JPS62253631A - Polyester film - Google Patents
Polyester filmInfo
- Publication number
- JPS62253631A JPS62253631A JP9889786A JP9889786A JPS62253631A JP S62253631 A JPS62253631 A JP S62253631A JP 9889786 A JP9889786 A JP 9889786A JP 9889786 A JP9889786 A JP 9889786A JP S62253631 A JPS62253631 A JP S62253631A
- Authority
- JP
- Japan
- Prior art keywords
- film
- titanium dioxide
- average particle
- particles
- particle size
- 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 21
- 239000002245 particle Substances 0.000 claims abstract description 70
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 abstract description 18
- 238000005299 abrasion Methods 0.000 abstract description 15
- 238000004804 winding Methods 0.000 abstract description 14
- -1 polyethylene terephthalate Polymers 0.000 abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 abstract 1
- 239000011112 polyethylene naphthalate Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 50
- 238000000034 method Methods 0.000 description 20
- 229920000728 polyester Polymers 0.000 description 17
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004883 computer application Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、平滑で巻き作業性が高度に改良された二軸延
伸ポリエステルフィルムに関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a biaxially oriented polyester film that is smooth and has highly improved winding workability.
〈従来の技術と発明が解決しようとする問題点〉ポリエ
チレンテレフタレートに代表されるポリエステルは、そ
の優れた機械的特性、電気的特性、耐薬品性、寸法安定
性の点から、磁気記録用、コンデンサー用、包装用、製
版用、電絶用、写真フィルム用等多くの分野で基材とし
てこれらにポリエステルフィルムが用いられる場合、各
用途に応じてその要求特性が異なるが、普遍的に要求さ
れる特性はフィルム取シ扱い時の作業性であシ、これを
改善するためにはフィルムの滑シ性即ち摩擦係数を減じ
る必要がある。<Prior art and problems to be solved by the invention> Polyesters, represented by polyethylene terephthalate, are used for magnetic recording and capacitors due to their excellent mechanical properties, electrical properties, chemical resistance, and dimensional stability. When polyester film is used as a base material in many fields such as printing, packaging, plate making, electrical disconnection, and photographic film, the required properties differ depending on each application, but they are universally required. The characteristic is workability when handling the film, and in order to improve this, it is necessary to reduce the slipperiness of the film, that is, the coefficient of friction.
また、近年伸びの著しいオーディオ、ビデオ、コンピュ
ーター用等のベースフィルムとしてそのフィルム表面に
磁性層を塗布し、磁気記録媒体として用いる場合には、
滑り性及び耐摩耗性が悪いと磁性層塗布時に於けるコー
ティングロールとフィルム表面との摩擦及び摩耗が激し
く、フィルム表面に擦り傷が発生しやすい。In addition, when a magnetic layer is applied to the surface of the film as a base film for audio, video, and computer applications, which have been growing rapidly in recent years, and used as a magnetic recording medium,
If the slipperiness and abrasion resistance are poor, the friction and abrasion between the coating roll and the film surface during application of the magnetic layer will be severe, and scratches will easily occur on the film surface.
また、磁性層塗布後のフィルムをオーディオ、ビデオ、
コンピューター用テープ等に加工し製品とした後でも、
リールやカセット等からの引出し巻き上げその他の操作
の際に、多くのガイド部、記録、再生ヘッド等の間に摩
擦及び摩耗が著しく生じ、ポリエステルフィルム表面の
削れ等による白粉状物質が生成するため、磁気記a層−
@−77’l々荒−91本Vロップ〒つに^十〜赤百因
となることが多い。In addition, the film after applying the magnetic layer can be used for audio, video,
Even after processing it into products such as computer tape,
During winding up of drawers from reels, cassettes, etc., significant friction and wear occurs between the many guide parts, recording and playback heads, etc., and white powdery substances are generated due to scratches on the surface of the polyester film, etc. , magnetic recording layer A-
@-77'l Ara-91 V-lops 〒It is often ^10 to red 100 reasons.
ポリエステルフィルムに要求されるこれらの特性を改良
するために、一般に採用されている方法は、フィルム表
面に凹凸を付与するためポリエステルに対し不活性な微
粒子を存在させる方法である。In order to improve these properties required of a polyester film, a method generally employed is to add inactive fine particles to the polyester in order to impart irregularities to the surface of the film.
この方法は大きく二つに分けられる。その一つは析出法
と呼ばれる方法であシ、エステル交換反応あるいはエス
テル化反応の前後にエチレングリコールに可溶な金属化
合物、例えばカルシュラム化合物、リチウム化合物等の
一種以上を添加しポリエステルに不溶の微粒子として沈
殿させる方法である。析出法と対比される今一つの方法
は添加法と呼ばれる方法であり、炭酸カルシュラム、硫
酸カルシュラム、カオリン、シリカ、二酸化チタン等を
そのままあるいは微粒子化したのちポリエステル合成時
、あるいは成型時に添加するものである。これらポリエ
ステル中の粒子は、その粒子径が大きいほど滑シ性の改
良効果が大きいことが一般的であるが、磁気テープ特に
ビデオ用のごとき精密用途にはその粒子自体が大きいこ
とがドロップアウト等の欠陥発生原因となシ得る−ため
、ポリエステル中に含まれる粒子は出来るだけ微細であ
る必要がある。しかしながら、このような相反する特性
を同時に満足することは非常に、難かしいのが現状であ
る。This method can be broadly divided into two. One of these methods is the precipitation method, in which one or more metal compounds soluble in ethylene glycol, such as calsulam compounds and lithium compounds, are added before and after the transesterification or esterification reaction to form fine particles insoluble in polyester. This is a method of precipitating it as Another method that is compared to the precipitation method is the addition method, in which calcilum carbonate, calcilum sulfate, kaolin, silica, titanium dioxide, etc. are added as they are or after being made into fine particles during polyester synthesis or molding. . Generally speaking, the larger the particle size of the particles in polyester, the greater the effect of improving lubricity, but for precision applications such as magnetic tape, especially video, the particles themselves are large, causing dropouts and other problems. Therefore, the particles contained in the polyester must be as fine as possible. However, it is currently extremely difficult to simultaneously satisfy these contradictory characteristics.
く問題点を解決するための手段〉
本発明者ら拡、磁気記録用テープの高精密化が一段と促
進され、磁気テープ用フィルムの滑り性及び耐摩耗性の
改良がよシ要求されつつある状況化に鑑みて、フィルム
表面が平滑で滑シ性及び耐摩耗性に優れ、ドロップアウ
ト等の欠陥発生が少なく、かつフィルム製造時の作業性
、その申でも特に巻き特性の優れた磁気テープ用全
フィルムを見い出し、本発明に到達するに泊ったO
即ち、本発明の要旨は、平均粒径が0.0/〜0.3θ
μmのルチル型二酸化チタンをQ、07〜/、0重量%
及び平均粒径が0.3/〜7.0μ噂のアナターゼ型二
酸化チタンを0.00.2〜0.3重量%を含有するこ
とを特徴とする二軸延伸ポリエステルフィルムに存する
。Means for Solving the Problems> The present inventors and others have discovered that as the precision of magnetic recording tapes continues to advance, improvements in the slipperiness and abrasion resistance of magnetic tape films are increasingly required. In light of the increasing demand for magnetic tapes, we have developed a complete film for magnetic tape that has a smooth film surface, excellent lubricity and abrasion resistance, fewer defects such as dropouts, and excellent workability during film production, especially in terms of winding properties. In other words, the gist of the present invention is that the average particle size is 0.0/~0.3θ
μm rutile titanium dioxide Q, 07~/, 0% by weight
and a biaxially stretched polyester film characterized by containing 0.00.2 to 0.3% by weight of anatase titanium dioxide, which is rumored to have an average particle size of 0.3/ to 7.0μ.
以下本発明についてよシ詳しく説明する。The present invention will be explained in detail below.
本発明にいうポリエステルとは、テレフタル酸、イソフ
タル酸、ナフタレンーコ、6−ジカルボン酸の如き芳香
族ジカルボン面又は、そのエステルとエチレングリコー
ル、ジエチレンクリコール、テトラメチレングリコール
、ネオペンチルグリコール等の如きグリコールとを重縮
合させて得ることのできるポリエステルである。The polyester referred to in the present invention refers to an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalene, 6-dicarboxylic acid, or an ester thereof and a glycol such as ethylene glycol, diethylene glycol, tetramethylene glycol, neopentyl glycol, etc. It is a polyester that can be obtained by polycondensing.
ポリエステルは、芳香族ジカルボン酸とグリコールを直
接重縮合させて得られる他、芳香族ジカルボン酸ジアル
キルエステルとグリコールとをエステル交換反応させた
後重縮合せしめるか、おるいは芳香族ジカルボン酸のジ
エステルを重縮合せしめる等の方法によっても得られる
。Polyester can be obtained by direct polycondensation of aromatic dicarboxylic acid and glycol, or by polycondensation after transesterification of aromatic dicarboxylic acid dialkyl ester and glycol, or by polycondensation after polycondensation of aromatic dicarboxylic acid dialkyl ester and glycol. It can also be obtained by methods such as polycondensation.
かかるポリマーの代表的なものとして、ポリエチレンテ
レフタレートやポリエチレン−296−ナフタレート等
が例示される。このポリマーはホモポリマーであっても
良く、また第3成分を共重合させたものでも良い。いず
れにしても本発明に於てはエチレンテレフタレート単位
及ヒ/又は、エチレンーコ、/−−ナフタレート単位を
Sθモルチ以上有するポリエステルが好ましいO
本発明の意図するところは、平均粒径の異なる二種類の
アナターゼ型二酸化チタンをそれぞれ特定量づつ添加す
ることにある。Typical examples of such polymers include polyethylene terephthalate and polyethylene-296-naphthalate. This polymer may be a homopolymer or may be a copolymer of a third component. In any case, in the present invention, polyesters having ethylene terephthalate units and/or ethylene co,/--naphthalate units of Sθ mol or more are preferable. The purpose is to add specific amounts of anatase titanium dioxide.
粒子径の小さいアナターゼ型二酸化チタンの平均粒径は
0.θ/〜0..30μmである必要があり、更には平
均粒径0.05〜θ、27μmであることが好ましい。The average particle size of anatase titanium dioxide, which has a small particle size, is 0. θ/~0. .. It needs to be 30 μm, and more preferably the average particle size is 0.05 to θ and 27 μm.
平均粒径0.074m未満では滑シ性及び耐摩耗性の改
良効果が不充分となるので好ましくない。逆に平均粒径
が0.、:10μmを越えるとフィルム表面の平滑性が
低下し、かつドロップアウト発生の原因となる大粒子が
多くなるので好壕しくない。If the average particle diameter is less than 0.074 m, the effect of improving lubricity and abrasion resistance will be insufficient, so it is not preferable. On the other hand, if the average particle size is 0. .: If it exceeds 10 μm, the smoothness of the film surface decreases and large particles, which cause dropouts, increase, which is not desirable.
またポリエステルに対する添加量は0.0/〜〜/、O
wt%とする必要があり、好ましくは添加量はQ、/〜
θ。711%がよい。添加量がQ、Q 7wt4未満で
は滑り性及び耐摩耗性の改良効果が不充分となるので好
ましくない。逆に添加量がi、。The amount added to polyester is 0.0/~~/, O
It is necessary to make it wt%, and preferably the amount added is Q, /~
θ. 711% is good. If the amount added is less than 7wt4, the effect of improving slipperiness and abrasion resistance will be insufficient, which is not preferable. Conversely, the amount added is i.
11%を越えるとフィルム表面の平滑性が低下しかつド
ロップアウト発生の原因となる粗大粒子の混入が多くな
るので好ましくない0
粒子径の大きいアナターゼ凰二酸化チタンの平均粒径は
、0.37〜7.0μ常の範囲が必要であシ、好ましく
は平均粒径θ、35〜0.70μmである。平均粒径0
.37μm未満では耐摩耗性及び巻き特性の改良効果が
不充分となるので好ましくない。平均粒径が/、0μ密
を越えるとフィルムの平滑性が低下し、かつドロップア
ウト発生の原因となる大粒子が多くなるので好ましくな
い。If it exceeds 11%, it is not preferable because the smoothness of the film surface decreases and the contamination of coarse particles that causes dropouts increases.0 The average particle size of anatase titanium dioxide with a large particle size is 0.37~ The average particle diameter θ is preferably in the range of 35 to 0.70 μm. Average particle size 0
.. If the thickness is less than 37 μm, the effect of improving wear resistance and winding properties will be insufficient, which is not preferable. If the average particle size exceeds a density of /0μ, the smoothness of the film decreases and the number of large particles, which causes dropouts, increases, which is not preferable.
また該ポリエステルに対する添加量は0.00コ〜o、
s 11%とする必要があシ、好ましくは、o、o o
s〜0.3wt%、よシ好ましくは0.00 !t〜
−0,09vtt%である。添加量が0.002vt%
未満では耐摩耗性及び巻き特性の改良効果が不充分とな
るので好ましくない0添加量−4g o、z 11%を
越えるとフィルム表面の平滑性が低下し、かつドロップ
アウト発生の原因となる粗大粒子の混入が多くなるので
好ましく−ない。Further, the amount added to the polyester is 0.00 to 0,
s Must be 11%, preferably o, o o
s~0.3wt%, preferably 0.00! t~
-0.09vtt%. Addition amount is 0.002vt%
If it is less than 11%, the improvement effect on abrasion resistance and winding properties will be insufficient, so it is undesirable. If it exceeds 11%, the smoothness of the film surface will decrease and the roughness will cause dropouts. This is not preferred because it increases the amount of particles mixed in.
なお滑シ性、耐摩耗性及び巻き特性向上のためには、小
粒径のアナターゼ型二酸化チタンと大粒径のアナターゼ
型二酸化チタンとの平均粒径の差は少なくとも0,70
μm以上であることが望ましい。In order to improve lubricity, wear resistance and winding properties, the difference in average particle size between small particle size anatase type titanium dioxide and large particle size anatase type titanium dioxide should be at least 0.70.
It is desirable that the thickness is μm or more.
本発明に於て用いるアナターゼ温二酸化チタンは先に規
定した条件を満たせばその製法その他なんら限定される
ものではない。また表面処理をしないものを用いても良
いし、表面処理を施したものを用いても良い◇
体積形状係数に関してはその値が0.70〜π/6の範
囲のものを用いるのが好ましい。The anatase-warm titanium dioxide used in the present invention is not limited in any way, including its manufacturing method, as long as it satisfies the conditions specified above. Moreover, a material without surface treatment may be used, or a material with surface treatment may be used. ◇ Regarding the volume shape coefficient, it is preferable to use a material whose value is in the range of 0.70 to π/6.
〔ただし、体積形状係数Fは次式で表わされる。[However, the volumetric shape factor F is expressed by the following equation.
IP−V/D”
式中Vは粒子体積(μm”)、Dは粒子の投影面に於け
る最大径(μm)を示す。〕
体積形状係数は粒子の球状の程度を表わすもので、π/
6に近づく程球状に近づく。IP-V/D" where V is the particle volume (μm") and D is the maximum diameter (μm) of the particle in the projected plane. ] The volume shape factor represents the degree of sphericity of the particle, and is π/
The closer it gets to 6, the more spherical it becomes.
ここでいう平均粒径とは、島津製作所製遠心沈降式粒度
分布測定装置で測定された等価球径分布に於ける積算(
重量基準)rOチの値を用いる。The average particle size here refers to the cumulative (
Weight basis) Use the value of rOchi.
なお本発明で用いる二酸化チタンの該ボリエくはエステ
ル化反応後重縮合前に添加するのが好ましい。The titanium dioxide used in the present invention is preferably added after the esterification reaction and before the polycondensation.
ても良いが、通常ポリエステル製造工程に粒子を添加す
るに際しては、自動化、計量化の容易さ、分散性の向上
、回収系の簡素化等の諸点から粒子をエチレングリコー
ルのスラリーとして添加するのが一般的である。粒子を
スラリー状に分散させる際には、できるだけ凝集の少な
い一次粒子の状態まで分散させる必要がある。このよう
に粒子を一次粒子の状態まで均一に分散させるためには
必要に応じ、分散、解砕、粉砕、分級、F3m等任意の
方法を採用することができる0
また所定の平均粒径の粒子を得るためには重版粒子の粉
砕、分級、濾過処理等の方法を採用してもよい。However, when adding particles to the polyester manufacturing process, it is usually preferable to add the particles as an ethylene glycol slurry from the viewpoint of automation, ease of metering, improved dispersibility, and simplification of the recovery system. Common. When dispersing particles into a slurry, it is necessary to disperse them into a state of primary particles with as little agglomeration as possible. In this way, in order to uniformly disperse the particles to the state of primary particles, any method such as dispersion, crushing, pulverization, classification, F3m, etc. can be adopted as necessary. Also, particles with a predetermined average particle size can be used. In order to obtain this, methods such as pulverization, classification, and filtration of reprinted particles may be employed.
粒子をエチレングリコールスラリーとして添加する際、
スラリー中の2μm以上の粗大粒子の割合が全粒子に対
してo、r重量%以下にして添加することがポリエステ
ルフィルムとした際のフィルム表面の粗大突起を低減さ
せる上で特に好ましい。When adding the particles as an ethylene glycol slurry,
It is particularly preferable to add coarse particles of 2 μm or more in the slurry at a ratio of o, r weight % or less based on the total particles in order to reduce coarse protrusions on the surface of the film when it is made into a polyester film.
大粒子と小粒子をポリエステル中に含有させる方法とし
て、ポリエステル製造時に、−株類の粒径の異なる粒子
を所定量同時に添加して得るか、またはコ種類の粒径の
粒子をそれぞれ別個に製′造して、製膜する際に配合す
る方法が挙げられるが、いずれの方法を用いてもよい。Large particles and small particles can be incorporated into polyester by simultaneously adding a predetermined amount of particles of different particle sizes during polyester production, or by separately producing particles of different particle sizes. An example of this is a method in which the components are mixed at the time of film formation, but any method may be used.
本発明に於て必要であれば粗大粒子数を増加させず、か
つフィルム表面の平滑性に対し悪形響を及ぼさない程度
の平均粒径及び含有量であれば二酸化チタン以外に不活
性粒子を併用しても良い。また上記不活性粒子以外に反
応系で触媒残渣とリン化合物との反応により析出させた
微粒子を併用することができる。In the present invention, if necessary, inert particles may be added in addition to titanium dioxide as long as the average particle size and content are such that they do not increase the number of coarse particles and do not adversely affect the smoothness of the film surface. May be used together. In addition to the above-mentioned inert particles, fine particles precipitated by a reaction between a catalyst residue and a phosphorus compound in the reaction system can be used in combination.
本発明に於ける二酸化チタンを含有するポリエステルの
重合に際しては公知の方法を採用し得る。例えば重縮合
反応の触媒として、アンチモン化合物、ゲルマニュウム
化合物、チタン化合物等の一種以上を用い、2Jθ〜J
CJO℃程度に加熱し、減圧下エチレングリコールを留
出させることにより反応を進行させる。In the present invention, known methods can be employed for polymerizing the polyester containing titanium dioxide. For example, as a catalyst for polycondensation reaction, one or more of antimony compounds, germanium compounds, titanium compounds, etc. are used, and 2Jθ~J
The reaction is allowed to proceed by heating to about CJO°C and distilling off ethylene glycol under reduced pressure.
またフィルム化に際しては公知の製膜方法、例えば27
0〜3θθ℃でポリエステルチップをフィルム状に溶融
押出後、亭θ〜70℃で冷却後固化し無定形シートとし
た後、縦、横に逐次二軸延伸あるいは同時二軸延伸しi
bo〜コlO℃で熱処理する等の方法(例えば特公昭j
fl)−j6j?号公報記載の方法)を採用することが
できる。In addition, when forming a film, a known film forming method such as 27
After melt-extruding polyester chips into a film at 0 to 3θθ℃, solidify after cooling at θ to 70℃ to form an amorphous sheet, and then sequentially or simultaneously biaxially stretched vertically and horizontally.
Methods such as heat treatment at 0°C (for example,
fl)-j6j? (method described in the above publication) can be adopted.
〈実施例〉
以下、本発明を実施例により更に詳細に説明するが本発
明はその要旨を越えない限夛以下の実施例によって限定
されるものではない。<Examples> Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples without exceeding the gist thereof.
なお種々の諸物性及び特性線以下の如く測定されたもの
であり、または定義されるものである。実施例中「部」
及び「チ」はそれぞれ1−重量部」及び「重fチ」を意
味する。In addition, various physical properties and characteristic lines are measured or defined as follows. “Part” in Examples
and "chi" mean "1 part by weight" and "part by weight", respectively.
(1) 平均粒径
島津製作所製遠心沈降式粒度分布測定装置5A−CP、
?形によって測定された等価球径分布に於ける積算(重
量基準)3θチの値を用いる〇
(2)フィルムの表面平滑性
J工S B80/−/971. 記載の方法によった
。(1) Average particle size Centrifugal sedimentation type particle size distribution measuring device 5A-CP manufactured by Shimadzu Corporation,
? 〇(2) Surface smoothness of film J Engineering S B80/-/971. Using the integrated (weight-based) 3θ value in the equivalent spherical diameter distribution measured by the shape. According to the method described.
測定は表面粗さ測定機モデルSE−,71!’(小板研
究所製)を用いて行った。触針径ユμ、触針圧30mg
g、カットオフ値0.Otwas、測定長はユj鴫とし
た。測定は72点行い、最大値、最小値をそれぞれカッ
トし、102点の平均値で示した。The measurement was carried out using a surface roughness measuring machine model SE-71! ' (manufactured by Koita Institute). Stylus diameter μ, stylus pressure 30mg
g, cutoff value 0. Ottawa, and the measurement length was set to 1. Measurement was performed at 72 points, the maximum value and minimum value were cut, and the average value of 102 points was shown.
(3)滑シ性
摩擦係数で代表し、摩擦係数はASTMD−/ff?≠
に準じてテープ状のサンプルで測定できるよう改良し九
方法で行った0測定時のサンプル大きさは幅/jm、長
さ15θ箇でその引張速度は一〇−である。測定は温度
コ/士コ℃、湿度6j±5%の雰囲下で行った。(3) Smoothness is represented by the coefficient of friction, and the coefficient of friction is ASTMD-/ff? ≠
The sample size at the time of 0 measurement, which was modified to allow measurement with a tape-shaped sample according to the above method, was width/jm, length 15θ, and the tensile speed was 10-. The measurements were carried out in an atmosphere with a temperature of C/C and a humidity of 6J±5%.
(4) 摩耗性(白粉の評価)
第1図に示す走行系でフィルムを50Om長にわたって
走行させ(I)で示した6順りの硬質クロム固定ビンに
付着した摩耗量を目視評価した。(4) Abrasion properties (evaluation of white powder) The film was run over a length of 500m using the running system shown in FIG. 1, and the amount of wear attached to the hard chrome fixing bottles in the 6th order shown in (I) was visually evaluated.
全く付着しない ○
若干付着する Δ
付着量が多い ×
(5)巻き特性
ロール状に巻き上げた際のロール表面及びロール端面の
外観を以下のように判定した。No adhesion at all ○ Slight adhesion Δ Large amount of adhesion × (5) Winding characteristics The appearance of the roll surface and roll end face when wound up into a roll was evaluated as follows.
ロール表面に殆んどシワやツブ状欠陥を有さずロール端
間が揃っているもの: ○ロール表面にシワは殆ん
どないが、ツブ状欠陥が若干発生し、ロール端面が少し
不揃いのもの: Δロール
表面にシワが発生したり、または、ロール端面が不揃の
もの; ×(6)粗大突起数
フィルム表面にアルミニュウムを蒸清し、干渉顕微鏡を
用いて二光束法にて測定した。There are almost no wrinkles or bulge-like defects on the roll surface, and the roll edges are evenly aligned: ○There are almost no wrinkles on the roll surface, but there are some bulge-like defects, and the roll end surfaces are slightly uneven. Items: Δ Wrinkles on the roll surface or roll end faces that are uneven; .
測定波長O,S≠μm1次以上の干渉組以上す突起個数
を、2よd当りに換算して示した0実施例/
ジメチルテレフタレート10O部とエチレングリコール
60部及び酢酸マグネシュウム・四本塩0.0?部を反
応器にとり、加熱昇温すると230℃に昇温し、実質的
にエステル交換反応を終了した。ついで平均粒径θ1.
2Sμ惰の小粒子アナターゼ盟二酸化チタンを予めエチ
レングリコール中に分散し、分級、−過処理したものを
o、、twt%と平均粒径o、p sμmの大粒子アナ
ターゼ型二酸化チタンを予めエチレングリコール中に分
散し、分級、−過処理したもの0.0りwt%を充分混
合し添加した後、更にエチルアシッドフォスフェートo
、o lI部、二酸化アンチモン0、Oj 5部を加え
ダ時間重縮合を行い極限粘度0.66のポリエチレンテ
レフタレート樹脂を得た。Measurement wavelength O, S≠ μm The number of protrusions in the interference group of the first order or higher is converted per 2 d. Example 1: 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, and 0.0 parts of magnesium acetate. 0? A portion of the mixture was placed in a reactor and heated to 230° C., substantially completing the transesterification reaction. Then, the average particle diameter θ1.
2S μm small particle anatase type titanium dioxide is pre-dispersed in ethylene glycol, classified and over-treated, and large particle anatase type titanium dioxide with an average particle diameter of o, p s μm is pre-dispersed in ethylene glycol. After thoroughly mixing and adding 0.0 wt% of ethyl acid phosphate dispersed, classified, and overtreated, ethyl acid phosphate
, 0 parts of o lI, 0 parts of antimony dioxide, and 5 parts of Oj were added and polycondensation was carried out for several hours to obtain a polyethylene terephthalate resin having an intrinsic viscosity of 0.66.
得られたポリエステルフィルムの特性を*/表に示す。The properties of the obtained polyester film are shown in */Table.
第1表に示す如く、得られたフィルムの表面平滑性、滑
シ性、耐摩耗性、巻き特性及び粗大突起数共に非常に良
好であり、磁気テープ用フィルムとして極めて満足すべ
きレベルであった。As shown in Table 1, the obtained film had very good surface smoothness, lubricity, abrasion resistance, winding properties, and number of coarse protrusions, and was at an extremely satisfactory level as a film for magnetic tape. .
実施側御
実施例/に於て使用した小粒子アナターゼ型は実施例/
と同様の方法にてこ軸延伸ポリエステルフィルムを得た
0得られたポリエステルフィルムの特性を第1表に示す
。得られたフィルムの特性は実施例1と同等であった0
比較例1
平均粒径0.25μmのアナターゼ屋二酸化チタンを予
めエチレングリコール中に分散し、分級、濾過処理した
ものをθ、、ywt%単独で添加する以外は実施例1と
同様の方法にて二軸延伸ポリエステルフィルムを得た。The small particle anatase type used in the implementation example/
A lever-stretched polyester film was obtained in the same manner as in Table 1. The properties of the obtained polyester film are shown in Table 1. The properties of the obtained film were the same as those of Example 1. Comparative Example 1 Anatase titanium dioxide with an average particle size of 0.25 μm was predispersed in ethylene glycol, classified and filtered, and then θ,,ywt A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that only % was added.
得られたポリエステルフィルムの特性を第1表に示す0
第1表に示す如く、得られたフィルムは耐摩耗性及び巻
き特性が劣っており磁気テープの特性としては不充分で
ある。The properties of the obtained polyester film are shown in Table 1.
As shown in Table 1, the resulting film had poor abrasion resistance and winding properties, and was insufficient for magnetic tape properties.
比較例λ
平均粒径o、4csμmの7ナターゼ型二酸化チタンを
予めエチレングリコール中に分散し、分級、−過処理し
たものを060りwt%単独で酢加した以外は、実施例
/と同様の方法にて二軸延伸ポリエステルフィルムを得
た。得られたポリエステルフィルムの特性を第1表に示
す。第1表に示す如く、得られたフィルムは滑り性、耐
摩耗性及び巻き特性が劣っており、磁気テープの特性と
しては不充分である0
比較例3
平均粒径O,コSμmの小粒子アナターゼ型二酸化チタ
ンを予めエチレングリコール中に分散し、分級、濾過処
理したものへコwt%と平均粒径o、qsμmの大粒子
アナターゼ型二酸化チタンを予めエチレングリコール中
に分散し、分級、濾過処理したもの0.07wt%を充
分混合し添加した以外は実施例/と同様の方法で二軸延
伸ポリエステルフィルムを得た。得られたポリエステル
フィルムの特性を第1表に示す。第1表に示す如く得ら
れたフィルムの滑り性及び耐摩耗性は満足すべき特性を
有しているが、巻き特性及び粗大突起数の点で劣ってお
り、磁気テープ用としては不充分である。Comparative Example λ 7 Natase type titanium dioxide with an average particle size o of 4 cs μm was previously dispersed in ethylene glycol, classified and overtreated, and 060% by weight was added with vinegar alone. A biaxially stretched polyester film was obtained by this method. The properties of the obtained polyester film are shown in Table 1. As shown in Table 1, the obtained film has poor slip properties, abrasion resistance, and winding properties, and is insufficient as a magnetic tape property. Comparative Example 3 Small particles with an average particle size of O, Sμm Anatase-type titanium dioxide is pre-dispersed in ethylene glycol, classified and filtered. Large particles of anatase-type titanium dioxide with wt% and average particle diameters of o and qs μm are pre-dispersed in ethylene glycol, classified and filtered. A biaxially stretched polyester film was obtained in the same manner as in Example 1, except that 0.07 wt% of the polyester resin was thoroughly mixed and added. The properties of the obtained polyester film are shown in Table 1. As shown in Table 1, the obtained film has satisfactory properties in terms of slipperiness and abrasion resistance, but it is inferior in terms of winding properties and the number of coarse protrusions, and is insufficient for use in magnetic tapes. be.
比較例弘
平均粒径O,コ5μmの小粒子アナターゼ型二酸化チタ
ンを予めエチレングリコール中に分数処理し、分級、−
過処理したものを0.3 wt%と平均粒径Q、lIj
μmの大粒子アナターゼ盟二酸化チタンを予めエチレン
グリコール中に分散し、分級、濾過処理したもの0.7
wt%を充分混合し添加した以外は実施例/と同様の方
法で二軸延伸ポリエステルフィルムを得た。得られたポ
リエステルフィルムの特性を第1表に示す0第1表に示
す如く、得られたフィルムの滑υ性及び耐摩耗性は満足
すべき特性を有しているが、巻き特性及び粗大突起数の
点で劣っており磁気テープ用としては不充分である。Comparative Example Small particle anatase type titanium dioxide with a Hiroshima average particle diameter of 0.5 μm was fractionally treated in ethylene glycol in advance, classified, -
The over-treated material is 0.3 wt% and the average particle size Q, lIj
0.7μm large particle anatase titanium dioxide dispersed in ethylene glycol, classified and filtered.
A biaxially stretched polyester film was obtained in the same manner as in Example except that the wt% was sufficiently mixed and added. The properties of the obtained polyester film are shown in Table 1.As shown in Table 1, the obtained film has satisfactory lubricity and abrasion resistance, but it has poor winding properties and coarse protrusions. They are inferior in number and are insufficient for magnetic tape applications.
〈発明の効果〉
以上詳述した如く、本発明のフィルムは特定粒径の小粒
子アナターゼ屋二酸化チタンと特定粒径の大粒子アナタ
ーゼ型二酸化チタンをそれぞれ特定量づつ含有して成る
フィルムであり、磁気テープ用ポリエステルフィルムと
して要求される表面平滑性、滑り性及びフィルム製造時
の作業性、その中でも特に巻き特性が優れている特徴を
有する。また耐摩耗性に優れ、磁気テープ製造時及び磁
気テープ使用時に於ける金属ロール面を走行する除虫じ
る白粉発生量が著しく少ない特徴を有し、併せてビデオ
チーズ用として用いた場合ドロップアウト発生の原因と
なる粗大突起数の著しく少ない特性を有していることか
ら磁気テープ用、蒸着用、コンデンサー用、包装用等の
広範な用途に使用ジることかできる。<Effects of the Invention> As detailed above, the film of the present invention is a film containing specific amounts of small-particle anatase-type titanium dioxide with a specific particle size and large-particle anatase-type titanium dioxide with a specific particle size, It has the characteristics of excellent surface smoothness, slipperiness, and workability during film production, which are required for a polyester film for magnetic tapes, especially in terms of winding properties. It also has excellent abrasion resistance, and has a characteristic that the amount of white powder generated when running on the metal roll surface during magnetic tape manufacturing and magnetic tape use is extremely small, and there is no dropout when used for video cheese. Since it has the characteristic of having a significantly small number of coarse protrusions that cause generation, it can be used in a wide range of applications such as magnetic tapes, vapor deposition, capacitors, and packaging.
第7図は耐摩耗性を評価する走行系を示す概略図であυ
、図中で(I)は10の硬質クロム固定ビン、(■)は
テンションメーターを示しσは/ J O”である。
代 理 人 弁理士長香川 −
ほか/名Figure 7 is a schematic diagram showing the running system for evaluating wear resistance.
In the figure, (I) indicates 10 hard chrome fixing bottles, (■) indicates a tension meter, and σ is /JO''. Agent: Patent Attorney Cho Kagawa - Others/Names
Claims (1)
型二酸化チタンを0.01〜1.0wt%及び平均粒径
が0.31〜1.0μmのアナターゼ型二酸化チタンを
0.002〜0.5wt%含有することを特徴とする二
軸延伸ポリエステルフィルム(1) 0.01 to 1.0 wt% of anatase titanium dioxide with an average particle size of 0.01 to 0.30 μm and 0.002 to 1.0 wt% of anatase titanium dioxide with an average particle size of 0.31 to 1.0 μm Biaxially oriented polyester film characterized by containing 0.5 wt%
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9889786A JPS62253631A (en) | 1986-04-28 | 1986-04-28 | Polyester film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9889786A JPS62253631A (en) | 1986-04-28 | 1986-04-28 | Polyester film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62253631A true JPS62253631A (en) | 1987-11-05 |
JPH0458813B2 JPH0458813B2 (en) | 1992-09-18 |
Family
ID=14231920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9889786A Granted JPS62253631A (en) | 1986-04-28 | 1986-04-28 | Polyester film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62253631A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20040022262A (en) * | 2002-09-03 | 2004-03-12 | 에스케이씨 주식회사 | Biaxially oriented polyethylenenaphthalate film for a copier belt |
-
1986
- 1986-04-28 JP JP9889786A patent/JPS62253631A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20040022262A (en) * | 2002-09-03 | 2004-03-12 | 에스케이씨 주식회사 | Biaxially oriented polyethylenenaphthalate film for a copier belt |
Also Published As
Publication number | Publication date |
---|---|
JPH0458813B2 (en) | 1992-09-18 |
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