JPH0277431A - Biaxially oriented thermoplastic resin film - Google Patents
Biaxially oriented thermoplastic resin filmInfo
- Publication number
- JPH0277431A JPH0277431A JP64000775A JP77589A JPH0277431A JP H0277431 A JPH0277431 A JP H0277431A JP 64000775 A JP64000775 A JP 64000775A JP 77589 A JP77589 A JP 77589A JP H0277431 A JPH0277431 A JP H0277431A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thermoplastic resin
- thickness
- particles
- inert particles
- 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.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 claims abstract description 129
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000001069 Raman spectroscopy Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 141
- 238000000034 method Methods 0.000 description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000010410 layer Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 238000005259 measurement Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 13
- 239000002344 surface layer Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- 239000008119 colloidal silica Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 150000002500 ions Chemical group 0.000 description 6
- -1 Argon ion Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 235000012771 pancakes Nutrition 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000003841 Raman measurement Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000003678 scratch resistant effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は二軸配向熱可塑性樹脂フィルムに関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a biaxially oriented thermoplastic resin film.
［従来の技術］
二軸配向熱可塑性樹脂フィルムとしては、熱可塑性樹脂
であるポリエステルにコロイド状シリカに起因する実質
的に球形のシリカ粒子を含有せしめたフィルムが知られ
ている（たとえば特開昭５９−１７１６２３号公報）。[Prior Art] As a biaxially oriented thermoplastic resin film, there is known a film in which substantially spherical silica particles caused by colloidal silica are contained in polyester, which is a thermoplastic resin (for example, in Japanese Patent Application Laid-open No. 59-171623).
［発明が解決しようとする課題］
しかし、上記従来の二軸配向熱可塑性樹脂フィルムは、
フィルムの加工工程、たとえば包装用途における印刷工
程、磁気媒体用途における磁性層塗布・カレンダー工程
あるいは感熱転写用途における感熱転写層塗布などの工
程速度の増大にともない、接触するロールによってフィ
ルム表面に傷がつくという欠点が最近、問題となってき
ている。[Problems to be Solved by the Invention] However, the above conventional biaxially oriented thermoplastic resin film has the following problems:
As the speed of film processing increases, such as the printing process in packaging applications, the magnetic layer coating/calendering process in magnetic media applications, or the thermal transfer layer coating in thermal transfer applications, the film surface is scratched by contacting rolls. This shortcoming has recently become a problem.
また、上記従来の二軸配向熱可塑性樹脂フィルムは高温
・高湿下で、フィルムを取り扱う時に摩擦係数が高くな
り、ハンドリング性が不良になるという問題点があった
。Furthermore, the above-mentioned conventional biaxially oriented thermoplastic resin film has a problem in that the coefficient of friction increases when the film is handled under high temperature and high humidity, resulting in poor handling properties.
さらに、フィルムの主要な用途であるビデオテープは、
最近、ソフト用（制作された映像作品をパッケージ媒体
に記録固定、複製・増製したもの）に用いられるケース
が多く、この場合、上記従来のビデオテープでは、「映
像作品を録画する工程」でマスターテープから高速でダ
ビング（記録複写）する時のＳ／Ｎ （シグナル／ノイ
ズ比、画質のパラメータ）の低下が大きく画質が悪くな
るという問題点も出てきている。Furthermore, videotape, which is the main use of film,
Recently, there are many cases where it is used for software (recording, fixing, copying, and increasing the produced video work on package media), and in this case, the conventional videotape mentioned above is used in the "process of recording the video work". Another problem has arisen in that when dubbing (recording and copying) from a master tape at high speeds, the S/N (signal/noise ratio, image quality parameter) is greatly reduced, resulting in poor image quality.
本発明はかかる問題点を改善し、表面が傷つきに＜＜（
以下耐スクラッチ性という）、高温・高湿下での摩擦係
数が小さく（以下、摩擦係数という）、かつ、ダビング
による画質（Ｓ／Ｎ）の低下が少ない（以下耐ダビング
性という）フィルムを提供することを課題とする。The present invention improves these problems and prevents scratches on the surface.
Provides a film that has a low friction coefficient (hereinafter referred to as "friction coefficient") under high temperature and high humidity (hereinafter referred to as "scratch resistance"), and has little deterioration in image quality (S/N) due to dubbing (hereinafter referred to as "dubbing resistance"). The task is to do so.
［課題を解決するための手段］
フィルム中に含有する不活性粒子の平均粒径がフィルム
厚さの０．１〜１０倍であって、該粒子の含有量が０．
５〜５０重量％であることを特徴とする厚さ０．００
５〜３μｍの二軸配向熱可塑性樹脂フィルムとしたもの
である。[Means for Solving the Problems] The average particle size of the inert particles contained in the film is 0.1 to 10 times the thickness of the film, and the content of the particles is 0.1 to 10 times the thickness of the film.
Thickness 0.00, characterized in that it is 5-50% by weight
It is a biaxially oriented thermoplastic resin film of 5 to 3 μm.
本発明を構成する熱可塑性樹脂Ａはポリエステル、ポリ
オレフィン、ポリアミド、ポリフェニレンスルフィドな
ど特に限定されることはないが、特に、ポリエステル、
中でも、エチレンテレフタレート、エチレンα、β−ビ
ス（２−クロルフェノキシ）エタン−４，４′−ジカル
ボキシレート、エチレン２．６−ナフタレート単位から
選ばれた少なくとも一種の構造単位を主要構成成分とす
る場合に耐スクラッチ性、耐ダビング性、摩擦係数がよ
り一層良好となるので望ましい。また、本発明を構成す
る熱可塑性樹脂は結晶性、あるいは溶融時光学異方性で
ある場合に耐スクラッチ性、耐ダビング性、摩擦係数が
より一層良好となるのできわめて望ましい。ここでいう
結晶性とはいわゆる非晶質ではないことを示すものであ
り、定量的には結晶化パラメータにおける冷結晶化温度
Ｔｃｃが検出され、かつ結晶化パラメータΔＴｃｇが１
５０℃以下のものである。さらに、示差走査熱量計で測
定された融解熱（融解エンタルピー変化）が７．５ｃａ
ｌ／ｇ以上の結晶性を示す場合に耐スクラッチ性、耐ダ
ビング性、摩擦係数がより一層良好となるのできわめて
望ましい。また、エチレンテレフタレートを主要構成成
分とするポリエステルの場合に耐ダビング性と耐スクラ
ッチ性がより一層良好となるので特に望ましい。なお、
本発明を阻害しない範囲内で、２種以上の熱可塑性樹脂
を混合しても良いし、共重合ポリマを用いても良い。The thermoplastic resin A constituting the present invention is not particularly limited to polyester, polyolefin, polyamide, polyphenylene sulfide, etc., but in particular, polyester, polyphenylene sulfide, etc.
Among them, the main constituent is at least one structural unit selected from ethylene terephthalate, ethylene α, β-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate, and ethylene 2,6-naphthalate units. In some cases, scratch resistance, dubbing resistance, and friction coefficient are further improved, which is desirable. Further, it is extremely desirable that the thermoplastic resin constituting the present invention be crystalline or optically anisotropic when melted, since this provides even better scratch resistance, dubbing resistance, and coefficient of friction. Crystallinity here indicates that it is not so-called amorphous, and quantitatively, the cold crystallization temperature Tcc in the crystallization parameter is detected, and the crystallization parameter ΔTcg is 1.
The temperature is 50°C or less. Furthermore, the heat of fusion (change in enthalpy of fusion) measured with a differential scanning calorimeter was 7.5 ca.
When the crystallinity is 1/g or more, the scratch resistance, dubbing resistance, and coefficient of friction become even better, which is extremely desirable. Further, polyester containing ethylene terephthalate as a main component is particularly desirable because it has even better dubbing resistance and scratch resistance. In addition,
Two or more types of thermoplastic resins may be mixed or a copolymer may be used within a range that does not impede the present invention.
本発明の熱可塑性樹脂Ａ中の不活性粒子は、フィルム中
での粒径比（粒子の長径／短径）が１゜０〜１．３の粒
子、特に、球形状の粒子の場合に耐スクラッチ性がより
一層良好となるので望ましい。The inert particles in the thermoplastic resin A of the present invention are particles with a particle size ratio (major axis/minor axis) of 1°0 to 1.3 in the film, especially spherical particles. This is desirable because the scratch resistance becomes even better.
また、本発明の熱可塑性樹脂Ａ中の不活性粒子はフィル
ム中での単一粒子指数が０．７以上、好ましくは０．９
以上である場合に耐スクラッチ性、耐ダビング性がより
一層良好となるので特に望ましい。Further, the inert particles in the thermoplastic resin A of the present invention have a single particle index in the film of 0.7 or more, preferably 0.9.
It is particularly desirable that the above is the case since scratch resistance and dubbing resistance become even better.
また、本発明の熱可塑性樹脂Ａ中の不活性粒子は、フィ
ルム中での相対標準偏差が０．６以下、好ましくは０６
５以下の場合に耐スクラッチ性、耐ダビング性がより一
層良好となるので望ましい。Further, the inert particles in the thermoplastic resin A of the present invention have a relative standard deviation of 0.6 or less in the film, preferably 0.6
A value of 5 or less is desirable because scratch resistance and dubbing resistance become even better.
本発明の熱可塑性樹脂Ａ中の不活性粒子の種類は特に限
定されないが、上記の好ましい粒子特性を満足するには
アルミナ珪酸塩、１次粒子が凝集した状態のシリカ、内
部析出粒子などは好ましくなく、コロイダルシリカに起
因する実質的に球形のシリカ粒子、架橋高分子による粒
子（たとえば架橋ポリスチレン）などがあるが、特に１
０重量％減量時温度（窒素中で熱重量分析装置島津Ｔ
Ｇ−３０Ｍを用いて測定。昇温速度２０℃／分）が３８
０℃以上になるまで架橋度を高くした架橋高分子粒子の
場合に耐スクラッチ性、耐ダビング、性がより一層良好
となるので特に望ましい。なお、。The type of inert particles in the thermoplastic resin A of the present invention is not particularly limited, but in order to satisfy the above preferable particle properties, alumina silicate, silica in a state where primary particles are aggregated, internally precipitated particles, etc. are preferable. There are substantially spherical silica particles caused by colloidal silica, particles made of crosslinked polymers (for example, crosslinked polystyrene), etc.
Temperature at 0% weight loss (Thermogravimetric analyzer Shimadzu T in nitrogen)
Measured using G-30M. heating rate 20℃/min) is 38
It is particularly desirable to use crosslinked polymer particles whose degree of crosslinking is increased to 0° C. or higher, since the scratch resistance, dubbing resistance, and properties are even better. In addition,.
コロイダルシリカに起因する球形シリカの場合にはアル
コキシド法で製造された、ナトリウム含有量が少ない、
実質的に球形のシリカの場合に耐スクラッチ性がより一
層良好となるので特に望ましい。しかしながら、その他
の粒子、例えば炭酸カルシウム、二酸化チタン、アルミ
ナ等の粒子でもフィルム厚さと平均粒径の適切なフント
ロールにより十分使いこなせるものである。In the case of spherical silica due to colloidal silica, produced by alkoxide method, low sodium content,
Substantially spherical silica is particularly preferred since it provides even better scratch resistance. However, other particles, such as particles of calcium carbonate, titanium dioxide, alumina, etc., can also be used satisfactorily with appropriate film thickness and average particle size.
本発明の熱可塑性樹脂Ａ中の不活性粒子の結晶化促進係
数は特に限定されないが、−１５〜１５℃、好ましくは
一５℃〜１０℃の場合に、耐スクラッチ性がより一層良
好となるので特に望ましい。The crystallization promotion coefficient of the inert particles in the thermoplastic resin A of the present invention is not particularly limited, but the scratch resistance becomes even better when the temperature is -15 to 15°C, preferably -5 to 10°C. Therefore, it is particularly desirable.
不活性粒子の大きさは、フィルム中での平均粒径がフィ
ルム厚さの０． １〜１０倍、好ましくは０．５〜５倍
、さらに好ましくは１，１〜３倍の範囲であることが必
要である。平均粒径／フィルム厚さ比が上記の範囲より
小さいと耐スクラッチ性、摩擦係数が不良となり、逆に
大きくても耐スクラッチ性、耐ダビング性、摩擦係数が
不良となるので好ましくない。The size of the inert particles is such that the average particle diameter in the film is 0.000 mm thick of the film thickness. It needs to be in the range of 1 to 10 times, preferably 0.5 to 5 times, more preferably 1.1 to 3 times. If the average particle diameter/film thickness ratio is smaller than the above range, the scratch resistance and friction coefficient will be poor, and if it is larger, the scratch resistance, dubbing resistance, and friction coefficient will be poor, which is not preferable.
また熱可塑性樹脂Ａ中の不活性粒子のフィルム中での平
均粒径（直径）が０．００７〜０．５μｍ、好ましくは
０．０２〜０．４５μｍの範囲である場合に、耐スクラ
ッチ性、耐ダビング性、摩擦係数がより一層良好となる
ので望ましい。In addition, when the average particle size (diameter) of the inert particles in the thermoplastic resin A in the film is in the range of 0.007 to 0.5 μm, preferably 0.02 to 0.45 μm, scratch resistance, This is desirable because the dubbing resistance and friction coefficient are even better.
本発明の熱可塑性樹脂Ａ中の不活性粒子の含有量は０．
５〜５ＯＮ量％、好ましくは１〜３０重量％、さらに
好ましくは２〜１５重量％であることが必要である。不
活性粒子の含有量が上記の範囲より少なくても、逆に大
きくても耐スクラッチ性が不良となるので好ましくない
。The content of inert particles in the thermoplastic resin A of the present invention is 0.
It is necessary that the amount of ON is 5 to 5% by weight, preferably 1 to 30% by weight, and more preferably 2 to 15% by weight. Even if the content of inert particles is less than the above-mentioned range, it is not preferable that the content is greater than the above range because the scratch resistance becomes poor.
本発明フィルムは上記熱可塑性樹脂Ａと不活性粒子から
なる組成物を主要成分とするが、本発明の目的を阻害し
ない範囲内で、他種ポリマをブレンドしてもよいし、ま
た酸化防止剤、熱安定剤、滑剤、紫外線吸収剤などの有
機添加剤が通常添加される程度添加されていてもよい。The main component of the film of the present invention is a composition consisting of the thermoplastic resin A and inert particles, but other types of polymers may be blended within a range that does not impede the purpose of the present invention, and antioxidants may be added. , heat stabilizers, lubricants, ultraviolet absorbers, and other organic additives may be added to the extent that they are normally added.
本発明フィルムは上記組成物を二軸配向せしめたフィル
ムである。−軸あるいは無配向フィルムでは耐スクラッ
チ性が不良となるので好ましくない。この配向の程度は
特に限定されないが、高分子の分子配向の程度の目安で
あるヤング率が長手方向、幅方向ともに３５０ｋｇ／ｍ
ｍ２以上である場合に耐スクラッチ性がより一層良好と
なるのできわめて望ましい。分子配向の程度の目安であ
るヤング率の上限は特に限定されないが、通常、５００
０ ｋ ｇ／ｍｍ２程度が製造上の限界である。The film of the present invention is a film in which the above composition is biaxially oriented. - Axial or non-oriented films are not preferred because they have poor scratch resistance. The degree of this orientation is not particularly limited, but the Young's modulus, which is a guideline for the degree of molecular orientation of polymers, is 350 kg/m in both the longitudinal and width directions.
If it is m2 or more, the scratch resistance will be even better, so it is extremely desirable. The upper limit of Young's modulus, which is a measure of the degree of molecular orientation, is not particularly limited, but is usually 500
The manufacturing limit is about 0 kg/mm2.
また、本発明フィルムは、ヤング率が上記範囲内であっ
ても、フィルムの厚さ方向の一部分、例えば、表層付近
のポリマ分子の配向が無配向、あるいは、−軸配向にな
っていない、すなわち、厚さ方向の全部分の分子配向が
二軸配向である場合に耐スクラッチ性、耐ダビング性、
摩擦係数がより一層良好となるので特に望ましい。In addition, even if the Young's modulus of the film of the present invention is within the above range, the orientation of the polymer molecules in a portion of the thickness direction of the film, for example, near the surface layer, is not oriented or is not oriented in the -axis direction, i.e. , Scratch resistance, dubbing resistance, when the molecular orientation in the entire thickness direction is biaxial orientation.
This is particularly desirable since the coefficient of friction becomes even better.
特にアツベ屈折率計、レーザーを用いた屈折率計、全反
射レーザーラマン法などによって測定される分子配向が
、表面、裏面ともに二軸配向である場合に耐スクラッチ
性、耐ダビング性、摩擦係数がより一層良好となるので
特に望ましい。In particular, when the molecular orientation measured by an Atsube refractometer, laser refractometer, total internal reflection laser Raman method, etc. is biaxially oriented on both the front and back surfaces, scratch resistance, dubbing resistance, and friction coefficient are This is particularly desirable because it provides even better results.
さらに熱可塑性樹脂Ａが結晶性ポリエステルであり、こ
れを主成分とする本発明フィルムの表面の全反射ラマン
結晶化指数が２０ｃｍ−’以下、好ましくは１８ｃｍ−
’以下、さらに１７ｃｍ−”以下の場合に耐スクラッチ
性、耐ダビング性、摩擦係数がより一層良好となるので
きわめて望ましい。Further, the thermoplastic resin A is a crystalline polyester, and the total reflection Raman crystallization index of the surface of the film of the present invention containing this as a main component is 20 cm-' or less, preferably 18 cm-'.
If the thickness is 17 cm or less, the scratch resistance, dubbing resistance, and friction coefficient will be even better, so it is extremely desirable.
本発明の熱可塑性樹脂へを主成分とするフィルムの２次
イオンマススペクトルによって測定される表層粒子濃度
比は特に限定されないが、１／１０以下、特に１１５０
以下である場合に摩擦係数、耐スクラッチ性がより一層
良好となるので特に望ましい。The surface layer particle concentration ratio measured by secondary ion mass spectrum of the film mainly composed of thermoplastic resin of the present invention is not particularly limited, but is 1/10 or less, especially 1150
It is particularly desirable that the value is below, since the friction coefficient and scratch resistance will be even better.
本発明の熱可塑性樹脂Ａを主成分とするフィルムの厚さ
は０．００５〜３μｍ１好ましくは０゜０１〜１μｍ１
さらに好ましくは０゜０３〜０゜５μｍであることが必
要である。フィルム厚さが上記の範囲より小さいと耐ダ
ビング性、摩擦係数が不良となり逆に大きいと耐スクラ
ッチ性が不良となるので好ましくない。The thickness of the film mainly composed of thermoplastic resin A of the present invention is 0.005 to 3 μm, preferably 0.01 to 1 μm.
More preferably, it is 0.03 to 0.5 μm. If the film thickness is smaller than the above range, the dubbing resistance and friction coefficient will be poor, and if it is larger, the scratch resistance will be poor, which is not preferable.
本発明の熱可塑性樹脂Ａを主成分とするフィルムの表面
の平均突起高さは５〜５００ｎｍ、好ましくは１・０〜
３００ｎｍ、さらに好ましくは１５〜２００ ｎｍの範
囲である場合に耐スクラッチ性、耐ダビング性、摩擦係
数がより一層良好となるので特に望ましい。The average protrusion height on the surface of the film mainly composed of thermoplastic resin A of the present invention is 5 to 500 nm, preferably 1.0 to 500 nm.
A range of 300 nm, more preferably 15 to 200 nm, is particularly desirable because scratch resistance, dubbing resistance, and coefficient of friction become even better.
本発明の熱可塑性樹脂Ａを主成分とするフィルムの平均
突起間隔は６μｍ以下、好ましくは４μｍ以下である場
合に耐スクラッチ性、耐ダビング性、摩擦係数がより一
層良好となるので特に望ましい。It is particularly desirable that the average distance between protrusions of the film containing thermoplastic resin A of the present invention as a main component is 6 μm or less, preferably 4 μm or less, since scratch resistance, dubbing resistance, and coefficient of friction become even better.
本発明の熱可塑性樹脂Ａを主成分とするフィルムの表面
の中心線深さＲｐは特に限定されないが、Ｒｐが１８０
ｎｍ以下、特に１６０ｎｍ以下の場合に耐ダビング性が
より一層良好となるので特に望ましい。また、上記Ｒｐ
と最大高さＲｔの比、Ｒｔ ／ Ｒｐが１．５〜２．５
、特に、１．７〜２゜３の場合に耐スクラッチ性、耐ダ
ビング性、摩擦係数がより一層良好となるので特に望ま
しい。The centerline depth Rp of the surface of the film mainly composed of thermoplastic resin A of the present invention is not particularly limited, but Rp is 180
It is particularly desirable to have a thickness of 160 nm or less, especially 160 nm or less, since the dubbing resistance will be even better. In addition, the above Rp
and the maximum height Rt, Rt/Rp is 1.5 to 2.5
In particular, a range of 1.7 to 2°3 is particularly desirable because scratch resistance, dubbing resistance, and coefficient of friction become even better.
本発明の熱可塑性樹脂Ａを主成分とするフィルムの表面
の中心線平均粗さＲａと最大高さＲｔの比、Ｒｔ ／
Ｒａが９．０以下、特に８．５以下の場合に耐スクラッ
チ性、耐ダビング性、摩擦係数がより一層良好となるの
で特に望ましい。Rt/
It is particularly desirable that Ra is 9.0 or less, particularly 8.5 or less, since scratch resistance, dubbing resistance, and friction coefficient become even better.
本発明フィルムは上述したように、構成する熱可塑性樹
脂が結晶性あるいは溶融光学異方性であることがきわめ
て望ましいが、溶融等方性フィルムの場合、結晶化パラ
メータΔＴｃｇが２５〜６５℃である場合に耐スクラッ
チ性、摩擦係数がより一層良好となるので特に望ましい
。As mentioned above, it is extremely desirable for the thermoplastic resin constituting the film of the present invention to be crystalline or melt optically anisotropic, but in the case of a melt isotropic film, the crystallization parameter ΔTcg is 25 to 65°C. This is particularly desirable in cases where the scratch resistance and friction coefficient are even better.
なお熱可塑性樹脂Ａがポリエステルの場合には熱可塑性
樹脂Ａ面の厚さ方向屈折率が１．５以下の場合に、耐ス
クラッチ性、耐ダビング性がより一層良好となるので特
に望ましい。In addition, when the thermoplastic resin A is polyester, it is particularly desirable that the refractive index of the thermoplastic resin A surface in the thickness direction is 1.5 or less, since scratch resistance and dubbing resistance become even better.
本発明フィルムを構成する熱可塑性樹脂Ａがポリエステ
ルの場合はフィルムの固有粘度が０．６０以上、特に０
．７０以上の場合に耐スクラッチ性がより一層良好とな
るので特に望ましい。When the thermoplastic resin A constituting the film of the present invention is polyester, the intrinsic viscosity of the film is 0.60 or more, particularly 0.
．． A value of 70 or more is particularly desirable because the scratch resistance becomes even better.
本発明フィルムを構成する熱可塑性樹脂Ａがポリエステ
ルの場合はフィルム中の低分子成分含有量が０．８重量
％以下、特に０．５重量％以下の場合に耐スクラッチ性
がより一層良好となるので特に望ましい。When the thermoplastic resin A constituting the film of the present invention is polyester, the scratch resistance becomes even better when the content of low molecular components in the film is 0.8% by weight or less, especially 0.5% by weight or less. Therefore, it is particularly desirable.
本発明フィルムは、もちろん単体（単層フィルム）でも
用いられるが、熱可塑性樹脂Ｂのフィルムの少なくとも
片面に上記熱可塑性樹脂Ａのフィルムを積層した後二軸
配向したフィルムの形で用いると、機械的特性が良好と
なるのみならず、耐スクラッチ性、耐ダビング性、摩擦
係数もより一層良好となるのできわめて望ましい。ここ
で熱可塑性樹脂ＡとＢは同じ種類でも、異なるものでも
良い。The film of the present invention can of course be used alone (single-layer film), but if it is used in the form of a biaxially oriented film in which a film of thermoplastic resin A is laminated on at least one side of a film of thermoplastic resin B, This is extremely desirable because not only the physical properties are improved, but also the scratch resistance, dubbing resistance, and coefficient of friction are further improved. Here, the thermoplastic resins A and B may be the same type or different types.
上記は積層構成がＡ／Ｂ／Ａ、Ａ／Ｈの場合であるが、
もちろん、Ａと異なる表面状態を有する０層をＡと反対
面に設けたＡ／Ｂ／Ｃでも、あるいはそれ以上の多層構
造でもよい。（ここで、ＡｌＢ、Ｃそれぞれの熱可塑性
樹脂の種類は同種でも、異種でもよい。また、少なくと
も片方の表面はＡ層であることが必要である。）
熱可塑性樹脂Ｂとしては結晶性ポリマが望ましく、特に
、結晶性パラメータΔＴｃｇが２０〜１００℃の範囲の
場合に、耐ダビング性がより一層良好となるので望まし
い。具体例として、ポリエステル、ポリアミド、ポリフ
ェニレンスルフィド、ポリオレフィンが挙げられるが、
ポリエステルの場合に耐ダビング性がより一層良好とな
るので特に望ましい。また、ポリエステルとしては、エ
チレンテレフタレート、エチレンα、β−ビス（２−ク
ロルフェノキシ）エタン−４，４１−ジカルボキシレ−
ト、エチレン２．６−ナフタレート単位から選ばれた少
なくとも一種の構造単位を主要構成成分とする場合に耐
ダビング性が特に良好となるので望ましい。ただし、本
発明を阻害しない範囲内、望ましい結晶性を損なわない
範囲内で、好ましくは５モル％以内であれば他成分が共
重合されていてもよい。The above is for the case where the laminated structure is A/B/A, A/H,
Of course, it may be an A/B/C structure in which a layer 0 having a surface state different from that of A is provided on the opposite surface, or a multilayer structure having more than that. (Here, the types of thermoplastic resins for AlB and C may be the same or different.Also, at least one surface needs to be layer A.) Thermoplastic resin B is a crystalline polymer. It is particularly desirable that the crystallinity parameter ΔTcg is in the range of 20 to 100° C., since the dubbing resistance will be even better. Specific examples include polyester, polyamide, polyphenylene sulfide, and polyolefin.
Polyester is particularly desirable because it provides even better dubbing resistance. In addition, as polyester, ethylene terephthalate, ethylene α, β-bis(2-chlorophenoxy)ethane-4,41-dicarboxylene
It is preferable that the main constituent is at least one structural unit selected from the group consisting of ethylene 2.6-naphthalate units and ethylene 2.6-naphthalate units, since the dubbing resistance is particularly good. However, other components may be copolymerized within a range that does not impede the present invention, within a range that does not impair desirable crystallinity, and preferably within 5 mol%.
本発明の熱可塑性樹脂Ｂにも、本発明の目的を阻害しな
い範囲内で、他種ポリマをブレンドしてもよいし、また
酸化防止剤、熱安定剤、滑剤、紫外線吸収剤などの有機
添加剤が通常添加される程度添加されていてもよい。The thermoplastic resin B of the present invention may also be blended with other types of polymers within the range that does not impede the purpose of the present invention, and organic additives such as antioxidants, heat stabilizers, lubricants, and ultraviolet absorbers may be added. The agent may be added to the extent that it is normally added.
熱可塑性樹脂Ｂを主成分とするフィルム中には不活性粒
子を含有している必要は特にないが、平均粒径が０．０
０７〜２μｍ、特に０．０２〜０゜４５μｍの不活性粒
子が０．００１〜０．２重量％、特に０．００５〜０．
１５重量％、さらには０．００５〜０．１２重量％含有
されていると、摩擦係数、耐スクラッチ性がより一層良
好となるのみならず、フィルムの巻姿が良好となるので
きわめて望ましい。含有する不活性粒子の種類は熱可塑
性樹脂Ａに望ましく用いられるものを使用することが望
ましい。熱可塑性樹脂ＡとＢに含有する粒子の種類、大
きさは同じでも異なっていても良い。It is not particularly necessary to contain inert particles in the film mainly composed of thermoplastic resin B, but if the average particle size is 0.0
0.07 to 2 μm, especially 0.02 to 0.45 μm inert particles in an amount of 0.001 to 0.2% by weight, especially 0.005 to 0.045 μm.
A content of 15% by weight, more preferably 0.005 to 0.12% by weight, is extremely desirable because not only the coefficient of friction and scratch resistance will be even better, but the winding appearance of the film will also be better. As for the type of inert particles contained, it is desirable to use those preferably used for thermoplastic resin A. The types and sizes of particles contained in thermoplastic resins A and B may be the same or different.
上記熱可塑性樹脂Ａと熱可塑性樹脂Ｂの結晶化パラメー
タΔＴｃｇの差（Ａ−Ｂ）は特に限定されないが、−３
０〜＋２０°Ｃの場合に、耐スクラッチ性、耐ダビング
性がより一層良好となるので特、に望ましい。The difference (A-B) in crystallization parameter ΔTcg between thermoplastic resin A and thermoplastic resin B is not particularly limited, but is -3
A temperature of 0 to +20°C is particularly desirable because scratch resistance and dubbing resistance become even better.
次に本発明フィルムの製造方法について説明する。Next, a method for producing the film of the present invention will be explained.
まず、熱可塑性樹脂Ａに不活性粒子を含有せしめる方法
としては、熱可塑性樹脂がポリエステルの場合には、ジ
オール成分であるエチレングリコールのスラリーの形で
分散せしめ、このエチレングリコールを所定のジカルボ
ン酸成分と重合せしめるのが延伸破れなく、本発明範囲
の厚さと平均粒径の関係、含有量、望ましい範囲の配向
状態のフィルムを得るのに有効である。また、不活性粒
子を含有するポリエステルの溶融粘度、共重合成分など
を調節して、その結晶化パラメータΔＴｃｇを４０〜６
５℃の範囲にしておく方法は延伸破れなく、本発明範囲
の厚さと平均粒径の関係、含有量、望ましい範囲の配向
状態、表層粒子濃度比、平均突起高さ、Ｒｔ／Ｒｐ比、
Ｒｔ ／ Ｒａ比のフィルムを得るのに有効である。First, as a method for incorporating inert particles into thermoplastic resin A, when the thermoplastic resin is polyester, it is dispersed in the form of a slurry of ethylene glycol, which is a diol component, and this ethylene glycol is mixed with a predetermined dicarboxylic acid component. It is effective to obtain a film that does not break during stretching, has a relationship between thickness and average particle size, has a content within the range of the present invention, and has an orientation state within the desired range. In addition, by adjusting the melt viscosity, copolymerization components, etc. of the polyester containing inert particles, its crystallization parameter ΔTcg was adjusted to 40 to 6.
The method of keeping the temperature in the range of 5°C does not cause tearing due to stretching, and the relationship between the thickness and the average grain size within the range of the present invention, the content, the orientation state within the desired range, the surface layer particle concentration ratio, the average protrusion height, the Rt/Rp ratio,
It is effective to obtain a film with Rt/Ra ratio.
また、不活性粒子のエチレングリコールのスラリーを１
４０〜２００°Ｃ１特に１８０〜２００°Ｃの温度で３
０分〜５時間、特に１〜３時間熱処理する方法は延伸破
れなく、本発明範囲の厚さと平均粒径の関係、含有量、
望ましい範囲の配向状態、表層粒子濃度比のフィルムを
得るのに有効である。Additionally, a slurry of ethylene glycol of inert particles was added to
40-200°C1 Especially at temperatures of 180-200°C3
The method of heat treatment for 0 minutes to 5 hours, especially 1 to 3 hours, does not cause stretching breakage, and the relationship between thickness and average particle size, content, and
This is effective in obtaining a film having a desirable range of orientation and surface layer particle concentration ratio.
また熱可塑性樹脂（ポリエステルも含めて）に不活性粒
子を含有せしめる方法として、粒子をエチレングリコー
ル中で１４０〜２００℃、特に１８０〜２００℃の温度
で３０分〜５時間、特に１〜３時間熱処理した後、溶媒
を水に置換したスラリーの形で熱可塑性樹脂と混合し、
ベント方式の２軸押比機を用いて混練して熱可塑性樹脂
に練り込む方法も本発明範囲の厚さと平均粒径の関係、
含有量、望ましい範囲の配向状態、表層粒子濃度比、平
均突起高さ、Ｒｔ／Ｒｐ比、Ｒｔ ／ Ｒａ比のフィル
ムを得るのにきわめて有効である。In addition, as a method of incorporating inert particles into thermoplastic resin (including polyester), particles are heated in ethylene glycol at a temperature of 140 to 200°C, particularly 180 to 200°C, for 30 minutes to 5 hours, especially 1 to 3 hours. After heat treatment, it is mixed with a thermoplastic resin in the form of a slurry in which the solvent is replaced with water.
The method of kneading and kneading into thermoplastic resin using a vent-type twin-screw press ratio machine also has the relationship between the thickness and average particle size within the range of the present invention,
It is extremely effective in obtaining a film having a desired content, orientation state, surface particle concentration ratio, average protrusion height, Rt/Rp ratio, and Rt/Ra ratio.
粒子の含有量を調節する方法としては、上記方法で高濃
度マスターを作っておき、それを製膜時に不活性粒子を
実質的に含有しない熱可塑性樹脂で希釈して粒子の含有
量を調節する方法が有効である。A method for adjusting the particle content is to prepare a high-concentration master using the above method, and then dilute it with a thermoplastic resin that does not substantially contain inert particles during film formation to adjust the particle content. The method is valid.
かくして、不活性粒子を所定量含有するペレットを必要
に応じて乾燥したのち、公知の溶融押出機に供給し、熱
可塑性樹脂の融点以上、分解点以下でスリット状のダイ
からシート状に押出し、キャスティングロール上で冷却
固化せしめて未延伸フィルムを作る。この場合、未延伸
フィルムに押出し成形する時の、口金スリット間隙／未
延伸フィルム厚さの比を５〜３０、好ましくは８〜２０
の範囲にすることが、延伸破れなく本発明範囲の厚さと
平均粒径の関係、含有量の範囲、望ましい範囲の配向状
態、表層粒子濃度比、全反射ラマン結晶化指数のフィル
ムを得るのに有効である。After drying the pellets containing a predetermined amount of inert particles as necessary, the pellets are supplied to a known melt extruder and extruded into a sheet through a slit-shaped die at temperatures above the melting point and below the decomposition point of the thermoplastic resin. It is cooled and solidified on a casting roll to form an unstretched film. In this case, when extruding into an unstretched film, the ratio of die slit gap/unstretched film thickness is 5 to 30, preferably 8 to 20.
In order to obtain a film with the relationship between thickness and average grain size, content range, orientation state within the desired range, surface layer particle concentration ratio, and total reflection Raman crystallization index within the range of the present invention without stretching tearing, It is valid.
次にこの未延伸フィルムを二軸延伸し、二軸配向せしめ
る。延伸方法としては、逐次二軸延伸法または同時二軸
延伸法を用いることができる。ただし、最初に長手方向
、次に幅方向の延伸を行なう逐次二軸延伸法を用い、長
手方向の延伸を３段階以上に分けて、総縦延伸倍率を３
．５〜６．５倍で行なう方法は延伸破れなく、本発明範
囲の厚さと平均粒径の関係、含有量、望ましい範囲の配
向状態、表層粒子濃度比のフィルムを得るのに有効であ
る。ただし、熱可塑性樹脂が溶融光学異方性樹脂である
場合は長手方向延伸倍率は１〜１゜１倍が適切である。Next, this unstretched film is biaxially stretched and biaxially oriented. As the stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. However, by using a sequential biaxial stretching method that first stretches in the longitudinal direction and then in the width direction, the longitudinal stretching is divided into three or more stages, and the total longitudinal stretching ratio is 3.
．． A method performed at a stretching ratio of 5 to 6.5 times is effective for obtaining a film without tearing due to stretching and having a relationship between thickness and average grain size, a content, an orientation state within a desirable range, and a surface layer particle concentration ratio within the range of the present invention. However, when the thermoplastic resin is a molten optically anisotropic resin, the stretching ratio in the longitudinal direction is suitably 1 to 1.times.1.
長手方向延伸温度は熱可塑性樹脂の種類によって異なり
一概には言えないが、通常、その１段目を５０〜１３０
℃とし、２段目以降はそれより高くすることが本発明範
囲の厚さと平均粒径の関係、含有量、望ましい範囲の配
向状態、平均突起高さ、表層粒子濃度比のフィルムを得
るのに有効である。長手方向延伸速度は５０００〜５０
０００％／分の範囲が好適である。幅方向の延伸方法と
してはステツクを用いる方法が一般的である。延伸倍率
は、３．０〜５．０倍の範囲が適当である。幅方向の延
伸速度は、１０００〜２００００％／分、温度は８０〜
１６０°Ｃの範囲が好適である。次にこの延伸フィルム
を熱処理する。この場合の熱処理温度は１７０〜２００
℃、特に１７０〜１９０℃、時間は０．５〜６０秒の範
囲が好適である。Although the longitudinal stretching temperature varies depending on the type of thermoplastic resin and cannot be generalized, it is usually 50 to 130 ℃ in the first stage.
℃, and higher than that for the second and subsequent stages to obtain a film with the relationship between thickness and average particle size, content, orientation state within the desired range, average protrusion height, and surface layer particle concentration ratio within the range of the present invention. It is valid. Longitudinal stretching speed is 5000-50
A range of 000%/min is preferred. A common method for stretching in the width direction is to use a stick. The appropriate stretching ratio is 3.0 to 5.0 times. The stretching speed in the width direction is 1000-20000%/min, and the temperature is 80-2000%/min.
A range of 160°C is preferred. Next, this stretched film is heat treated. The heat treatment temperature in this case is 170-200
C., particularly 170 to 190.degree. C., and a time period of 0.5 to 60 seconds is suitable.
次に、熱可塑性樹脂Ｂを主成分とするフィルムの少なく
とも片面に熱可塑性樹脂Ａを主成分とするフィルムを積
層する方法としては、次の方法が有効である。Next, as a method for laminating a film mainly composed of thermoplastic resin A on at least one side of a film mainly composed of thermoplastic resin B, the following method is effective.
所定の熱可塑性樹脂フィルムと熱可塑性樹脂Ｂ（Ａ、Ｂ
は同種、異種どちらでもよい）を公知の溶融積層用押出
機に供給し、スリット状のダイからシート状に押出し、
キャスティングロール上で冷却固化せしめて未延伸フィ
ルムを作る。すなわち、２または３台の押出し機、２ま
たは３層のマニホールドまたは合流ブロックを用いて、
熱可塑性樹脂Ａ、Ｂを積層し、口金から２または３層の
シートを押し出し、キャスティングロールで冷却して未
延伸フィルムを作る。この場合、熱可塑性樹脂Ａのポリ
マ流路に、スタティックミキサー、ギヤポンプを設置す
る方法は延伸破れなく、本発明範囲の厚さと平均粒径の
関係、含有量、望ましい範囲の配向状態、平均突起高さ
、Ｒｔ ／ Ｒｐ比、Ｒｔ ／ Ｒａ比、表層粒子濃度
比のフィルムを得るのに有効である。また、熱可塑性樹
脂Ａ側の押し出し機の溶融温度を、熱可塑性樹脂Ｂ側よ
り、１０〜４０℃高くすることが、延伸破れなく、本発
明範囲の厚さと平均粒径の関係、含有量、望ましい範囲
の配向状態、平均突起高さ、Ｒｔ ／ Ｒｐ比、Ｒｔ
／ Ｒａ比、表層粒子濃度比、全反射ラマン結晶化指数
のフィルムを得るのに有効である。Predetermined thermoplastic resin film and thermoplastic resin B (A, B
may be the same or different types) is fed to a known melt lamination extruder and extruded into a sheet from a slit-shaped die,
It is cooled and solidified on a casting roll to form an unstretched film. That is, using 2 or 3 extruders, 2 or 3 layer manifolds or merging blocks,
Thermoplastic resins A and B are laminated, two or three layers of sheets are extruded from a die, and the sheets are cooled with a casting roll to form an unstretched film. In this case, the method of installing a static mixer and a gear pump in the polymer flow path of thermoplastic resin A will not cause stretching breakage, and the relationship between the thickness and average particle size within the range of the present invention, the content, the orientation state within the desired range, and the average protrusion height. It is effective to obtain a film with a high Rt/Rp ratio, Rt/Ra ratio, and surface particle concentration ratio. In addition, setting the melting temperature of the extruder on the thermoplastic resin A side 10 to 40°C higher than that on the thermoplastic resin B side will prevent stretching breakage, and the relationship between the thickness and average particle size, the content, and the content within the range of the present invention. Desired range of orientation state, average protrusion height, Rt/Rp ratio, Rt
/Ra ratio, surface layer particle concentration ratio, and total reflection Raman crystallization index.
次にこの未延伸フィルムを二軸延伸し、二軸配向せしめ
る方法のポイントは、基本的に上述した単層フィルムと
同様である。ただし、積層フィルムの場合の延伸温度の
設定は熱可塑性樹脂Ｂを基準として設定する必要がある
。さらに２層積層フィルムの熱処理工程は、熱可塑性樹
脂Ａ層に吹き付ける熱風温度を熱可塑性樹脂Ｂ層よりも
３〜２０℃低くすることが、本発明範囲の厚さと平均粒
径の関係、含有量、望ましい範囲の配向状態、平均突起
高さ、Ｒｔ／Ｒｐ比、Ｒｔ ／ Ｒａ比、表層粒子濃度
比、全反射ラマン結晶化指数のフィルムを得るのに有効
である。Next, the points of the method for biaxially stretching this unstretched film to achieve biaxial orientation are basically the same as those for the single-layer film described above. However, in the case of a laminated film, the stretching temperature must be set based on thermoplastic resin B. Furthermore, in the heat treatment process of the two-layer laminated film, the temperature of the hot air blown onto the thermoplastic resin A layer is 3 to 20°C lower than that of the thermoplastic resin B layer. , is effective in obtaining a film with desired range of orientation state, average protrusion height, Rt/Rp ratio, Rt/Ra ratio, surface layer particle concentration ratio, and total reflection Raman crystallization index.
［作用コ
本発明は含有する粒子の大きさとフィルム厚さの関係、
含有量、フィルム厚さを特定範囲とした熱可塑性樹脂フ
ィルムあるいはその積層フィルムとしたので、従来の溶
融製膜／二軸延伸プロセスでは得られない表面形態とす
ることができたため、本発明の効果が得られたものと推
定される。[Function] The present invention is based on the relationship between the size of the particles contained and the film thickness;
Since the thermoplastic resin film or its laminated film was used with the content and film thickness within a specific range, it was possible to obtain a surface morphology that could not be obtained with conventional melt film forming/biaxial stretching processes. It is estimated that this was obtained.
［物性の測定方法ならびに効果の評価方法］本発明の特
性値の測定方法並びに効果の評価方法は次の通りである
。[Method of Measuring Physical Properties and Evaluating Effects] The methods of measuring the characteristic values and evaluating the effects of the present invention are as follows.
（１）粒子の平均粒径
フィルムからポリエステルをプラズマ低温灰化処理法（
たとえばヤマト科学製ＰＲ−５０３型）で除去し粒子を
露出させる。処理条件はポリエスチルは灰化されるが粒
子はダメ−ジを受けない条件を選択する。これをＳＥＭ
（走査型電子顕微鏡）で観察し、粒子の画像（粒子によ
ってできる光の濃淡）をイメージアナライザー（たとえ
ばケンブリッジインストルメント製ＱＴＭ９００）に結
び付け、観察箇所を変えて粒子数５０００個以上で次の
数値処理を行ない、それによって求めた数平均径りを平
均粒径とする。(1) Polyester is removed from a film of average particle size by plasma low-temperature ashing process (
For example, the particles are removed using a printer (Model PR-503 manufactured by Yamato Kagaku Co., Ltd.) to expose the particles. The processing conditions are selected so that the polyester is incinerated but the particles are not damaged. This is an SEM
(Scanning Electron Microscope) and connect the image of the particles (shades of light created by the particles) to an image analyzer (for example, Cambridge Instrument QTM900), change the observation location, and perform the next numerical processing when the number of particles is 5000 or more. The number average diameter obtained thereby is taken as the average particle diameter.
Ｄ＝ΣＤ、／Ｎ ここで、Ｄｌは粒子の円相当径、Ｎは個数である。D=ΣD, /N Here, Dl is the circle-equivalent diameter of the particle, and N is the number of particles.
（２）粒子の含有量
ポリエステルは溶解し粒子は溶解させない溶媒を選択し
、粒子をポリエステルから遠心分離し、粒子の全体重量
に対する比率（重量％）をもって粒子含有量とする。場
合によっては赤外分光法の併用も有効である。(2) Particle content A solvent is selected that dissolves the polyester but does not dissolve the particles, centrifuges the particles from the polyester, and defines the particle content as the ratio (% by weight) to the total weight of the particles. In some cases, infrared spectroscopy may also be effective.
（３）結晶化パラメータΔＴｃｇ、融解熱パーキンエル
マー社製のＤＳＣ（示差走査熱量計）■型を用いて測定
した。ＤＳＣの測定条件は次の通りである。すなわち、
試料１０ｍｇをＤＳＣ装置にセットし、３００℃の温度
で５分間溶融した後、液体窒素中に急冷する。この急冷
試料を１０℃／分で昇温し、ガラス転移点Ｔｇを検知す
る。(3) Crystallization parameter ΔTcg, heat of fusion was measured using a DSC (differential scanning calorimeter) type II manufactured by PerkinElmer. The DSC measurement conditions are as follows. That is,
10 mg of the sample is set in a DSC device, melted at a temperature of 300° C. for 5 minutes, and then rapidly cooled in liquid nitrogen. This rapidly cooled sample is heated at a rate of 10° C./min, and the glass transition point Tg is detected.
さらに昇温を続け、ガラス状態からの結晶化発熱ピーク
温度をもって冷結晶化温度Ｔｃｃとした。The temperature was further increased, and the exothermic peak temperature of crystallization from the glass state was defined as the cold crystallization temperature Tcc.
さらに昇温を続け、融解ピークから融解熱を求めた。こ
こでＴｃＣとＴｇの差（Ｔ（ｃ−Ｔ ｇ）を結晶化パラ
メータΔＴｃｇと定義する。The temperature was further increased, and the heat of fusion was determined from the melting peak. Here, the difference between TcC and Tg (T(c-Tg)) is defined as a crystallization parameter ΔTcg.
（４）表面の分子配向（屈折率）
ナトリウムＤ線（５８９ｎｍ）を光源として、アツベ屈
折率計を用いて測定した。マウント液にはヨウ化メチレ
ンを用い、２５℃、６５％ＲＨにて測定した。ポリマの
二軸配向性は長手方向、幅方向、厚さ方向の屈折率をＮ
１、Ｎ２、Ｎ３とした時、（ＮＩ Ｎ２）の絶対値が
０．０７以下、かつ、Ｎ３ ／ ［（Ｎ、＋Ｎ２ ）／
２］が０．９５以下であることをひとつの基準とできる
。また、レーザー型屈折率計を用いて屈折率を測定して
も良い。さらに、この方法では測定が難しい場合は全反
射レーザーラマン法を用いることもできる。(4) Surface molecular orientation (refractive index) Measured using an Atsube refractometer using sodium D line (589 nm) as a light source. Methylene iodide was used as the mounting solution, and the measurement was performed at 25° C. and 65% RH. The biaxial orientation of the polymer has a refractive index of N in the longitudinal direction, width direction, and thickness direction.
1, N2, and N3, the absolute value of (NI N2) is 0.07 or less, and N3 / [(N, +N2 ) /
2] is 0.95 or less. Alternatively, the refractive index may be measured using a laser refractometer. Furthermore, if measurement is difficult with this method, total internal reflection laser Raman method can also be used.
レーザー全反射ラマンの測定は、Ｊｏｂｉｎ−Ｙｖｏｎ
社製Ｒａｍａｎｏｒ Ｕ −１０００ラマンシステムに
より、全反射ラマンスペクトルを測定し、例えばＰＥＴ
の場合では、１６１５ｃｍ−’（ベンゼン環の骨格振動
）と１７３０ｃｍ−”（カルボニル基の伸縮振動）のバ
ンド強度比の偏光測定比（ＹＹ／ＸＸ比など。Laser total internal reflection Raman measurement is performed by Jobin-Yvon
The total reflection Raman spectrum was measured using a Ramanor U-1000 Raman system manufactured by
In the case of , the polarization measurement ratio (YY/XX ratio, etc.) of the band intensity ratio of 1615 cm-' (skeletal vibration of benzene ring) and 1730 cm-' (stretching vibration of carbonyl group).
ここでＹＹ：レーザーの偏光方向をＹにしてＹに対して
平行なうマン光検出、ＸＸ：レーザーの偏光方向をＸに
してＸに対して平行なうマン光検出）が分子配向と対応
することを利用できる。ポリマの二軸配向性はラマン測
定から得られたパラメータを長手方向、幅方向の屈折率
に換算して、その絶対値、差などから判定できる。この
場合の測定条件は次のとおりである。Here, YY: detection of Mann light parallel to Y with the polarization direction of the laser set to Y; XX: detection of Mann light parallel to X with the polarization direction of the laser set to X) corresponds to molecular orientation. Available. The biaxial orientation of a polymer can be determined by converting the parameters obtained from Raman measurement into refractive indices in the longitudinal direction and width direction, and based on their absolute values, differences, etc. The measurement conditions in this case are as follows.
■光源
アルゴンイオンレーザ−（５１４５人）■試料のセツテ
ィング
フィルム表面を全反射プリズムに圧着させ、レーザのプ
リズム・＼の入射角（フィルム厚さ方向との角度）は６
０°とした。■Light source Argon ion laser (5145 people) ■Setting the sample The surface of the film is pressed against a total reflection prism, and the incident angle of the laser prism (angle with the film thickness direction) is 6
It was set to 0°.
■検出器
ＰＭ ： ＲＣＡ３１０３４／Ｐｈｏｔｏｎ Ｃｏｕｎ
ｔｉｎｇ Ｓｙｓｔｅｍ（Ｈａｍａｍａｆｓｕ Ｃ１２
３［１） （ｓｕｐｐｌｙ １６００Ｖ）■測定条件
５ＬＩＴ １０００μｍ
ＬＡＳＥＲ１００ｍＷ
ＧＡＴＥ ＴＩＭＥ １．０ｓｅｃＳＣＡＮ
５ＰＥＥＤ １２ｃｍ−’／ｍｉｎＳＡＭＰＬ
ＩＮＧ ＩＮＴＥＲＶＡＬ ０．２ｃｍ −’ＲＥＰＥ
ＡＴ ＴＩＭＥ ６
（５）全反射ラマン結晶化指数
１ｏｂｉｎ−Ｙｖｏｎ社製Ｒａｍａｎｏｒ Ｕ−１００
０ラマンシステムにより、全反射ラマンスペクトルを測
定し、カルボニル基の伸縮振動である１７３０ｃｍ〜１
の半価幅をもって表面の全反射ラマン結晶化指数とした
。測定条件は次のとおりである。測定深さは、表面から
５００〜１０００オングストロ一ム程度である。■Detector PM: RCA31034/Photon Coun
ting System (Hamamafsu C12
3[1] (supply 1600V) ■Measurement conditions 5LIT 1000μm LASER100mW GATE TIME 1.0secSCAN
5PEED 12cm-'/minSAMPL
ING INTERVAL 0.2cm -'REPE
AT TIME 6 (5) Total reflection Raman crystallization index 1 obin-Yvon Ramanor U-100
The total reflection Raman spectrum was measured using the 0 Raman system, and the stretching vibration of the carbonyl group was measured from 1730 cm to 1.
The half width of the surface was taken as the total reflection Raman crystallization index of the surface. The measurement conditions are as follows. The measurement depth is about 500 to 1000 angstroms from the surface.
■光源
アルゴンイオンレーザ−（５１４５八）■試料のセツテ
ィング
レーザー偏光方向（Ｓ偏光）とフィルム長手方向が平行
となるようにフィルム表面を全反射プリズムに圧着させ
、レーザのプリズムへの入射角（フィルム厚さ方向との
角度）は６０° とした。■Light source: Argon ion laser (51458) ■Setting the sample Press the film surface to a total reflection prism so that the laser polarization direction (S polarization) and the film longitudinal direction are parallel, and the incident angle of the laser to the prism ( The angle with respect to the film thickness direction was 60°.
■検出器
ＰＭ ： ＲＣＡ３１０３４／Ｐｈｏｔｏｎ Ｃｏｕｎ
ｔｉｎｇ Ｓｙｓｔｅｍ（Ｈａｍａｍａｔｓｕ Ｃ１２
３０） （ｓｕｐｐｌｙ １６００Ｖ）■測定条件
５ＬＩＴ １０００μｍ
ＬＡＳＥＲ１００ｍＷ
ＧＡＴＥ ＴＩＭＥ １．０ｓｅｃＳＣＡＮ
５ＰＥＥＤ １２ｃｍ””／ｍｉｎＳＡＭＰＬ
ＩＮＧ ＩＮＴＥＲＶＡＬ Ｏ’、 ２ｃｍ −’ＲＥ
ＰＥＡＴ ＴＩＭＥ 、 ６
（６）表面突起の平均高さ
２検出着方式の走査型電子顕微鏡［ＥＳＭ−３２００、
エリオニクス（株）製］と断面測定装置［ＰＭＳ−１、
エリオニクス（株）製］においてフィルム表面の平坦面
の高さを０として走査した時の突起の高−さ測定値を画
像処理装置［Ｉ ＢＡＳ２０００、カールツアイス（株
）製］に送り、画像処理装置上にフィルム表面突起画像
を再構築する。次に、この表面突起画像で突起部分を２
値化して得られた個々の突起の面積から円相当径を求め
これをその突起の平均径とする。また、この２値化され
た個々の突起部分の中で最も高い値をその突起の高さと
し、これを個々の突起について求める。この測定を場所
をかえて５００回繰返し、突起個数を求め、測定された
全突起についてその高さの平均値を平均高さとした。ま
た個々の突起の高さデータをもとに、高さ分布の標準偏
差を求めた。また走査型電子顕微鏡の倍率は、１０００
〜８０００倍の間の値を選択する。なお、場合によって
は、高精度光干渉式３次元表面解析装置（ＷＹＫＯ社製
ＴＯＰＯ−３Ｄ、対物レンズ＝４０〜２００倍、高解像
度カメラ使用が有効）を用いて得られる高さ情報を上記
ＳＥＭの値に読み替えて用いてもよい。■Detector PM: RCA31034/Photon Coun
ting System (Hamamatsu C12
30) (supply 1600V) ■Measurement conditions 5LIT 1000μm LASER100mW GATE TIME 1.0secSCAN
5PEED 12cm””/minSAMPL
ING INTERVAL O', 2cm-'RE
PEAT TIME, 6 (6) Average height of surface protrusions 2-detection type scanning electron microscope [ESM-3200,
manufactured by Elionix Co., Ltd.] and a cross-sectional measuring device [PMS-1,
The measured height of the protrusions when scanned with the height of the flat surface of the film set as 0 is sent to the image processing device [I BAS2000, manufactured by Carl Zeiss Co., Ltd.], and the image processing device Reconstruct the film surface projection image on top. Next, use this surface protrusion image to mark the protrusion part by 2.
The equivalent circle diameter is determined from the area of each protrusion obtained by converting it into a value, and this is taken as the average diameter of the protrusion. Furthermore, the highest value among the binarized individual protrusion portions is determined as the height of the protrusion, and this value is determined for each protrusion. This measurement was repeated 500 times at different locations to determine the number of protrusions, and the average value of the heights of all the measured protrusions was taken as the average height. Furthermore, the standard deviation of the height distribution was determined based on the height data of each protrusion. Also, the magnification of a scanning electron microscope is 1000
Choose a value between ~8000x. In some cases, the height information obtained using a high-precision optical interferometric three-dimensional surface analyzer (TOPO-3D manufactured by WYKO, objective lens = 40 to 200 times, effective use of a high-resolution camera) may be used in the above-mentioned SEM. It may be used instead of the value of .
（７）中心線平均表面粗さＲａ、中心線深さＲｐ。(7) Centerline average surface roughness Ra, centerline depth Rp.
最大高さＲｔ、突起間隔Ｓｍ
小板研究所製の高精度薄膜段差測定器ＥＴ−１０を用い
て測定した。条件は下記のとおりであり、２０回の測定
の平均値をもって値とした。Maximum height Rt, protrusion spacing Sm Measured using a high-precision thin film step measuring instrument ET-10 manufactured by Koita Research Institute. The conditions were as follows, and the average value of 20 measurements was taken as the value.
・触針先端半径二〇、５μｍ
・触針荷重 ： ５ｍｇ
・測定長 ：１ｍｍ
・カットオフ値：０．０８ｍｍ
なお、Ｒａ、Ｒｐ、Ｒｔ、Ｓｍの定義は、たとえば、奈
良治部著「表面粗さの測定・評価法」 （総合技術セン
ター、１９８３）に示されているものである。・Stylus tip radius 20.5μm ・Stylus load: 5mg ・Measurement length: 1mm ・Cutoff value: 0.08mm The definitions of Ra, Rp, Rt, and Sm are, for example, “Surface Roughness” by Jibu Nara. This method is described in "Methods for Measuring and Evaluating Quality" (Sogo Technological Center, 1983).
（８）ヤング率
Ｊ Ｉ ５−Ｚ−１７０２に規定された方法にしたがっ
て、インストロンタイプの引っ張り試験機を用いて、２
５℃、６５％ＲＨにて測定した。(8) Young's modulus 2 using an Instron type tensile tester according to the method specified in J I 5-Z-1702.
Measurement was performed at 5° C. and 65% RH.
（９）固有粘度［η］ （単位はｄｉ／ｇ）オルソクロ
ルフェノール中、２５℃で測定した溶液粘度から下記式
から計算される値を用いる。(9) Intrinsic viscosity [η] (unit: di/g) A value calculated from the following formula from the solution viscosity measured at 25° C. in orthochlorophenol is used.
すなわち、
η、、／Ｃ＝［η］ ＋Ｋ ［ηコ ２ ・ にこで、
η５Ｆ＝（溶液粘度／溶媒粘度）−１、Ｃは溶媒１００
ｍ ｌあたりの溶解ポリマ重量（ｇ／１００ｍ１．通常
１．２）、Ｋはハギンス定数（０，３４３とする）。ま
た、溶液粘度、溶媒粘度はオストワルド粘度計を用いて
測定した。That is, η,, /C=[η] +K [ηko 2 ・ With a smile,
η5F=(solution viscosity/solvent viscosity)-1, C is solvent 100
Dissolved polymer weight per ml (g/100ml, usually 1.2), K is Huggins constant (assumed to be 0,343). In addition, solution viscosity and solvent viscosity were measured using an Ostwald viscometer.
（１０）表層粒子濃度比
２次イオンマススペクトル（Ｓ ＩＭＳ）を用いて、フ
ィルム中の粒子に起因する元素の内のもっとも高濃度の
元素とポリエステルの炭素元素の濃度比を粒子濃度とし
、厚さ方向の分析を行なう。(10) Surface layer particle concentration ratio Using secondary ion mass spectrometry (SIMS), the concentration ratio of the element with the highest concentration among the elements caused by particles in the film and the carbon element of the polyester is defined as the particle concentration, and the thickness Perform an analysis in the horizontal direction.
ＳＩＭＳによって測定される最表層粒子濃度（深さ０の
点）における粒子濃度Ａとさらに深さ方向の分析を続け
て得られる最高濃度Ｂの比、Ａ／Ｂを表層濃度比と定義
した。測定装置、条件は下記のとおりである。測定装置
、条件は下記のとおりである。The ratio of the particle concentration A at the outermost layer particle concentration (point at depth 0) measured by SIMS to the maximum concentration B obtained by further analysis in the depth direction, A/B, was defined as the surface layer concentration ratio. The measuring device and conditions are as follows. The measuring device and conditions are as follows.
■ 測定装置
２次イオン質量分析装置（Ｓ ＩＭＳ）***、ＡＴＯＭ
ＩＫＡ社製 Ａ−ＤＩＤＡ３１）［１０■ 測定条件
１次イオン種 ：０゜“
１次イオン加速電圧：１２ＫＶ
１次イオン電流：２００ｎＡ
ラスター領 域＝４００μｍ口
分析領域：ゲート３０％
測定真空度： ６．０ ’ｘ １０−９ＴｏｒｒＥ
−Ｇ Ｕ Ｎ：０．５ＫＹ−３，０Ａ（１１）単一
粒子指数
フィルムの断面を透過型電子顕微鏡（ＴＥＭ）で写真観
察し、粒子を検知する。観察倍率を１０ｏｏｏｏ倍程度
にすれば、それ以上分けることができない１個の粒子が
観察できる。粒子の占める全面積をＡ１その内２個以上
の粒子が凝集している凝集体の占める面積をＢとした時
、（Ａ−Ｂ）／Ａをもって、単一粒子指数とする。ＴＥ
Ｍ条件は下記のとおりであり１視野面積：２μｍ２の測
定を場所を変えて、５００視野測定する。■ Measuring device Secondary ion mass spectrometer (SIMS) West Germany, ATOM
IKA A-DIDA31) [10■ Measurement conditions Primary ion species: 0゜" Primary ion acceleration voltage: 12KV Primary ion current: 200nA Raster area = 400μm Mouth analysis area: Gate 30% Measurement vacuum: 6 .0' x 10-9TorrE
-GU N: 0.5KY-3,0A (11) A cross section of the single particle index film is photographically observed using a transmission electron microscope (TEM) to detect particles. If the observation magnification is set to about 1000 times, a single particle that cannot be separated any further can be observed. When the total area occupied by particles is A1 and the area occupied by aggregates in which two or more particles are aggregated is B, (A-B)/A is defined as a single particle index. T.E.
The M conditions are as follows: one field of view area: 2 μm2 is measured at different locations, and 500 fields of view are measured.
・装置：日本電子製ＪＥＭ−１２００ＥＸ・観察倍率：
１０００００倍
・加速電圧：１００ｋＶ
・切片厚さ：約１０００オングストローム（１２）粒径
比
上記（１）の測定において個々の粒子の長径の平均値／
短径の平均値の比である。・Equipment: JEOL JEM-1200EX ・Observation magnification:
100,000 times Acceleration voltage: 100 kV Section thickness: Approximately 1000 angstroms (12) Particle size ratio Average value of the long diameter of each particle in the measurement of (1) above /
It is the ratio of the average value of the short axis.
すなわち、下式で求められる。That is, it can be obtained using the following formula.
長径＝ΣＤ１．／Ｎ
短径＝ΣＤ２＋／Ｎ
Ｄｌｌ 、Ｄ２１はそれぞれ個々の粒子の長径（最大径
）、短径（最短径）、Ｎは総個数である。Long axis=ΣD1. /N short axis=ΣD2+/N Dll , D21 is the long axis (maximum diameter) and short axis (shortest axis) of each individual particle, and N is the total number.
（１３）粒径の相対標準偏差
上記（１）の方法で測定された個々の突起径ＤＩ、平均
径Ｄ１粒子総数Ｎから計算される標準偏差σ（−ｆ（Σ
（Ｄ、−Ｄ） ２／Ｎ＋ ）を平均径りで割った値（σ
／Ｄ）で表わした。(13) Relative standard deviation of particle size Standard deviation σ(-f(Σ
(D, -D) 2/N+) divided by the average diameter (σ
/D).
（１４）低分子成分含有量
試料ポリマを粉砕しソックスレー抽出器を用いて、クロ
ロホルムを溶媒として、還流下で２４時間抽出を行なう
。クロロホルムを蒸発させて得られた抽出物の重量のも
との試料の重量に対する比率（重量％）をもって低分子
成分含有量とした。(14) Low molecular component content The sample polymer is ground and extracted using a Soxhlet extractor under reflux using chloroform as a solvent. The ratio (wt%) of the weight of the extract obtained by evaporating chloroform to the weight of the original sample was defined as the low molecular component content.
（１５）結晶化促進係数
上記（３）の方法で粒子を１重量％含有するポリエステ
ルのΔＴａｇ （Ｉ） 、およびこれから粒子を除去し
た同粘度のポリエステルのΔＴｃｇ（ｎ）を測定し、Δ
Ｔｃｇ（ＩＩ）とΔＴｃｇ（Ｉ）の差［ΔＴｃｇ（ＩＩ
）−ΔＴｃｇ（Ｉ）］をもって、結晶化促進係数とした
。(15) Crystallization promotion coefficient ΔTg (I) of a polyester containing 1% by weight of particles by the method described in (3) above, and ΔTcg (n) of a polyester of the same viscosity from which particles have been removed, and Δ
Difference between Tcg(II) and ΔTcg(I) [ΔTcg(II
)−ΔTcg(I)] was taken as the crystallization promotion coefficient.
（１６）積層フィルム中の熱可塑性樹脂Ａ層の厚さ
２次イオン質量分析装置（ＳＩＭＳ）を用いて、フィル
ム中の粒子の内最も高濃度の粒子に起因する元素とポリ
エステルの炭素元素の濃度比（Ｍ＋／Ｃ＋）を粒子濃度
とし、熱可塑性樹脂Ａ層の表面から深さ（厚さ）方向の
分析を行なう。表層では表面という界面のために粒子濃
度は低く表面から遠ざかるにつれて粒子濃度は高（なる
。本発明フィルムの場合は深さ［Ｉ］でいったん極大値
となった粒子濃度がまた減少し始める。この濃度分布曲
線をもとに極大値の粒子濃度の１／２になる深さ［■］
（ここでＩＩ＞Ｉ）を積層厚さとした。(16) Thickness of the thermoplastic resin layer A in the laminated film Using a secondary ion mass spectrometer (SIMS), the concentration of elements originating from the particles with the highest concentration among the particles in the film and the carbon element of the polyester Using the ratio (M+/C+) as the particle concentration, analysis is performed in the depth (thickness) direction from the surface of the thermoplastic resin A layer. In the surface layer, the particle concentration is low due to the interface called the surface, and as it moves away from the surface, the particle concentration increases (in the case of the film of the present invention, the particle concentration once reached a maximum value at depth [I] and begins to decrease again. Based on the concentration distribution curve, the depth at which the maximum particle concentration is 1/2 [■]
(Here, II>I) was taken as the lamination thickness.
条件は測定法（１０）と同様である。The conditions are the same as in measurement method (10).
なお、フィルム中にもっとも多く含有する粒子が有機高
分子粒子の場合はＳ ＩＭＳでは測定が難しいので、表
面からエツチングしなからＸＰＳ（Ｘ線光電子分光法）
、ＩＲ（赤外分光法）あるいはコンフォーカル顕微鏡な
どで、その粒子濃度のデプスプロファイルを測定し、上
記同様の手法から積層厚さを求めても良い。Note that if the most abundant particles in the film are organic polymer particles, it is difficult to measure them using SIMS, so we recommend using XPS (X-ray photoelectron spectroscopy) instead of etching them from the surface.
The depth profile of the particle concentration may be measured using IR (infrared spectroscopy) or a confocal microscope, and the layer thickness may be determined using the same method as described above.
さらに、上述した粒子濃度のデプスプロファイルからで
はなく、フィルムの断面観察あるいは薄膜段差測定機等
によって熱可塑性樹脂Ａの積層厚さを求めても良い。Furthermore, the laminated thickness of the thermoplastic resin A may be determined not from the depth profile of the particle concentration described above, but by observing the cross section of the film, using a thin film step measuring device, or the like.
なお、単層フィルムの場合の厚さは、公知の方法、例え
ばダイヤルゲージ法、光干渉法、重量法、薄膜段差測定
法等によって求めること−ができる。In the case of a single layer film, the thickness can be determined by a known method such as a dial gauge method, an optical interference method, a gravimetric method, and a thin film step measurement method.
（１７）耐スクラッチ性
フィルムを幅１／２インチのテープ状にスリットしたも
のをテープ走行性試験機を使用して、ガイドピン（表面
粗度：Ｒａでｉ０１００ｎ上を走行させる（走行速度１
０００ｍ／分、走行回数１０パス、巻き付は角＝６０°
、走行張カニ２０ｇ）。(17) A scratch-resistant film slit into a tape with a width of 1/2 inch was run on a guide pin (surface roughness: Ra and i0100n (running speed 1) using a tape runnability tester.
000m/min, 10 passes, wrapping angle = 60°
, running crab 20g).
この時、フィルムに入った傷を顕微鏡で観察し、幅２．
５μｍ以上の傷がテープ幅あたり２本未満は優、２本以
上１０本未満は良、１０本以上は不良と判定した。優が
望ましいが、良でも実用的には使用可能である。At this time, the scratches in the film were observed under a microscope, and the width was 2.
If there were less than two scratches per tape width of 5 μm or more, it was determined to be excellent, if there were 2 or more and less than 10 scratches, it was determined to be good, and if there were 10 or more scratches, it was determined to be poor. Excellent is desirable, but good is still usable for practical purposes.
（１８）耐ダビング性
フィルムに下記組成の磁性塗料をグラビヤロールにより
塗布し、磁気配向させ、乾燥させる。さらに、小型テス
トカレンダー装置（スチールロール／ナイロンロール、
５段）で、温度ニア０℃、線圧： ２００ｋｇ／ｃｍで
カレンダー処理した後、７０℃、４８時間キユアリング
する。上記テープ原反を１／２インチにスリットし、パ
ンケーキを作成した。このパンケーキから長さ２５０ｍ
の長さをＶＴＲカセットに組み込みＶＴＲカセットテー
プとした。(18) A magnetic paint having the following composition is applied to the dubbing-resistant film using a gravure roll, magnetically oriented, and dried. In addition, a small test calender device (steel roll/nylon roll,
After calendering at a temperature of near 0°C and a linear pressure of 200 kg/cm, the product was cured at 70°C for 48 hours. The original tape was slit into 1/2 inch pieces to make pancakes. 250m long from this pancake
This length was incorporated into a VTR cassette to make a VTR cassette tape.
（磁性塗料の組成）
・ｃｏ含有酸イヒ鉄（ＢＥＴ値５０ｍ２／ｇ）２１００
重量部
・エスレックＡ（種水化学製塩化ビニル／酢酸ビニル共
重合体） ：１０重量部・ニラポラン
２３０４ （日本ポリウレタン製ポリウレタンエラスト
マ） ＝１０重量部・コロネートしく日本ポ
リウレタン製ポリイソシアネート）
＝５重量部・レシチン ：１重
量部・メチル・エチルケトン ニア５重量部・
メチルイソブチルケトン ニア５重量部・トルエン
ニア５重量部・カーボンブラック
：２重量部・ラウリン酸
：１．５重量部このテープに家庭用ＶＴＲを用いてシ
バツク製のテレビ試験波形発生器（ＴＧ７／Ｕ７０６）
により１００％クロマ信号を記録し、その再生信号から
シバツク製カラービデオノイズ測定器（９２５Ｄ／１）
でクロマＳ／Ｎを測定しＡとした。また上記と同じ信号
を記録したマスターテープのパンケーキを磁界転写方式
のビデオソフト高速プリントシステム（たとえばソニー
マグネスケール■製のスプリンタ）を用いてＡを測定し
たのと同じ試料テープ（未記録）のパンケーキへダビン
グした後のテープのクロマＳ／Ｎを上記と同様にして測
定し、Ｂとした。このダビングによるクロマＳ／Ｎの低
下（Ａ−Ｂ）が３ｄＢ未満の場合は耐ダビング性：優、
３ｄＢ以上５ｄＢ未満の場合は良、５ｄＢ以上は不良と
判定した。優が望ましいが、良でも実用的には使用可能
である。(Composition of magnetic paint) ・Co-containing iron oxide (BET value 50m2/g) 2100
Parts by weight: S-LEC A (vinyl chloride/vinyl acetate copolymer manufactured by Tanezu Chemical Co., Ltd.): 10 parts by weight, Niraporan 2304 (polyurethane elastomer manufactured by Nippon Polyurethane) = 10 parts by weight, Coronate (polyisocyanate manufactured by Nippon Polyurethane)
= 5 parts by weight Lecithin: 1 part by weight Methyl ethyl ketone 5 parts by weight
Methyl isobutyl ketone 5 parts by weight, toluene 5 parts by weight, carbon black: 2 parts by weight, lauric acid
: 1.5 parts by weight This tape was used with a home VTR and a Shibatsu TV test waveform generator (TG7/U706) was applied.
100% chroma signal was recorded, and the playback signal was measured using Shibaku color video noise measuring instrument (925D/1).
The chroma S/N was measured and given as A. In addition, the same sample tape (unrecorded) on which A was measured using a magnetic field transfer type video software high-speed printing system (for example, Sony Magnescale's Sprinter) on the master tape pancake on which the same signal as above was recorded. The chroma S/N of the tape after dubbing it onto pancakes was measured in the same manner as above, and it was designated as B. If the chroma S/N reduction (A-B) due to dubbing is less than 3 dB, dubbing resistance is excellent.
A value of 3 dB or more and less than 5 dB was determined to be good, and a value of 5 dB or more was determined to be bad. Excellent is desirable, but good is still usable for practical purposes.
（１９）摩擦係数μに
フィルムを幅１／２インチのテープ状にスリットしたも
のをテープ走行性試験機ＴＢＴ−３００型（■横浜シス
テム研究新製）を使用し、６０℃、８０％ＲＨ雰囲気で
走行させ、初期の摩擦係数を下記の式より求めた（フィ
ルム幅は１／２インチとした）。(19) The film was slit into a tape shape with a width of 1/2 inch to give a coefficient of friction μ, and was measured using a tape runnability tester TBT-300 model (manufactured by Yokohama System Research Co., Ltd.) at 60°C and in an 80% RH atmosphere. The initial friction coefficient was determined using the following formula (the film width was 1/2 inch).
μに＝０．７３３ ｌｏｇ （Ｔ２ ／ＴＩ ）ここで
Ｔ８は入側張力、Ｔ２は出側張力である。μ = 0.733 log (T2 /TI) where T8 is the inlet tension and T2 is the outlet tension.
ガイド径は５ｎ＋ｎ＋φであり、ガイド材質は５ＵＳ２
７（表面粗度０．２Ｓ）、巻き付は角は１８０°、走行
速度は３．３ｃｍ／秒である。この測定によって得られ
たμｋが０．３５以下の場合は摩擦係数：良好、０．３
５を越える場合は摩擦係数：不良と判定した。このμに
はフィルムを磁気記録媒体、コンデンサ、包装用などの
加工する時のハンドリング性を左右する臨界点である。The guide diameter is 5n+n+φ, and the guide material is 5US2.
7 (surface roughness 0.2S), the winding angle is 180°, and the running speed is 3.3 cm/sec. If μk obtained by this measurement is 0.35 or less, the friction coefficient is good, 0.3
If it exceeds 5, the friction coefficient is determined to be poor. This μ is a critical point that determines the handling properties when processing the film into magnetic recording media, capacitors, packaging, etc.
（２０）耐削れ性
フィルムを幅１／２インチにテープ状にスリットしたも
のに片刃を垂直に押しあて、さらに０． ５ａｍ押し込
んだ状態で２０ｃｍ走行させる（走行張力＝５００ ｇ
、走行速度：６．７ｃｍ／秒）。この時片刃の先に付着
したフィルム表面の削れ物の高さを顕微鏡で読みとり、
削れ量とした（単位はμｍ）。(20) Press one blade perpendicularly against a tape-like slit of 1/2 inch wide scratch-resistant film, and then Run 20cm with 5am pushed in (running tension = 500 g
, running speed: 6.7 cm/sec). At this time, the height of the scraped material on the film surface attached to the tip of the single blade was read using a microscope.
It was defined as the amount of abrasion (unit: μm).
少なくとも片面について、この削れ量が１０μｍ以下の
場合は耐削れ性：良好、１０μｍを越える場合は耐削れ
性：不良と判定した。この削れ量：１０μｍという値は
、印刷工程やカレンダー工程などの加工工程で、フィル
ム表面が削れることによって、工程上、製品性能上のト
ラブルがおこるか否かを判定するための臨界点である。For at least one side, if the amount of abrasion was 10 μm or less, the abrasion resistance was determined to be good, and if it exceeded 10 μm, the abrasion resistance was determined to be poor. This value of 10 μm of the amount of abrasion is a critical point for determining whether or not problems in process and product performance will occur due to abrasion of the film surface during processing steps such as printing and calendering.
［実施例］ 本発明を実施例に基づいて説明する。[Example] The present invention will be explained based on examples.
実施例１〜１０、比較例１〜７
平均粒径の異なる架橋ポリスチレン粒子、コロイダルシ
リカに起因するシリカ粒子を含有するエチレングリコー
ルスラリーを調製し、このエチレングリコールスラリー
を１９０℃で１．５時間熱処理した後、テレフタル酸ジ
メチルとエステル交換反応後、重縮合し、該粒子を０．
３〜５５重量％含有するポリエチレンテレフタレート（
以下ＰＥＴと略記する）のペレットを作った。また、実
施例９はポリエチレンα、β−ビス（２−クロルフェノ
キシ）エタン−４，４′−ジカルボキシレートを、実施
例１０はポリエチレン２．６−ナフタレートを用いた。Examples 1 to 10, Comparative Examples 1 to 7 Ethylene glycol slurry containing crosslinked polystyrene particles and silica particles derived from colloidal silica with different average particle sizes was prepared, and this ethylene glycol slurry was heat-treated at 190°C for 1.5 hours. After that, the particles were subjected to transesterification reaction with dimethyl terephthalate, followed by polycondensation, and the particles were reduced to 0.
Polyethylene terephthalate containing 3 to 55% by weight (
(hereinafter abbreviated as PET) pellets were made. Further, in Example 9, polyethylene α,β-bis(2-chlorophenoxy)ethane-4,4′-dicarboxylate was used, and in Example 10, polyethylene 2,6-naphthalate was used.
この時、重縮合時間を調節し固有粘度を０゜７０とした
（熱可塑性樹脂Ａ）。また、常法によって、固有粘度０
．６２の実質的に不活性粒子を含有しないＰＥＴを製造
し、熱可塑性樹脂Ｂとした。これらのポリマをそれぞれ
１８０℃で３時間減圧乾燥（３Ｔｏｒｒ） した。熱可
塑性樹脂Ａを押出機１に供給し３１０℃で溶融し、さら
に、熱可塑性樹脂Ｂを押出機２に供給、２８０°Ｃで溶
融し、これらのポリマを合流ブロック（フィードブロッ
ク）で合流積層し、静電印加キャスト法を用いて表面温
度３０℃のキャスティング・ドラムに巻きつけて冷却固
化し、２層構造の未延伸フィルムを作った。この時、口
金スリット間隙／未延伸フィルム厚さの比を１０として
未延伸フィルムを作った。また、それぞれの押出機の吐
出量を調節し総厚さ、熱可塑性樹脂Ａ層の厚さを調節し
た。この未延伸フィルムを温度８０℃にて長手方向に４
゜５倍延伸した。この延伸は２組ずつのロールの周速差
で、４段階で行なった。この−軸延伸フィルムをステン
タを用いて延伸速度２０００％／分で１００℃で幅方向
に４．０倍延伸し、定長下で、２００℃にて５秒間熱処
理し、総厚さ１５μｍ、熱可塑性樹脂Ａ層厚さ０．００
３〜５μｍの二軸配向積層フィルムを得た。これらのフ
ィルムの本発明のパラメータは第１表に示したとおりで
あり、本発明のパラメータが範囲内の場合は耐スクラッ
チ性、耐ダビング性、摩擦係数は第１表に示したとおり
優または良であったが、そうでない場合は耐スクラッチ
性、耐ダビング性、摩擦係数を兼備するフィルムは得ら
れなかった。At this time, the polycondensation time was adjusted so that the intrinsic viscosity was 0.70 (thermoplastic resin A). In addition, by a conventional method, the intrinsic viscosity is 0.
．． 62 substantially inert particle-free PET was produced and designated as Thermoplastic Resin B. Each of these polymers was dried under reduced pressure (3 Torr) at 180° C. for 3 hours. Thermoplastic resin A is supplied to extruder 1 and melted at 310°C, thermoplastic resin B is further supplied to extruder 2 and melted at 280°C, and these polymers are merged and laminated in a merging block (feed block). Then, using an electrostatic casting method, the film was wound around a casting drum with a surface temperature of 30° C., and cooled and solidified to produce an unstretched film with a two-layer structure. At this time, an unstretched film was prepared with a ratio of die slit gap/unstretched film thickness of 10. In addition, the total thickness and the thickness of the thermoplastic resin A layer were adjusted by adjusting the discharge amount of each extruder. This unstretched film was stretched 4 times in the longitudinal direction at a temperature of 80°C.
It was stretched 5 times. This stretching was carried out in four stages with a difference in peripheral speed between two sets of rolls. This -axially stretched film was stretched 4.0 times in the width direction at 100°C at a stretching rate of 2000%/min using a stenter, and then heat treated at 200°C for 5 seconds under constant length to give a total thickness of 15 μm. Plastic resin A layer thickness 0.00
A biaxially oriented laminated film of 3 to 5 μm was obtained. The parameters of the present invention for these films are as shown in Table 1, and when the parameters of the present invention are within the range, the scratch resistance, dubbing resistance, and friction coefficient are excellent or good as shown in Table 1. However, in other cases, a film having good scratch resistance, dubbing resistance, and coefficient of friction could not be obtained.
実施例１１〜１４
実施例１に用いた熱可塑性樹脂Ａの原料を押出機１に供
給し、平均粒径０． ３〜１． ０μｍの架橋ポリスチ
レンの粒子を所定量含有する固有粘度０．６のＰＥＴを
熱可塑性樹脂Ｂとしてこれを押出機２に供給して、実施
例１と同様にして、ただしＡ／Ｂ／Ａの３層構造の総厚
さ１５μｍ１熱可塑性樹脂Ａ層（片側）の厚さが０．０
６〜０．３μｍのフィルムを作った。これらのフィルム
の本発明パラメータは本発明範囲であり、耐スクラ・ン
チ性、耐ダビング性ともに優れたフィルムであった（第
２表）。Examples 11 to 14 The raw material for thermoplastic resin A used in Example 1 was supplied to extruder 1, and the average particle size was 0. 3-1. PET with an intrinsic viscosity of 0.6 containing a predetermined amount of crosslinked polystyrene particles of 0 μm was supplied as thermoplastic resin B to the extruder 2, and the same procedure as in Example 1 was carried out, except that A/B/A was 3. Total thickness of layer structure: 15 μm 1 Thickness of thermoplastic resin A layer (one side): 0.0
Films of 6-0.3 μm were made. The inventive parameters of these films were within the inventive range, and the films were excellent in both scratch resistance and dubbing resistance (Table 2).
実施例１５〜１８、比較例８〜９
平均粒径の異なるコロイダルシリカに起因するシリカ粒
子を含有するエチレングリコールを調製し、ナトリウム
含有量を粒子に対し０．０２〜１゜５重量％とした。こ
のエチレングリコールスラリーを１９０℃で１．５時間
熱処理した後、テレフタル酸ジメチルとエステル交換反
応後、重縮合し、コロイダルシリカに起因するシリカ粒
子を所定量含有するＰＥＴのペレットを作った。この時
、重縮合時間を調節し固有粘度を０． ７とした。また
、実施例１８、比較例９はＰＥＴとｐ−オキシ安息香酸
メチルの共重合体からなる溶融光学異方性ポリエステル
（出光石油化学製ＬＣＰ１００Ｅ）と、コロイダルシリ
カに起因するシリカ粒子を含有するエチレングリコール
スラリーを１９０℃で１゜５時間熱処理した後溶媒を水
に置換したスラリーとを、ベント方式の２軸押比機を用
いて混練し、コロイダルシリカに起因するシリカ粒子を
所定量含有するポリマを作った。これらのペレットをそ
れぞれ１８０℃で３時間減圧乾燥（３Ｔｏｒｒ） Ｌ、
、押出機に供給し、３００°Ｃで溶融し、静電印加キャ
スト法を用いて表面温度３０℃のキャスティング・ドラ
ムに巻きつけて冷却固化し未延伸フィルムを作った。こ
の未延伸フィルムを温度８０℃にて長手方向に１〜４．
５倍延伸した。この延伸は２組ずつのロールの周速差で
、延伸段数を１〜４段階で変更して行なった。この−軸
延伸フィルムをステンタを用いて延伸速度２０００％／
分で１００℃で幅方向に４．０倍延伸し、定長下で、１
９０℃にて５秒間熱処理し、厚さ０６５〜３μｍの二軸
配向フィルムを得た。これらのフィルムの本発明のパラ
メータおよび性能は第３表に示したとおりであり、本発
明のパラメータが本発明範囲内である場合は耐スクラッ
チ性、摩擦係数は優または良であるが、パラメータが本
発明範囲外である場合には耐スクラッチ性、摩擦係数を
兼備したフィルムは得られないことがわかる。Examples 15 to 18, Comparative Examples 8 to 9 Ethylene glycol containing silica particles derived from colloidal silica with different average particle sizes was prepared, and the sodium content was set to 0.02 to 1.5% by weight based on the particles. . This ethylene glycol slurry was heat-treated at 190° C. for 1.5 hours, followed by transesterification with dimethyl terephthalate, followed by polycondensation to produce PET pellets containing a predetermined amount of silica particles derived from colloidal silica. At this time, adjust the polycondensation time to reduce the intrinsic viscosity to 0. It was set at 7. In addition, Example 18 and Comparative Example 9 used a fused optically anisotropic polyester (LCP100E manufactured by Idemitsu Petrochemical Co., Ltd.) consisting of a copolymer of PET and methyl p-oxybenzoate, and ethylene containing silica particles originating from colloidal silica. The glycol slurry was heat-treated at 190°C for 1°5 hours and the solvent was replaced with water, and the slurry was kneaded using a vent type twin-screw presser to produce a polymer containing a predetermined amount of silica particles originating from colloidal silica. made. These pellets were dried under reduced pressure (3 Torr) at 180°C for 3 hours, respectively.
The mixture was supplied to an extruder, melted at 300°C, wound around a casting drum with a surface temperature of 30°C using an electrostatic casting method, and cooled and solidified to produce an unstretched film. This unstretched film was stretched 1 to 4 times in the longitudinal direction at a temperature of 80°C.
It was stretched 5 times. This stretching was carried out by changing the number of stretching stages from 1 to 4 by changing the peripheral speed of each two sets of rolls. This -axially stretched film was stretched at a stretching speed of 200%/
Stretched 4.0 times in the width direction at 100°C for 1 minute, then stretched at a constant length for 1
Heat treatment was performed at 90° C. for 5 seconds to obtain a biaxially oriented film with a thickness of 065 to 3 μm. The parameters and performance of the present invention of these films are shown in Table 3. When the parameters of the present invention are within the range of the present invention, the scratch resistance and friction coefficient are excellent or good, but the parameters are not within the range of the present invention. It can be seen that a film having both scratch resistance and friction coefficient cannot be obtained when the content is outside the range of the present invention.
実施例１９〜２４、比較例１０〜１１
熱可塑性樹脂Ａ、Ｂとして、ＰＥＴ、ポリフェニレンス
ルフィド、ナイロン６を準備した。熱可塑性樹脂Ａには
各種粒子を含有するエチレングリコールスラリーを１９
０℃で１．５時間熱処理した後、溶媒を水に置換したス
ラリーをベント方式の２軸押出機を用いて熱可塑性樹脂
と混練し、各種粒子を所定量含有する熱可塑性樹脂Ａを
作った。Examples 19-24, Comparative Examples 10-11 As thermoplastic resins A and B, PET, polyphenylene sulfide, and nylon 6 were prepared. Thermoplastic resin A contains ethylene glycol slurry containing various particles.
After heat treatment at 0°C for 1.5 hours, the slurry in which the solvent was replaced with water was kneaded with a thermoplastic resin using a vented twin-screw extruder to produce thermoplastic resin A containing a predetermined amount of various particles. .
熱可塑性樹脂Ａを押出機１に供給し３１０〜３３０℃で
溶融し、さらに、実質的に粒子を含有しない熱可塑性樹
脂Ｂを押出機２に供給、２９０〜３１０℃で溶融し、こ
れらの熱可塑性樹脂を第４表のように組み合わせて、合
流ブロック（フィードブロック）で合流積層し、静電印
加キャスト法を用いて表面温度３０℃のキャスティング
・ドラムに巻きつけて冷却固化し、３層構造（Ａ／Ｂ／
Ａ）の未延伸フィルムを作った。この時、口金スリット
間隙／未延伸フィルム厚さの比を１０として未延伸フィ
ルムを作った。また、それぞれの押出機の吐出量を調節
し総厚さ、熱可塑性樹脂Ａ層の厚さを調節した。この未
延伸フィルムを温度５０〜９５℃にて長手方向に４．５
倍延伸した。この延伸は２組ずつのロールの周速差で、
４段階で行なった。この−軸延伸フィルムをステンタを
用いて延伸速度２０００％／分で１００℃で幅方向に４
゜０倍延伸し、定長下で、１８０℃にて５秒間熱処理し
、総厚さ１５μｍ１熱可塑性樹脂Ａ層の厚さおよび厚さ
と含有する粒子の径の比、含有量が異なるサンプルを作
った。これらのフィルムの本発明のパラメータは第４表
に示したとおりであり、本発明のパラメータが範囲内の
場合は耐スクラッチ性、耐ダビング性、摩擦係数は第４
表に示したとおり優または良であったが、そうでない場
合は耐スクラッチ性、耐ダビング性、摩擦係数を兼備す
るフィルムは得られなかった。Thermoplastic resin A is supplied to extruder 1 and melted at 310 to 330°C, and thermoplastic resin B, which does not substantially contain particles, is supplied to extruder 2 and melted at 290 to 310°C. Plastic resins are combined as shown in Table 4, combined and laminated in a feed block, and then wrapped around a casting drum with a surface temperature of 30°C using the electrostatic casting method and cooled and solidified to create a three-layer structure. (A/B/
A) unstretched film was made. At this time, an unstretched film was prepared with a ratio of die slit gap/unstretched film thickness of 10. In addition, the total thickness and the thickness of the thermoplastic resin A layer were adjusted by adjusting the discharge amount of each extruder. This unstretched film was heated to 4.5 mm in the longitudinal direction at a temperature of 50 to 95°C.
Stretched twice. This stretching is done by the difference in circumferential speed between the two sets of rolls.
It was done in 4 stages. This -axially stretched film was stretched in the width direction at 100°C at a stretching speed of 2000%/min using a stenter.
゜0 times stretched and heat treated at 180°C for 5 seconds under constant length to make samples with a total thickness of 15 μm 1 The ratio of the thickness of the thermoplastic resin A layer to the diameter of the contained particles, and the content. Ta. The parameters of the present invention for these films are shown in Table 4, and when the parameters of the present invention are within the range, the scratch resistance, dubbing resistance, and friction coefficient are as shown in Table 4.
As shown in the table, the results were excellent or good; otherwise, a film having both scratch resistance, dubbing resistance, and coefficient of friction could not be obtained.
［発明の効果］
本発明は、製法の工夫により、不活性粒子を含有する熱
可塑性樹脂を用いて、粒子の大きさとフィルム厚さの関
係、含有量、フィルム厚さを特定範囲としたフィルムあ
るいはその積層フィルムとしたので、耐スクラッチ性、
摩擦係数が優れたフィルムとなり、また磁気記録媒体用
に用いた時の耐ダビング性に優れたフィルムが得られた
ものであり、各用途でのフィルム加工速度の増大に対応
できるものである。本発明フィルムの用途は特に限定さ
れないが、加工工程でのフィルム表面の傷が加工工程上
、製品性能上特に問題となる磁気記録媒体用ベースフィ
ルムとして特に有用である。[Effects of the Invention] The present invention utilizes a thermoplastic resin containing inert particles by devising a manufacturing method to produce a film or film with a specific range of the relationship between particle size and film thickness, content, and film thickness. The laminated film has scratch resistance and
A film with an excellent coefficient of friction and excellent dubbing resistance when used for magnetic recording media was obtained, and can respond to increases in film processing speed in various applications. Although the use of the film of the present invention is not particularly limited, it is particularly useful as a base film for magnetic recording media, where scratches on the film surface during processing are particularly problematic in terms of processing and product performance.
また、本発明フィルムのうち２層構造のものは熱可塑性
樹脂Ａ面が走行面（磁気記録媒体用では磁性層を塗布し
ない面、その他の用途では印刷やその地塗材の塗布など
の処理がほどこされない面）として用いることが好まし
い。In addition, for films of the present invention with a two-layer structure, the thermoplastic resin side A is the running surface (for magnetic recording media, the surface is not coated with a magnetic layer, and for other uses, it is the surface that is not coated with a magnetic layer, and for other uses, it is the surface that is not coated with a magnetic layer, and for other uses, it is the surface that is not coated with a magnetic layer). It is preferable to use it as an unfinished surface.
また、本発明は製膜工程内で、コーティングなどの操作
なしで直接複合積層によって作ったフィルムであり、製
膜工程中あるいはその後のコーティングによって作られ
る積層フィルムに比べて、最表層の分子も二軸配向であ
るため、上述した特性以外、例えば、表面の耐削れ性も
はるかに優れ、しかもコスト面、品質の安定性などにお
いて有利であるものである。In addition, the present invention is a film made by direct composite lamination without any operations such as coating during the film-forming process, and compared to laminated films made during the film-forming process or by subsequent coating, the outermost layer has two molecules. Since it is axially oriented, it has far superior properties other than those described above, such as surface abrasion resistance, and is advantageous in terms of cost and quality stability.
Claims (6)
ィルムであって、該フィルム中に含有される不活性粒子
の平均粒径がフィルム厚さの０．１〜１０倍、該粒子の
含有量が０．５〜５０重量％であることを特徴とする厚
さ０．００５〜３μｍの二軸配向熱可塑性樹脂フィルム
。(1) A film containing thermoplastic resin A and inert particles as main components, wherein the average particle diameter of the inert particles contained in the film is 0.1 to 10 times the thickness of the film; A biaxially oriented thermoplastic resin film having a thickness of 0.005 to 3 μm, the content of which is 0.5 to 50% by weight.
を主成分とするフィルムの少なくとも片面に、請求項（
１）に記載の熱可塑性樹脂フィルムが積層されてなるこ
とを特徴とする二軸配向熱可塑性樹脂フィルム。(2) Thermoplastic resin B that does not substantially contain inert particles
At least one side of the film mainly composed of
A biaxially oriented thermoplastic resin film, characterized in that the thermoplastic resin films described in item 1) are laminated.
不活性粒子とを主成分とし、該不活性粒子の含有量が０
．００１〜０．２重量％であるフィルムの少なくとも片
面に、請求項（１）に記載の熱可塑性樹脂フィルムが積
層されてなることを特徴とする二軸配向熱可塑性樹脂フ
ィルム。(3) Thermoplastic resin B and inert particles with an average particle size of 0.007 to 2 μm are the main components, and the content of the inert particles is 0.
．． A biaxially oriented thermoplastic resin film, characterized in that the thermoplastic resin film according to claim 1 is laminated on at least one side of the film in an amount of 0.001 to 0.2% by weight.
つ、熱可塑性樹脂Ａを主成分とするフィルムの表面の全
反射ラマン結晶化指数が２０ｃｍ＾−＾１以下であるこ
とを特徴とする請求項（１）〜（３）のいずれかに記載
の二軸配向熱可塑性樹脂フィルム。(4) A claim characterized in that the thermoplastic resin A is a crystalline polyester, and the total reflection Raman crystallization index of the surface of the film containing the thermoplastic resin A as a main component is 20 cm^-^1 or less The biaxially oriented thermoplastic resin film according to any one of items (1) to (3).
れる不活性粒子が粒径比１．０〜１．３の粒子であるこ
とを特徴とする請求項（１）〜（４）のいずれかに記載
の二軸配向熱可塑性樹脂フィルム。(5) Claims (1) to (4) characterized in that the inert particles contained in the film containing thermoplastic resin A as a main component are particles with a particle size ratio of 1.0 to 1.3. The biaxially oriented thermoplastic resin film according to any one of the above.
れる不活性粒子の相対標準偏差が０．６以下であること
を特徴とする請求項（１）〜（５）のいずれかに記載の
二軸配向熱可塑性樹脂フィルム。(6) According to any one of claims (1) to (5), wherein the relative standard deviation of the inert particles contained in the film containing thermoplastic resin A as a main component is 0.6 or less. biaxially oriented thermoplastic resin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP64000775A JPH0780282B2 (en) | 1988-06-08 | 1989-01-05 | Biaxially oriented thermoplastic resin film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14197288 | 1988-06-08 | ||
| JP63-141972 | 1988-06-08 | ||
| JP64000775A JPH0780282B2 (en) | 1988-06-08 | 1989-01-05 | Biaxially oriented thermoplastic resin film |
Related Child Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6017497A Division JP2804434B2 (en) | 1988-06-08 | 1994-02-14 | Biaxially oriented thermoplastic resin film |
| JP6017499A Division JP2827880B2 (en) | 1988-06-08 | 1994-02-14 | Biaxially oriented thermoplastic resin film |
| JP1749894A Division JP2892273B2 (en) | 1988-06-08 | 1994-02-14 | Biaxially oriented thermoplastic resin film |
| JP18933696A Division JPH0912745A (en) | 1996-07-18 | 1996-07-18 | Biaxially oriented thermoplastic resin film |
| JP9134838A Division JPH1052890A (en) | 1988-06-08 | 1997-05-26 | Biaxialy oriented thermoplastic resin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0277431A true JPH0277431A (en) | 1990-03-16 |
| JPH0780282B2 JPH0780282B2 (en) | 1995-08-30 |
Family
ID=26333841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP64000775A Expired - Lifetime JPH0780282B2 (en) | 1988-06-08 | 1989-01-05 | Biaxially oriented thermoplastic resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780282B2 (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0399847A (en) * | 1989-09-14 | 1991-04-25 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH0399848A (en) * | 1989-09-14 | 1991-04-25 | Toray Ind Inc | Biaxially oriented thermoplastic resin film for magnetic tape base |
| JPH03175034A (en) * | 1989-12-05 | 1991-07-30 | Toray Ind Inc | Biaxially oriented polyester film and worked matter thereof |
| JPH03187741A (en) * | 1989-12-18 | 1991-08-15 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH03207651A (en) * | 1990-01-10 | 1991-09-10 | Toray Ind Inc | Biaxially oriented polyester film |
| JPH04119845A (en) * | 1990-09-10 | 1992-04-21 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH04278349A (en) * | 1991-03-06 | 1992-10-02 | Toray Ind Inc | Biaxially oriented laminated polyester film |
| JPH04341841A (en) * | 1991-05-20 | 1992-11-27 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH0592483A (en) * | 1991-09-30 | 1993-04-16 | Toray Ind Inc | Biaxially-oriented laminated film |
| JPH05269838A (en) * | 1992-03-27 | 1993-10-19 | Toray Ind Inc | Biaxially oriented laminated film |
| JPH0643123B2 (en) * | 1989-07-27 | 1994-06-08 | ローヌ―プーラン・フイルム | Use as composite polyester film and protective layer for photopolymer plate and photopolymer plate containing said film |
| JPH06198827A (en) * | 1992-12-28 | 1994-07-19 | Toray Ind Inc | Biaxially oriented polyester film |
| JPH06256542A (en) * | 1988-06-08 | 1994-09-13 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH06290515A (en) * | 1993-02-11 | 1994-10-18 | Philips Electron Nv | Device for at least one of record and reproduction for tape-type recording carrier |
| US5401559A (en) * | 1991-11-18 | 1995-03-28 | Toray Industries, Inc. | Biaxially oriented thermoplastic resin film |
| US5458964A (en) * | 1992-08-12 | 1995-10-17 | Toray Industries, Inc. | Biaxially oriented film comprising organic particles |
| US5532047A (en) * | 1993-08-30 | 1996-07-02 | Toray Industries, Inc. | Biaxially oriented, laminated polyester film |
| EP0845351A3 (en) * | 1996-11-14 | 1999-03-10 | Teijin Limited | Biaxially oriented laminate polyester film |
| EP1325809A1 (en) * | 2001-12-27 | 2003-07-09 | Toray Industries, Inc. | Biaxially oriented, laminated polyester film |
| JP2006274112A (en) * | 2005-03-30 | 2006-10-12 | Toray Ind Inc | Biaxially oriented polyester film |
| JP2009166424A (en) * | 2008-01-18 | 2009-07-30 | Teijin Ltd | Biaxially stretched polyester film |
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|---|---|---|---|---|
| JPS518387A (en) * | 1974-07-11 | 1976-01-23 | Toray Industries | HORIESUTER USEKISOFUIRUMU |
| JPS60254415A (en) * | 1984-04-16 | 1985-12-16 | ヘキスト アクチエンゲゼルシヤフト | Multilayer biaxially stretched support sheet for informationsupport by magnetism and manufacture thereof |
| JPS61149353A (en) * | 1984-12-24 | 1986-07-08 | 東洋紡績株式会社 | Thermoplastic resin film laminate and manufacture thereof |
| JPS62152850A (en) * | 1985-12-27 | 1987-07-07 | 東洋紡績株式会社 | Thermoplastic-resin film laminate and manufacture thereof |
| JPS62225345A (en) * | 1986-02-14 | 1987-10-03 | ロ−ヌ−プ−ラン・フイルム | Transparent composite polyester film capable of being particularly used for manufacturing metallic glossy film having high gloss and manufacture thereof |
| JPS62259304A (en) * | 1986-05-06 | 1987-11-11 | 帝人株式会社 | Polyester film for capacitor dielectric |
| JPS62290535A (en) * | 1986-06-11 | 1987-12-17 | 東レ株式会社 | Polyester film for magnetic record medium and manufacture thereof |
| JPS63108037A (en) * | 1986-08-27 | 1988-05-12 | Teijin Ltd | Biaxially oriented polyester film |
| JPS63316419A (en) * | 1987-06-18 | 1988-12-23 | Diafoil Co Ltd | Biaxially drawn polyester film for capacitor |
-
1989
- 1989-01-05 JP JP64000775A patent/JPH0780282B2/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS518387A (en) * | 1974-07-11 | 1976-01-23 | Toray Industries | HORIESUTER USEKISOFUIRUMU |
| JPS60254415A (en) * | 1984-04-16 | 1985-12-16 | ヘキスト アクチエンゲゼルシヤフト | Multilayer biaxially stretched support sheet for informationsupport by magnetism and manufacture thereof |
| JPS61149353A (en) * | 1984-12-24 | 1986-07-08 | 東洋紡績株式会社 | Thermoplastic resin film laminate and manufacture thereof |
| JPS62152850A (en) * | 1985-12-27 | 1987-07-07 | 東洋紡績株式会社 | Thermoplastic-resin film laminate and manufacture thereof |
| JPS62225345A (en) * | 1986-02-14 | 1987-10-03 | ロ−ヌ−プ−ラン・フイルム | Transparent composite polyester film capable of being particularly used for manufacturing metallic glossy film having high gloss and manufacture thereof |
| JPS62259304A (en) * | 1986-05-06 | 1987-11-11 | 帝人株式会社 | Polyester film for capacitor dielectric |
| JPS62290535A (en) * | 1986-06-11 | 1987-12-17 | 東レ株式会社 | Polyester film for magnetic record medium and manufacture thereof |
| JPS63108037A (en) * | 1986-08-27 | 1988-05-12 | Teijin Ltd | Biaxially oriented polyester film |
| JPS63316419A (en) * | 1987-06-18 | 1988-12-23 | Diafoil Co Ltd | Biaxially drawn polyester film for capacitor |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2804434B2 (en) * | 1988-06-08 | 1998-09-24 | 東レ株式会社 | Biaxially oriented thermoplastic resin film |
| JPH06256542A (en) * | 1988-06-08 | 1994-09-13 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH0643123B2 (en) * | 1989-07-27 | 1994-06-08 | ローヌ―プーラン・フイルム | Use as composite polyester film and protective layer for photopolymer plate and photopolymer plate containing said film |
| JPH0399847A (en) * | 1989-09-14 | 1991-04-25 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH0399848A (en) * | 1989-09-14 | 1991-04-25 | Toray Ind Inc | Biaxially oriented thermoplastic resin film for magnetic tape base |
| JPH03175034A (en) * | 1989-12-05 | 1991-07-30 | Toray Ind Inc | Biaxially oriented polyester film and worked matter thereof |
| JPH03187741A (en) * | 1989-12-18 | 1991-08-15 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH03207651A (en) * | 1990-01-10 | 1991-09-10 | Toray Ind Inc | Biaxially oriented polyester film |
| JPH04119845A (en) * | 1990-09-10 | 1992-04-21 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH04278349A (en) * | 1991-03-06 | 1992-10-02 | Toray Ind Inc | Biaxially oriented laminated polyester film |
| JPH04341841A (en) * | 1991-05-20 | 1992-11-27 | Toray Ind Inc | Biaxially oriented thermoplastic resin film |
| JPH0592483A (en) * | 1991-09-30 | 1993-04-16 | Toray Ind Inc | Biaxially-oriented laminated film |
| US5401559A (en) * | 1991-11-18 | 1995-03-28 | Toray Industries, Inc. | Biaxially oriented thermoplastic resin film |
| JPH05269838A (en) * | 1992-03-27 | 1993-10-19 | Toray Ind Inc | Biaxially oriented laminated film |
| US5458964A (en) * | 1992-08-12 | 1995-10-17 | Toray Industries, Inc. | Biaxially oriented film comprising organic particles |
| JPH06198827A (en) * | 1992-12-28 | 1994-07-19 | Toray Ind Inc | Biaxially oriented polyester film |
| JPH06290515A (en) * | 1993-02-11 | 1994-10-18 | Philips Electron Nv | Device for at least one of record and reproduction for tape-type recording carrier |
| US5532047A (en) * | 1993-08-30 | 1996-07-02 | Toray Industries, Inc. | Biaxially oriented, laminated polyester film |
| US5677034A (en) * | 1993-08-30 | 1997-10-14 | Toray Industries, Inc. | Biaxially oriented, laminated polyester film |
| EP0845351A3 (en) * | 1996-11-14 | 1999-03-10 | Teijin Limited | Biaxially oriented laminate polyester film |
| US6068909A (en) * | 1996-11-14 | 2000-05-30 | Teijin Limited | Biaxially oriented laminate polyester film |
| EP1325809A1 (en) * | 2001-12-27 | 2003-07-09 | Toray Industries, Inc. | Biaxially oriented, laminated polyester film |
| JP2006274112A (en) * | 2005-03-30 | 2006-10-12 | Toray Ind Inc | Biaxially oriented polyester film |
| JP2009166424A (en) * | 2008-01-18 | 2009-07-30 | Teijin Ltd | Biaxially stretched polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0780282B2 (en) | 1995-08-30 |
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