JPH02214736A - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester filmInfo
- Publication number
- JPH02214736A JPH02214736A JP3512289A JP3512289A JPH02214736A JP H02214736 A JPH02214736 A JP H02214736A JP 3512289 A JP3512289 A JP 3512289A JP 3512289 A JP3512289 A JP 3512289A JP H02214736 A JPH02214736 A JP H02214736A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- film
- average particle
- particle
- range
- 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
- 229920006267 polyester film Polymers 0.000 title claims description 14
- 239000002245 particle Substances 0.000 claims abstract description 183
- 238000005299 abrasion Methods 0.000 abstract description 19
- 239000012770 industrial material Substances 0.000 abstract description 2
- 229920006280 packaging film Polymers 0.000 abstract description 2
- 239000012785 packaging film Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 17
- 239000008188 pellet Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011146 organic particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 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 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、二軸配向ポリエステルフィルムに関し、とく
に磁気テープ用ペースフーイルム、包装用、各種産業資
材用フィルムとして好適な、耐スクラッチ性や耐摩耗性
に優れた二軸配向ポリエステルフィルムに関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a biaxially oriented polyester film, and particularly to a biaxially oriented polyester film that is suitable for use as a film for magnetic tapes, packaging, and various industrial materials, and has excellent scratch resistance and resistance. This invention relates to a biaxially oriented polyester film with excellent abrasion resistance.
［従来の技術］
先に本出願人により、包装用、コンデンサ用あるいは磁
気テープ用ベースフィルムとして、平均粒径Ｏ，ＯＳ〜
２．０μｍ、モース硬度７以上の粒子を含有させた二軸
配向ポリエステルフィルムが提案されている（特開昭６
３−２３０７４１！公報）。[Prior Art] Previously, the present applicant used base films for packaging, capacitors, or magnetic tapes with average particle diameters of O, OS~
A biaxially oriented polyester film containing particles with a diameter of 2.0 μm and a Mohs hardness of 7 or more has been proposed (Japanese Patent Laid-Open No. 6
3-230741! Public bulletin).
このフィルムにおいては、硬い粒子を含有させることに
より、フィルム表面の耐摩耗性を向上しつつ、該粒子の
粒径を比較的大きなものとすることにより、フィルム加
工時や製品としたときの良好な滑り性、走行性を確保す
るようにしているへ。、−ｍ＝［発明が解決しようとす
る課題］
ところが、ポリエステルフィルム、とくに磁気テープ用
ベースフィルムや高い機械的特性が要求される包装用フ
ィルムとして使用される二軸配向ポリエステルフィルム
には、さらに高い耐摩耗性、ざらに優れた耐スクラッチ
性が要求されてきており、上記特開昭６３−２３０７４
１号公報提案のフィルムでは、未だ十分とはいえなくな
ってぎた。In this film, by incorporating hard particles, the abrasion resistance of the film surface is improved, and by making the particle size of the particles relatively large, the film has good properties during film processing and when used as a product. We try to ensure slipperiness and running properties. , -m=[Problem to be Solved by the Invention] However, polyester films, especially biaxially oriented polyester films used as base films for magnetic tapes and packaging films that require high mechanical properties, have even higher Abrasion resistance and scratch resistance with excellent roughness have been required, and
The film proposed in Publication No. 1 was still insufficient.
たとえば、各種工゛程等の速度増大に伴い、工程中にあ
る各種高速臼−ルと接触してもフィルム表面に傷が付か
ないだけの高い耐スクラッチ性が要求されつつあるが、
上記提案フィルムの如く単に比較的粒径の大きな一種類
の硬い粒子を含有させるだけでは、該粒子によりフィル
ム表面上に突起状に突出する部分については硬度が高め
られ耐摩耗性は向上されるものの１．フィルムの地肌（
上記突出部以外の表面部）自身については補強されない
ため、この地肌部分にかき傷が入るおそれがある。For example, as the speed of various processes increases, there is a growing demand for high scratch resistance that will not damage the film surface even if it comes into contact with various high-speed mortars during the process.
If only one type of hard particles with a relatively large particle size were included as in the proposed film mentioned above, the hardness and abrasion resistance would be improved in the areas where the particles protrude like protrusions on the film surface. 1. The background of the film (
Since the surface (other than the protrusions) itself is not reinforced, there is a risk of scratches on this bare surface.
また、地肌部分が補強されない結果、フィルム表面部に
ある、耐摩耗性向上のための粒子の保持力が十分とはい
えず、接触するロール等から受ける外力によって粒子部
がフィルム粉として削られるおそれがあり、該削れが生
じると、それがロール表面等に付着し該付着物によって
さらにフィルム表面が傷付けられるとともに、脱落フィ
ルム粉が異物となって、各種加工工程の外乱となったり
、製品自身の性能を低下させたりするおそれがある。In addition, as a result of not reinforcing the background part, the retention force of the particles on the film surface part, which are used to improve wear resistance, is not sufficient, and there is a risk that the particulate parts will be scraped off as film powder by external forces received from contacting rolls, etc. When this scraping occurs, it adheres to the roll surface, etc., and the film surface is further damaged by the deposits, and the film powder that falls off becomes foreign matter, which may cause disturbances in various processing steps or damage the product itself. There is a risk that performance may deteriorate.
本発明は、上記のような問題点に看目し、二輪配向ポリ
エステルフィルムの表面の耐スクラッチ性および削れ等
に対する耐摩耗性をさらに向上することを目的とする。In view of the above-mentioned problems, the present invention aims to further improve the surface scratch resistance and abrasion resistance against abrasion and the like of a two-wheel oriented polyester film.
［課題を解決するための手段］
この目的に沿う本発明の二軸配向ポリエステルフィルム
は、２種の粒子Ａ、Ｂを含有し、粒子Ａは、平均粒径が
５〜３００１ｍ 、含有量が０．１〜２重量％であり、
粒子Ｂは、平均粒径が３００〜２０００ｎｍ、含有量が
ｏ、ｏｏｓ〜０．５重量％であり、かつ粒子Ｂの近傍領
域における粒子Ａの濃度が他の領域における濃度よりも
高いものから成る。[Means for Solving the Problem] The biaxially oriented polyester film of the present invention that meets this objective contains two types of particles A and B, and the particles A have an average particle size of 5 to 3001 m and a content of 0. .1 to 2% by weight,
Particles B have an average particle diameter of 300 to 2000 nm, a content of o, oos to 0.5% by weight, and the concentration of particles A in the region near the particles B is higher than the concentration in other regions. .
本発明におけるポリエステルは、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−４，４′−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。ただし、本発明を阻害しな
い範囲内、好ましくは１５モル％以内であれば伯成分が
共重合されていてもよい。The polyester in the present invention includes ethylene terephthalate, ethylene α/β-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate, ethylene 2,6
- Contains at least one structural unit selected from naphthalate units as a main constituent. However, the component may be copolymerized within a range that does not impede the present invention, preferably within 15 mol%.
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スクラッチ性がより良好となるの
で特に望ましい。Further, polyester containing ethylene terephthalate as a main component is particularly desirable because it has better scratch resistance.
本発明のフィルムには、二種の粒子Ａ、Ｂが含有される
。The film of the present invention contains two types of particles A and B.
粒子Ａは、比較的平均粒径の小さな粒子であり、主とし
てフィルムの地肌部分を補強するが、この地肌補強効果
を高めるために、硬度の高い粒子あるいはフィルムとの
親和性が良好な粒子が選択される。硬度の高い粒子とし
ては、δ−アルミナ、チタニアゾル、窒化チタンからな
る粒子が好ましく、親和性の良好な粒子としては、有機
粒子、が挙げられる。ただし、粒子への材質としては、
これらに限定されない。Particle A is a particle with a relatively small average particle size, and mainly reinforces the background part of the film, but in order to enhance this background reinforcement effect, particles with high hardness or particles with good affinity with the film are selected. be done. As particles with high hardness, particles made of δ-alumina, titania sol, and titanium nitride are preferable, and as particles with good affinity, organic particles can be mentioned. However, as the material for the particles,
Not limited to these.
上記有機粒子どしては例えば架橋スチレン−ジビニルベ
ンゼン共重合体粒子、シリコン粒子、ポリイミド粒子、
架橋ポリエステル粒子、テフロン粒子、架橋ポリエーテ
ルスルフォン粒子などが挙げられるが、なかでも架橋球
状スチレン−ジビニルベンゼン共重合体粒子などの高分
子架橋重合体粒子が好ましい。Examples of the organic particles include crosslinked styrene-divinylbenzene copolymer particles, silicon particles, polyimide particles,
Examples include crosslinked polyester particles, Teflon particles, crosslinked polyethersulfone particles, and among them, crosslinked polymer particles such as crosslinked spherical styrene-divinylbenzene copolymer particles are preferred.
本発明のポリエステルフィルムに高分子架ｆｆ１ｆｆ１
合体粒子を用いる場合には、高分子架橋重合体粒子の架
橋度は、２５％以上、好ましくは３５％以上であること
が望ましい。The polyester film of the present invention has a polymer cross sectionff1ff1
When using combined particles, the degree of crosslinking of the crosslinked polymer particles is desirably 25% or more, preferably 35% or more.
本発明のポリニスデルフィルムに含有される不活性粒子
の結晶化促進係数は、−５〜＋１０℃の範囲である場合
好ましい。The crystallization promotion coefficient of the inert particles contained in the polynisder film of the present invention is preferably in the range of -5 to +10°C.
有機粒子の弾性率は、特に限定されないが、４０〜５０
００Ｋｇ／Ｗｎ２ 好ましくは１００〜２００ Ｋ’
Ｊ／ｍｍ２の範囲であると好ましい。The elastic modulus of the organic particles is not particularly limited, but is 40 to 50.
00Kg/Wn2 Preferably 100-200K'
The range is preferably J/mm2.
また、有機粒子の耐熱性は、窒素雰囲気下、３００℃、
２時間での減量率が５％未満であると好ましい。In addition, the heat resistance of organic particles is 300℃ under nitrogen atmosphere,
Preferably, the weight loss rate in 2 hours is less than 5%.
また、有機粒子はポリエステルと実質的に反応しないほ
うが好ましい。実質的に反応しない粒子とは、粒子がポ
リエステル中に含有されているときにポリニスデルと化
学反応を起こすことなく、かつ、粒子とポリエステルの
間に共有結合やイオン結合などの化学的結合を持たない
粒子のことを示す。粒子とポリエステルが反応する場合
には、粒子同志の凝集も多くなり粗大粒子となって、耐
削れ性が不良となるので好ましくない。Further, it is preferable that the organic particles do not substantially react with the polyester. Substantially unreactive particles are particles that do not cause a chemical reaction with polynisdel when contained in polyester, and do not have chemical bonds such as covalent bonds or ionic bonds between the particles and the polyester. Indicates particles. When the particles and polyester react, it is not preferable because the agglomeration of the particles increases, resulting in coarse particles and poor abrasion resistance.
また粒子と共に分散剤を添加することは、粒子の凝集を
防ぎ、耐削れ性をより一層良好とするのに好ましい。Further, it is preferable to add a dispersant together with the particles in order to prevent particle agglomeration and further improve the abrasion resistance.
また、粒子Ａは、平均粒径ｄ１が５〜３００ｎｌｌｌの
比較的小さな粒子である。平均粒径がこの範囲よりも小
さいと、フィルム地肌部の補強効果が薄れ、耐スクラッ
チ性が不良となるので好ましくない。Moreover, the particles A are relatively small particles with an average particle diameter d1 of 5 to 300 nlll. If the average particle size is smaller than this range, the reinforcing effect of the film background will be weakened and the scratch resistance will be poor, which is not preferable.
また、平均粒径が上記範囲よりも大きいと、粒子の分布
が粗くなりすぎ、フィルム地肌補強効果が薄れ、粒子Ｂ
あるいは粒子Ｂにより形成されたフィルム表面突起を保
持する強度が低下し、粒子Ｂあるいはそれによるフィル
ム表面突起が削られやすくなる。また、粒子Ａによるフ
ィルム表面突起自身についても削られる機会が増大する
ので好ましくない。In addition, if the average particle size is larger than the above range, the particle distribution will become too coarse, the film background reinforcing effect will be weakened, and the particle B
Alternatively, the strength for holding the film surface protrusions formed by the particles B is reduced, and the particles B or the film surface protrusions caused by them are likely to be scraped. Furthermore, the chances of the protrusions on the film surface themselves being scraped by the particles A increase, which is not preferable.
また粒子Ａの含有量は０．１〜２．０重量％の範囲に調
製される。この範囲よりも少ないと、粒子Ａ含有による
フィルム地肌補強効果が薄れ、望ましい耐スクラッチ性
が得られない。この範囲よりも多いと、含有物が多くな
りすぎるので構造的に脆くなるおそれがあり、フィルム
白身が削り取られやすくなったり、含有粒子が脱落しや
すくなったりするので好ましくない。Further, the content of particles A is adjusted to a range of 0.1 to 2.0% by weight. If the amount is less than this range, the effect of reinforcing the film background due to the inclusion of Particle A will be weakened, and desired scratch resistance will not be obtained. If the amount is more than this range, there is a risk that the content will be too large and the structure may become brittle, and the white of the film may be easily scraped off or the contained particles may easily fall off, which is not preferable.
粒子Ｂは、粒子Ａよりも平均粒径の大ぎな粒子であり、
粒子Ｂによって形成されたフィルム表面突起によりフィ
ルム表面の粗さを増し、表面の摩擦係数を下げることに
より、耐スクラッチ性を向上しつつ、加工時等にＯ−ル
等の他の面に接触する際の抵抗を減らし、フィルム表面
が削りとられにくいようにすることを犯ったものである
。また、耐削れ性を良くするために、フィルムと親和性
の良いものが好ましい。これらを達成可能な粒子Ｂの材
質として、シリカ、炭酸カルシウム、および＃機材料が
挙げられ、有機粒子については前述の粒子Ａと同様の材
質を採り得る。ただし粒子Ｂの材質についても、とくに
上記のものには限定されない。Particle B is a particle having a larger average particle size than particle A,
The film surface protrusions formed by particles B increase the roughness of the film surface and lower the coefficient of friction on the surface, improving scratch resistance and making it easier to contact other surfaces such as O-ru during processing. The purpose of this technique is to reduce the resistance at the time of contact and make it difficult for the film surface to be scraped off. In addition, in order to improve the abrasion resistance, it is preferable to use a material that has good affinity with the film. Examples of materials for particles B that can achieve these goals include silica, calcium carbonate, and organic materials, and the same materials as those for particles A described above can be used for organic particles. However, the material of the particles B is not particularly limited to those mentioned above.
また、粒子Ｂは、平均粒径ｄ２が３００〜２００００ｍ
の比較的大きな粒子であり、粒子Ａの平均粒径ｄ１より
も大きく設定される。この粒子Ｂは、比較的大ぎな粒子
であるため、該粒子によって形成されるフィルム表面突
起の高さを、粒子Ａによるものよりは高くでき、その部
分の表面粗さを粗くできる。粗くなると、摩擦係数を低
減できるので、結果的にフィルム表面の耐スクラッチ性
が良くなるが、平均粒径ｄ２が上記範囲よりも小さいと
、フィルム表面を粗くする効果が小さくなり、その分銅
スクラッチ性が悪くなるので、好ましくない。In addition, the particles B have an average particle diameter d2 of 300 to 20,000 m.
These are relatively large particles, and are set larger than the average particle diameter d1 of particles A. Since the particles B are relatively large particles, the height of the film surface protrusions formed by the particles can be made higher than that by the particles A, and the surface roughness of the portions can be made rougher. When the grain size becomes rough, the coefficient of friction can be reduced, resulting in better scratch resistance on the film surface. However, if the average particle diameter d2 is smaller than the above range, the effect of roughening the film surface will be reduced, and its weight scratch resistance will be improved. This is not preferable because it makes the condition worse.
逆に上記範囲よりも大きいと、粒子Ｂ自身あるいは粒子
Ｂにより形成された表面突起部分が削りとられヤずくな
るので、好ましくない。On the other hand, if it is larger than the above range, the particles B themselves or the surface protrusions formed by the particles B will be scraped off, which is not preferable.
粒子Ｂの含有間はｏ、 ｏｏｓ〜０．５重石％の範囲に
調製される。この範囲よりも少ないと、粒子Ｂ含有によ
る摩擦係数低減効果が薄れるので、望ましい耐スクラッ
チ性が得られない。逆に上記範囲よりも多いと、粒子Ａ
により補強されたフィルム地肌部分の受けもつ、粒子Ｂ
あるいは粒子Ｂによるフィルム表面突起部分が多くなり
すぎ、削りとられやすくなるので、好ましくない。The content of particles B is adjusted to a range of o, oos to 0.5%. If the amount is less than this range, the effect of reducing the coefficient of friction due to the inclusion of particles B will be weakened, making it impossible to obtain desired scratch resistance. Conversely, if the amount exceeds the above range, particles A
Particle B, which supports the film background part reinforced by
Alternatively, the number of protrusions on the film surface caused by the particles B becomes too large, making it easy to be scraped off, which is not preferable.
本発明のフィルムにおいては、粒子Ｂの近傍領域におけ
る粒子Ａの濃度が伯の領域（以下、バルク領域と称する
こともある。）における濃度よりも高い。つまり、粒子
Ａがバルク領域に対し粒子Ｂ周囲に偏在し、平均粒径の
小さな粒子Ａが平均粒径の大きな粒子Ｂ周囲に凝集して
いる。この粒子Ａの偏在度、粒子Ｂの近傍領域の定義に
ついては後述する。粒子Ａが粒子Ｂの近傍領域に偏在す
ることにより、粒子Ａが均一に分散されている場合に比
べ、粒子Ａによるフィルム地肌補強効果が粒子８周りで
とくに高められることになり、該補強されたフィルム地
肌および周囲にある粒子八自身により、粒子Ｂの保持強
度が高められる。その結果、粒子Ｂあるいは粒子Ｂによ
り形成されたフィルム表面突起が削られにくくなるとと
もに、その部分が傷の起点になりにくくなるので耐スク
ラッチ性も同時に向上される。In the film of the present invention, the concentration of particles A in the region near particles B is higher than the concentration in the region (hereinafter sometimes referred to as bulk region). That is, particles A are unevenly distributed around particles B with respect to the bulk region, and particles A with a small average particle size are aggregated around particles B with a large average particle size. The degree of uneven distribution of particles A and the definition of the vicinity area of particles B will be described later. Because particles A are unevenly distributed in the vicinity of particles B, the effect of reinforcing the film background by particles A is particularly enhanced around particles 8, compared to when particles A are uniformly dispersed, and the reinforced The holding strength of the particles B is increased by the film background and the surrounding particles themselves. As a result, the particles B or the protrusions on the film surface formed by the particles B are less likely to be scraped, and the scratch resistance is also improved at the same time since these portions are less likely to become a starting point for scratches.
本発明のフィルムは前述の組成物を主成分とするが、本
発明の目的を阻害しない範囲内で他種ボリマをブレンド
しても良いし、また酸化防止剤、熱安定剤、滑剤、紫外
線吸収剤などの無機または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 film of the present invention has the above-mentioned composition as its main component, but other types of volima may be blended within the range that does not impede the purpose of the present invention, and antioxidants, heat stabilizers, lubricants, ultraviolet absorbers, etc. Inorganic or organic additives such as 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。未延伸フィルム、−軸配向フィルムでは、
耐スクラッチ性が不良となり、粒子あるいは粒子により
形成されたフィルム表面突起が脱落しやすくなるので好
ましくない。The film of the present invention is a film in which the above composition is biaxially oriented. For unstretched films and -axially oriented films,
This is not preferable because the scratch resistance becomes poor and the particles or film surface protrusions formed by the particles tend to fall off.
また、その二軸配向の程度を表わす面配向指数は特に限
定されないが、０．９３５〜（）、９７５ 、特に０゜
９４０〜０．９７０の範囲である場合に耐スクラッチ性
、耐摩耗性がより一層良好となるので望ましい。また、
本発明フィルムの密磨指数は、０．０２〜０．０５の範
囲である場合に耐スクラッチ性、耐摩耗性がより一層良
好となるので特に望ましい。In addition, the plane orientation index representing the degree of biaxial orientation is not particularly limited, but scratch resistance and wear resistance are improved when it is in the range of 0.935 to (), 975, especially 0°940 to 0.970. This is desirable because it provides even better results. Also,
It is particularly desirable that the polishing index of the film of the present invention be in the range of 0.02 to 0.05, since this provides even better scratch resistance and abrasion resistance.
また、本発明フィルムは、幅方向の表面平均粗さＲａが
０．００５〜０．０３０ ｔｌｍ、特に０．００７〜０
．０２５μｍの範囲にある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。Further, the film of the present invention has an average surface roughness Ra in the width direction of 0.005 to 0.030 tlm, particularly 0.007 to 0.
．． A thickness in the range of 0.025 μm is particularly desirable because the scratch resistance becomes even better.
本発明におけるフィルムの摩擦係数μｋが０．２０〜０
．３５の範囲にある場合に、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 friction coefficient μk of the film in the present invention is 0.20 to 0.
．． A value in the range of 35 is particularly desirable because the scratch resistance becomes even better.
また本発明フィルムの表面固有抵抗がｌＸ１０１５Ω・
αよりも小さい場合に耐スクラッチ性、耐摩耗性が一層
良好となるので特に望ましい。この値以上になると、仮
にフィルム粉が削りとられた場合、該フィルム粉が静電
気等により塊状になりやすくなり、塊状になったフィル
ム粉がフィルム面を傷付けやすくなるので、好ましくな
い。Furthermore, the surface resistivity of the film of the present invention is 1×1015Ω・
It is particularly desirable that the value is smaller than α because scratch resistance and wear resistance become even better. If the film powder exceeds this value, it is not preferable because if the film powder is scraped off, the film powder tends to become agglomerated due to static electricity, etc., and the agglomerated film powder tends to damage the film surface.
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、所定のポリエステルに粒子Ａ、Ｂを含有せしめる
方法としては、重合前、重合中、重合後のいずれに添加
することも可能であるが、とくに、ポリエステルの重合
前、つまりポリエステルのジオール成分であるエチレン
グリコールなどに、スラリーの形で混合、分散せしめて
添加する方法が好ましい。First, as a method for incorporating particles A and B into a given polyester, it is possible to add them before, during, or after polymerization, but in particular, before polymerization of polyester, that is, as a diol component of polyester. A preferred method is to mix and disperse the compound in a slurry, such as ethylene glycol, and then add the compound.
特に、２種の粒子を混合させるのは、スラリーの段階、
またはエステル交換反応直後の段階であると、粒子回り
凝集度（偏在度）を本発明の範囲内、つまり粒子Ｂの近
傍領域における粒子Ａの濃度をバルク領域における濃度
よりも高くするのに特に有効である。In particular, mixing two types of particles is at the slurry stage.
Alternatively, the stage immediately after the transesterification reaction is particularly effective for increasing the degree of agglomeration (degree of maldistribution) around the particles within the range of the present invention, that is, the concentration of particles A in the region near the particles B is higher than the concentration in the bulk region. It is.
また、この時、微細なガラスピーズ等をメディアとして
分散させたのち、ガラスピーズを除去するメディア分散
法などで粒子を分散させると好ましい。また、エチレン
グリコールスラリーの段階で粒子に加熱処理を行なう方
法も粒子回り凝集度を本発明の範囲内とするのに特に有
効である。Further, at this time, it is preferable to disperse the particles by a media dispersion method in which fine glass beads or the like are dispersed as a media and then the glass beads are removed. Furthermore, a method of heat-treating the particles at the stage of forming the ethylene glycol slurry is also particularly effective in bringing the degree of agglomeration around the particles within the range of the present invention.
また、粒子の含有聞を調節する方法としては、高濃度の
マスターペレットを製膜時に稀釈する方法を用いると粒
子回り凝集度を本発明の範囲内とするのに特に有効であ
る。Further, as a method for adjusting the content of particles, a method of diluting a highly concentrated master pellet during film formation is particularly effective in controlling the degree of agglomeration around the particles within the range of the present invention.
かくして、高濃度のマスターペレットと粒子Ａ１Ｂを含
有しないペレットとを混合し、所定濃度の粒子Ａ１Ｂを
含有するポリエステルペレットを十分乾燥させた後、公
知の溶融押出機に供給し、２７０℃〜３３０℃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
ル上で冷却同化上しめて未延伸フィルムを作る。この未
延伸フィルムを作る場合、キャスト時のドラフト比（口
金のスリット幅／未延伸フィルムの厚み）は、１６倍以
上の高い値であることが好ましい。高ドラフトキャスト
を行なうと粒子が表層部へ集中舊るという特異な現染が
起こり、粒子Ａ、Ｂにそれぞれねらった機能を発揮させ
やすくなるため、このような高ドラフトキャストを行な
うことが本発明において特に有効である。Thus, the high-concentration master pellets and pellets not containing particles A1B are mixed, and the polyester pellets containing particles A1B at a predetermined concentration are sufficiently dried, and then supplied to a known melt extruder and heated at 270°C to 330°C. The film is then extruded into a sheet through a slit die, cooled and assimilated on a casting roll to form an unstretched film. When producing this unstretched film, the draft ratio (slit width of die/thickness of unstretched film) during casting is preferably a high value of 16 times or more. When high draft casting is performed, a unique dyeing occurs in which the particles are concentrated on the surface layer, making it easier for particles A and B to perform their intended functions. It is particularly effective in
次にこの未延伸フィルムを二Ｉｋｌ１１１１伸し二軸配
向せしめる。延伸方法としては、逐次二輪延伸法、また
は同時二輪延伸法を用いることができる。逐次二軸延伸
法の場合は艮手力向、幅方向の順に延伸するのが一般的
であるが、この順を逆にして延伸してもよい。二輪延伸
の条件は延伸方法、ポリマの種類などによって必ずしも
一定ではないが、通常長手方向、幅方向ともに８０〜１
６０℃、好ましくは９０〜１５０℃の範囲で、延伸倍率
はそれぞれ３゜０〜５．０倍、好ましくは３．２〜４．
５倍の範囲が、また延伸速度は１０００〜７０．０００
％／分の範囲が好適である。Next, this unstretched film is stretched twice to make it biaxially oriented. As the stretching method, a sequential two-wheel stretching method or a simultaneous two-wheel stretching method can be used. In the case of the sequential biaxial stretching method, it is common to stretch in the order of the hand force direction and the width direction, but this order may be reversed. The conditions for two-wheel stretching are not necessarily constant depending on the stretching method, type of polymer, etc., but are usually 80 to 1 in both the longitudinal and width directions.
At 60°C, preferably in the range of 90 to 150°C, the stretching ratio is 3° to 5.0 times, preferably 3.2 to 4.
The range is 5 times, and the stretching speed is 1000 to 70,000.
A range of %/min is preferred.
次にこの延伸フィルムを熱処理する。熱処理条件は定長
下、および幅方向に１〜１５％、好ましくは２〜１０％
の弛緩下で、また、幅方向に１．０１〜１゜２倍、好ま
しくは１．０５〜１．１５倍微延伸下で、１５０〜２３
０°Ｃ１好ましくは１７０〜２２０°Ｃの範囲で０．５
〜６０秒間が好適である。Next, this stretched film is heat treated. The heat treatment conditions are 1 to 15%, preferably 2 to 10% in the constant length and width direction.
under relaxation of
0°C1 preferably 0.5 in the range of 170-220°C
~60 seconds is suitable.
［物性の測定方法ならびに効果の評価方法］本発明の特
性値の測定方法なら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）粒子の含＃最（重量％）
ポリエステル１Ｊをプラズマ装置で灰化させ、原子吸光
分析装置（たとえば島津製作所製ＡＡ−６８０型〉を用
いてポリエステル中の各元素の量を定吊し、その元素か
らなる粒子の量を粒子の分子量から検線して、重量％と
して求める。尚、粒子の化学組成はＸａ回折などの方法
で知ることができる。(1) Particle content (weight %) 1J of polyester is incinerated with a plasma device, and the amount of each element in the polyester is determined using an atomic absorption spectrometer (for example, AA-680 model manufactured by Shimadzu Corporation). The amount of particles consisting of the element is determined as a percentage by weight by checking the molecular weight of the particles.The chemical composition of the particles can be determined by a method such as Xa diffraction.
また、必要に応じて、螢光Ｘ線分析法や、熱分解ガスク
ロマトグラフィー、赤外線吸収、ラマン散乱などを用い
て定母することもできる。Furthermore, if necessary, a constant value can be determined using fluorescent X-ray analysis, pyrolysis gas chromatography, infrared absorption, Raman scattering, or the like.
（２）粒子の平均粒径（ｎ ｍ ）
粒子を含有したフィルムを、フィルム平面に垂直に厚さ
１ｏｏｏへの超薄切片とし、透過型電子顕微鏡（例えば
日本電子製ＪＥＨ−１２００ＥＸなど）を用いて粒子を
観察し、１００ｐＡ野について平均した値を平均粒径と
した。但し、ここで、平均粒径とは一次粒子の平均粒径
であり、粒子が凝集状態にある場合でも個々の一次粒子
の実効径から求めたものをいう。(2) Average particle diameter of particles (nm) The film containing the particles was cut into ultrathin sections perpendicular to the plane of the film to a thickness of 100 mm, and sliced using a transmission electron microscope (for example, JEOL JEH-1200EX, etc.). The particles were observed, and the average value for the 100 pA field was taken as the average particle diameter. However, the average particle size herein refers to the average particle size of primary particles, and is determined from the effective diameter of each primary particle even when the particles are in an agglomerated state.
（３）粒子Ａの偏在度
粒子を含有したフィルムを、フィルム表面に垂直に厚さ
１０００への超薄切片とし、透過型電子顕微鏡を用いて
２〜１０万倍程度の倍率で観察し写真層形する。上記写
真で一次粒径０．３μ７ｎ以上の粒子を粒子Ｂとし、−
次粒径０．３μ７ｎ未満の粒子をＡとする。またここで
、粒子Ｂとポリエステルとの界面からポリエステル側に
０．２μｍ以内の領域を粒子Ｂの近傍領域とする。(3) Degree of uneven distribution of particles A The film containing the particles was cut into ultrathin sections perpendicular to the film surface to a thickness of 1000 mm, and observed at a magnification of about 20,000 to 100,000 times using a transmission electron microscope. Shape. In the above photograph, particles with a primary particle size of 0.3μ7n or more are defined as particles B, and -
Particles having a secondary particle size of less than 0.3μ7n are designated as A. Further, here, a region within 0.2 μm from the interface between particle B and polyester to the polyester side is defined as a region near particle B.
この透過型電子顕微鏡写真において、粒子Ｂの近傍領域
に存在する粒子Ａの一次粒子数をカウントし、近傍領域
の面積（μｍ”）で削ったものをＮに（個／μ７ｒｔ２
）とする。また粒子Ｂから０．２μ７ｎ以上離れた場所
において１μＴｒＬ全中に存在する粒子Ａの一次粒子数
をＮｍとする この測定を１００視野について行ない、
平均した値をそれぞれＮＫ、ＮＭとし、ＮＫ／ＮＭを粒
子Ａの偏在度とする。In this transmission electron micrograph, the number of primary particles of particle A existing in the vicinity of particle B was counted, and the number of primary particles shaved by the area of the vicinity (μm'') was expressed as N (particles/μ7rt2).
). Further, the number of primary particles of particle A existing in 1 μTrL at a place 0.2 μ7n or more away from particle B is Nm. This measurement is performed for 100 fields of view,
Let the average values be NK and NM, respectively, and let NK/NM be the degree of uneven distribution of particles A.
したがって、粒子Ｂの近傍領域における粒子Ａの濃度が
他の領域（バルク領域）（おける８１度よりも高いとい
うことは、上記定義による偏在度〉１を意味する。この
偏在度は、好ましくは２よりも大きく、さらに、３より
も大きいことがより好ましい。Therefore, the fact that the concentration of particles A in the region near particle B is higher than 81 degrees in other regions (bulk region) means that the degree of uneven distribution>1 according to the above definition.This degree of uneven distribution is preferably 2. More preferably, it is larger than 3, and more preferably larger than 3.
尚、粒子の種類はＴＥＸ−ＸＭＡにて、確認することも
できる。Incidentally, the type of particles can also be confirmed by TEX-XMA.
（４）面配向指数
ナトリウムＤ線（波長５８９ｎｍ ＞を光源としてアツ
ベ屈折率Ｗ１を用いて、二軸配向フィルムの厚さ方向の
屈折率（Ａとする）および溶融プレス後１０℃の水中へ
急冷して作った無配向（アモルファス）フィルムの厚さ
方向の屈折率（Ｂとする）を測定し、Ａ／Ｂをもって面
配向指数とした。マウント液にはヨウ化メチレンを用い
、２５°ｃ１６５％Ｒ１１にて測定した。(4) Planar orientation index sodium D line (wavelength 589 nm) Using Atsube's refractive index W1 as a light source, determine the refractive index in the thickness direction of the biaxially oriented film (denoted as A) and quench it in water at 10°C after melt pressing. The refractive index (referred to as B) in the thickness direction of the non-oriented (amorphous) film made by Measured at R11.
（５）密度指数
ｎ−へブタン／四塩化炭素からなる密度勾配管を用いて
測定したフィルムの密度をρ１（ｇ／ｃＩＩｔ）とし、
このフィルムを溶融プレス後、１０℃の水中へ急冷して
作った無配向（アモルファス）フィルムの密度ρ２との
差（ρ１−ρ２）を・しって密［ａ指数とした。(5) Density index The density of the film measured using a density gradient tube made of n-hebutane/carbon tetrachloride is ρ1 (g/cIIt),
After melt-pressing this film, the difference (ρ1-ρ2) from the density ρ2 of a non-oriented (amorphous) film made by rapidly cooling it in water at 10° C. was determined to be the density [a index].
（６）摩擦係数μに
テープ走行性試験１ｆｆＴＢＴ−３００型［株式会社横
浜システム研究所製］を使用し、２０℃、６０％ＲＨ雰
囲気で走行させ、初期のμｋ（摩擦係数）を下記の式よ
り求めた。(6) Tape runability test for friction coefficient μ Using a 1ff TBT-300 model [manufactured by Yokohama System Research Institute Co., Ltd.], run in an atmosphere of 20°C and 60% RH, and calculate the initial μk (friction coefficient) using the following formula. I asked for more.
μに＝０．７３３ ＋ｏｏ （Ｔ−１／１’０ ＞こ
こで、Ｔｏは入側張力、Ｔ１は出側張力である。ガイド
径は６＃Φであり、ガイド材質は５ＵＳ２７（表面粗度
０．２８）、巻き付は角は１８０゜走行速度は３．３ｃ
ｍ／秒である。μ = 0.733 +oo (T-1/1'0 > Here, To is the inlet tension, T1 is the outlet tension. The guide diameter is 6#Φ, and the guide material is 5US27 (surface roughness 0.28), wrapping angle is 180°, running speed is 3.3c
m/sec.
（７）表面固有抵抗
超絶縁訂［川口電機製作所株式会社製］ ＶＥ−４０型
を使用して測定した。(7) Surface specific resistance Super insulation correction [manufactured by Kawaguchi Electric Seisakusho Co., Ltd.] Measured using VE-40 model.
（８）耐スクラッチ性
７ ７ 走行試！１ｉＨＪｔ Ｔ Ｂ Ｔ−３００Ｄ
／ ｔ−１型［株式会社横浜システム研究所］を使用し
、フィルムを幅１／２インチのテープ状にスリットし、
張力３ＪＪ、走行速度２５０１ｎ／分で、ビデオカセッ
トのテープガイドピン（表面粗さがＲｔで２５００ｎｍ
程度の表面を持ったスデンレス製ガイドビン）上を巻付
角６０°で６０ｍ走行させ、その時につく傷の四を次の
基準にしたがい目視で判定した。(8) Scratch resistance 7 7 Driving test! 1iHJt T B T-300D
/ Using the T-1 model [Yokohama System Research Institute Co., Ltd.], slit the film into a tape shape with a width of 1/2 inch.
At a tension of 3JJ and a running speed of 2501n/min, the video cassette tape guide pin (surface roughness Rt is 2500nm)
The test piece was run for 60 m at a wrapping angle of 60° on a stainless steel guide bottle (with a surface of about 100 degrees), and the scratches formed during the run were visually judged according to the following criteria.
まったく傷のないもの・・・・・・・・・５点浅い傷の
あるもの・・・・・・・・・・・・・・・３点深い傷の
あるもの・・・・・・・・・・・・・・・１点また、５
点と３点の中間を４点、３点と１点の中間を２点とした
。この時、３点以上を耐スクラッチ性良好、３点未満を
耐スクラッチ性不良とした。Items with no scratches at all...5 points Items with shallow scratches...3 points Items with deep scratches...・・・・・・・・・1 point and 5
The middle point between points and three points was set as 4 points, and the middle point between 3 points and 1 point was set as 2 points. At this time, a score of 3 or more was considered good scratch resistance, and a score of less than 3 was considered poor scratch resistance.
この時の判定で３点未満のフィルムは、フィルムの加工
時や製品としたときの走行時にフィルム表面が摩耗して
深い傷が発生するため、製品の品質が著しく悪くなる。If the film scores less than 3 points at this time, the quality of the product will be significantly poor because the surface of the film will be abraded and deep scratches will occur during processing or during running when the film is made into a product.
（９）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０．５ｍｎ押し込ん
だ状態で２０ｃｍ走行させる（走行張力＝５００ｇ、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）この削れ量の両面の平均値が５
μｍ以下の場合は耐削れ性：非常に良好、５〜７μｍの
場合は耐削れ性：良好、７μｍを越える場合は耐削れ性
：不良と判定した。この７μｍ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、■捏上、製品性能上のトラブルがおこ
るか否かを厳しく判定するための臨界点である。(9) Press one blade perpendicularly against a 1/2 inch wide tape-shaped slit of the abrasion-resistant film, push it further by 0.5 mm, and run it for 20 cm (running tension = 500 g, running speed: 6. 7cm/sec). At this time, the height of the scraped material on the surface of the film attached to the tip of the single blade was read using a microscope, and the scraped amount was determined (unit: μm).The average value of this scraped amount on both sides was 5.
If it was less than μm, it was determined that the abrasion resistance was very good, if it was 5 to 7 μm, it was determined that the abrasion resistance was good, and if it was more than 7 μm, it was determined that the abrasion resistance was poor. This value of 7 .mu.m is a critical point for strictly determining whether or not the surface of the film is scraped during processing steps such as printing and calendering, thereby causing troubles in processing and product performance.
［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１〜１２
粒子Ａとして、平均粒径ｄ１がそれぞれ異なるが本発明
範囲内である、δ−アルミナ、チタニアゾル、窒化チタ
ン、高分子架橋重合体粒子を選び、粒子Ｂとして、平均
粒径ｄ２がそれぞれ異なるが本発明範囲内である、シリ
カ、炭酸カルシウム、高分子架橋重合体粒子を選び、そ
れぞれ、■チレングリコール中に均一に分散させ、１９
５℃で２時間熱処理したのち、テレフタル酸ジメヂルと
エステル交換反応後重縮合し、粒子Ａ、Ｂをともに本発
明で規定した範囲よりは相当高い濃度で含有するポリエ
ステルを作成し、それをマスターペレットにした。この
マスターペレット作成の段階で、該マスターペレット中
に含有される粒子Ａと粒子Ｂの比率を決めた。Examples 1 to 12 As particles A, δ-alumina, titania sol, titanium nitride, and crosslinked polymer particles were selected, each having a different average particle size d1 but within the range of the present invention, and as particles B, average particle size d2 was selected. Select silica, calcium carbonate, and crosslinked polymer particles each having different values but within the scope of the present invention, and uniformly disperse them in 19 ethylene glycol.
After heat treatment at 5°C for 2 hours, polycondensation is carried out after transesterification with dimedyl terephthalate to create a polyester containing both particles A and B in a concentration considerably higher than the range specified in the present invention, which is then made into master pellets. I made it. At the stage of preparing this master pellet, the ratio of particles A and B contained in the master pellet was determined.
各マスターペレットと、粒子を含有していないポリエス
テルペレットとを、粒子Ａおよび粒子Ｂが本発明の含有
率の範囲となるように混合し、混合したペレットを１８
０’Ｃで３時間域Ｌ１−乾燥（３−「ｏｒｒ）した。こ
のペレットを押出機に供給し、２９０℃で溶融押出し、
静電印加キャスト法を用いて表面温度３０°Ｃのキレス
ティング・ドラムに巻き付けて冷却固化し厚さ約１８０
μＩｎの未延伸フィルムを作った。このとぎのドラフト
比は２２であった。Each master pellet and a polyester pellet that does not contain particles are mixed so that the content of particles A and B is within the range of the present invention, and the mixed pellet is
Area L1-dried (3-"orr) for 3 hours at 0'C. The pellets were fed to an extruder and melt extruded at 290C,
Using the electrostatic casting method, it is wrapped around a chelating drum with a surface temperature of 30°C and cooled and solidified to a thickness of approximately 180°C.
An unstretched film of μIn was made. The draft ratio at this point was 22.
この未延伸フィルムを９０°Ｃにて長手方向に３．４倍
延伸した。この延伸は２組のロール周速差で行なわれ、
延伸速度は１００００％／分であった。この−軸フイル
ムをステンターを用いて延伸、＆ Ｉｆｆ ３０００％
／分で１００℃で幅り向に３．６倍延伸し、幅方向に１
．０５倍微延伸させつつ、２１０°Ｃにて５秒間熱処理
し、厚さ１５μｍの二軸配向ポリエステルフィルムを得
た。これらのフィルムの性能は第１表に示した通り、粒
子Ａ、Ｂの平均粒径、含イ１量が本発明範囲であり、か
つ粒子Ａの偏在度が１よりも大きいので、耐スクラッチ
性、耐削れ＋！１ともに優れたフィルムが１ｑられた。This unstretched film was stretched 3.4 times in the longitudinal direction at 90°C. This stretching is performed with a difference in the peripheral speed of two sets of rolls,
The stretching speed was 10,000%/min. Stretch this -axis film using a stenter, & If 3000%
Stretched 3.6 times in the width direction at 100℃/min, and stretched 1 times in the width direction.
．． A biaxially oriented polyester film having a thickness of 15 μm was obtained by heat treatment at 210° C. for 5 seconds while slightly stretching the film by a factor of 0.05. As shown in Table 1, the performance of these films is that the average particle diameter of particles A and B and the 1 content are within the range of the present invention, and the degree of uneven distribution of particle A is greater than 1, so the scratch resistance is excellent. , Abrasion resistance +! 1 and 1 were both excellent films.
比較例１〜１０
粒子Ａ、Ｂの平均粒径が本発明の範囲から外れるもの、
含有量が本発明の範囲から外れるもの、および、粒子Ａ
が均一に分散され、粒子への偏在度が実質的に１である
もの、あるいは偏在度が１よりも小さくバルク領域の粒
子Ａの濃度の方が高いものについて、それぞれ前記実施
例と同一の製造方法にて厚さ１５μ７ｎの二軸配向ポリ
エステルフィルムを得た。これらのフィルムの性能は第
２表に示した通り、粒子Ａ、［３の平均粒径、含有量あ
るいは粒子への偏在度のいずれが本発明の範囲から外れ
ても、耐スクラッチ性、耐削れ性を両立させることので
きるフィルムは得られなかった。なお、実施例、比較例
ともにポリ１スプルはポリエチレンテレフタレートであ
った。Comparative Examples 1 to 10 Particles A and B whose average particle diameters are outside the scope of the present invention,
Those whose content falls outside the scope of the present invention, and particles A
are uniformly dispersed and the degree of maldistribution in the particles is substantially 1, or the degree of maldistribution is less than 1 and the concentration of particles A in the bulk region is higher, respectively, by the same production as in the above example. A biaxially oriented polyester film with a thickness of 15μ7n was obtained by this method. As shown in Table 2, the performance of these films is that even if the average particle size, content, or uneven distribution of particles A and [3 in the particles are outside the scope of the present invention, scratch resistance and abrasion resistance are maintained. It was not possible to obtain a film that was compatible with both properties. In addition, the poly 1 sprue in both Examples and Comparative Examples was polyethylene terephthalate.
［発明の効果］
以上説明したように、本発明によれば、特定の範囲の平
均粒径、含＠吊を有する二種の粒子Ａ、Ｂを含有量、か
つ粒子Ａの偏在曵が１よりも大きい二軸配向ポリエステ
ルフィルムとしたので、最近の苛酷な使用条何にも耐え
得る、優れた耐スクラッチ性、耐削れ性（耐摩耗性）を
備えたフィルムが得られる。[Effects of the Invention] As explained above, according to the present invention, the content of two types of particles A and B having an average particle diameter in a specific range and a concentration of Since the biaxially oriented polyester film has a large diameter, it is possible to obtain a film with excellent scratch resistance and abrasion resistance (abrasion resistance) that can withstand all the harsh conditions of use these days.
Claims (1)
５〜３００ｎｍ、含有量が０．１〜２重量％であり、粒
子Ｂは、平均粒径が３００〜２０００ｎｍ、含有量が０
．００５〜０．５重量％であり、かつ粒子Ｂの近傍領域
における粒子Ａの濃度が他の領域における濃度よりも高
いことを特徴とする二軸配向ポリエステルフィルム。 ２、表面固有抵抗が１×１０＾１＾５Ω・ｃｍよりも小
さい請求項１記載の二軸配向ポリエステルフィルム。[Claims] Contains one or two types of particles A and B, where particle A has an average particle diameter of 5 to 300 nm and a content of 0.1 to 2% by weight, and particle B has an average particle size of 5 to 300 nm and a content of 0.1 to 2% by weight. Diameter is 300-2000nm, content is 0
．． 005 to 0.5% by weight, and the concentration of particles A in a region near particles B is higher than the concentration in other regions. 2. The biaxially oriented polyester film according to claim 1, which has a surface resistivity smaller than 1×10^1^5 Ω·cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1035122A JP2513826B2 (en) | 1989-02-16 | 1989-02-16 | Biaxially oriented polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1035122A JP2513826B2 (en) | 1989-02-16 | 1989-02-16 | Biaxially oriented polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02214736A true JPH02214736A (en) | 1990-08-27 |
| JP2513826B2 JP2513826B2 (en) | 1996-07-03 |
Family
ID=12433127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1035122A Expired - Lifetime JP2513826B2 (en) | 1989-02-16 | 1989-02-16 | Biaxially oriented polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2513826B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1270669A1 (en) * | 1991-08-13 | 2003-01-02 | Teijin Limited | Biaxially oriented, unidirectionally long polyethylene-2,6-naphthalate film and magnetic tape therefrom |
| JP2008519903A (en) * | 2004-11-12 | 2008-06-12 | イーストマン ケミカル カンパニー | Polyester polymer and copolymer compositions comprising titanium nitride particles |
| JP2008534739A (en) * | 2005-03-31 | 2008-08-28 | イーストマン ケミカル カンパニー | Polyester polymer and copolymer compositions comprising particles of one or more transition metal compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01311131A (en) * | 1988-06-09 | 1989-12-15 | Diafoil Co Ltd | Polyester film for magnetic recording medium |
-
1989
- 1989-02-16 JP JP1035122A patent/JP2513826B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01311131A (en) * | 1988-06-09 | 1989-12-15 | Diafoil Co Ltd | Polyester film for magnetic recording medium |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1270669A1 (en) * | 1991-08-13 | 2003-01-02 | Teijin Limited | Biaxially oriented, unidirectionally long polyethylene-2,6-naphthalate film and magnetic tape therefrom |
| JP2008519903A (en) * | 2004-11-12 | 2008-06-12 | イーストマン ケミカル カンパニー | Polyester polymer and copolymer compositions comprising titanium nitride particles |
| TWI392700B (en) * | 2004-11-12 | 2013-04-11 | 葛魯波派楚泰克斯公司 | Polyester polymer and copolymer compositions containing titanium nitride particles |
| JP2008534739A (en) * | 2005-03-31 | 2008-08-28 | イーストマン ケミカル カンパニー | Polyester polymer and copolymer compositions comprising particles of one or more transition metal compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2513826B2 (en) | 1996-07-03 |
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