JPH04278350A - Biaxially oriented laminated polyester film - Google Patents
Biaxially oriented laminated polyester filmInfo
- Publication number
- JPH04278350A JPH04278350A JP6378491A JP6378491A JPH04278350A JP H04278350 A JPH04278350 A JP H04278350A JP 6378491 A JP6378491 A JP 6378491A JP 6378491 A JP6378491 A JP 6378491A JP H04278350 A JPH04278350 A JP H04278350A
- Authority
- JP
- Japan
- Prior art keywords
- biaxially oriented
- polyester film
- outermost layer
- laminated polyester
- film
- 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 abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000003746 surface roughness Effects 0.000 claims abstract description 5
- 238000009826 distribution Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 3
- 229940043430 calcium compound Drugs 0.000 abstract description 3
- 150000001674 calcium compounds Chemical class 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 4
- 239000010410 layer Substances 0.000 description 39
- 238000005299 abrasion Methods 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- -1 ester compounds Chemical class 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007790 scraping 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000012771 pancakes Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005809 transesterification reaction 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination 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
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate 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
- 239000000843 powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Magnetic Record Carriers (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、二軸配向積層ポリエス
テルフイルムに関し、特にスタンダードタイプのビデオ
テープの基材として用いて最適なフイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially oriented laminated polyester film, and more particularly to a film suitable for use as a base material for standard type video tapes.
【０００２】0002
【従来の技術】二軸配向ポリエステルフイルム、たとえ
ばビデオテープの基材として用いることのできる二軸配
向ポリエステルフイルムとしては、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
有せしめたフイルムが知られている（たとえば特開昭５
９−１７１６２３号公報）。BACKGROUND OF THE INVENTION Biaxially oriented polyester films, such as biaxially oriented polyester films that can be used as base materials for video tapes, include films containing substantially spherical silica particles derived from colloidal silica in polyester. is known (for example, Japanese Patent Application Publication No. 5
9-171623).
【０００３】0003
【発明が解決しようとする課題】しかし、フイルムの加
工工程、特に磁気媒体用途における磁性層塗布・カレン
ダー及び巻取、カセット組み込み工程などの工程速度の
増大に伴い、接触するロールやガイドでフイルム表面、
とくに微小凹凸を有するフイルム表面が削り取られやす
いという欠点があった。また、従来のものでは、高速磁
界転写などによるダビングの増速化にともない、ダビン
グ時の画質低下のために、画質すなわちＳ／Ｎ（シグナ
ル／ノイズ比）も不十分という欠点があった。[Problems to be Solved by the Invention] However, as the speed of film processing processes increases, particularly in magnetic layer coating, calendering and winding, and cassette assembly processes in magnetic media applications, the film surface is ,
In particular, there was a drawback that the surface of the film, which had minute irregularities, was easily scraped off. In addition, the conventional devices had the disadvantage that the image quality, that is, the S/N (signal/noise ratio), was insufficient because the image quality during dubbing deteriorated as the speed of dubbing increased due to high-speed magnetic field transfer.
【０００４】本発明は、かかる問題点を解決し、高速工
程でフイルム表面が削り取られにくく（以下高速削れ性
に優れるという）、かつ磁気媒体用途とした時にダビン
グ時等の画質低下の少ない、つまり電磁変換特性のよい
（以下電磁変換特性に優れるという）、安価でスタンダ
ードタイプのビデオテープ用基材として最適な二軸配向
積層ポリエステルフイルムを提供することを目的とする
。The present invention solves these problems and makes it difficult for the surface of the film to be scraped off during high-speed processes (hereinafter referred to as "excellent high-speed scraping property"), and when used as a magnetic medium, there is little deterioration in image quality during dubbing. The object of the present invention is to provide a biaxially oriented laminated polyester film that has good electromagnetic conversion characteristics (hereinafter referred to as "excellent electromagnetic conversion characteristics"), is inexpensive, and is optimal as a base material for standard type video tapes.
【０００５】[0005]
【課題を解決するための手段】この目的に沿う本発明の
二軸配向積層ポリエステルフイルムは、少なくとも３層
以上の積層構造からなる二軸配向積層ポリエステルフイ
ルムにおいて、その少なくとも片面の最表層部に内部析
出型粒子を含有し、最表層部の内部析出型粒子の含有量
が中間層部における含有量より多いものから成る。[Means for Solving the Problems] The biaxially oriented laminated polyester film of the present invention in accordance with this object has a biaxially oriented laminated polyester film having a laminate structure of at least three layers, in which the outermost layer of at least one side of the biaxially oriented polyester film has an internal structure. It contains precipitated particles, and the content of internally precipitated particles in the outermost layer is greater than the content in the middle layer.
【０００６】まず、本発明のポリエステルフイルムは少
なくとも３層以上の積層構造である必要がある。３層以
上であれば、４層でも５層でもかまわないが３層構造の
場合に本発明の効果がより一層良好となり好ましい。し
かし、単層や２層構造のフイルムでは高速削れ性や電磁
変換特性を満足させることはできない。First, the polyester film of the present invention must have a laminated structure of at least three layers. As long as there are three or more layers, it may be four or five layers, but a three-layer structure is preferred because the effects of the present invention are even better. However, single-layer or double-layer films cannot satisfy high-speed abrasion properties and electromagnetic conversion characteristics.
【０００７】次に、本発明のポリエステルフイルムは、
これを構成する上記各層の少なくとも一層が二軸に配向
している必要がある。３層以上の積層構造の内、全部の
層が二軸に配向していると特に好ましい。全ての層が無
配向や一軸配向では本発明の特性を満足することはでき
ない。Next, the polyester film of the present invention is
At least one of the layers constituting this must be biaxially oriented. In a laminated structure of three or more layers, it is particularly preferable that all the layers are biaxially oriented. If all the layers are non-oriented or uniaxially oriented, the characteristics of the present invention cannot be satisfied.
【０００８】本発明を構成するポリエステルは特に限定
されないが、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
とする場合に特に好ましい。中でも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が特に好
ましい。なお、本発明を阻害しない範囲内で、２種以上
のポリエステルを混合しても良いし、共重合ポリマを用
いても良い。The polyester constituting the present invention is not particularly limited, but includes ethylene terephthalate, ethylene α, β
It is particularly preferred when the main constituent is at least one structural unit selected from -bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate and ethylene 2,6-naphthalate units. Among these, polyester containing ethylene terephthalate as a main component is particularly preferred. Note that two or more types of polyesters may be mixed or a copolymer may be used within a range that does not impede the present invention.
【０００９】本発明のポリエステルフイルムは、少なく
とも片面の最表層部に内部析出型粒子を含有している。
この内部析出型粒子は、基材との親和性がよく、基材と
の間に強固な結合を達成しつつ表面突起の形成が可能な
ものである。外部粒子を含有させることなく、容易にか
つ安価に表面突起を形成できるので、とくにスタンダー
ドタイプのビデオテープ用基材等として最適な表面形態
のフイルムが得られる。所望の表面突起形成により、高
速削れ性、電磁変換特性を向上することができる。また
、本発明のポリエステルフイルムは、中間層部には必ず
しも内部析出型粒子を含有している必要はないが、中間
層部にも内部析出型粒子を含有することが望ましい。
この場合、最表層部の内部析出型粒子の含有量が中間層
のそれの含有量より多いことが必要である。The polyester film of the present invention contains internally precipitated particles in the outermost layer on at least one side. These internally precipitated particles have good affinity with the base material and are capable of forming surface protrusions while achieving strong bonding with the base material. Since surface protrusions can be easily and inexpensively formed without incorporating external particles, a film with a surface morphology suitable for use as a base material for standard type video tapes, etc. can be obtained. By forming desired surface protrusions, high-speed machinability and electromagnetic conversion characteristics can be improved. Further, in the polyester film of the present invention, it is not necessary that the intermediate layer portion contains internally precipitated particles, but it is desirable that the intermediate layer portion also contains internally precipitated particles. In this case, it is necessary that the content of internally precipitated particles in the outermost layer is greater than that in the intermediate layer.
【００１０】この内部析出型粒子によって形成される最
表層部の突起に関しては、その表面粗さパラメータＰ１
０が３５０ｎｍ以下であることが好ましい。この値より
も大きいと、高速削れ性が低下するとともに、電磁変換
特性が低下するおそれがある。Regarding the protrusions on the outermost layer formed by the internally precipitated particles, the surface roughness parameter P1
0 is preferably 350 nm or less. If it is larger than this value, there is a risk that high-speed machinability will decrease and electromagnetic conversion characteristics will decrease.
【００１１】また、上記最表層部表面の突起高さに関し
ては、その突起高さ分布の相対標準偏差が１．２以下で
あることが好ましい。この値よりも大きいと、望ましく
ない粗大突起が存在し、その部分が削り取られやすくな
って高速削れ性が低下するとともに、電磁変換特性も低
下するおそれがある。[0011] Regarding the height of the protrusions on the surface of the outermost layer, it is preferable that the relative standard deviation of the protrusion height distribution is 1.2 or less. If the value is larger than this value, undesirable coarse protrusions will be present, and these portions will be likely to be scraped off, leading to a decrease in high-speed scraping properties and a risk of deterioration in electromagnetic conversion characteristics.
【００１２】さらに本発明フイルムにおいては、中間層
は特に限定されないが、最表層部において、上述の如く
高速削れ性に優れ、均一な所望突起高さの突起が形成さ
れ電磁変換特性に優れた表面を形成できるので、中間層
にいわゆるリサイクルポリマを含有させることが好まし
い。なおここでリサイクルポリマとは、ポリエステルの
末端カルボン酸が５５当量／１０６ ｇ以上でポリマの
溶液ヘイズが１８％以下のものをいう。Furthermore, in the film of the present invention, although the intermediate layer is not particularly limited, the outermost layer has a surface that is excellent in high-speed abrasion properties, has protrusions of a uniform desired protrusion height, and has excellent electromagnetic conversion characteristics as described above. Therefore, it is preferable that the intermediate layer contains a so-called recycled polymer. Note that the recycled polymer herein refers to a polyester having a terminal carboxylic acid of 55 equivalents/10 6 g or more and a polymer solution haze of 18% or less.
【００１３】本発明の二軸配向積層ポリエステルフイル
ムの最表層部には、上記内部析出型粒子以外にも外部粒
子が同時に含有されていても良いが、内部析出型粒子よ
りも含有量が多くなりすぎないようにして、高速削れ性
、電磁変換特性を悪化させないのが好ましい。The outermost layer of the biaxially oriented laminated polyester film of the present invention may contain external particles in addition to the internally precipitated particles, but the content is greater than that of the internally precipitated particles. It is preferable to avoid deterioration of high-speed machining properties and electromagnetic conversion characteristics by not causing too much.
【００１４】また本発明のフイルム中には、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 film of the present invention may also contain other polymers, such as antioxidants, heat stabilizers, lubricants, and ultraviolet absorbers, as long as they do not impede the purpose of the present invention. Organic additives may be added to the extent that they are normally added.
【００１５】本発明の積層ポリエステルフイルムの最表
層積層部のポリマＩＶは、０．４〜０．９の範囲である
と高速削れ性をより一層良好とするので特に好ましい。
さらに基層部とのポリマＩＶの差が０．１以内であると
より一層高速削れ性が良好となるので非常に好ましい。It is particularly preferable that the polymer IV of the outermost laminated portion of the laminated polyester film of the present invention is in the range of 0.4 to 0.9, since this further improves high-speed abrasion properties. Furthermore, it is very preferable that the difference in polymer IV from the base layer portion is within 0.1 because high-speed machinability becomes even better.
【００１６】次に本発明フイルムの製造方法について説
明する。まず、内部析出型粒子の生成方法は次の方法が
有効である。すなわち、内部析出型粒子は、■所定のジ
カルボン酸とエチレングリコールとの直接エステル化を
経て重縮合する過程あるいは、■所定のジカルボン酸の
ジメチルエステルとエチレングリコールとのエステル交
換反応を経て重縮合を行なう過程において、グリコール
に可溶性のカルシウム化合物、マグネシウム化合物、マ
ンガン化合物、リチウム化合物のすくなくとも一種と、
好ましくは、リンの酸および／またはエステル化合物を
適当な方法で添加することによって生成される。内部析
出型粒子を生成するための化合物の添加は、エステル化
反応またはエステル交換反応が実質的に終了した時点か
ら重縮合反応のあまり進んでいない初期の段階までの任
意の時期に、カルシウム化合物、リチウム化合物の少な
くとも一種をグリコール溶液として反応系に添加するの
がよい。Next, a method for manufacturing the film of the present invention will be explained. First, the following method is effective for producing internally precipitated particles. In other words, internally precipitated particles undergo polycondensation through direct esterification of a predetermined dicarboxylic acid and ethylene glycol, or ■polycondensation through a transesterification reaction between dimethyl ester of a predetermined dicarboxylic acid and ethylene glycol. In the process, at least one of glycol-soluble calcium compounds, magnesium compounds, manganese compounds, and lithium compounds,
Preferably, it is produced by adding phosphorus acid and/or ester compounds in a suitable manner. The addition of the compound to produce the internally precipitated particles can be carried out at any time from the point at which the esterification or transesterification reaction is substantially completed to the early, less advanced stage of the polycondensation reaction, by adding a calcium compound, It is preferable to add at least one lithium compound to the reaction system as a glycol solution.
【００１７】ここで使用しうるカルシウム、マグネシウ
ム、マンガン、リチウム化合物としては、ハロゲン化物
、硝酸塩、硫酸塩などの無機酸塩、酢酸塩、シュウ酸塩
、安息香酸塩などの有機酸塩、水素化物および酸化物な
どのグリコール可溶性の化合物が最も好ましく使用され
るが、二種以上併用しても構わない。また、リン化合物
としてはリン酸、亜リン酸、ホスホン酸、およびこれら
のエステル類、部分エステル類の一種以上が用いられる
。内部析出型粒子の生成には、無機粒子等を結晶核剤と
して用いないのが好ましい。Calcium, magnesium, manganese, and lithium compounds that can be used here include halides, inorganic acid salts such as nitrates and sulfates, organic acid salts such as acetates, oxalates, and benzoates, and hydrides. Glycol-soluble compounds such as and oxides are most preferably used, but two or more types may be used in combination. Further, as the phosphorus compound, one or more of phosphoric acid, phosphorous acid, phosphonic acid, and esters and partial esters thereof are used. In the production of internally precipitated particles, it is preferable not to use inorganic particles or the like as a crystal nucleating agent.
【００１８】内部析出型粒子の量を調節する方法として
は、上記方法で高濃度の粒子マスターを作っておき、そ
れを製膜時に内部析出型粒子を実質的に含有しないポリ
エステルで希釈して内部析出型粒子の量を調節する方法
が有効である。As a method for adjusting the amount of internally precipitated particles, a highly concentrated particle master is prepared by the method described above, and then diluted with polyester that does not substantially contain internally precipitated particles during film formation. An effective method is to control the amount of precipitated particles.
【００１９】次にこのポリエステルのペレットを用いて
３層以上の積層構造をもったポリエステルフイルムとす
る。上記の方法にて得られたポリエステルのペレットを
所定の割合で混合し、乾燥したのち、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
フイルムを作る。すなわち、２または３台以上の押出機
、３層以上のマニホールドまたは合流ブロック（例えば
角型合流部を有する合流ブロック）を用いて積層し、口
金から３層以上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イルムを作る。この場合、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
方法は有効である。また、最表層積層部側のポリマーを
押出す押出機の溶融温度を基層部側より５〜１０℃低く
することが、有効である。Next, the polyester pellets are used to form a polyester film having a laminated structure of three or more layers. The polyester pellets obtained by the above method are mixed in a predetermined ratio, dried, and then fed to a known extruder for melt lamination, extruded into a sheet through a slit die, and cooled and solidified on a casting roll. At least make an unstretched film. That is, the sheets are laminated using two or three or more extruders, a manifold with three or more layers, or a merging block (for example, a merging block with a square merging part), extruding three or more layers of sheets from a die, and cooling with a casting roll. to make an unstretched film. In this case, it is effective to install a static mixer or a gear pump in the polymer flow path. Furthermore, it is effective to lower the melting temperature of the extruder for extruding the polymer on the outermost layer layer side by 5 to 10° C. than on the base layer side.
【００２０】次にこの未延伸フイルムを二軸延伸し、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倍で行なう方法は特に好まし
い。長手方向延伸温度はポリエステルの種類によって異
なり一概には言えないが、通常、その１段目を５０〜１
３０℃とし、２段目以降はそれより高くすることが有効
である。長手方向延伸速度は５０００〜５００００％／
分の範囲が好適である。幅方向の延伸方法としてはステ
ンタ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℃の
範囲が好適である。次にこの延伸フイルムを熱処理する
。この場合の熱処理温度は１７０〜２２０℃、特に１８
０〜２００℃、時間は０．２〜２０秒の範囲が好適であ
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, a sequential biaxial stretching method is used in which stretching is first performed in the longitudinal direction and then in the width direction, and the longitudinal stretching is divided into three or more stages, with a total longitudinal stretching ratio of 3.5 to 6.5 times. The method is particularly preferred. The stretching temperature in the longitudinal direction varies depending on the type of polyester and cannot be generalized, but usually the first stage is 50 to 1
It is effective to set the temperature to 30°C and raise the temperature higher than that for the second and subsequent stages. The longitudinal stretching speed is 5,000 to 50,000%/
A range of minutes is preferred. A common method for stretching in the width direction is to use a stenter. The stretching ratio is 3.0
A range of 5.0 times is appropriate. The stretching speed in the width direction is
Preferably, the rate is 1,000 to 20,000%/min and the temperature is in the range of 80 to 160°C. Next, this stretched film is heat treated. The heat treatment temperature in this case is 170-220℃, especially 18
Preferably, the temperature is 0 to 200°C and the time is 0.2 to 20 seconds.
【００２１】［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。
（１）表面突起の高さ分布の標準偏差
２検出器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］においてフイルム表面の平坦面
の高さを０として走査したときの突起の高さ測定値を画
像処理装置［ＩＢＡＳ２０００、カールツァイス（株）
製］に送り、画像処理装置上にフイ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、測定された突起についてその高
さ分布を正規分布（高さ０の点を中心とする正規分布）
とみなして最小２乗法で近似して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、１０００〜８
０００倍の間を選択する。[Method for Measuring Physical Properties and Evaluating Effects] Methods for measuring characteristic values and evaluating effects of the present invention are as follows. (1) Standard deviation of height distribution of surface protrusions Two-detector scanning electron microscope [ESM-3200,
manufactured by Elionix Co., Ltd.] and a cross-sectional measuring device [PMS-1,
The height of the protrusions was measured using an image processing device [IBAS2000, Carl Zeiss Co., Ltd.] when the height of the flat surface of the film was set as 0.
[Manufacturer] and reconstructs the image of the film surface protrusions on an image processing device. Next, a circular equivalent diameter is determined from the area of each protrusion obtained by binarizing the protrusion portion using this surface protrusion image, 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 is repeated 500 times at different locations, and the height distribution of the measured protrusions is normal distribution (normal distribution centered on the point of height 0)
The standard deviation of the height distribution was determined by approximation using the least squares method. Furthermore, the magnification of a scanning electron microscope is 1000 to 8
Select between 000 times.
【００２２】（２）表面粗さパラメータＰ１０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、画像処理装置上にフイルム表面突起画像を
構築する。この表面突起画像で突起部分の最も高い値か
ら１０点について平均をＰ１０と定義した。２０回の測
定の平均値をもって値とした（単位ｎｍ）。(2) Surface roughness parameter P10 Using an optical interference type three-dimensional surface analyzer (TOPO-3D manufactured by WYKO, objective lens: 40 to 200 times, effective use of a high-resolution camera), to construct a film surface protrusion image. In this surface protrusion image, the average of the 10 points from the highest value of the protrusion portion was defined as P10. The average value of 20 measurements was taken as the value (unit: nm).
【００２３】（３）ポリマＩＶ
ｏ−クロロフェノールを溶媒として２５℃にて測定した
。(3) Polymer IV Measured at 25°C using o-chlorophenol as a solvent.
【００２４】（４）高速削れ性
フイルムを１／２インチ幅のテープ状にスリットしたも
のに角度９０°で片刃を押しあて、０．５ｍｍ押し込ん
で２００ｍ走行させる（速度：２００ｍ／ｍｉｎ 、張
力：１００ｇ）。片刃に削りとられた粉の付着高さを顕
微鏡で読み取り、削れ量（μｍ）とした。この削れ量が
１８０μｍ以下の場合耐削れ性が良好、それを越える場
合耐削れ性が不良である。(4) Press one blade against a 1/2-inch wide tape-shaped slit of high-speed abrasion film at an angle of 90°, push it in 0.5 mm, and run it for 200 m (speed: 200 m/min, tension: 100g). The adhesion height of the powder scraped off by one blade was read using a microscope and was defined as the scraping amount (μm). If the amount of abrasion is 180 μm or less, the abrasion resistance is good, and if it exceeds this, the abrasion resistance is poor.
【００２５】（５）電磁変換特性
フイ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：７０℃、線圧：２００ｋｇ／ｃｍ で
カレンダー処理した後、７０℃、４８時間キュアリング
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。
（磁性塗料の組成）
・Ｃｏ含有酸化鉄 ：
１００重量部・塩化ビニル／酢酸ビニル共重合体：
１０重量部・ポリウレタンエラストマ
： １０重量部・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 ：
７５重量部・メチルイソプチルケトン
： ７５重量部・トルエン
： ７５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を用いてテ
レビ試験波形発生器により１００％クロマ信号を記録し
、その再生信号からカラービデオノイズ測定器でクロマ
Ｓ／Ｎを測定した。(5) A magnetic paint having the following composition is applied to the electromagnetic conversion film using a gravure roll, magnetically oriented, and dried. In addition, a small test calender device (steel roll/nylon roll,
5 stages) at a temperature of 70°C and a linear pressure of 200 kg/cm 2 , followed by curing at 70°C for 48 hours. The original tape was slit into 1/2 inch pieces to make pancakes. A length of 250 m from this pancake was assembled into a VTR cassette to make a VTR cassette tape. (Composition of magnetic paint) ・Co-containing iron oxide:
100 parts by weight of vinyl chloride/vinyl acetate copolymer:
10 parts by weight polyurethane elastomer
: 10 parts by weight polyisocyanate
: 5 parts by weight/lecithin
: 1 part by weight ・Methyl ethyl ketone :
75 parts by weight methyl isobutyl ketone
: 75 parts by weight/toluene
: 75 parts by weight Carbon black : 2 parts by weight Lauric acid
: 1.5 parts by weight A 100% chroma signal was recorded on this tape using a TV test waveform generator using a home VTR, and the chroma S/N was measured from the reproduced signal using a color video noise measuring device.
【００２６】[0026]
【実施例】次に実施例に基づき、本発明の実施態様を説
明する。
実施例１（表１）
内部析出型粒子含有ペレットを５０重量部、さらに粒子
を含有しないポリエチレンテレフタレートのペレットを
５０重量部混ぜ合わせ、ベント式二軸混練押出機１に供
給し、２８０℃で溶解した（ポリマＩ）。更に、もう一
台の押出機２を用意し、リサイクルポリマ３５重量部と
粒子を含有しないペレット６５重量部を混ぜ合わせた後
、１８０℃で３時間減圧乾燥（３Ｔｏｒｒ）し、押出機
に供給して２９０℃で溶解した（ポリマＩＩ）。この２
つのポリマを、それぞれ高精度濾過した後、矩形積層部
を備えた３層合流ブロックにて、基層部にポリマＩＩを
、両面表層積層部にポリマＩがくるように積層し、フィ
ッシュテール型の口金よりシート状にして押し出した後
、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、厚さ約１６０
μｍの未延伸フイルムを作った。この時のドラフト比は
６．５であった。EXAMPLES Next, embodiments of the present invention will be described based on examples. Example 1 (Table 1) 50 parts by weight of pellets containing internally precipitated particles and 50 parts by weight of polyethylene terephthalate pellets containing no particles were mixed together, supplied to a vented twin-screw kneading extruder 1, and melted at 280°C. (Polymer I). Furthermore, another extruder 2 was prepared, and after mixing 35 parts by weight of recycled polymer and 65 parts by weight of pellets containing no particles, the mixture was dried under reduced pressure (3 Torr) at 180°C for 3 hours and then fed to the extruder. (Polymer II). This 2
After high-precision filtration of each of the two polymers, they were laminated in a three-layer merging block with a rectangular laminated part so that Polymer II was placed on the base layer part and Polymer I was placed on the double-sided surface laminated part, and a fishtail-shaped cap was formed. After extruding it into a sheet, it is wrapped around a casting drum with a surface temperature of 30°C using an electrostatic casting method and cooled and solidified to a thickness of approximately 160°C.
An unstretched film of μm was made. The draft ratio at this time was 6.5.
【００２７】この未延伸フイルムを長手方向に３段階に
分け、１２３℃で１．２倍、１２６℃で１．４５倍、１
１４℃で２．３倍それぞれ延伸した。この一軸フイルム
をステンタを用いて幅方向に２段階に分け、１１１℃で
３．７倍、１１３℃で１．２倍延伸し、定長下で２００
℃にて５秒間熱処理し、厚さ１３μｍのフイルムを得た
。This unstretched film was divided into three stages in the longitudinal direction, 1.2 times at 123°C, 1.45 times at 126°C, and 1
Each was stretched 2.3 times at 14°C. This uniaxial film was divided into two stages in the width direction using a stenter, stretched 3.7 times at 111°C and 1.2 times at 113°C, and stretched 200 times at a constant length.
A heat treatment was performed at .degree. C. for 5 seconds to obtain a film with a thickness of 13 .mu.m.
【００２８】このフイルムの電磁変換特性を測定すると
、＋２．０であった。また、高速削れ性も８５（μｍ）
と良好であった。このように、最表層積層部に含有され
る粒子の種類及び積層構成が本発明の範囲内である場合
には、電磁変換特性、高速削れ性ともに良好なフイルム
とすることができる。The electromagnetic conversion characteristics of this film were measured and found to be +2.0. In addition, high-speed machinability is 85 (μm)
It was good. As described above, when the types of particles contained in the outermost laminated portion and the laminated structure are within the scope of the present invention, a film having good electromagnetic conversion characteristics and high-speed abrasion properties can be obtained.
【００２９】実施例２、比較例１〜４（表１）実施例１
と同様にして、二軸配向ポリエステルフイルムを作成し
たが、最表層部の内部析出型粒子含有の有無および積層
構成が本発明の範囲内でない場合には、電磁変換特性、
高速削れ性ともに良好なフイルムとすることができなか
った。Example 2, Comparative Examples 1 to 4 (Table 1) Example 1
A biaxially oriented polyester film was prepared in the same manner as above, but if the presence or absence of internally precipitated particles in the outermost layer and the laminated structure are not within the scope of the present invention, electromagnetic conversion characteristics,
A film with good high-speed abrasion properties could not be obtained.
【００３０】[0030]
【表１】[Table 1]
【００３１】[0031]
【発明の効果】本発明の二軸配向積層ポリエステルフイ
ルムによれば、少なくとも片面の薄層最表層部表面に内
部析出型粒子により均一かつ削れにくい突起を形成して
、所望の表面粗さ形態とすることができるので、高速で
の優れた耐削れ性を発揮させつつ、磁気媒体用としての
優れた電磁変換特性を発揮することができる。Effects of the Invention According to the biaxially oriented laminated polyester film of the present invention, uniform and hard-to-scrape protrusions are formed on the surface of the outermost layer of the thin layer on at least one side by the internally precipitated particles, and the desired surface roughness can be achieved. Therefore, it is possible to exhibit excellent abrasion resistance at high speeds and to exhibit excellent electromagnetic conversion characteristics for use in magnetic media.
【００３２】また、最表層部に上記のような優れた特性
をもたせることができるので、中間層に、問題を生じる
ことなくリサイクルポリマを含有させることができ、生
産性の向上を図ることもできる。[0032] Furthermore, since the outermost layer can have the above-mentioned excellent properties, the intermediate layer can contain a recycled polymer without causing any problems, and productivity can be improved. .
Claims (4)
る二軸配向積層ポリエステルフイルムにおいて、その少
なくとも片面の最表層部に内部析出型粒子を含有し、最
表層部の内部析出型粒子の含有量が中間層部における含
有量より多いことを特徴とする二軸配向積層ポリエステ
ルフイルム。Claim 1: A biaxially oriented laminated polyester film having a laminated structure of at least three layers, wherein the outermost layer of at least one side thereof contains internally precipitated particles, and the content of internally precipitated particles in the outermost layer is A biaxially oriented laminated polyester film characterized in that the content is higher than that in the middle layer.
ている請求項１の二軸配向積層ポリエステルフイルム。2. The biaxially oriented laminated polyester film according to claim 1, wherein the intermediate layer portion contains a recycled polymer.
１０が３５０ｎｍ以下である請求項１又は２の二軸配向
積層ポリエステルフイルム。[Claim 3] Surface roughness parameter P of the outermost layer portion
The biaxially oriented laminated polyester film according to claim 1 or 2, wherein 10 is 350 nm or less.
相対標準偏差が１．２以下である請求項１ないし３のい
ずれかに記載の二軸配向積層ポリエステルフイルム。4. The biaxially oriented laminated polyester film according to claim 1, wherein the relative standard deviation of the protrusion height distribution on the surface of the outermost layer portion is 1.2 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3063784A JP2859973B2 (en) | 1991-03-06 | 1991-03-06 | Biaxially oriented laminated polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3063784A JP2859973B2 (en) | 1991-03-06 | 1991-03-06 | Biaxially oriented laminated polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04278350A true JPH04278350A (en) | 1992-10-02 |
| JP2859973B2 JP2859973B2 (en) | 1999-02-24 |
Family
ID=13239351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3063784A Expired - Lifetime JP2859973B2 (en) | 1991-03-06 | 1991-03-06 | Biaxially oriented laminated polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2859973B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5532047A (en) * | 1993-08-30 | 1996-07-02 | Toray Industries, Inc. | Biaxially oriented, laminated polyester film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6569515B2 (en) | 1998-01-13 | 2003-05-27 | 3M Innovative Properties Company | Multilayered polymer films with recyclable or recycled layers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61258751A (en) * | 1985-05-10 | 1986-11-17 | 凸版印刷株式会社 | Multilayer vessel |
| JPS6228333A (en) * | 1985-07-31 | 1987-02-06 | 東洋製罐株式会社 | Multilayer gas barrier polyester vessel and manufacture thereof |
| JPS6363745A (en) * | 1986-09-03 | 1988-03-22 | Toray Ind Inc | Base film for magnetic recording medium |
| JPH02214657A (en) * | 1989-02-16 | 1990-08-27 | Teijin Ltd | Laminate biaxially oriented film |
| JPH02286721A (en) * | 1989-04-28 | 1990-11-26 | Toray Ind Inc | Biaxially oriented polyester film |
-
1991
- 1991-03-06 JP JP3063784A patent/JP2859973B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61258751A (en) * | 1985-05-10 | 1986-11-17 | 凸版印刷株式会社 | Multilayer vessel |
| JPS6228333A (en) * | 1985-07-31 | 1987-02-06 | 東洋製罐株式会社 | Multilayer gas barrier polyester vessel and manufacture thereof |
| JPS6363745A (en) * | 1986-09-03 | 1988-03-22 | Toray Ind Inc | Base film for magnetic recording medium |
| JPH02214657A (en) * | 1989-02-16 | 1990-08-27 | Teijin Ltd | Laminate biaxially oriented film |
| JPH02286721A (en) * | 1989-04-28 | 1990-11-26 | Toray Ind Inc | Biaxially oriented polyester film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2859973B2 (en) | 1999-02-24 |
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