JPH0717153A - Film for high-sensitivity thermal stencil printing raw paper - Google Patents
Film for high-sensitivity thermal stencil printing raw paperInfo
- Publication number
- JPH0717153A JPH0717153A JP4705594A JP4705594A JPH0717153A JP H0717153 A JPH0717153 A JP H0717153A JP 4705594 A JP4705594 A JP 4705594A JP 4705594 A JP4705594 A JP 4705594A JP H0717153 A JPH0717153 A JP H0717153A
- Authority
- JP
- Japan
- Prior art keywords
- film
- heat
- stencil printing
- particles
- weight
- 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
Landscapes
- Printing Plates And Materials Therefor (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、感熱孔版印刷原紙用ポ
リエステルフィルムに関する。さらに詳しくは、本発明
は穿孔感度に優れ、印刷時の画像の解像度、濃度等の印
字品性に優れた高感度感熱孔版印刷原紙用フィルムに関
する。FIELD OF THE INVENTION The present invention relates to a polyester film for heat-sensitive stencil printing base paper. More specifically, the present invention relates to a high-sensitivity, heat-sensitive stencil sheet for stencil sheet, which has excellent perforation sensitivity and excellent printing properties such as image resolution and density during printing.
【0002】[0002]
【従来の技術および発明が解決しようとする課題】従
来、感熱孔版印刷用原紙としては、ポリエステル等の熱
可塑性樹脂フィルムに多孔性薄葉紙をラミネートしたも
のが知られており、かかる用途に用いられるフィルムに
は、以下のような特性が要求される。 (1)熱穿孔感度が良いこと。すなわち、少量の熱量で
溶融し、かつ、印刷時の画像が鮮明になるような適度な
大きさの穿孔が得られるような十分な熱収縮率を有する
こと。 (2)多孔性薄葉紙とのラミネートおよび印刷時の作業
に十分耐え得る強度、弾性率を有すること。また、かか
る作業において、加熱工程があっても、その影響で原紙
の著しいカール等の問題が生じないこと。 (3)熱穿孔の階調性が良いこと。原紙として使用する
際、穿孔されるべき部分以外が周囲の穿孔の影響で溶融
してしまうと、印刷画像の階調性が劣るようになり、好
ましくない。すなわち、穿孔される部分と穿孔されない
部分とがはっきり区別できるような熱穿孔特性を有する
こと。2. Description of the Related Art Conventionally, as a base paper for heat-sensitive stencil printing, a laminate of porous thin paper on a thermoplastic resin film such as polyester has been known, and a film used for such application. Is required to have the following characteristics. (1) The thermal perforation sensitivity is good. That is, it must have a sufficient heat shrinkage ratio that it can be melted with a small amount of heat and that a perforation of an appropriate size can be obtained so that an image at the time of printing becomes clear. (2) It should have strength and elastic modulus sufficient to withstand the work of laminating with porous thin paper and printing. Also, in such work, even if there is a heating step, the problem such as a remarkable curl of the base paper does not occur due to the influence of the heating step. (3) The gradation of thermal perforation is good. When used as a base paper, if the portion other than the portion to be perforated is melted due to the influence of the perforations in the periphery, the gradation of the printed image becomes inferior, which is not preferable. That is, it should have a thermal perforation property that allows a clear distinction between the perforated portion and the non-perforated portion.
【0003】また、これらの要件に加え、フィルム製造
時および原紙作成時の取扱い性、生産性にも優れている
ことが求められる。具体的には、フィルム製造時には、
延伸性が良好で、破断等のトラブルを起こさず、また、
巻取性、スリット性も良好で、巻取時にシワが入った
り、巻きずれを起こしたりしないことが必要である。原
紙作成時においても、フィルムの巻出しや、工程内での
フィルム走行等でのトラブルが発生しないことが必要で
ある。従来、かかる用途に用いるフィルムとして熱可塑
性樹脂を対象とした二軸延伸フィルムであって、その熱
的特性を規定することにより印刷特性を改善したフィル
ム(特開昭62−149496号公報)、表面の粗度お
よび突起個数を規定したフィルム(特開昭63−227
634号公報)、あるいは熱収縮特性を規定したフィル
ム(特開昭62−282983号公報、特開昭63−1
60895号公報、特開昭63−312192号公報、
特開平3−30996号公報)等が提案されているが、
上記した課題をすべて解決できるものではなかった。In addition to these requirements, it is also required to be excellent in handleability and productivity during film production and base paper production. Specifically, during film production,
Stretchability is good, troubles such as breakage do not occur, and
It is necessary to have good winding and slitting properties, and to prevent wrinkles and winding misalignment during winding. Even when the base paper is prepared, it is necessary that the problems such as the unwinding of the film and the running of the film in the process do not occur. Conventionally, a biaxially stretched film intended for a thermoplastic resin as a film used for such an application, the film having improved printing characteristics by defining its thermal characteristics (JP-A-62-149496), surface Of which the roughness and the number of protrusions are specified (Japanese Patent Laid-Open No. 63-227
No. 634) or a film having a specified heat shrinkage property (Japanese Patent Laid-Open No. 62-282983, Japanese Patent Laid-Open No. 63-1).
No. 60895, Japanese Patent Laid-Open No. 63-321192,
Japanese Laid-Open Patent Publication No. 3-30996) and the like have been proposed.
Not all of the above problems could be solved.
【0004】[0004]
【課題を解決するための手段】本発明者らは、上記課題
に鑑み、鋭意検討した結果、特定の組成のポリエステル
からなり、収縮率および加熱収縮応力が特定の条件を満
足する二軸配向フィルムが、感熱孔版印刷原紙用として
好適であることを見いだし、本発明を完成するに至っ
た。DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above problems, the present inventors have made a biaxially oriented film made of polyester having a specific composition and having shrinkage and heat shrinkage stress satisfying specific conditions. However, they have found that they are suitable for use as heat-sensitive stencil printing base paper, and have completed the present invention.
【0005】すなわち、本発明の要旨は、ポリブチレン
テレフタレートを20〜80重量%含有するポリエステ
ル組成物からなる、厚み0.5〜6.0μmの二軸配向
フィルムであって、60〜140℃の範囲でのフィルム
の加熱収縮応力の縦方向および横方向の平均値の最大値
が300g/mm2 を超え、100℃で3分処理後の熱
収縮率が20%以上であることを特徴とする高感度感熱
孔版印刷原紙用フィルムに存する。That is, the gist of the present invention is a biaxially oriented film having a thickness of 0.5 to 6.0 μm and comprising a polyester composition containing 20 to 80% by weight of polybutylene terephthalate, and having a temperature of 60 to 140 ° C. The maximum value of the average value of the heat shrinkage stress of the film in the machine direction and the transverse direction in the range exceeds 300 g / mm 2, and the heat shrinkage rate after treatment for 3 minutes at 100 ° C. is 20% or more. It exists in the film for high-sensitivity heat-sensitive stencil printing base paper.
【0006】以下、本発明を詳細に説明する。本発明で
いうポリブチレンテレフタレート(PBT)とは、ジカ
ルボン酸成分の70モル%以上、好ましくは80モル%
以上がテレフタル酸、グリコール成分の50モル%以
上、好ましくは70モル%以上が1,4ーブタンジオー
ルであるポリエステルを指す。また、本発明でいうPB
Tを20〜80重量%含有するポリエステル組成物と
は、PBTとPBT以外の一種以上のポリエステルとを
含有する組成物を指す。ここでいうポリエステルとは、
テレフタル酸、イソフタル酸、2,6−ナフタレンジカ
ルボン酸等のジカルボン酸成分、およびエチレングリコ
ール等のグリコール成分からなるポリエステルを指す
が、それ以外の成分を含む共重合体であってもよい。か
かる共重合可能な成分としては、上記した成分以外に、
フタル酸、セバシン酸、アジピン酸等のジカルボン酸、
ジエチレングリコール、トリエチレングリコール、ール
成分、およびp−ヒドロキシ安息香酸等のオキシカルボ
ン酸等が挙げられる。The present invention will be described in detail below. The polybutylene terephthalate (PBT) referred to in the present invention means 70 mol% or more, preferably 80 mol% of the dicarboxylic acid component.
The above refers to a polyester in which 50 mol% or more, preferably 70 mol% or more of terephthalic acid and glycol components are 1,4-butanediol. In addition, PB in the present invention
The polyester composition containing 20 to 80% by weight of T means a composition containing PBT and one or more polyesters other than PBT. What is polyester here?
It refers to a polyester composed of a dicarboxylic acid component such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and a glycol component such as ethylene glycol, but may be a copolymer containing other components. As such a copolymerizable component, in addition to the above components,
Dicarboxylic acids such as phthalic acid, sebacic acid, adipic acid,
Examples thereof include diethylene glycol, triethylene glycol, a polyol component, and oxycarboxylic acid such as p-hydroxybenzoic acid.
【0007】かかるポリエステル組成物を得る方法とし
ては、PBTと他のポリエステルとをブレンドして、溶
融混練りする方法が好ましく用いられる。本発明におけ
るPBTの含有量は、好ましくは30〜80重量%、更
に好ましくは40〜70重量%である。20重量%以下
では、高度な穿孔感度を得るための収縮特性が得られな
くなるため好ましくない。また、80重量%を超える
と、フィルム製造時に延伸性が著しく悪化し、生産性の
低下をもたらすようになるため好ましくない。本発明の
ポリエステルの融点はフィルムとしたときに150〜2
40℃の範囲であることが好ましく、さらに好ましくは
160〜230℃の範囲である。融点が240℃より高
い場合には、高度な穿孔感度が得られなくなりことがあ
り、150℃未満では、フィルムの耐熱寸法安定性が悪
化して原紙を製造する工程や、原紙の保存中にカールが
発生したり、印刷画像の階調性が劣ることがある。As a method of obtaining such a polyester composition, a method of blending PBT and another polyester and melt-kneading is preferably used. The content of PBT in the present invention is preferably 30 to 80% by weight, more preferably 40 to 70% by weight. When it is 20% by weight or less, the shrinkage property for obtaining a high perforation sensitivity cannot be obtained, which is not preferable. On the other hand, if it exceeds 80% by weight, the stretchability is remarkably deteriorated during the production of the film and the productivity is lowered, which is not preferable. The melting point of the polyester of the present invention is 150 to 2 when formed into a film.
It is preferably in the range of 40 ° C, and more preferably in the range of 160 to 230 ° C. If the melting point is higher than 240 ° C, high perforation sensitivity may not be obtained, and if the melting point is lower than 150 ° C, the heat-resistant dimensional stability of the film deteriorates and the curl is produced during the process of manufacturing the base paper or during storage of the base paper. May occur, or the gradation of the printed image may be poor.
【0008】また、かかる融点はDSC(差動熱量分
析)により測定されるが、融解吸熱ピークが2ケ所以上
に得られることが更に高度な穿孔感度を得るためには好
ましい。かかる融解吸熱温度の差は、好ましくは5℃以
上、更に好ましくは10℃以上である。このような場合
本発明においては、最も低温度のピーク(I)から算出
されるエネルギーが溶融の全ピークから算出されるエネ
ルギー合計の30%以上である場合は、ピーク(I)の
頂点の温度を融点とし、30%未満の場合は、最も溶融
エネルギーの大きいピークの頂点の温度を融点とする。The melting point is measured by DSC (differential calorimetry), but it is preferable to obtain melting endothermic peaks at two or more points in order to obtain higher perforation sensitivity. The difference between the melting endothermic temperatures is preferably 5 ° C. or higher, more preferably 10 ° C. or higher. In such a case, in the present invention, when the energy calculated from the lowest temperature peak (I) is 30% or more of the total energy calculated from all the melting peaks, the temperature at the peak of the peak (I) Is the melting point, and when it is less than 30%, the temperature at the apex of the peak with the largest melting energy is the melting point.
【0009】本発明においては60〜140℃の範囲で
のフィルムの加熱収縮応力の縦および横方向の平均値の
最大値が300g/mm2 を超えることが必要である。
300g/mm2 以下では、穿孔時に穴が広がる力が不
足して、印刷時に鮮明な画像が得られるほどの十分な大
きさを有する穿孔が得られなくなるため好ましくない。
かかる加熱収縮応力の最大値は好ましくは500〜15
00g/mm2 、さらに好ましくは550〜1300k
g/mm2 である。本発明においては、温度100℃で
のフィルムの縦方向の加熱収縮応力をSm、横方向の加
熱収縮応力をStとしたときに、下記式(1)および
(2)を同時に満足することが好ましい。In the present invention, it is necessary that the maximum value of the average value in the longitudinal and transverse directions of the heat shrinkage stress of the film in the range of 60 to 140 ° C. exceeds 300 g / mm 2 .
If it is 300 g / mm 2 or less, the force for expanding the holes at the time of perforation is insufficient, and perforations having a size sufficient to obtain a clear image at the time of printing cannot be obtained, which is not preferable.
The maximum value of the heat shrinkage stress is preferably 500 to 15
00 g / mm 2 , more preferably 550 to 1300 k
It is g / mm 2 . In the present invention, it is preferable that the following equations (1) and (2) are simultaneously satisfied, where Sm is the heat shrinkage stress in the longitudinal direction of the film at 100 ° C. and St is the heat shrinkage stress in the lateral direction. .
【数3】 (Sm+St)/2≧300g/mm2 ……(1) 1.2≦Sm/St≦5 ……(2) (上記式中、Smは温度100℃でのフィルム縦方向の
加熱収縮応力(g/mm 2 )、Stは同温度でのフィル
ム横方向の加熱収縮応力(g/mm2 )を表す)(3) (Sm + St) / 2 ≧ 300 g / mm2 (1) 1.2 ≦ Sm / St ≦ 5 (2) (In the above formula, Sm is the film longitudinal direction at a temperature of 100 ° C.)
Heat shrinkage stress (g / mm 2), St is the fill at the same temperature
Lateral heat shrinkage stress (g / mm2))
【0010】フィルムの加熱収縮応力の縦、横の平均値
((Sm+St)/2)が300g/mm2 未満では、
穿孔時に穴が広がる力が不足して、印刷時に鮮明な画像
が得られるほどの十分な大きさを有する穿孔が得られな
くなることがある。かかる加熱収縮応力平均値は、好ま
しくは500〜1500g/mm2 、さらに好ましくは
550〜1300kg/mm2 である。When the average value of the heat shrinkage stress of the film in the vertical and horizontal directions ((Sm + St) / 2) is less than 300 g / mm 2 ,
In some cases, the force for expanding the holes during punching may be insufficient, and it may not be possible to obtain punches having a size large enough to obtain a clear image during printing. The average value of such heat shrinkage stress is preferably 500 to 1500 g / mm 2 , and more preferably 550 to 1300 kg / mm 2 .
【0011】また、フィルムの縦方向と横縦方向の加熱
収縮応力の比(Sm/St)は1.2〜5の範囲、さら
には1.5〜3.5の範囲が好ましい。かかる比の値が
1.2未満、すなわち縦方向の加熱収縮応力が大きくな
い場合は、穿孔感度や印刷時の耐刷性が劣ることがあ
る。一方、Sm/Stが5を越える場合は、穿孔形状の
均一性が悪化し、印刷時の画像濃度や解像度が劣ること
がある。これらの要件に加え、本発明においてはフィル
ムの100℃3分処理後の収縮率が20%以上である必
要があり、好ましくは30〜80%である。20%未満
では、穿孔感度が不足して印刷的の画像濃度が低下する
ようになるため好ましくない。The ratio (Sm / St) of heat shrinkage stress in the machine direction to the machine direction in the machine direction is preferably 1.2 to 5, more preferably 1.5 to 3.5. When the value of this ratio is less than 1.2, that is, when the heat shrinkage stress in the longitudinal direction is not large, the perforation sensitivity and printing durability during printing may be poor. On the other hand, when Sm / St exceeds 5, the uniformity of the perforated shape is deteriorated, and the image density and resolution during printing may be poor. In addition to these requirements, in the present invention, the shrinkage rate of the film after treatment at 100 ° C. for 3 minutes needs to be 20% or more, preferably 30 to 80%. If it is less than 20%, the perforation sensitivity is insufficient and the print-like image density is lowered, which is not preferable.
【0012】本発明のフィルムは、フィルム製造時の巻
上げ工程、原紙作成時のコーティング、貼合せ工程およ
び印刷時の作業性を向上させるため、あるいは、熱穿孔
時のサーマルヘッドとフィルムとの融着を防止するた
め、表面を粗面化してフィルムに適度な滑り性を付与す
ることが望ましく、通常、表面を適度に粗面化するため
にフィルムに平均粒径0.05〜2.0μmの微粒子を
0.01〜2.0重量%、好ましくは0.1〜1.5重
量%含有させる。かかる微粒子の例としては、炭酸カル
シウム、炭酸マグネシウム、炭酸バリウム、硫酸カルシ
ウム、硫酸バリウム、リン酸カルシウム、リン酸リチウ
ム、リン酸マグネシム、フッ化リチウム、酸化アルミニ
ウム、酸化ケイ素、酸化チタン、カオリン、タルク、カ
ーボンブラック、窒化ケイ素、窒化ホウ素および特公昭
59−5216号公報に記載されたような架橋高分子微
粉体を挙げることができるが、これらに限定されるもの
ではない。この際、配合する微粒子は、単成分でもよ
く、また、2成分以上を同時に用いてもよい。2成分以
上用いる場合は、それらの全体の平均粒径および含有量
が上記した範囲内にあることが好ましい。平均粒径が
0.05μm未満であったり、微粒子の含有量が0.0
1重量%未満である場合は、フィルム表面の粗面化が不
足し十分に効果が得られない恐れがある。また、平均粒
径が2.0μmを超える場合や含有量が2.0重量%を
超える場合には、フィルム表面の粗面化の度合いが大き
過ぎて熱伝達にムラが生じ、穿孔が不均一となり、解像
度が劣ったり、印字品位性を損なったりすることがあ
る。The film of the present invention is used to improve workability during winding process during film production, coating process during base paper preparation, laminating process and printing, or fusion between the thermal head and film during thermal perforation. In order to prevent the above, it is desirable to roughen the surface to impart appropriate slipperiness to the film, and in order to appropriately roughen the surface, fine particles having an average particle size of 0.05 to 2.0 μm are usually used. 0.01 to 2.0% by weight, preferably 0.1 to 1.5% by weight. Examples of such fine particles include calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium phosphate, lithium phosphate, magnesium phosphate, lithium fluoride, aluminum oxide, silicon oxide, titanium oxide, kaolin, talc, carbon. Examples thereof include black, silicon nitride, boron nitride, and crosslinked polymer fine powders described in JP-B-59-5216, but are not limited thereto. At this time, the fine particles to be mixed may be a single component, or two or more components may be used at the same time. When two or more components are used, it is preferable that the total average particle size and content of them are within the ranges described above. The average particle size is less than 0.05 μm, or the content of fine particles is 0.0
If it is less than 1% by weight, roughening of the film surface may be insufficient and sufficient effects may not be obtained. When the average particle size exceeds 2.0 μm or the content exceeds 2.0% by weight, the degree of roughening of the film surface is too large and uneven heat transfer occurs, resulting in uneven perforation. Therefore, the resolution may be inferior or the print quality may be impaired.
【0013】特に好ましいフィルム表面の粗面化方法
は、平均粒径(d1 )が0.6〜3.0μmでモース硬
度5以上の粒子(A)と平均粒径(d2 )が0.06〜
0.8μmでd1 /d2 が2〜10である粒子(B)と
を含有させる方法である。モース硬度が高い粒子が感熱
ヘッド汚れに良好な結果をもたらす作用機構は明確にな
っていないが、感熱ヘッドと同等以上の硬度を有する粒
子に顕著な効果があることから、フィルム表面突起を形
成する粒子が感熱ヘッドに付着した汚れと共にヘッドを
研磨することでクリーニング効果が得られるものと考え
られる。A particularly preferred method for roughening the surface of the film is a particle (A) having an average particle size (d 1 ) of 0.6 to 3.0 μm and a Mohs hardness of 5 or more and an average particle size (d 2 ) of 0. 06 ~
This is a method in which particles (B) having a particle size of 0.8 μm and d 1 / d 2 of 2 to 10 are contained. The mechanism by which particles having a high Mohs hardness give good results for the thermal head stain is not clear, but particles having a hardness equal to or higher than that of the thermal head have a remarkable effect and thus form film surface protrusions. It is considered that the cleaning effect can be obtained by polishing the head together with the dirt that the particles adhere to the thermal head.
【0014】本発明で用いる粒子(A)のモース硬度が
5未満では多数回製版時の感熱ヘッドに汚れが付着し、
穿孔感度が低下することがある。粒子(A)の平均粒径
が0.6μm未満では巻き特性が劣ることがある。ま
た、粒子(A)の平均粒径が3.0μを超える場合はフ
ィルム表面の平面性が損なわれて熱伝達にムラが生じ、
穿孔が不均一となり、解像度が劣ったり、印字品位性を
損なったりすることがある。 粒子(B)の平均粒径が
0.06μm未満の場合は滑り性が不足し作業性が低下
することがあり、0.8μmを超えると、フィルム表面
の平面性が損なわれて熱伝達にムラが生じ、穿孔が不均
一となり、解像度が劣ったり、印字品位性を損なったり
する恐れがある。When the Mohs hardness of the particles (A) used in the present invention is less than 5, dirt adheres to the thermal head during plate making many times,
Perforation sensitivity may be reduced. If the average particle size of the particles (A) is less than 0.6 μm, the winding property may be poor. When the average particle size of the particles (A) exceeds 3.0 μ, the flatness of the film surface is impaired and uneven heat transfer occurs.
Perforations may be uneven, resulting in poor resolution and impaired print quality. When the average particle diameter of the particles (B) is less than 0.06 μm, slipperiness may be insufficient and workability may be reduced. When it exceeds 0.8 μm, the flatness of the film surface is impaired and heat transfer becomes uneven. May occur, resulting in uneven perforation, poor resolution, and impaired print quality.
【0015】不活性粒子(A)の平均粒径(d1 )と粒
子(B)の平均粒径(d2 )との比(d1 /d2 )が2
〜10の範囲のときに、フィルムを巻き取る際の随伴空
気層を素早く減少させることができ、良好なフィルム巻
き特性を享受することができる。さらに、d1 /d2 が
10を超えるとフィルム表面の粗面化の度合いが大き過
ぎて熱伝達にムラが生じ、穿孔が不均一となり、解像度
が劣ったり、印字品位性を損なったりすることがある。[0015] The ratio of the average particle sizes of (d 1) and the particles of inert particles (A) (B) (d 2) (d 1 / d 2) 2
When it is in the range of 10 to 10, the associated air layer at the time of winding the film can be rapidly reduced, and good film winding characteristics can be enjoyed. Further, if d 1 / d 2 exceeds 10, the degree of roughening of the film surface is too large, uneven heat transfer occurs, uneven perforation, poor resolution, and impaired print quality. There is.
【0016】本発明で用いる粒子(A)のモース硬度は
好ましくは5.5以上、粒子(A)の平均粒径は0.8
〜2.0μmがさらに好ましく、粒子(B)の平均粒径
は0.1〜0.6μmがさらに好ましい。粒子(A)の
フィルムへの前述のとおりであるが、ポリエステルレジ
ン1g中の粒子数は通常、8.85×105 〜1.33
×1010個の範囲であり、さらにはフィルムへの添加量
が0.01〜0.2重量%、粒子数がポリエステルレジ
ン1g中1.77×106 〜8.84×109 個の範囲
が好ましい。粒子(A)のフィルムへの添加量が上記範
囲未満ではフィルム巻き特性が劣ることがある。また、
添加量または粒子数が上記範囲を超えるとフィルム表面
の粗面化の度合いが大き過ぎて、熱伝達にムラが生じ、
穿孔が不均一となり、解像度が劣ったり、印字品位性を
損なったりすることがある。The Mohs hardness of the particles (A) used in the present invention is preferably 5.5 or more, and the average particle diameter of the particles (A) is 0.8.
The average particle size of the particles (B) is more preferably 0.1 to 0.6 μm. The number of particles in 1 g of the polyester resin is usually 8.85 × 10 5 to 1.33 as described above for the film of the particles (A).
× 10 a 10 range, more addition amount 0.01 to 0.2% by weight of the film, the range number 1.77 × 10 6 ~8.84 × 10 9 pieces in the polyester resin 1g particles Is preferred. If the amount of the particles (A) added to the film is less than the above range, the film winding property may be poor. Also,
When the amount of addition or the number of particles exceeds the above range, the degree of roughening of the film surface is too large, resulting in uneven heat transfer,
Perforations may be uneven, resulting in poor resolution and impaired print quality.
【0017】粒子(B)の含有量は前述のとおりである
が、ポリエステルレジン1g中の粒子数は通常、4.6
7×108 〜2.65×1014個の範囲であり、さらに
は添加量が0.1〜2重量%、粒子数が9.33×10
8 〜1.77×1014個の範囲が好ましい。粒子(B)
の含有量と粒子数が上記範囲未満の場合、滑り性が不足
し、作業性が低下することがある。また、粒子(B)の
含有量と粒子数が上記範囲を超えると、フィルム表面の
平面性が損なわれて熱伝達にムラが生じ、上記と同様の
不都合を生じることがある。The content of the particles (B) is as described above, but the number of particles in 1 g of the polyester resin is usually 4.6.
The range is 7 × 10 8 to 2.65 × 10 14 , and the addition amount is 0.1 to 2% by weight and the number of particles is 9.33 × 10.
The range of 8 to 1.77 × 10 14 is preferable. Particle (B)
When the content and the number of particles are less than the above range, slipperiness may be insufficient and workability may be deteriorated. When the content of the particles (B) and the number of particles exceed the above ranges, the flatness of the film surface is impaired, heat transfer becomes uneven, and the same inconvenience as described above may occur.
【0018】本発明で用いるモース硬度5以上の不活性
粒子(A)の例としては、酸化ケイ素、酸化チタン、ゼ
オライト、窒化ケイ素、窒化ホウ素、セライト、アルミ
ナ等を挙げることができるが、これらに限定されるもの
ではない。本発明においては、上記したような方法によ
り、表面を適度に粗面化したフィルムを得ることが好ま
しいが、穿孔時にフィルムの溶融した部分がサーマルヘ
ッドに付着することによる感度の低下を防止し、かつ印
刷時の解像度、印字品位性をさらに高度に満足させるた
めに、微粒子の粒径分布がシャープなものを用いること
が好ましい。すなわち、後述の方法で測定した粒径分布
のうち、d25/d75が、好ましくは1.0〜1.5、さ
らに好ましくは1.1〜1.3である。d25/d75が
1.5を超えると、広がりの大きな突起が増加する傾向
がある。かかる観点から、フィルムに含有させる粒子と
して、球状シリカ、合成法による炭酸カルシウム、特開
平2−194049号公報に記載されたような単分散の
架橋高分子微粉体から選ばれた1種以上を用いることが
最も好ましい。フィルムに粒子を含有させる方法は、ポ
リエステルの重合工程に添加する方法またはフィルム化
前に溶融混練りする方法が好ましい。Examples of the inert particles (A) having a Mohs hardness of 5 or more used in the present invention include silicon oxide, titanium oxide, zeolite, silicon nitride, boron nitride, celite, alumina, and the like. It is not limited. In the present invention, by the method as described above, it is preferable to obtain a film whose surface is appropriately roughened, but prevents the decrease in sensitivity due to the melted portion of the film adhering to the thermal head during perforation, In addition, in order to further satisfy the resolution and printing quality during printing, it is preferable to use fine particles having a sharp particle size distribution. That is, in the particle size distribution measured by the method described below, d 25 / d 75 is preferably 1.0 to 1.5, more preferably 1.1 to 1.3. If d 25 / d 75 exceeds 1.5, protrusions with a large spread tend to increase. From this viewpoint, as the particles to be contained in the film, one or more selected from spherical silica, synthetic calcium carbonate, and monodisperse crosslinked polymer fine powder as described in JP-A-2-194049 are used. Is most preferred. The method of incorporating particles into the film is preferably a method of adding to the polymerization step of polyester or a method of melt-kneading before forming into a film.
【0019】本発明においては上記したような方法によ
り表面を適度に粗面化したフィルムを得るが、作業性や
印刷時の解像度、印字品位性をさらに高度に満足させる
ためには、フィルム表面の中心線平均粗さ(Ra)が
0.01〜0.4μmであることが好ましく、さらに好
ましくは0.02〜0.3μmの範囲であり、またフィ
ルム表面の最大高さ(Rt)が0.4〜3μmであるこ
とが好ましく、さらに好ましくは0.5〜2μmの範囲
であり、かかる範囲となるよう適宜、条件を選択するこ
とが望ましい。In the present invention, a film whose surface is appropriately roughened by the above-mentioned method is obtained, but in order to further satisfy workability, resolution during printing, and print quality, the film surface is The center line average roughness (Ra) is preferably 0.01 to 0.4 μm, more preferably 0.02 to 0.3 μm, and the maximum height (Rt) of the film surface is 0. The thickness is preferably 4 to 3 μm, more preferably 0.5 to 2 μm, and it is desirable to appropriately select the conditions so as to fall within this range.
【0020】本発明のフィルムの厚さは0.5〜6μ
m、好ましくは0.8〜3μmである。フィルムの厚さ
が薄いほど熱伝導距離が短縮され、その結果、穿孔時に
必要な熱エネルギーも減少して穿孔性が向上するととも
に印字品位性が向上する。しかしながら、フィルム厚さ
が0.5μm未満の場合は、印字が不鮮明で濃淡ムラが
生じやすく、耐刷性も低下する。また、フィルム厚さが
5μmを超えると、印刷時にムラが生じる。本発明のフ
ィルムは、極めて薄いフィルムであるので、フィルムの
長手方向と幅方向の引張弾性率を共に通常300kg/
mm2 以上、好ましくは350kg/mm2 以上とする
ことにより、取り扱い作業性や耐刷性がより良好とな
る。The thickness of the film of the present invention is 0.5 to 6 μm.
m, preferably 0.8 to 3 μm. The thinner the film is, the shorter the heat conduction distance is. As a result, the thermal energy required at the time of perforation is reduced, the perforation property is improved, and the printing quality is improved. However, when the film thickness is less than 0.5 μm, the printing is unclear, uneven density is likely to occur, and the printing durability is deteriorated. When the film thickness exceeds 5 μm, unevenness occurs during printing. Since the film of the present invention is an extremely thin film, the tensile elastic modulus in both the longitudinal direction and the width direction of the film is usually 300 kg /
When it is at least 2 mm 2 , preferably at least 350 kg / mm 2 , handling workability and printing durability will be better.
【0021】次に本発明のポリエステルフィルムの製造
方法について説明する。本発明においては、ポリマーを
エクストルーダーに代表される周知の溶融押出装置に供
給し、該ポリマーの融点以上の温度に加熱し溶融する。
次いで、溶融したポリマーをスリット状のダイから押し
出し、回転冷却ドラム上でガラス転移温度以下の温度に
なるように急冷固化し、実質的に非晶状態の未配向シー
トを得る。この場合、シートの平面性を向上させるた
め、シートと回転冷却ドラムとの密着性を高める必要が
あり、本発明においては静電印加密着法および/または
液体塗布密着法が好ましく採用される。Next, the method for producing the polyester film of the present invention will be described. In the present invention, the polymer is supplied to a well-known melt extrusion apparatus typified by an extruder, and heated to a temperature equal to or higher than the melting point of the polymer to melt it.
Next, the melted polymer is extruded from a slit die and rapidly cooled and solidified on a rotating cooling drum to a temperature not higher than the glass transition temperature to obtain a substantially amorphous unoriented sheet. In this case, in order to improve the flatness of the sheet, it is necessary to enhance the adhesion between the sheet and the rotary cooling drum, and the electrostatic application adhesion method and / or the liquid coating adhesion method are preferably adopted in the present invention.
【0022】静電印加密着法とは、通常、シートの上面
側にシートの流れと直交する方向に線状電極を張り、該
電極に約5〜10kVの直流電圧を印加することにより
シートに静電荷を与え、ドラムとの密着性を向上させる
方法である。また、液体塗布密着法とは、回転冷却ドラ
ム表面の全体または一部(例えばシート両端部と接触す
る部分のみ)に液体を均一に塗布することにより、ドラ
ムとシートとの密着性を向上させる方法である。本発明
においては必要に応じ両者を併用してもよい。The electrostatic application adhesion method is usually a method in which a linear electrode is placed on the upper surface of the sheet in a direction orthogonal to the flow of the sheet, and a DC voltage of about 5 to 10 kV is applied to the electrode to statically apply the sheet. This is a method of applying an electric charge to improve the adhesion to the drum. In addition, the liquid application contact method is a method for improving the adhesion between the drum and the sheet by uniformly applying the liquid to the whole or part of the surface of the rotary cooling drum (for example, only the portions that contact both ends of the sheet). Is. In the present invention, both may be used together if necessary.
【0023】本発明においては、このようにして得られ
たシートを通常、2軸方向に延伸してフィルム化する。
延伸条件について具体的に述べると、前記未延伸シート
を好ましくは20〜100℃、さらに好ましくは25〜
80℃の温度範囲で、まず一方向にロールもしくはテン
ター方式の延伸機により3.0〜7倍、好ましくは3.
5〜7倍に延伸する。次に一段目と直交する方向に好ま
しくは20〜100℃、さらに好ましくは25〜90℃
の温度範囲で3.0〜7倍、好ましくは3.5〜7倍、
さらに好ましくは4.0〜7倍に延伸を行い、2軸に配
向したフィルムを得る。なお、一方向の延伸を2段階以
上で行う方法も用いることができるが、その場合も最終
的な延伸倍率が上記した範囲に入ることが望ましい。ま
た、前記未延伸シートを面積倍率が10〜40倍になる
ように同時二軸延伸することも可能である。かくして得
られたフィルムを熱処理してもよく、また必要に応じ熱
処理を行う前または後に再度縦および/または横方向に
延伸してもよい。本発明においては、上記した熱収縮特
性を有するフィルムを得るために、延伸倍率を面積倍率
として15倍以上、延伸後の熱処理を実質的に行わない
か、行ったとしても110℃以下、さらには90℃以下
とし、熱処理時間は1秒〜5分間でフィルムを30%以
内の伸長または定長下で行うことが好ましい。In the present invention, the sheet thus obtained is usually biaxially stretched to form a film.
Describing the stretching conditions specifically, the unstretched sheet is preferably 20 to 100 ° C., more preferably 25 to 100 ° C.
In the temperature range of 80 ° C., first, in one direction, by a roll or tenter type stretching machine, 3.0 to 7 times, preferably 3.
Stretch 5 to 7 times. Next, it is preferably 20 to 100 ° C, more preferably 25 to 90 ° C in the direction orthogonal to the first stage.
In the temperature range of 3.0 to 7 times, preferably 3.5 to 7 times,
More preferably, the film is stretched 4.0 to 7 times to obtain a biaxially oriented film. A method in which unidirectional stretching is performed in two or more stages can be used, but in that case as well, it is desirable that the final stretching ratio falls within the above range. It is also possible to simultaneously biaxially stretch the unstretched sheet so that the area ratio becomes 10 to 40 times. The film thus obtained may be heat-treated, and if necessary, may be stretched in the machine direction and / or the transverse direction before or after the heat treatment. In the present invention, in order to obtain a film having the above-mentioned heat shrinkage property, the stretching ratio is 15 times or more as an area ratio, and the heat treatment after stretching is not substantially performed or 110 ° C. or less even if it is performed, and further, It is preferable that the temperature is 90 ° C. or lower, the heat treatment time is 1 second to 5 minutes, and the film is stretched within 30% or under a fixed length.
【0024】なお、本発明においては、製膜に供するポ
リエステル全量に対し、10重量%程度以下の他のポリ
マー(例えばポリエチレン、ポリスチレン、ポリカーボ
ネート、ポリスルホン、ポリフェニレンスルフィド、ポ
リアミド、ポリイミド等)を含有させることができる。
また、必要に応じ、酸化防止剤、熱安定剤、潤滑剤、帯
電防止剤、染料、顔料等の添加剤を配合してもよい。か
くして得られた本発明のポリエステルフィルムは、常法
に従って所定の多孔性薄葉紙を公知の接着剤を用いてラ
ミネートすることにより、優れた熱穿孔性を有し、か
つ、印刷時の解像度および階調性に優れた感熱孔版印刷
用原紙とすることができる。In the present invention, about 10% by weight or less of another polymer (for example, polyethylene, polystyrene, polycarbonate, polysulfone, polyphenylene sulfide, polyamide, polyimide, etc.) is contained with respect to the total amount of polyester used for film formation. You can
Further, if necessary, additives such as an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a dye and a pigment may be added. Thus obtained polyester film of the present invention, by laminating a predetermined porous thin paper using a known adhesive according to a conventional method, has excellent thermal piercing property, and the resolution and gradation during printing. A heat-sensitive stencil printing base paper having excellent properties can be obtained.
【0025】[0025]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明は、その要旨を越えない限り、以下の
実施例に限定されるものではない。なお、本発明で用い
た物性測定法を以下に示す。 (1)極限粘度 ポリマー1gをフェノール/テトラクロロエタン(50
/50(重量比))の混合溶媒100ml中に溶解さ
せ、エベローデ型粘度計にて30℃で測定した。 (2)微粒子の平均粒径 (株)島津製作所製遠心沈降式粒度分布測定装置SA−
CP3型を用いてストークスの抵抗則に基づく沈降法に
よって粒子の大きさを測定した。測定により得られた粒
子の等価球形分布における積算(重量基準)50%の値
を用いて平均粒径(d50)とした。また同様に大粒子側
から25%の値をd25,75%の値をd 75とした。EXAMPLES The present invention will be described in more detail below with reference to examples.
As will be understood, the present invention is as follows unless the gist thereof is exceeded.
It is not limited to the examples. Used in the present invention
The methods for measuring physical properties are shown below. (1) Intrinsic viscosity 1 g of polymer was added to phenol / tetrachloroethane (50
/ 50 (weight ratio))
And measured with an Everode viscometer at 30 ° C. (2) Average particle size of fine particles Centrifugal sedimentation type particle size distribution analyzer SA- manufactured by Shimadzu Corporation
For the sedimentation method based on Stokes' resistance law using CP3 type
Therefore, the size of the particles was measured. Grains obtained by measurement
50% cumulative (weight basis) in the equivalent spherical distribution of the child
Average particle size (d50). Similarly, on the large particle side
25% value from dtwenty five, 75% value is d 75And
【0026】(3)フィルム厚み シチズン時計製厚さ計ミューメトロンを用いて測定し
た。 (4)融点 セイコー電子工業(株)製差動熱量計SSC580DS
C20型を用いて測定した。DSC測定条件は以下のと
おりである。即ち、試料フィルム10mgをDSC装置
にセットし、10℃/minの速度で昇温し、0℃〜3
00℃の範囲で測定し、融点を融解吸熱ピークの頂点と
して測定した。 (5)縦横平均熱収縮率 試料を無張力状態で100℃に保ったオーブン中、3分
間熱処理し、その前後の試料の長さを測定して次式にて
熱収縮率を算出した。(3) Film thickness The thickness was measured using a Citizen watch thickness meter, Mumetron. (4) Melting point Differential calorimeter SSC580DS manufactured by Seiko Instruments Inc.
It measured using C20 type. The DSC measurement conditions are as follows. That is, 10 mg of the sample film was set in the DSC apparatus, the temperature was raised at a rate of 10 ° C / min, and 0 ° C to 3 ° C.
The melting point was measured in the range of 00 ° C, and the melting point was measured as the apex of the melting endothermic peak. (5) Average horizontal and vertical thermal shrinkage The sample was heat-treated in an oven kept at 100 ° C. in a tensionless state for 3 minutes, the length of the sample before and after that was measured, and the thermal shrinkage was calculated by the following formula.
【0027】[0027]
【数4】 フィルム縦方向と横方向に5点ずつ測定し、平均値を求
めた。[Equation 4] Five points were measured in the longitudinal direction and the transverse direction of the film, and an average value was obtained.
【0028】(6)加熱収縮応力 フィルムを幅10mmの短冊状に切り出し、一端を荷重
検出器のチャックに、もう一方を固定チャックにセット
し、チャック間は50mmとした。初期荷重をかけない
状態で、フィルムを所定温度のオイルバス中に浸漬し、
浸漬開始から5秒後の応力値を測定した。浸漬前のフィ
ルム断面積から加熱収縮応力(g/mm 2 )を算出し
た。フィルム縦方向と横方向に5点ずつ測定し、平均値
を求めた。測定は60℃〜140℃の範囲で10℃ごと
に行い、その9点の温度での測定値の中で最大のものを
最大値とした。(6) Heat shrinkage stress The film is cut into a strip with a width of 10 mm and one end is loaded.
Set to the detector chuck and the other to the fixed chuck
The distance between the chucks was 50 mm. Do not apply initial load
In that state, immerse the film in an oil bath at a predetermined temperature,
The stress value was measured 5 seconds after the start of immersion. Before soaking
Rum cross-sectional area to heat shrinkage stress (g / mm 2) Is calculated
It was Measured at 5 points in the film lengthwise and widthwise directions, and averaged
I asked. Measurement is in the range of 60 ℃ -140 ℃ every 10 ℃
The maximum of the measured values at the 9 points.
The maximum value.
【0029】(7)中心線平均粗さ(Ra) (株)小坂研究所社製表面粗さ測定機(SE−3F)を
用いて次のようにして求めた。すなわち、フィルム断面
曲線からその中心線方向に基準長さL(2.55mm)
の部分を抜き取り、この抜き取り部分の中心線をx軸、
縦倍率の方向をy軸として粗さ曲線y=f(x)で表し
た時、次の式で与えられた値を〔μm〕で表す。中心線
平均粗さは、試料フィルム表面から10本の断面曲線を
求め、これらの断面曲線から求めた抜き取り部分の中心
線平均粗さの平均値で表した。なお、触針の先端半径は
2μm、荷重は30mmgとし、カットオフ値は0.0
8mmとした。(7) Center Line Average Roughness (Ra) It was determined as follows using a surface roughness measuring instrument (SE-3F) manufactured by Kosaka Laboratory Ltd. That is, the reference length L (2.55 mm) from the film section curve in the direction of the center line
The part of is drawn out, and the center line of this extracted part is the x-axis,
When the roughness curve y = f (x) is represented with the direction of the longitudinal magnification as the y-axis, the value given by the following formula is represented by [μm]. The center line average roughness was represented by the average value of the center line average roughness of the extracted portions obtained from the 10 section curves obtained from the surface of the sample film. The tip radius of the stylus was 2 μm, the load was 30 mmg, and the cutoff value was 0.0.
It was 8 mm.
【数5】Ra=(1/L)∫L 0|f(x)|dx[Number 5] Ra = (1 / L) ∫ L 0 | f (x) | dx
【0030】(8)最大高さ(Rt) 中心線平均粗さを測定した際に得られた断面曲線の抜き
取り部分(2.5mm)の中心線に平行な2直線で該抜
き取り部分を挟んだとき、この2直線の間隔を断面曲線
の縦倍率の方向に測定して、その値を抜き取り部分の最
大高さ(μm)とした。最大高さは、試料フィルム表面
から10本の断面曲線を求め、これらの断面曲線から求
めた抜き取り部分の最大高さの平均値で表した。(8) Maximum Height (Rt) The center line average roughness was measured, and the extracted part was sandwiched by two straight lines parallel to the center line of the extracted part (2.5 mm) of the cross-section curve obtained. At this time, the distance between these two straight lines was measured in the direction of the longitudinal magnification of the sectional curve, and the value was taken as the maximum height (μm) of the extracted portion. The maximum height was obtained by calculating 10 cross-section curves from the surface of the sample film and expressing the average value of the maximum heights of the extracted portions obtained from these cross-section curves.
【0031】(9)感熱孔版印刷原紙実用特性 フィルムに和紙を貼り合わせて原紙を作製した。得られ
た原紙をサーマルヘッドにより、印加エネルギー0.0
9mJおよび0.12mJにて文字画像および16段階
の階調画像を製版した。製版された原紙のフィルム側か
ら顕微鏡で階調画像部の穿孔状態を観察し、以下の項目
について評価した。 (i)穿孔感度 ○;所定の穿孔が確実に行われ、穿孔の大きさも十分で
あり良好。 △;稀に所定の穿孔が得られない部分や穿孔の大きさが
不十分な部分があるが、実用は可能。 ×;所定の穿孔が得られない部分が数多くあり、穿孔の
大きさも不十分であり、実用上支障がある。 また、製版原紙を用い、理想科学工業(株)製リソグラ
フAP7200印刷機を用いて実際に印刷し、得られた
文字、画像について、下記の特性を目視で判定した。(9) Practical characteristics of heat-sensitive stencil printing base paper Washi paper was stuck to the film to prepare base paper. The obtained base paper is applied with a thermal head at an applied energy of 0.0.
A character image and a 16-step gradation image were prepared at 9 mJ and 0.12 mJ. The perforated state of the gradation image area was observed with a microscope from the film side of the plate-making base paper, and the following items were evaluated. (I) Perforation sensitivity ◯: Predetermined perforation was reliably performed, and the size of perforation was sufficient, which was good. Δ: Practical use is possible, although there are rarely parts where the desired perforation cannot be obtained or parts where the perforation size is insufficient. X: There are many portions where the predetermined perforation cannot be obtained, and the perforation size is insufficient, which is a practical problem. Moreover, the following characteristics were visually determined for the characters and images obtained by actually printing using a lithographic base paper and a lithograph AP7200 printing machine manufactured by Ideal Science Co., Ltd.
【0032】(ii)印字品位性 ○;濃度のムラ、にじみがなく、鮮明に印字でき、良
好。 △;わずかに濃淡のムラ、にじみが認められ、やや鮮明
さに欠ける。 ×;濃淡のムラ、あるいはにじみ、かすれがはっきり出
ている。 (iii)耐刷性 ○…2000枚以上印刷しても画像濃度、解像度が変化
しない △…1000枚程度の印刷により、画像のにじみがやや
認められる ×…数百枚の印刷で、画像のにじみが著しく、実用上支
障がある (10)巻き特性 直径15cmの紙管にラインスピード約170m/分で
製造されるフィルムを6000m巻き取り、端面の状態
を観察し、次の3ランクの基準で評価した。 ◎…端面がすべて揃っている 〇…端面がほぼ揃い、実用可能 △…端面の一部が不揃いである ×…端面の下なりの部分が不揃いである(Ii) Print quality: Good; clear printing is possible without uneven density and bleeding. Δ: Slight unevenness in shades and bleeding were observed, and the image was slightly lacking in sharpness. ×: The unevenness of light and shade, bleeding, and blurring are clearly seen. (Iii) Printing durability ◯ ... Image density and resolution do not change even after printing 2000 sheets or more. Δ ... Image bleeding is slightly recognized after printing about 1000 sheets. X ... Image bleeding after printing several hundred sheets. The film produced at a line speed of 170 m / min is wound up to 6000 m on a paper tube with a diameter of 15 cm and the state of the end face is observed, and evaluated according to the following 3 rank criteria. did. ◎ ... The end faces are all aligned 〇 ... The end faces are almost aligned and can be used for practical use △ ... A part of the end face is not aligned × ... The lower part of the end face is not aligned
【0033】実施例1 テレフタル酸ジメチル100部、1,4−ブタンジオー
ル56部、およびテトラブチルチタネート0.0075
部を反応器にとり、反応開始温度を150℃とし、メタ
ノールの留去と共に徐々に反応温度を上昇させ、3時間
後に210℃まで昇温した。さらに、1時間反応を行っ
た後、常法により重縮合反応を行った。この反応は、温
度を徐々に高めると共に圧力を常圧より徐々に減じ、2
時間後、温度を260℃、圧力を0.3mmHgとし
た。反応開始後、4時間を経た時点で反応を停止し、窒
素加圧下ポリマーを吐出させた。得られたPBTの極限
粘度は、0.90であった。また、テレフタル酸ジメチ
ル100部とエチレングリコール60部とを出発原料と
し、触媒として酢酸マグネシウム・四水塩0.09部を
加え、エステル交換反応を行った。Example 1 100 parts dimethyl terephthalate, 56 parts 1,4-butanediol, and 0.0075 tetrabutyl titanate.
Part of the mixture was placed in a reactor, the reaction starting temperature was set to 150 ° C., the reaction temperature was gradually raised as methanol was distilled off, and the temperature was raised to 210 ° C. after 3 hours. Furthermore, after the reaction was carried out for 1 hour, a polycondensation reaction was carried out by a conventional method. In this reaction, the temperature is gradually raised and the pressure is gradually reduced from normal pressure,
After hours, the temperature was 260 ° C. and the pressure was 0.3 mmHg. After 4 hours from the start of the reaction, the reaction was stopped and the polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained PBT was 0.90. Also, 100 parts of dimethyl terephthalate and 60 parts of ethylene glycol were used as starting materials, and 0.09 part of magnesium acetate / tetrahydrate as a catalyst was added to carry out a transesterification reaction.
【0034】次いで、平均粒径1.1μm、d25/d75
が1.2の球状シリカ粒子をエチレングリコールスラリ
ーとして添加し、エチルアシッドフォスフェート0.0
4部、三酸化アンチモン0.04部を加えて、4時間重
縮合反応を行い、ポリエチレンテレフタレートAを得
た。該ポリエステルの極限粘度は0.65であり、ポリ
マー中での球状シリカ粒子の含有量は0.7重量%であ
った。得られたポリエステルA50部と、PBT50部
とを混合し、280℃にて押出機よりシート状に押出
し、表面温度を20℃に設定した回転冷却ドラムで静電
印加冷却法を利用して急冷固化させ、厚み32μmの実
質的に非晶質のシートを得た。次いで得られたシートを
縦方向に65℃で4.3倍、横方向に70℃で4.6倍
に延伸し、さらに90℃で6秒間熱処理を施し、厚み
2.0μmの二軸配向フィルムを製造した。Then, the average particle size is 1.1 μm, and d 25 / d 75
Spherical silica particles of 1.2 are added as an ethylene glycol slurry to give ethyl acid phosphate 0.0
4 parts and 0.04 part of antimony trioxide were added and polycondensation reaction was carried out for 4 hours to obtain polyethylene terephthalate A. The intrinsic viscosity of the polyester was 0.65, and the content of spherical silica particles in the polymer was 0.7% by weight. 50 parts of the obtained polyester A and 50 parts of PBT are mixed, extruded in a sheet form from an extruder at 280 ° C., and rapidly cooled and solidified by a static cooling method using a rotary cooling drum whose surface temperature is set to 20 ° C. Thus, a substantially amorphous sheet having a thickness of 32 μm was obtained. Then, the obtained sheet was stretched in the longitudinal direction by 4.3 times at 65 ° C. and in the transverse direction at 70 ° C. by 4.6 times and further heat-treated at 90 ° C. for 6 seconds to give a biaxially oriented film of 2.0 μm in thickness. Was manufactured.
【0035】実施例2 酸成分の80モル%がテレフタル酸、20モル%がイソ
フタル酸、グリコール成分がエチレングリコールであ
る。極限粘度が0.68のポリエチレンテレフタレート
・イソフタレート共重合体Bを製造した。該共重合体B
には、平均粒径0.6μm、d25/d75が1.25の単
分散架橋高分子粒子(主成分スチレン、ジビニルベンゼ
ン)0.7重量%を含有していた。実施例1で製造した
PBT45部と共重合体B55部とを混合したものを原
料として実施例1と同様にして、厚み35μmの実質的
に非晶質のシートを得た。得られたシートを60℃で縦
方向に4.2倍、横方向に4.5倍に延伸し、85℃に
て6秒間定長下で熱処理を行って、厚み2.0μmの二
軸配向フィルムを得た。 実施例3 実施例1で製造したPBT70部と共重合体B30部と
を混合したものを原料として実施例1と同様にして、厚
み40μmの実質的に非晶質のシートを得た。得られた
シートを70℃にて4.5×4.5倍に同時二軸延伸
し、95℃にて30秒間定長下で熱処理を行って、厚み
2.2μmの二軸配向フィルムを得た。Example 2 80 mol% of the acid component is terephthalic acid, 20 mol% is isophthalic acid, and the glycol component is ethylene glycol. A polyethylene terephthalate / isophthalate copolymer B having an intrinsic viscosity of 0.68 was produced. The copolymer B
Contained 0.7% by weight of monodisperse crosslinked polymer particles (main component styrene and divinylbenzene) having an average particle size of 0.6 μm and ad 25 / d 75 of 1.25. A mixture of 45 parts of PBT produced in Example 1 and 55 parts of copolymer B was used as a raw material and a substantially amorphous sheet having a thickness of 35 μm was obtained in the same manner as in Example 1. The obtained sheet was stretched 4.2 times in the longitudinal direction and 4.5 times in the transverse direction at 60 ° C., and heat-treated at 85 ° C. for 6 seconds under a constant length to obtain a biaxial orientation of 2.0 μm in thickness. I got a film. Example 3 A mixture of 70 parts of PBT produced in Example 1 and 30 parts of copolymer B was used as a raw material in the same manner as in Example 1 to obtain a substantially amorphous sheet having a thickness of 40 μm. The obtained sheet is simultaneously biaxially stretched at 70 ° C. to 4.5 × 4.5 times, and heat-treated at 95 ° C. for 30 seconds under a constant length to obtain a biaxially oriented film having a thickness of 2.2 μm. It was
【0036】比較例1 熱処理温度を140℃とし、熱処理時に幅方向に10%
の弛緩を行った以外は、実施例1と同様にして、厚み
2.0μmの二軸配向フィルムを得た。 比較例2 ポリマー押出量を調節して、厚み6.0μmとした以外
は実施例1と同様にして、二軸配向フィルムを得た。Comparative Example 1 The heat treatment temperature was 140 ° C., and 10% in the width direction during the heat treatment.
A biaxially oriented film having a thickness of 2.0 μm was obtained in the same manner as in Example 1 except that the relaxation was performed. Comparative Example 2 A biaxially oriented film was obtained in the same manner as in Example 1 except that the polymer extrusion rate was adjusted to a thickness of 6.0 μm.
【0037】比較例3 実施例1において、原料の混合比を、PBT15部、ポ
リエチレンテレフタレートA85部とし、延伸温度を縦
85℃、横100℃とした以外は実施例1と同様にし
て、厚み2.0μmの二軸配向フィルムを得た。 比較例4 実施例1において、原料の混合比をPBT85部、ポリ
エチレンテレフタレートA15部とした以外は実施例1
と同様にして二軸配向フィルムを製造しようとしたが、
延伸性が悪くフィルム破断が頻発し、満足なフィルムは
得られなかった。 以上、得られたフィルムを常法に従い、多孔性薄葉紙に
貼り合わせて感熱孔版印刷用原紙を作成し、謄写印刷を
行った。フィルムの物性および謄写印刷特性を下記表1
および2にまとめて示す。Comparative Example 3 A thickness of 2 was obtained in the same manner as in Example 1 except that the mixing ratio of the raw materials was 15 parts of PBT and 85 parts of polyethylene terephthalate A, and the stretching temperature was 85 ° C. and 100 ° C. A biaxially oriented film of 0.0 μm was obtained. Comparative Example 4 Example 1 except that the mixing ratio of the raw materials in Example 1 was 85 parts PBT and 15 parts polyethylene terephthalate A.
I tried to produce a biaxially oriented film in the same manner as
The stretchability was poor and the film was frequently broken, and a satisfactory film could not be obtained. The film thus obtained was adhered to a porous thin paper according to a conventional method to prepare a base paper for heat-sensitive stencil printing, which was imprinted. The physical properties of the film and the printing characteristics are shown in Table 1 below.
And 2 collectively.
【0038】[0038]
【表1】 [Table 1]
【0039】[0039]
【表2】 [Table 2]
【0040】実施例1〜3のフィルムは、フィルム製造
時、原紙作成時の取り扱い性に優れ、これらを用いて作
成した原紙は、熱穿孔感度に優れているため、良好な謄
写印刷特性を示すものであった。これらに対し、比較例
1は、収縮応力が不足するため、比較例2は厚みが厚過
ぎるため、比較例3は、PBTを所定量含有しないた
め、いずれも熱穿孔感度が劣るものであった。The films of Examples 1 to 3 are excellent in handleability at the time of producing the film and at the time of making the base paper, and the base papers made by using them are excellent in thermal perforation sensitivity, and thus show good copy printing characteristics. It was a thing. On the other hand, in Comparative Example 1, the shrinkage stress was insufficient, and in Comparative Example 2, the thickness was too thick. In Comparative Example 3, PBT was not contained in a predetermined amount. .
【0041】実施例4 テレフタル酸ジメチル90部とイソフタル酸ジメチル1
0部とエチレングリコール60部とを出発原料とし、触
媒として酢酸マグネシウム・四水塩0.09部を加え、
エステル交換反応を行った。次いで、平均粒径1.1μ
m、d25/d75が1.2の球状シリカ粒子をエチレング
リコールスラリーとして添加し、エチルアシッドフォス
フェート0.04部、三酸化アンチモン0.04部を加
えて、4時間重縮合反応を行い、ポリエチレ得られたポ
リエステルC50部と、実施例1で製造したPBT50
部とを混合し、280℃にて押出機よりシート状に押出
し、表面温度を20℃に設定した回転冷却ドラムで静電
印加冷却法を利用して急冷固化させ、厚み32μmの実
質的に非晶質のシートを得た。次いで得られたシートを
縦方向に60℃で4.5倍、横方向に70℃で4.0倍
に延伸し、さらに90℃で6秒間熱処理を施し、厚み
1.9μmの二軸配向フィルムを製造した。ンテレフタ
レート・イソフタレート共重合体Cを得た。該ポリエス
テルの極限粘度は0.67であり、ポリマー中での球状
シリカ粒子の含有量は1.0重量%であった。Example 4 90 parts of dimethyl terephthalate and dimethyl 1 isophthalate
Using 0 parts and 60 parts of ethylene glycol as starting materials, 0.09 parts of magnesium acetate / tetrahydrate as a catalyst was added,
A transesterification reaction was performed. Then average particle size 1.1μ
Spherical silica particles having m, d 25 / d 75 of 1.2 were added as ethylene glycol slurry, 0.04 part of ethyl acid phosphate and 0.04 part of antimony trioxide were added, and polycondensation reaction was carried out for 4 hours. Polyethylene, 50 parts of the obtained polyester C, and PBT50 prepared in Example 1.
Parts and extruded into a sheet form from an extruder at 280 ° C., and rapidly cooled and solidified by using an electrostatic cooling method with a rotating cooling drum whose surface temperature is set to 20 ° C. A crystalline sheet was obtained. Then, the obtained sheet was stretched in the machine direction at 60 ° C. by 4.5 times, and in the transverse direction at 70 ° C. at 4.0 times, and further heat-treated at 90 ° C. for 6 seconds to give a 1.9 μm-thick biaxially oriented film. Was manufactured. A terephthalate / isophthalate copolymer C was obtained. The intrinsic viscosity of the polyester was 0.67, and the content of spherical silica particles in the polymer was 1.0% by weight.
【0042】実施例5 実施例1で製造したPBTの場合と同様にして、テレフ
タル酸ジメチル80部とイソフタル酸ジメチル20部と
1,4−ブタンジオール56部とを原料としてPBT共
重合体Cを製造した。得られたポリマーに平均粒径0.
6μm、d25/d75が1.45の合成炭酸カルシウムを
二軸押出機を用いて0.4重量%配合した。得られた粒
子含有ポリマーの極限粘度は0.85であった。該ポリ
マーを用いて、実施例1と同様にして、厚み2.2μm
の二軸配向フィルムを得た。以上、得られたフィルムを
常法に従い、多孔性薄葉紙に貼り合わせて感熱孔版印刷
用原紙を作成し、謄写印刷を行った。フィルムの物性お
よび謄写印刷特性を下記表3および4にまとめて示す。Example 5 PBT copolymer C was prepared in the same manner as in the case of PBT produced in Example 1, using 80 parts of dimethyl terephthalate, 20 parts of dimethyl isophthalate and 56 parts of 1,4-butanediol as raw materials. Manufactured. The obtained polymer had an average particle size of 0.
0.4 wt% of 6 μm and synthetic calcium carbonate having ad 25 / d 75 of 1.45 were compounded by using a twin-screw extruder. The intrinsic viscosity of the obtained particle-containing polymer was 0.85. Using this polymer, in the same manner as in Example 1, the thickness was 2.2 μm.
A biaxially oriented film of was obtained. The film thus obtained was adhered to a porous thin paper according to a conventional method to prepare a base paper for heat-sensitive stencil printing, which was imprinted. The physical properties and the imprinting characteristics of the film are summarized in Tables 3 and 4 below.
【0043】[0043]
【表3】 [Table 3]
【0044】[0044]
【表4】 [Table 4]
【0045】実施例4および5のフィルムは、フィルム
製造時、原紙作成時の取り扱い性に優れ、これらを用い
て作成した原紙は、熱穿孔感度に優れているため、良好
な謄写印刷特性を示すものであった。 実施例6〜11 (ポリエステルの製造−1)テレフタル酸ジメチル80
重量部、イソフタル酸ジメチル20重量部およびエチレ
ングリコール60部とを出発原料とし、触媒として酢酸
マグネシウム・四水塩0.09重量部を反応器にとり、
反応開始温度を150℃とし、メタノールの留去と共に
徐々に反応温度を上昇させ、3時間後に230℃とし
た。4時間後、実質的にエステル交換反応の終了したこ
の反応混合物に平均粒径が0.35μm、粒度分布値
(r)が1.4の有機粒子を0.6重量部を含有するエ
チレングリコールスラリー10重量部を添加し、エチル
アシッドフォスフェート0.04部、三酸化アンチモン
0.04部を加えて、4時間重縮合反応を行った。すな
わち、温度を230℃から徐々に昇温し280℃とし、
圧力は常圧より徐々に減じ最終的には0.3mmHgと
した。反応開始後、4時間を経た時点で反応を停止し、
窒素加圧下ポリマーを吐出させた。得られたポリエステ
ルの極限粘度は0.72であった。このポリエステルを
ポリエステルEとした。また同様の方法でポリエステル
Iを製造し、その組成は下記表5に示すとおりである。The films of Examples 4 and 5 are excellent in handleability at the time of producing the film and at the time of making the base paper, and the base paper made by using them has excellent thermal perforation sensitivity, and thus shows good copy printing characteristics. It was a thing. Examples 6 to 11 (Production of Polyester-1) Dimethyl terephthalate 80
Parts by weight, 20 parts by weight of dimethyl isophthalate and 60 parts by weight of ethylene glycol are used as starting materials, and 0.09 parts by weight of magnesium acetate / tetrahydrate as a catalyst is placed in a reactor,
The reaction start temperature was set to 150 ° C., and the reaction temperature was gradually raised as the methanol was distilled off, and the temperature was set to 230 ° C. after 3 hours. After 4 hours, an ethylene glycol slurry containing 0.6 parts by weight of organic particles having an average particle size of 0.35 μm and a particle size distribution value (r) of 1.4, was added to the reaction mixture in which the transesterification reaction was substantially completed. 10 parts by weight were added, 0.04 part of ethyl acid phosphate and 0.04 part of antimony trioxide were added, and polycondensation reaction was carried out for 4 hours. That is, the temperature is gradually raised from 230 ° C. to 280 ° C.,
The pressure was gradually reduced from normal pressure to finally set to 0.3 mmHg. After 4 hours from the start of the reaction, the reaction is stopped,
The polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained polyester was 0.72. This polyester was designated as polyester E. Polyester I was produced by the same method, and its composition is shown in Table 5 below.
【0046】(ポリエステルの製造−2)テレフタル酸
ジメチル100重量部、1,4−ブタンジオール56重
量部およびテトラブチルチタネート0.005重量部を
反応器にとり、反応開始温度を150℃とし、メタノー
ルの留去と共に徐々に反応温度を上昇させ、3時間後に
210℃とした。4時間後実質的にエステル交換反応の
終了したこの反応混合物に平均粒径が1.0μm、d25
/d75が1.2の球状シリカ粒子を0.1重量部を含有
する1,4−ブタンジオールスラリー10重量部を添加
した。さらに重合触媒としてテトラブチルチタネート
0.005重量部を加え、常法により重縮合反応を行っ
た。すなわち、温度を210℃から徐々に昇温し260
℃とし、圧力は常圧より徐々に減じ最終的には0.3m
mHgとした。反応開始後、4時間を経た時点で反応を
停止し、窒素加圧下ポリマーを吐出させた。得られたポ
リエステルの極限粘度は0.90であった。このポリエ
ステルをポリエステルFとした。また同様の方法でポリ
エステルG、ポリエステルH、ポリエステルJ、ポリエ
ステルKを製造し、その組成は表5に示すとおりであ
る。(Production of Polyester-2) 100 parts by weight of dimethyl terephthalate, 56 parts by weight of 1,4-butanediol and 0.005 parts by weight of tetrabutyl titanate were placed in a reactor and the reaction start temperature was set to 150 ° C. The reaction temperature was gradually increased as the solvent was distilled off, and the temperature was adjusted to 210 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially completed and the reaction mixture had an average particle size of 1.0 μm and d 25
10 parts by weight of a 1,4-butanediol slurry containing 0.1 part by weight of spherical silica particles having a / d 75 of 1.2 was added. Further, 0.005 parts by weight of tetrabutyl titanate was added as a polymerization catalyst, and polycondensation reaction was carried out by a conventional method. That is, the temperature is gradually raised from 210 ° C. to 260
℃, the pressure is gradually reduced from normal pressure and finally 0.3 m
It was set to mHg. After 4 hours from the start of the reaction, the reaction was stopped and the polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained polyester was 0.90. This polyester was designated as polyester F. Polyester G, polyester H, polyester J, and polyester K were produced in the same manner, and their compositions are as shown in Table 5.
【0047】[0047]
【表5】 [Table 5]
【0048】(フィルムの製造)下記表6に示す種々の
ポリエステルを用い、280℃にて押出機よりシート状
に押出し、表面温度を30℃に設定した回転冷却ドラム
で静電印加冷却法を利用して急冷固化させ、厚み32μ
mの実質的に非晶質のシートを得た。得られたシートを
縦方向に65℃で4.5倍、横方向に70℃で4.3倍
に延伸し、さらに90℃で6秒間熱処理を施し、厚み
1.5μmの二軸配向フィルムを製造した。得られたフ
ィルムを常法に従い、多孔性薄葉紙に貼り合わせて感熱
孔版印刷用原紙を作成し、謄写印刷を行った。フィルム
の物性および原紙実用特性を下記表6〜8に示す。(Manufacture of Film) Various polyesters shown in Table 6 below were used to extrude a sheet at 280 ° C. from an extruder, and a static cooling method was applied using a rotary cooling drum whose surface temperature was set to 30 ° C. And rapidly solidify to a thickness of 32μ
A substantially amorphous sheet of m was obtained. The obtained sheet was stretched 4.5 times in the longitudinal direction at 65 ° C. and 4.3 times in the transverse direction at 70 ° C., and further heat treated at 90 ° C. for 6 seconds to obtain a biaxially oriented film having a thickness of 1.5 μm. Manufactured. The obtained film was adhered to a porous thin paper according to a conventional method to prepare a base paper for heat-sensitive stencil printing, which was imprinted. The physical properties of the film and the practical properties of the base paper are shown in Tables 6 to 8 below.
【0049】[0049]
【表6】 [Table 6]
【0050】[0050]
【表7】 [Table 7]
【0051】[0051]
【表8】 [Table 8]
【0052】[0052]
【発明の効果】本発明のポリエステルフィルムは、取り
扱い性が良好で、かつ該フィルムを用いた感熱孔版印刷
用原紙は熱穿孔性、印刷時の解像度および印字品位性に
優れたものであり、その工業的価値は高い。EFFECT OF THE INVENTION The polyester film of the present invention has good handleability, and the heat-sensitive stencil printing base paper using the film is excellent in heat perforation, resolution at printing and print quality. Industrial value is high.
Claims (4)
0重量%含有するポリエステル組成物からなる、厚み
0.5〜6.0μmの二軸配向フィルムであって、60
〜140℃の範囲でのフィルムの加熱収縮応力の縦方向
および横方向の平均値の最大値が300g/mm2 を超
え、100℃で3分処理後の熱収縮率が20%以上であ
ることを特徴とする高感度感熱孔版印刷原紙用フィル
ム。1. Polybutylene terephthalate 20 to 8
A biaxially oriented film having a thickness of 0.5 to 6.0 μm, which comprises a polyester composition containing 0% by weight, and is 60
The maximum value of the average value of the heat shrinkage stress of the film in the longitudinal direction and the transverse direction of the film in the range of to 140 ° C exceeds 300 g / mm 2, and the thermal shrinkage rate after the treatment at 100 ° C for 3 minutes is 20% or more. A film for high-sensitivity heat-sensitive stencil printing base paper.
する、請求項1に記載の高感度感熱孔版印刷原紙用フィ
ルム。 【数1】(Sm+St)/2≧300 ……(1) 1.2≦Sm/St≦5 ……(2) (上記式中、Smは温度100℃でのフィルム縦方向の
加熱収縮応力(g/mm 2 )、Stは同温度でのフィル
ム横方向の加熱収縮応力(g/mm2 )を表す)2. The following expressions (1) and (2) are satisfied at the same time.
The high-sensitivity heat-sensitive stencil printing stencil sheet according to claim 1.
Rum. ## EQU1 ## (Sm + St) /2.gtoreq.300 (1) 1.2.ltoreq.Sm/St.ltoreq.5 (2) (In the above formula, Sm is the longitudinal direction of the film at a temperature of 100.degree.
Heat shrinkage stress (g / mm 2), St is the fill at the same temperature
Lateral heat shrinkage stress (g / mm2))
は2に記載の高感度感熱孔版印刷原紙用フィルム。3. The film for high-sensitivity heat-sensitive stencil printing base paper according to claim 1, which has a melting point of 150 to 240 ° C. 3.
1 )が0.6〜3.0μmの粒子(A)を0.005〜
0.3重量%および平均粒径(d2 )が0.06〜0.
8μmの粒子(B)を0.05〜3重量%を含有し、か
つ下記式(3)を満足することを特徴とする請求項1〜
3のいずれにか記載の高感度感熱孔版印刷原紙用ポリエ
ステルフィルム。 【数2】2≦d1 /d2 ≦10 ……(3)4. A Mohs hardness of 5 or more and an average particle diameter (d
1 ) 0.005 to 0.65 to 3.0 μm of particles (A)
0.3% by weight and an average particle size (d 2 ) of 0.06 to 0.
The particles (B) having a diameter of 8 μm are contained in an amount of 0.05 to 3% by weight and satisfy the following formula (3).
The polyester film for high-sensitivity heat-sensitive stencil printing base paper according to any one of 3 above. [Equation 2] 2 ≦ d 1 / d 2 ≦ 10 (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4705594A JP3481995B2 (en) | 1993-03-25 | 1994-03-17 | High-sensitivity heat-sensitive stencil film for base paper |
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6678393 | 1993-03-25 | ||
JP10277493 | 1993-04-28 | ||
JP10690493 | 1993-05-07 | ||
JP5-66783 | 1993-05-07 | ||
JP5-106904 | 1993-05-07 | ||
JP5-102774 | 1993-05-07 | ||
JP4705594A JP3481995B2 (en) | 1993-03-25 | 1994-03-17 | High-sensitivity heat-sensitive stencil film for base paper |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0717153A true JPH0717153A (en) | 1995-01-20 |
JP3481995B2 JP3481995B2 (en) | 2003-12-22 |
Family
ID=27461986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4705594A Expired - Fee Related JP3481995B2 (en) | 1993-03-25 | 1994-03-17 | High-sensitivity heat-sensitive stencil film for base paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3481995B2 (en) |
-
1994
- 1994-03-17 JP JP4705594A patent/JP3481995B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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JP3481995B2 (en) | 2003-12-22 |
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