長手方向へ分子配向を付与する方法と
して、二輪延伸を行い、次いで低い温度で熱固定を行な
った後のフィルムを、再度長手方向に延伸（以後再延伸
と略称する）する方法もある。この場合、再延伸をする
ための二輪延伸フィルムの配向は、複屈折率（Δｎ）で
−ｏ、ｏｉｏ〜０、０３０であるような縦横バランスフ
ィルム乃至は長手方向にやや優位に配向しているものが
好ましい。複屈折率（Δｎ）が−０，０１０未満である
二輪延伸フィルムでは、再延伸を行なってもヤング率が
３１０ ｋｇ／ｍｎ＋”を超えないことがあり、また、
０．０３０を超える複屈折率（Δｎ）を有する二輪延伸
フィルムでは、既に長手方向に高配向しており、更なる
再延伸より長手方向に非常に裂は易いフィルムとなって
好ましくない。再延伸を行うための二輪延伸フィルムの
製造方法は、従来から知られている、縦・横１段ずつで
行う遂時二軸延伸または同時二輪延伸によって製造され
たものでもよいし、前述したような、長手方向に２段階
で延伸しである二輪延伸フィルムであってもよい。Another method for imparting molecular orientation in the longitudinal direction of a film is to perform two-wheel stretching, then heat set at a low temperature, and then stretch the film again in the longitudinal direction (hereinafter referred to as re-stretching). be. In this case, the orientation of the two-wheel stretched film for re-stretching is a vertically and horizontally balanced film with a birefringence index (Δn) of -0, oio to 0,030, or a slightly predominant orientation in the longitudinal direction. Preferably. In a two-wheel stretched film with a birefringence index (Δn) of less than -0,010, the Young's modulus may not exceed 310 kg/mn+'' even after re-stretching, and
A two-wheel stretched film having a birefringence index (Δn) exceeding 0.030 is already highly oriented in the longitudinal direction, and further re-stretching results in a film that is extremely susceptible to tearing in the longitudinal direction, which is undesirable. The two-wheel stretched film for re-stretching may be produced by conventionally known final biaxial stretching or simultaneous two-wheel stretching performed in one vertical and one horizontal step, or as described above. Alternatively, it may be a two-wheel stretched film that is stretched in two stages in the longitudinal direction.
特に後者の方法で、０．０１０〜０．０２０の複屈折率
（△ｎ）を有するフィルムを再延伸した場合、再延伸も
含めた製膜連続性が良好で、しかも長手方向の強度・ヤ
ング率に優れたフィルムとなり好ましい。In particular, when a film with a birefringence (△n) of 0.010 to 0.020 is re-stretched using the latter method, the continuity of film formation including re-stretching is good, and the strength in the longitudinal direction and the This is preferable since it becomes a film with excellent ratio.
再延伸により、強度・ヤング率を向上させるには、二軸
延伸したフィルムをあらかじめ１２０〜１４０ ’Ｃの
低い温度で１秒〜１分間熱固定することが必要である。In order to improve the strength and Young's modulus by re-stretching, it is necessary to heat set the biaxially stretched film in advance at a low temperature of 120 to 140'C for 1 second to 1 minute.
この熱固定温度が１２０°Ｃ未満では、フィルムの結晶
化が不足して、再延伸の効果が不充分であり、１４０°
Ｃを超える場合には逆に結晶化が促進され過ぎて、再延
伸することができなくなる。If this heat setting temperature is less than 120°C, the crystallization of the film will be insufficient and the effect of re-stretching will be insufficient;
If it exceeds C, on the contrary, crystallization is promoted too much and re-stretching becomes impossible.
再延伸には、ロール延伸法を用いることが好ましく、こ
の場合、フィルムの実質温度を前述した低温度での熱固
定温度よりも５〜１５°Ｃ低い温度になるよう加熱ある
いは冷却した後、１．０５〜１゜３０倍の倍率で長手方
向に延伸すると良い。この際に、延伸時の応力により、
延伸ロールの表面をフィルムが滑る現象が見られるとき
には、延伸ロールの適当な位置に、ゴム材質でできた対
向ロールを設置するか、あるいは、静電印加装置を設置
して、フィルムを延伸ロールに密着させて再延伸を行う
必要がある。上記方法のうち、特に静電印加により密着
させる方法は、フィルム表面にキズをつけることが少な
く好ましい。It is preferable to use a roll stretching method for re-stretching. In this case, the film is heated or cooled to a temperature 5 to 15°C lower than the above-mentioned low temperature heat-setting temperature, and then 1 It is preferable to stretch in the longitudinal direction at a magnification of .05 to 1.30 times. At this time, due to stress during stretching,
If the phenomenon of the film slipping on the surface of the stretching roll is observed, install a counter roll made of rubber material at an appropriate position on the stretching roll, or install an electrostatic application device to prevent the film from sliding on the stretching roll. It is necessary to bring them into close contact and re-stretch them. Among the above methods, the method of adhesion by electrostatic application is particularly preferable because it causes less damage to the film surface.
再延伸を行なったフィルムは、次にテンター内で１８０
〜２６０℃、好ましくは２２０〜２５０°Ｃの温度で、
１秒〜５分間熱風を当てて、熱固定を行う。この時熱固
定後のフィルムの密度が１．２２０〜１．２５０ ｇ／
ｃｔＡ好ましくは１．２２４〜１．２４０ｇ／ｃ＋ａの
範囲となるように熱固定を施す。また、必要に応じて、
フィルムの幅方向に弛緩処理を行うこともできる。The re-stretched film is then heated to 180° in a tenter.
at a temperature of ~260°C, preferably 220-250°C,
Heat-fix by applying hot air for 1 second to 5 minutes. At this time, the density of the film after heat setting is 1.220 to 1.250 g/
Heat setting is performed so that the ctA is preferably in the range of 1.224 to 1.240 g/c+a. Also, if necessary,
Relaxation treatment can also be performed in the width direction of the film.
かくして得られた二軸配向ポリエステルフィルムは、長
手方向のヤング率が３１０〜４００ｋｇ／ＩＩＩＩＩ＋
２となり、従来知られているＰＣＴフィルムよりも１０
〜４０％程度、高強度のものとなる。また、再延伸によ
り長平方向のヤング率を向上させた場合には、前述した
長手方向に２段延伸を行なってヤング率を向上させた場
合と比べて、幅方向のヤング率の低下が少ない場合が多
く好ましい。The thus obtained biaxially oriented polyester film has a longitudinal Young's modulus of 310 to 400 kg/III+
2, which is 10 times higher than the conventionally known PCT film.
It has a high strength of about 40%. In addition, when the Young's modulus in the longitudinal direction is improved by re-stretching, the decrease in the Young's modulus in the transverse direction is smaller than when the Young's modulus is improved by performing two-step stretching in the longitudinal direction as described above. It is preferable because there are many.
本発明の二軸延伸ポリエステルフィルムは、ヤング率が
大きいため、特に厚みが２５μｍ以下の薄いフィルムに
おいては、工業的に有利となるが、２５μｍ以上の厚み
を有するフイ、ルムであってもその効果は充分発揮され
る。Since the biaxially stretched polyester film of the present invention has a large Young's modulus, it is industrially advantageous, especially for thin films with a thickness of 25 μm or less, but even films with a thickness of 25 μm or more have no effect. is fully demonstrated.
以下、実施例により、更に具体的に本発明を説明するが
、本発明は、その要旨を越えない限り以下の実施例に限
定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
なお、本発明のフィルムの特性評価法を下記に示す。The method for evaluating the characteristics of the film of the present invention is shown below.
（１）複屈折率（Δｎ）１面配向度（ΔＰ）、平均屈折
率ｎ）
アタゴ光学社製ａｂｂｅ式屈折計を用い、フィルム面内
の長手方向の屈折率をｎＭＤ、それに直角方向（幅方向
）の屈折率をｎｔｏ、及びフィルムの厚さ方向の屈折率
をｎｃ、とじて測定し、次式より各々のパラメーターを
求めた。なお、屈折率の測定は、ナトリウムＤ線を用い
、２３°Ｃで行なった。(1) Birefringence (Δn) degree of one-plane orientation (ΔP), average refractive index n) Using an ABBE refractometer manufactured by Atago Optical Co., Ltd., the refractive index in the longitudinal direction in the film plane is nMD, and the direction perpendicular to it (width The refractive index in the film thickness direction was measured as nto, and the refractive index in the thickness direction of the film as nc, and each parameter was determined from the following equation. Note that the refractive index was measured using sodium D line at 23°C.
複屈折率（Δｎ）−ｎ、ｎ ｎＴＤ
面配向度（ΔＰ ） ＝ （（ｎＭＤ＋ ｎＴＤ）／２
） ｎ ＆平均屈折率（ｎ） ＝（ｎ、ｔ＋＋ｎｙ
ｏ＋ｎｚ）／３（２）フィルム密度
ｎ−へブタン−四塩化炭素の混合液を満たした密度勾配
管を用い、２５°Ｃで測定した。Birefringence (Δn) - n, nTD plane orientation degree (ΔP) = ((nMD+nTD)/2
) n & average refractive index (n) = (n, t++ny
o+nz)/3(2) Film density Measured at 25°C using a density gradient tube filled with a mixture of n-hebutane and carbon tetrachloride.
（３）フィルムのヤング率
インテスコ株製引張試験機インテスコモデル２００１型
を用いて、温度２３°Ｃ湿度５ｏ％ＲＨに調節された室
内において、長さ３００ｍｍ幅２０ｍｍの試料フィルム
を、１０％／ｍｉｎのひずみ速度で引張り、引張応力−
ひすみ曲線の初めの直線部分を用いて次の式によって計
算した。(3) Young's Modulus of Film Using a tensile tester Intesco Model 2001 manufactured by Intesco Co., Ltd., a sample film with a length of 300 mm and a width of 20 mm was tested at 10% Tensile at a strain rate of min, tensile stress -
It was calculated using the following formula using the first straight line part of the helix curve.
なお、試料フィルムは、測定時と同温度、同湿度にて２
４時間以上調温・調湿したものを使用した。In addition, the sample film was incubated at the same temperature and humidity as during the measurement.
The temperature and humidity were controlled for at least 4 hours before use.
（４）フィルムの破断強度
インテスコ■製引張試験機インテスコモデル２００１型
を用いて、温度２３°Ｃ湿度５０％ＲＨに調節された室
内において、長さ５０ｍｍ１、幅１５１の試料フィルム
を、２００ ｍｍ／ｍｉｎの速度で引張り、下記式より
求めた。(4) Breaking strength of film Using a tensile tester Intesco Model 2001 manufactured by Intesco ■, a sample film with a length of 50 mm1 and a width of 151 mm was tested in a room controlled at a temperature of 23° C. and a humidity of 50% RH. It was calculated from the following formula by pulling at a speed of /min.
破断強度−Ｆ／Ｓ（ｋｇ／ｍｍ２）
（５）熱収縮率
無張力状態で２００°Ｃ（±２°Ｃ）の雰囲気中１０分
間熱処理し、その前後のサンプルの長さを測定し、次式
で算出した。Breaking strength - F/S (kg/mm2) (5) Heat shrinkage rate Heat treated in an atmosphere of 200°C (±2°C) for 10 minutes under no tension, measured the length of the sample before and after that, and then It was calculated using the formula.
×ｌ Ｏｏ
実施例１
（ポリマーの作成）
ジカルボン酸成分としてテレフタル酸単位を９５モル％
、イソフタル酸単位を５モル％、グリコール成分として
ｃｉｓ：ｔｒａｎｓ比が１：３の１４−シクロヘキサン
ジメタノールを１００％用い、触媒として酸化チタンを
酸化成分に対して０．０６モル％添加して、重合槽中で
撹拌下加熱してエステル化した。ここで滑剤として平均
粒径１゜３０μｍのサイロイドをポリマー中０．２０ｗ
ｔ％となるように添加した後、重縮合を行い、［η］＝
０．６５のポリ（１，４−シクロヘキサンジメチレンテ
レフタレート）共重合体を得た。このポリマーをチップ
化した後、窒素気流下で固相重合を行い最終的に［η］
＝１．０５のポリエステルを得た。×l Oo Example 1 (Preparation of polymer) 95 mol% of terephthalic acid unit as dicarboxylic acid component
, using 5 mol% of isophthalic acid units, 100% of 14-cyclohexanedimethanol with a cis:trans ratio of 1:3 as the glycol component, and adding 0.06 mol% of titanium oxide to the oxidized component as a catalyst. Esterification was carried out by heating in a polymerization tank while stirring. Here, as a lubricant, 0.20w of thyroid with an average particle size of 1°30μm was added to the polymer.
After adding so that it becomes t%, polycondensation is performed, [η]=
A poly(1,4-cyclohexane dimethylene terephthalate) copolymer of 0.65 was obtained. After this polymer is made into chips, it is subjected to solid phase polymerization under a nitrogen stream and finally [η]
=1.05 polyester was obtained.
（フィルムの製膜）
上記のポリエステル乾燥した後、３０５°Ｃで溶融押出
し、４０゛Ｃに保持したキャスティングドラム上へ静電
印加冷却法を用いて密着させ、厚さ約８０μｍの未延伸
シートを得た。この未延伸シートを、表面がフッ素系樹
脂で非粘着加工され、１１０’Ｃに調節されたロール上
に接触させ予熱した後、赤外線ヒーターを照射しつつ周
速差のあるロール間で２．５０倍長手方向に延伸した。(Film production) After drying the above polyester, it was melt-extruded at 305°C and adhered to a casting drum maintained at 40°C using an electrostatic cooling method to form an unstretched sheet with a thickness of approximately 80 μm. Obtained. This unstretched sheet was brought into contact with a roll whose surface was treated with a non-adhesive fluororesin and was adjusted to 110'C and preheated, and then heated at 2.50°C between the rolls with a difference in circumferential speed while irradiating with an infrared heater. Stretched twice in the longitudinal direction.
この時、延伸区間にあるフィルムの実質温度を輻射温度
計にて測定したところ１１０°Ｃであった。この延伸フ
ィルムを一旦ガラス転移点温度以下に冷却した後、再び
９０°Ｃに調節された金属ロール上に接触させて予熱し
、赤外線ヒーターを照射しつつ、１゜８０倍長手方向に
更に延伸した。この時のフィルムの実質温度は９０ ’
Ｃであった。この２段延伸後のフィルムの複屈折率（Δ
ｎ）は０．０９６で、平均屈折率（ｎ）は１．５５８１
であった。次にこの延伸フィルムをテンターに導き、１
００℃で３．６０倍幅方向に延伸した。更に続けて、２
５０’Ｃで約１０秒間熱固定を行い、厚さ５μｍの二軸
配向フィルムを得た。また、熱固定時に幅方向に３％の
弛緩処理を行なった。このフィルム物性を表１に示す。At this time, the actual temperature of the film in the stretching section was measured with a radiation thermometer and found to be 110°C. After this stretched film was once cooled to below the glass transition temperature, it was again brought into contact with a metal roll adjusted to 90°C to preheat it, and further stretched 1°80 times in the longitudinal direction while irradiating it with an infrared heater. . The actual temperature of the film at this time is 90'
It was C. The birefringence index (Δ
n) is 0.096 and the average refractive index (n) is 1.5581
Met. Next, this stretched film is introduced into a tenter and 1
The film was stretched 3.60 times in the width direction at 00°C. Continuing further, 2
Heat setting was performed at 50'C for about 10 seconds to obtain a biaxially oriented film with a thickness of 5 μm. Further, during heat setting, a 3% relaxation treatment was performed in the width direction. The physical properties of this film are shown in Table 1.
実施例２
実施例１において使用したポリマーを用いて、実施例１
と同様に溶融押出・シート化を行い、厚さ約７０ｔ１ｍ
の未延伸シートを得た。この未延伸シートを、実施例１
で使用した非粘着ロールを用い、１１０″Ｃで予熱を行
なった後、赤外線ヒーターを照射しつつ長手方向に２．
００倍延伸した。この時、延伸区間のフィルム実質温度
は１１０″Ｃであった。この延伸フィルムを一旦Ｔｇ以
下に冷却した後、再び９０″Ｃに調節された金属ロール
上に接触させて予熱し、赤外線ヒーターを照射しつつ、
２．００倍長手方向に更に延伸した。この時のフィルム
の実質温度は９０°Ｃであった。この２段延伸後のフィ
ルムの複屈折率（Δｎ）は０．０９１で、平均屈折率（
ｎ）は１．５５８３であった。次にこの延伸フィルムを
テンターに導き、１１０°Ｃで３゜６０倍幅方向に延伸
した。更に続けて、２５０″Ｃで約１０秒間熱固定を行
い、厚さ５μｍの二軸配向フィルムを得た。また熱固定
時に、幅方向に３％の弛緩処理を行なった。このフィル
ムの物性を表１に示す。Example 2 Using the polymer used in Example 1, Example 1
Melt extrusion and sheeting were carried out in the same manner as above, and the thickness was approximately 70t1m.
An unstretched sheet was obtained. This unstretched sheet was prepared in Example 1.
After preheating at 110"C using the non-adhesive roll used in 2.2.
00 times stretched. At this time, the actual temperature of the film in the stretching section was 110"C. After the stretched film was once cooled to below Tg, it was again brought into contact with a metal roll adjusted to 90"C and preheated, and an infrared heater was turned on. While irradiating
It was further stretched 2.00 times in the longitudinal direction. The actual temperature of the film at this time was 90°C. The birefringence index (Δn) of the film after this two-step stretching was 0.091, and the average refractive index (
n) was 1.5583. Next, this stretched film was introduced into a tenter and stretched 3.times.60 times in the width direction at 110.degree. Further, heat setting was carried out at 250''C for about 10 seconds to obtain a biaxially oriented film with a thickness of 5 μm.Furthermore, during heat setting, a relaxation treatment of 3% in the width direction was performed.The physical properties of this film were It is shown in Table 1.
実施例３
実施例１において使用したポリマーを用いて、実施例１
と同様に溶融押出・シート化を行い、厚さ約６０μｍの
未延伸シートを得た。この未延伸シートを１００″Ｃに
調節された金属ロール上に接触させ予熱した後、赤外線
ヒーターを照射しつつ３、００倍長手方向に延伸した。Example 3 Using the polymer used in Example 1, Example 1
Melt extrusion and sheet formation were carried out in the same manner as above to obtain an unstretched sheet with a thickness of about 60 μm. This unstretched sheet was brought into contact with a metal roll adjusted to 100''C and preheated, and then stretched 3,00 times in the longitudinal direction while being irradiated with an infrared heater.
この時、延伸区間のフィルム実質温度は１００℃であっ
た。また、この延伸フィルムの複屈折率（Δｎ）は０．
０８１で、平均屈折率（ｎ）は１．５５８６であった０
次にこのフィルムをテンターに導き、１１０°Ｃで３゜
６０倍幅方向に延伸した。更に続けて１３０℃で約５秒
間熱固定を行なった。この時のフィルムの複屈折率は−
０，００２であった。この二軸延伸フィルムを更に長手
方向に再延伸すべく、１２０°Ｃに調節された金属ロー
ルで予熱した後、１．１５倍延伸を行なった。この際に
、静電密着法を用いて延伸ロール上をフィルムが滑らな
いよう密着させて行なった。また再延伸の延伸区間での
フィルム実質温度は１２０°Ｃであった。この再延伸を
行なったフィルムを再びテンターに導き、２５０℃で約
１０秒間熱固定を行ない、厚さ５ｐｍの二軸配向フィル
ムを得た。また熱固定時に、幅方向に３％の割合で弛緩
処理を行なった。このフィルムの物性を表１に示す。At this time, the actual temperature of the film in the stretching section was 100°C. Moreover, the birefringence index (Δn) of this stretched film is 0.
081, and the average refractive index (n) was 1.5586.
Next, this film was introduced into a tenter and stretched at 110°C by 3°60 times in the width direction. Further, heat fixation was continued at 130° C. for about 5 seconds. The birefringence of the film at this time is -
It was 0,002. In order to further re-stretch this biaxially stretched film in the longitudinal direction, it was preheated with a metal roll adjusted to 120°C and then stretched 1.15 times. At this time, an electrostatic adhesion method was used to bring the film into close contact with the stretching roll so that it would not slip. Further, the actual temperature of the film in the stretching section of the re-stretching was 120°C. This re-stretched film was introduced into the tenter again and heat-set at 250° C. for about 10 seconds to obtain a biaxially oriented film with a thickness of 5 pm. Further, during heat setting, relaxation treatment was performed at a rate of 3% in the width direction. Table 1 shows the physical properties of this film.
比較例１
実施例３において、長手方向の再延伸を行なわずに、幅
方向の延伸が終了した後、続けてテンター内で２５０℃
で約１０秒間熱固定を行なって、厚さ５．８μｍの二軸
配向フィルムを得た。また、熱固定時に幅方向に３％の
弛緩処理を行なった。Comparative Example 1 In Example 3, after the stretching in the width direction was completed without re-stretching in the longitudinal direction, the stretching was continued at 250°C in a tenter.
Heat setting was performed for about 10 seconds to obtain a biaxially oriented film with a thickness of 5.8 μm. Further, during heat setting, a 3% relaxation treatment was performed in the width direction.
このフィルムの物性を表１に示す。Table 1 shows the physical properties of this film.
比較例２
実施例１において、二輪延伸後の熱固定温度を１６０°
Ｃとする以外は、すべて実施例１と同様に行ない、厚さ
５μｍの二軸配向フィルムを得た。Comparative Example 2 In Example 1, the heat setting temperature after two-wheel stretching was set at 160°.
A biaxially oriented film having a thickness of 5 μm was obtained by carrying out everything in the same manner as in Example 1 except for using C.
このフィルムの物性を表１に示す。Table 1 shows the physical properties of this film.
比較例３
平均粒径１．３０μｍのサイロイドをポリマー中０．２
０ｗｔ％となるように添加して、常法に従い１００％ポ
リエチレンテレフタレートを重合した。Comparative Example 3 Thyroid with an average particle size of 1.30 μm was mixed into a polymer with a diameter of 0.2 μm.
0 wt % was added, and 100% polyethylene terephthalate was polymerized according to a conventional method.
このポリマーの極限粘度［η］は０．６６であった。The intrinsic viscosity [η] of this polymer was 0.66.
このポリマーを用いて、樹脂温２９０°Ｃとしてあとは
実施例１と同様に溶融押出・シート化を行い、厚さ約７
５μｍの未延伸シートを得た。この未延伸シートを、表
面温度８４℃に調節された金属ロールで予熱した後、赤
外線ヒーター照射しつつ長手方向に３．８０倍延伸した
。この時、延伸区間のフィルム実質温度は８４°Ｃであ
り、また延伸後のフィルムの複屈折率（△ｎ）は０．１
２０であった。Using this polymer, melt extrusion and sheet formation were performed in the same manner as in Example 1 at a resin temperature of 290°C.
An unstretched sheet of 5 μm was obtained. This unstretched sheet was preheated with a metal roll whose surface temperature was adjusted to 84° C., and then stretched 3.80 times in the longitudinal direction while being irradiated with an infrared heater. At this time, the actual temperature of the film in the stretching section was 84°C, and the birefringence index (△n) of the film after stretching was 0.1
It was 20.
次にこの延伸フィルムをテンターに導き、１１０°Ｃで
３．９４倍幅方向に延伸した。更に続けて２３５°Ｃで
約１０秒間熱固定を行い、厚さ５μｍの二軸配向フィル
ムを得た。なお、熱固定時に幅方向に３％の弛緩処理を
行なった。このフィルムの物性を表１に示す。Next, this stretched film was introduced into a tenter and stretched 3.94 times in the width direction at 110°C. Further, heat setting was performed at 235° C. for about 10 seconds to obtain a biaxially oriented film with a thickness of 5 μm. Note that during heat setting, a 3% relaxation treatment was performed in the width direction. Table 1 shows the physical properties of this film.
本発明の二軸配向ポリエステルフィルムは、優れた耐熱
性を有し、その強度は、従来知られているＰＣＴフィル
ムと比べ１０〜４０％程度大きいため、連続加工中に伸
びを生ずることが少なくなり、工業用フィルムとして有
利なものである。The biaxially oriented polyester film of the present invention has excellent heat resistance, and its strength is about 10 to 40% higher than that of conventionally known PCT films, so it is less likely to elongate during continuous processing. , which is advantageous as an industrial film.
また、本発明の二軸配向ポリエステルフィルムは、製膜
連続性が良好であり、しかも長手方向の延伸倍率を上げ
られることから生産性の点で利点を有し、その工業的価
値は高い。Furthermore, the biaxially oriented polyester film of the present invention has good film forming continuity and can increase the stretching ratio in the longitudinal direction, so it has advantages in terms of productivity, and its industrial value is high.
出 願 人 ダイアホイル株式会社Applicant: Diafoil Co., Ltd.
Claims (1)
ール成分の９０モル％以上が１，４−シクロヘキサンジ
メタノールで構成されたポリエステルフィルムであって
、該フィルムの密度が１．２２０〜１．２５０ｇ／ｃｍ
＾３、複屈折率が０．０１０〜０．０４０であり、かつ
フィルム長手方向のヤング率が３１０〜４００ｋｇ／ｍ
ｍ＾２であることを特徴とする二軸配向ポリエステルフ
ィルム。(1) A polyester film in which 80 mol% or more of the acid component is terephthalic acid and 90 mol% or more of the glycol component is 1,4-cyclohexanedimethanol, and the film has a density of 1.220 to 1.22%. 250g/cm
^3, the birefringence is 0.010 to 0.040, and the Young's modulus in the longitudinal direction of the film is 310 to 400 kg/m
A biaxially oriented polyester film characterized in that m^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20529389A JPH0367630A (en) | 1989-08-08 | 1989-08-08 | Biaxially oriented polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20529389A JPH0367630A (en) | 1989-08-08 | 1989-08-08 | Biaxially oriented polyester film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0367630A true JPH0367630A (en) | 1991-03-22 |
Family
ID=16504572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20529389A Pending JPH0367630A (en) | 1989-08-08 | 1989-08-08 | Biaxially oriented polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0367630A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6848360B2 (en) | 2002-04-30 | 2005-02-01 | Miyakoshi Printing Machinery Co., Ltd. | Form dampening roller driving apparatus |
| JP2008524396A (en) * | 2004-12-16 | 2008-07-10 | イーストマン ケミカル カンパニー | Biaxially stretched copolyester film and laminate comprising copper |
| WO2017209218A1 (en) * | 2016-05-31 | 2017-12-07 | 大日本印刷株式会社 | Battery packaging material, production method therefor, battery, and polyester film |
| WO2019167815A1 (en) * | 2018-03-02 | 2019-09-06 | 三菱ケミカル株式会社 | Biaxially oriented film |
-
1989
- 1989-08-08 JP JP20529389A patent/JPH0367630A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6848360B2 (en) | 2002-04-30 | 2005-02-01 | Miyakoshi Printing Machinery Co., Ltd. | Form dampening roller driving apparatus |
| JP2008524396A (en) * | 2004-12-16 | 2008-07-10 | イーストマン ケミカル カンパニー | Biaxially stretched copolyester film and laminate comprising copper |
| KR20220025279A (en) * | 2016-05-31 | 2022-03-03 | 다이니폰 인사츠 가부시키가이샤 | Battery packaging material, production method therefor, battery, and polyester film |
| CN109219898A (en) * | 2016-05-31 | 2019-01-15 | 大日本印刷株式会社 | Battery use packing material and its manufacturing method, battery and polyester film |
| KR20190013806A (en) * | 2016-05-31 | 2019-02-11 | 다이니폰 인사츠 가부시키가이샤 | Packing material for battery, production method thereof, battery, and polyester film |
| JPWO2017209218A1 (en) * | 2016-05-31 | 2019-04-04 | 大日本印刷株式会社 | Packaging material for battery, method for producing the same, battery, and polyester film |
| JP2021193666A (en) * | 2016-05-31 | 2021-12-23 | 大日本印刷株式会社 | Battery packaging material, production method therefor, battery, and polyester film |
| WO2017209218A1 (en) * | 2016-05-31 | 2017-12-07 | 大日本印刷株式会社 | Battery packaging material, production method therefor, battery, and polyester film |
| US11370160B2 (en) | 2016-05-31 | 2022-06-28 | Dai Nippon Printing Co., Ltd. | Battery packaging material, production method therefor, battery, and polyester film |
| CN114725589A (en) * | 2016-05-31 | 2022-07-08 | 大日本印刷株式会社 | Battery packaging material, method for producing same, battery, and polyester film |
| JP2023011590A (en) * | 2016-05-31 | 2023-01-24 | 大日本印刷株式会社 | Package material for battery, manufacturing method thereof, battery, and polyester film |
| US11707880B2 (en) | 2016-05-31 | 2023-07-25 | Dai Nippon Printing Co., Ltd. | Battery packaging material, production method therefor, battery, and polyester film |
| WO2019167815A1 (en) * | 2018-03-02 | 2019-09-06 | 三菱ケミカル株式会社 | Biaxially oriented film |
| JPWO2019167815A1 (en) * | 2018-03-02 | 2021-03-04 | 三菱ケミカル株式会社 | Biaxially stretched film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI633993B (en) | Polyester film | |
| US20130123459A1 (en) | Heat setting optical films | |
| JPS62135801A (en) | Uniaxially highly oriented film comprising polyethylene naphthalate for polarizing plate | |
| JPS62135338A (en) | Monoaxially high-orientated film of polyethylene-naphthalate for liquid crystal panel substrate | |
| JP2009288395A (en) | Optical film having optical anisotropy and method for manufacturing the same | |
| JP2001329078A (en) | Releasing film | |
| JPH0367630A (en) | Biaxially oriented polyester film | |
| JPH1017683A (en) | Polyester film for large-sized molded transfer foil | |
| JP3852979B2 (en) | Polyester film for transfer foil | |
| JP2611421B2 (en) | Method for producing polyester film | |
| JP3316900B2 (en) | Polyester film molding method | |
| KR20160116702A (en) | Polyester and manufacturing method thereof | |
| JP2569471B2 (en) | Method for producing toughened polyester film | |
| JP2788775B2 (en) | Method for producing biaxially stretched polyester film | |
| JPH0367629A (en) | Biaxially oriented polyester film for molding | |
| JP2010013569A (en) | Longitudinally monoaxially oriented polyethylene naphthalate film and method for producing the same | |
| JPH0196641A (en) | Biaxial oriented polyester film for photoresist | |
| JPH02130125A (en) | Production of polyester film | |
| JPH03215B2 (en) | ||
| JPH0516258A (en) | Heat-treating method of polyester film | |
| JP2555707B2 (en) | Process for producing polyethylene 2,6-naphthalate film | |
| JPH03161319A (en) | Manufacture of biaxially-oriented polyester film | |
| JPS6374622A (en) | Production of film | |
| JPH02270532A (en) | Manufacture of law shrinkable polyester film | |
| JPS6360731A (en) | Preparation of biaxially oriented polyethylene-2,6-naphthalate film having high strength in longitudinal direction |