JPH04164929A - Shrink polyester film - Google Patents
Shrink polyester filmInfo
- Publication number
- JPH04164929A JPH04164929A JP28987890A JP28987890A JPH04164929A JP H04164929 A JPH04164929 A JP H04164929A JP 28987890 A JP28987890 A JP 28987890A JP 28987890 A JP28987890 A JP 28987890A JP H04164929 A JPH04164929 A JP H04164929A
- Authority
- JP
- Japan
- Prior art keywords
- film
- acid
- shrinkage
- polyester
- propanediol
- 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.)
- Pending
Links
- 229920006267 polyester film Polymers 0.000 title description 2
- 229920000728 polyester Polymers 0.000 claims abstract description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002009 diols Chemical class 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001361 adipic acid Substances 0.000 claims abstract description 7
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 6
- OJMJOSRCBAXSAQ-UHFFFAOYSA-N 2,2-dibutylpropane-1,3-diol Chemical compound CCCCC(CO)(CO)CCCC OJMJOSRCBAXSAQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920006300 shrink film Polymers 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 230000002087 whitening effect Effects 0.000 abstract description 5
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229940035437 1,3-propanediol Drugs 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012371 Aseptic Filling Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は低温熱収縮特性に優れ、シュリンクラヘルや電
線被覆等に用いられるポリエステル系シュリンクフィル
ムに関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyester shrink film that has excellent low-temperature heat shrink properties and is used for shrink shells, electric wire coverings, and the like.
〈従来の技術）
従来、ガラスをはじめとする各種容器に用いられるンエ
リンクラベル用フィルムとしては、ポリ塩化ビニル、又
はポリスチレンよりなるフィルムが主として用いられて
来た。<Prior Art> Conventionally, films made of polyvinyl chloride or polystyrene have been mainly used as films for plastic labels used for various containers including glass.
一方、ジュース、酒、茶、しょう油等の食品容器を中心
としてポリエチレンテレフタレート（以下ＰＥＴと略記
）ボトルが広く普及して来ており、しかも、ＰＥＴボト
ルの種類としては、従来、温水殺菌消毒に耐える耐熱性
ＰＥＴボトルが主流であったのに対し、近年においては
、無菌充填方式を採用することにより、温水殺菌消毒工
程を省略して、コストの低い非耐熱性ＰＥＴボトルの使
用が進められている。On the other hand, polyethylene terephthalate (hereinafter abbreviated as PET) bottles are becoming widely used mainly for food containers such as juice, alcohol, tea, and soy sauce. While heat-resistant PET bottles were the mainstream, in recent years, by adopting an aseptic filling method and omitting the hot water sterilization process, the use of low-cost non-heat-resistant PET bottles has been promoted. .
しかしながら、非耐熱性ＰＥＴボトルは、約８０℃以上
の温度をかけると体積変化を起こすため、８０℃以上で
高い収縮率を示す前記のポリ塩化ビニルまたはポリスチ
レン等のフィルムを使用することが出来ず、より低い温
度で高収縮率を示すフィルムが所望されている。また、
ＰＥＴボトルは回収再利用することが工業的及び社会的
に要請されており、従ってボトルとラベルが異なる組成
では、分離工程が必要なため、ボトルとラベルをそのま
ま分離せずに再利用すべく、ラベル用途においてもポリ
エステル系ンユリンクフィルムが望まれている。However, non-heat-resistant PET bottles undergo volume changes when heated to temperatures above 80°C, so films such as polyvinyl chloride or polystyrene, which have a high shrinkage rate at temperatures above 80°C, cannot be used. , films that exhibit high shrinkage at lower temperatures are desired. Also,
It is industrially and socially required that PET bottles be collected and reused. Therefore, if the bottle and label have different compositions, a separation process is required, so in order to reuse the bottle and label without separating them, Polyester-based Nyulink films are also desired for label applications.
このような所望に対し、最近、各種ジオールあるいはイ
ソフタル酸等を共重合させた非晶質のコポリエステルを
用いることにより、収縮率が大きく、且ツヒートシール
性に優れたフィルムが得うれることが開示されており、
例えば、特開昭６３−１５６８３３号公報、特開昭６３
−２０２４２９号公報、特公昭６３−７５７３号公報等
がある。In response to these demands, it has recently been disclosed that by using an amorphous copolyester copolymerized with various diols or isophthalic acid, it is possible to obtain a film with a large shrinkage rate and excellent heat sealability. has been
For example, JP-A-63-156833, JP-A-63
-202429, Japanese Patent Publication No. 63-7573, etc.
しかしながら、これ等のうち比較的良好なネオペンチル
グリコールを共重合させたフィルムはガラス転移温度が
７５℃前後と高く、そのため、８０℃以上における熱収
縮挙動としては大きな収縮率及び均一に収縮するという
、比較的硬れた性能を発揮するものの十分とはいえない
、また８０℃未満における、熱酸収縮動は、収縮不足等
によるクルミが発生するという欠点を有する。However, among these films, films copolymerized with relatively good neopentyl glycol have a high glass transition temperature of around 75 degrees Celsius, and therefore, their thermal shrinkage behavior at temperatures above 80 degrees Celsius is said to be large and uniform. Although it exhibits relatively hard performance, it cannot be said to be sufficient, and thermal acid shrinkage at temperatures below 80°C has the disadvantage that walnuts occur due to insufficient shrinkage.
一方、イソフタル酸を共重合させたフィルムは、ガラス
転移温度を６５℃前後迄低下させることが可能となり、
８０℃未満の温度においても大きな収縮率を得ることが
出来る。しかし、このフィルムは収縮トンネル装置内で
加熱されると、加熱初期において、瞬時に収縮してしま
い、引続き行なわれる加熱に対してもそれ以上はほとん
ど収縮しないという独特な収縮挙動を示すため、フィル
ムは収縮斑が起こり、しわ、波うち等が発生する。On the other hand, films copolymerized with isophthalic acid can lower the glass transition temperature to around 65°C,
A large shrinkage rate can be obtained even at temperatures below 80°C. However, when this film is heated in a shrink tunnel device, it shrinks instantly at the initial stage of heating, and exhibits a unique shrinkage behavior in which it hardly shrinks any further when heated. Shrinkage spots occur, causing wrinkles, waves, etc.
これらの問題を改善するため、熱収縮率、シール強度あ
るいは熱収縮応力等を調節する試みが提案されているが
、実際の操業工程上これらをうまくコントロールするこ
とは非常に難しく、僅かの条件変動によってもフィルム
に収縮斑が発生し易く、収縮後のラベルの上端部あるい
は下端部が斜めになったり、図柄の歪み等が頻発すると
いう問題が生ずる。In order to improve these problems, attempts have been made to adjust the heat shrinkage rate, seal strength, heat shrinkage stress, etc., but it is very difficult to control these well in the actual operating process, and it is difficult to control these properly in the actual operating process. This also tends to cause shrinkage spots on the film, resulting in frequent problems such as the upper or lower end of the label being slanted after shrinkage and the design becoming distorted.
〈発明が解決しようとする課題）
本発明者らは、これらの課題を達成するために、鋭意検
討の結果、特定の組成のジカルボン酸成分とジオール成
分を特定の割合配合することにより、低温熱収縮特性に
優れたポリエステル系シュリンクフィルムが得られるこ
とを見い出し、本発明に到達したものである。即ち、本
発明の目的は、低温熱収縮特性が優れ、かつＰＥＴボト
ルへの密着性が良好であり、収縮斑、白化及びシワなど
が見られない、外観上にも優れたシュリンクフィルムを
提供することにある。<Problems to be Solved by the Invention> In order to achieve these problems, the present inventors have made extensive studies and found that by blending a dicarboxylic acid component with a specific composition and a diol component in a specific ratio, The inventors have discovered that a polyester shrink film with excellent shrinkage properties can be obtained, and have arrived at the present invention. That is, an object of the present invention is to provide a shrink film that has excellent low-temperature heat shrinkability, good adhesion to PET bottles, and is free from shrinkage spots, whitening, and wrinkles, and has an excellent appearance. There is a particular thing.
く課題を解決するための手段〉
上記の目的は、フィルムを構成するポリエステルが、ジ
カルボン酸成分として、テレフタル酸を９５〜６０ ｍ
ｏ １．％、イソフタル酸を５〜３０ｍｏｆｆｉ％、
アジピン酸を０〜１０ｍｏ １％含み、ジオール成分と
して、エチレングリコールを９５〜７０ｍｏ １％、２
，２−ジブチル−１，３−プロパンジオールまたは２−
エチル−２−ブチル−１，３−プロパンジオールを５〜
３０ｍｏ １％含み、かつ７５℃グリセリン浴中３０秒
での該フィルムの熱収縮率が、縦方向または横方向のう
ちいずれか一方向において４０％以上であることを特徴
とするポリエステル系シュリンクフィルムによって達成
される。Means for Solving the Problems> The above object is such that the polyester constituting the film contains 95 to 60 m of terephthalic acid as a dicarboxylic acid component.
o 1. %, isophthalic acid 5-30 moffi%,
Contains 0 to 10 mo 1% adipic acid, and 95 to 70 mo 1%, 2 ethylene glycol as a diol component.
, 2-dibutyl-1,3-propanediol or 2-
Ethyl-2-butyl-1,3-propanediol from 5 to
By a polyester shrink film containing 1% of 30mo and characterized in that the heat shrinkage rate of the film in 30 seconds in a 75°C glycerin bath is 40% or more in either the longitudinal direction or the transverse direction. achieved.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のポリエステル系フィルムを構成する各成分の組
成比は、本発明において重要な要件の一つであり、ジカ
ルボン酸成分として、テレフタル酸を９５〜６０ｍｏｌ
％、好ましくは８５〜６８ｍｏｎ％、イソフタル酸を５
〜３０ｍｏ １％、好ましくは１０〜’ｌ Ｑ ｍ ｏ
１％、アジピン酸を０〜１０ｍｏｌ％、好ましくは３
〜８ｍｏｌ％含有し、ジオール成分として、エチレング
リコールを９５〜７０ｍｏｌ％、好ましくは９２〜８０
ｍ ｏ １％、２．２−ジブチル１，３−プロパンジ
オールまたは２−エチル−２−ブチル−１，３−プロパ
ンジオールを５〜３０ｍｏ １％、好ましくは８〜２０
ｍｏｌ％を含有することが肝要である。The composition ratio of each component constituting the polyester film of the present invention is one of the important requirements in the present invention.
%, preferably 85 to 68 mon%, isophthalic acid
~30mo 1%, preferably 10~'l Q m o
1%, adipic acid from 0 to 10 mol%, preferably 3
Contains ~8 mol% of ethylene glycol as a diol component, preferably 95 to 70 mol%, preferably 92 to 80 mol%.
mo 1%, 2.2-dibutyl 1,3-propanediol or 2-ethyl-2-butyl-1,3-propanediol from 5 to 30 mo 1%, preferably 8 to 20
It is important to contain mol%.
該組成比を持つフィルムはボトルに装着後シュリンクト
ンネル装置内を通過させフィルムを収縮させる際に、従
来の他の成分からなるポリエステル系シュリンクフィル
ムとは異なり、低温熱収縮特性に優れ、しわ、たるみ等
の発生のない、ラベル用シュリンクフィルムとして好適
なものとなる。A film with this composition ratio has excellent low-temperature heat shrinkage properties and does not wrinkle or sag, unlike conventional polyester shrink films made of other components, when it is attached to a bottle and passed through a shrink tunnel device to shrink the film. It is suitable as a shrink film for labels without the occurrence of such problems.
その理由としては、上記組成比のものは他の組成のもの
に比べ、より均一な共重合の形態を取り易く、そのため
ポリエステル本来の優れた機械的性能を保持し、なおか
つ他の各々の成分の長所を最大限に発揮し易い構造にな
っているということができる。イソフタル酸あるいはア
ジピン酸配合により、ガラス転移温度が降下し、収縮開
始温度を下げることが出来るため、８０’ｃ未満の低温
度領域においても十分、熱収縮することが可能となる。The reason for this is that polyesters with the above composition ratios tend to form a more uniform copolymerization form than those with other compositions, and therefore retain the excellent mechanical properties inherent to polyester, while maintaining the same characteristics as each other component. It can be said that it has a structure that makes it easy to maximize its strengths. By blending isophthalic acid or adipic acid, the glass transition temperature can be lowered and the shrinkage start temperature can be lowered, so that sufficient heat shrinkage can be achieved even in a low temperature range of less than 80'C.
また、イソフタル酸配合により、シュリンク装置内を通
過させる際の加熱初期において大きな収縮率が得られ、
更に引き続き行なわれる加熱に対しては、２，２−ジプ
チル−１，３−プロパンジオールまたは２−エチル−２
−ブチル１，３−プロパンジオールに起因すると思われ
るゆるやがな二次収縮挙動によって、初期の収縮で発生
し易い収縮斑の修正、均一化、さらに仕上げの収縮が行
なわれる。In addition, by incorporating isophthalic acid, a large shrinkage rate can be obtained at the initial stage of heating when passing through the shrink equipment.
For further heating, 2,2-dipyl-1,3-propanediol or 2-ethyl-2
The gradual secondary shrinkage behavior believed to be caused by -butyl 1,3-propanediol corrects and equalizes the shrinkage spots that tend to occur during initial shrinkage, and further allows for finishing shrinkage.
８０℃未満での優れた熱収縮挙動を得るためには、イソ
フタル酸あるいはアジピン酸を適量に含有させることが
必要であるが多量に入れるとフィルムは著しい強度低下
が起こり、満足な製品を得ることは不可能であった。従
って、本発明のごとき特定の範囲の組成比を満足させる
ことによって初めて目的を達することが可能となるので
ある。In order to obtain excellent heat shrinkage behavior at temperatures below 80°C, it is necessary to contain a suitable amount of isophthalic acid or adipic acid, but if too much is added, the strength of the film will significantly decrease, making it difficult to obtain a satisfactory product. was impossible. Therefore, the purpose of the present invention can only be achieved by satisfying a specific range of composition ratios.
また、上記組成成分はいずれも工業的に大量に生産され
ており、化度性の面でも好適である。Further, all of the above composition components are industrially produced in large quantities and are suitable in terms of chemical properties.
本発明における各成分の配合割合についてであるが、フ
ィルム中のジカルボン酸成分として、イソフタル酸が３
０ｍｏ １％を趙えると、フィルムの耐溶剤性が低下し
好ましくなく、一方、５ｍｏ／％未満であれば収縮率が
低下し好ましくない、又、アジピン酸が１０ｍｏ １％
を超えるとフィルムのガラス転移温度が低下しすきたり
、着色、劣化が著しくなる。Regarding the blending ratio of each component in the present invention, as the dicarboxylic acid component in the film, isophthalic acid is
If the amount is less than 0mo/1%, the solvent resistance of the film will decrease, which is undesirable.On the other hand, if it is less than 5mo/%, the shrinkage rate will decrease, which is not preferable.
If the temperature exceeds 100%, the glass transition temperature of the film decreases, and cracking, discoloration, and deterioration become significant.
一方、ジオール成分として、２．２−ジブチル−１，３
−プロパンジオールまたは２−エチル−２−ブチル−１
，３〜プロパンジオールが３０ｍｏ１％を趙えると、フ
ィルムの強度、耐熱性が低下し、一方、５ ｍ ｏ １
％未満であれば、二次収縮挙動が不可能となり、収縮斑
が解消されず、シワ等が発生し好ましくない。On the other hand, as a diol component, 2,2-dibutyl-1,3
-propanediol or 2-ethyl-2-butyl-1
,3~When propanediol exceeds 30 mo1%, the strength and heat resistance of the film decrease;
If it is less than %, secondary shrinkage behavior becomes impossible, shrinkage spots are not eliminated, and wrinkles etc. occur, which is not preferable.
本発明のフィルムにおいては、その性質を変えない範囲
で上記成分以外の共重合成分を含有させてもよい、上記
成分以外の成分としては、ジカルボン酸成分として、シ
ュウ酸、マロンｔｌ！、コハク酸、アゼライン酸、セバ
シン酸、フタル酸、ナフタレンジカルボン酸、ジフェニ
ルエーテルジカルボン酸等、また、ジオール成分として
、プロピレングリコール、トリメチレングリコール、テ
トラメチレングリコール、ネオペンチルグリコール。In the film of the present invention, copolymerized components other than the above-mentioned components may be contained within a range that does not change its properties.As components other than the above-mentioned components, examples of the dicarboxylic acid component include oxalic acid, malon tl! , succinic acid, azelaic acid, sebacic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, etc. Also, as a diol component, propylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol.
ヘキサメチレングリコール、ジエチレングリコール、ポ
リアルキレングリコール、１，４−シクロヘキサンジメ
タツール等を含有させることが出来るさらに他の共重合
成分、例えば、ｐ−オキノ安息香酸、ｐ−オキンエトキ
ノ安息香酸のごときオキソカルボン酸、安息香酸、ヘン
ヅイル安息香酸。Other copolymer components that can contain hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimetatool, etc., such as oxocarboxylic acids such as p-okinobenzoic acid and p-okynethoquinobenzoic acid. , benzoic acid, hendylbenzoic acid.
メトキシポリアルキレングリコールのごとき一官能性化
合物、グリセするペンタエリスリトール。Monofunctional compounds such as methoxypolyalkylene glycols, glycerinated pentaerythritol.
トリメチロールエタン、トリメチロールエタンのごとき
多官能性化合物も、生成物が実質的に線状の高分子を保
持出来る範囲内で使用してもよい。Polyfunctional compounds such as trimethylolethane and trimethylolethane may also be used to the extent that the product retains a substantially linear polymer.
さらに、本発明のフィルムに本発明の要旨を変えない範
囲で他のポリエステル他のポリマー又は各種添加側を添
加、混合してもよい。例えば、フィルムの５滑性を向上
させる無機滑荊、有機滑剤としてカオリン、クレー、炭
酸カルシウム、酸化ケイ素、テレフタル酸カルシウム、
酸化アルミニウム、酸化チタン、リン酸カルシウム、フ
ッ化リチウム等の公知の不活性外部粒子、ポリエステル
樹脂の溶融製膜に際して配合する不溶な高融点有機化合
物、架橋ポリマー、アルカリ金属化合物またはアルカリ
土類金属化合物等のポリエステル製造時に使用する金属
化合物触媒等のポリエステル製造時に、ポリマー内部に
形成される内部粒子が挙げられる。また、必要に応して
安定剤９着色側。Furthermore, other polyesters, other polymers, or various additives may be added to or mixed with the film of the present invention without changing the gist of the present invention. For example, inorganic lubricants that improve the lubricity of the film, kaolin, clay, calcium carbonate, silicon oxide, calcium terephthalate, organic lubricants, etc.
Known inert external particles such as aluminum oxide, titanium oxide, calcium phosphate, and lithium fluoride, insoluble high-melting point organic compounds, crosslinked polymers, alkali metal compounds, and alkaline earth metal compounds that are blended during melt film formation of polyester resins. Examples include internal particles formed inside the polymer during polyester production, such as metal compound catalysts used during polyester production. Also, if necessary, add stabilizer 9 to the colored side.
酸化防止側、消泡剤等を含有させてもよい。フィルム中
に含まれる該微粒子は、通常、０．０ Ｏ５〜０．５重
量％である。Antioxidant, antifoaming agent, etc. may be included. The fine particles contained in the film are usually 0.05 to 0.5% by weight.
また、本発明のフィルムの極限粘度は、好ましくは０．
５以上、より好ましくは０．６０以上である。Further, the intrinsic viscosity of the film of the present invention is preferably 0.
It is 5 or more, more preferably 0.60 or more.
フィルムの極限粘度が０５０未満であるとフィルムの強
度や耐衝撃性が十分でなくなる傾向にある。If the intrinsic viscosity of the film is less than 0.50, the strength and impact resistance of the film tend to be insufficient.
本発明のフィルムは、該フィルムの縦又は横の少なくと
もいずれか一方向における７５°Ｃグリセリン浴中３０
秒での収縮率が４０％以上が必要であり、好ましくは４
５％以上、より好ましくは５０％以上である。収縮率が
４０％未満のフィルムは非耐熱性ＰＥＴボトル用に用い
られるンユリンクトン不ルでは収縮ゾーンの設定温度が
８０°Ｃ未満と低いため、十分容器に密着することが出
来ず好ましくない。The film of the present invention is prepared in a 75°C glycerin bath for 300°C in at least one of the longitudinal and transverse directions of the film.
The shrinkage rate in seconds is required to be 40% or more, preferably 40% or more.
It is 5% or more, more preferably 50% or more. Films with a shrinkage rate of less than 40% are not preferable because they cannot adhere sufficiently to the container because the set temperature of the shrinkage zone is low, less than 80°C, in the case of unfavorable films used for non-heat-resistant PET bottles.
また、本発明のフィルムを構成するポリエステルのガラ
ス転移温度は、好ましくは５０°Ｃ以上７０℃以下、よ
り好ましくは６５℃以下である。Further, the glass transition temperature of the polyester constituting the film of the present invention is preferably 50°C or more and 70°C or less, more preferably 65°C or less.
該温度が７０℃を超える場合はフィルムの収縮開始温度
を低下させることが難しくなり、そのため８０℃未満の
シュリンクトンネル内を通過させても、収縮不足のため
容器に十分密着することが出来に＜＜、たるみが発生し
易くなる。また、ガラス転移温度が５０℃未満では、シ
ュリンクフィルムの未収縮フィルムでの保管、取扱いに
問題を生しる傾向にある。If the temperature exceeds 70°C, it will be difficult to lower the shrinkage start temperature of the film, and therefore, even if the film is passed through a shrink tunnel at a temperature of less than 80°C, it will not be able to sufficiently adhere to the container due to insufficient shrinkage. <, sagging is likely to occur. Furthermore, if the glass transition temperature is less than 50° C., problems tend to occur in storage and handling of the shrink film as an unshrinkable film.
次に、本発明のフィルム製造方法について示す。Next, the film manufacturing method of the present invention will be described.
本発明の組成をもつポリエステルを用いて、押出し法や
カレンダー法等の任意の方法で得たフィルムを、例えば
、一方向に２．０倍以上５．０倍以下、好ましくは２．
５倍以上４．５倍以下に延伸し、該方向と直角方向に１
．０倍以上２．０倍以下、好ましくは１．１倍以上１．
８倍以下に延伸する。最初の延伸は、高い収縮率を得る
ために行われるものであり、該方向と直角方向への延伸
は、該方向に延伸されたフィルムの耐衝撃性や引裂抵抗
性の悪さを解決するために行なわれる。延伸手段につい
て特別の制限はなく、コール延伸、テンター延伸等の方
法が適用され、形状面においてはフラット状、チューブ
状等の如何であっても良い。Using a polyester having the composition of the present invention, a film obtained by any method such as an extrusion method or a calendar method is produced, for example, by 2.0 times or more and 5.0 times or less in one direction, preferably 2.0 times or more and 5.0 times or less in one direction.
Stretched 5 times or more and 4.5 times or less, and 1
．． 0 times or more and 2.0 times or less, preferably 1.1 times or more 1.
Stretch to 8 times or less. The initial stretching is performed to obtain a high shrinkage rate, and the stretching in the direction perpendicular to this direction is performed to solve the problem of poor impact resistance and tear resistance of the film stretched in this direction. It is done. There is no particular restriction on the stretching means, and methods such as coal stretching and tenter stretching may be applied, and the shape may be flat, tubular, etc.
また、延伸は逐次２軸延伸、同時２軸延伸、ｌ軸延伸あ
るいはこれらの組合せ等で行なわれ、本発明のフィルム
に対しては、例えば縦１軸、横１軸、縦横２軸等の延伸
を行ない、特に２軸延伸では、縦横方向の延伸は、どち
らか一方を先に行なう逐次２軸延伸が有効である。なお
、これら延伸におけるヒートセントは目的に応じて実施
されるが９０℃以下の加熱ゾーンを１秒から３０秒間通
すことが推奨される。このようにして得られたフィルム
の厚さは特に限定されないが５〜２５０μｍの範囲が実
用的である。Further, the stretching may be carried out by sequential biaxial stretching, simultaneous biaxial stretching, l-axis stretching, or a combination thereof. Particularly in biaxial stretching, successive biaxial stretching in which one of the longitudinal and lateral directions is carried out first is effective. Note that the heat cent in the stretching may be carried out depending on the purpose, but it is recommended that the film be passed through a heating zone of 90° C. or lower for 1 to 30 seconds. The thickness of the film thus obtained is not particularly limited, but a range of 5 to 250 μm is practical.
〈発明の効果〉
以上のように、本願発明の構成要件を満たすポリエステ
ル系シュリンクフィルムは、８０℃未満の低温で熱収縮
し、ＰＥＴボトルへの密着性が優れ、収縮斑、白化及び
シワなどが見られない外観上にも優れたポリエステル系
シュリンクフィルムであり、産業上極めて有用である。<Effects of the Invention> As described above, the polyester shrink film that satisfies the constituent requirements of the present invention is heat-shrinkable at a low temperature of less than 80°C, has excellent adhesion to PET bottles, and is free from shrinkage spots, whitening, wrinkles, etc. This is a polyester shrink film that is invisible and has an excellent appearance, making it extremely useful industrially.
以下、実施例にて、本発明を具体的に説明するが、本発
明はこれらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
なお、測定及び評価方法を以下に示す。The measurement and evaluation methods are shown below.
（１）収縮率
フィルムを７５°Ｃ±０．５°Ｃグリセリン浴中に無荷
重の状態で３０秒間熱収縮させ下記式に従い求めた。(1) Shrinkage rate The film was heat-shrinked in a 75°C±0.5°C glycerin bath for 30 seconds under no load and was determined according to the following formula.
（２）極限粘度〔η］
試料２００ｍｇをフェノール／テトラクロロエタン＝５
０１５０の混合溶媒２０ｍｌに加え、約１１０°Ｃで１
時間加熱溶解した後、３０°Ｃで測定した。(2) Intrinsic viscosity [η] 200 mg of sample is phenol/tetrachloroethane = 5
Add to 20 ml of mixed solvent of 0150 and add 1 at about 110°C
After heating and dissolving for a period of time, measurements were taken at 30°C.
（３）ガラス転移温度・Ｔｇ（”Ｃ）
パーキンエルマー社製ＤＳ（、−ＩＢにより昇温速度４
°Ｃ／ ｍ ｉ ｎにて測定した。(3) Glass transition temperature/Tg ("C) PerkinElmer DS (, -IB, heating rate 4
Measured at °C/min.
（４）収縮フィルムとしての評価
フィルムを収縮ラベルとして円筒形にした後、ＰＥＴボ
トルに被せ、設定温度７５°Ｃのシュリンクトンネルを
通過させて収縮させた。トン茅ル通過後、該フィルムが
十分に密着しているかを視覚で判定し、密着度の良好な
ものを○、良好でないものを×で表記した。又、該フィ
ルムの収縮斑は、上端部又は下端部が収縮後斜めになっ
たり歪んでいないかを視覚で判定し、同様にＱ、ｘで表
記した。(4) Evaluation as a Shrink Film The film was made into a cylindrical shape as a shrink label, placed on a PET bottle, and allowed to shrink by passing through a shrink tunnel at a set temperature of 75°C. After passing through the tunnel, it was visually determined whether the film had sufficient adhesion, and those with good adhesion were marked with ◯, and those with poor adhesion were marked with ×. In addition, shrinkage spots on the film were determined visually by whether the upper end or the lower end was slanted or distorted after shrinkage, and similarly expressed as Q and x.
総合評価として上記２項目を満足し、収縮後のフィルム
に白化、シワ等が全く見られないものを○、そうでない
ものを×とした。As a comprehensive evaluation, a film that satisfies the above two items and shows no whitening, wrinkles, etc. in the film after shrinkage is rated ○, and a film that does not is rated x.
〈実施例１〜６〉 テレフタル酸ジメチル、イソフタル酸ジメチル。<Examples 1 to 6> Dimethyl terephthalate, dimethyl isophthalate.
エチレングリコール、２，２−ジブチル−１，３−プロ
パンジオールまたは２−エチル−２−ブチル−１，３−
プロパンジオールを表１に示す割合で配合し、触媒とし
て酢酸カルシウム−水塩０、０５ ｍ ｏ １をステン
レス製オートクレーブに採り、窒素気流下１５０〜２４
０ ’Ｃでエステル交換反応を行った。次いで更にアジ
ピン酸、三酸化アンチモン４００ｐｐｍ（対ポリマー）
、リン酸トリメチル１０１００ｐｐ対ポリマー〕を投入
しエステル化を実施した。そしてエステル化終了後、２
８０°Ｃに昇温し、減圧下にて重縮合を行いポリエステ
ルを製造した。このポリエステルを用い押出機で２７０
°Ｃに熔融し、Ｔダイより押出して厚さ１８０μｍの未
延伸フィルムを得た。Ethylene glycol, 2,2-dibutyl-1,3-propanediol or 2-ethyl-2-butyl-1,3-
Propanediol was blended in the proportions shown in Table 1, and 0.05 mol of calcium acetate hydrate was placed in a stainless steel autoclave as a catalyst, and heated at 150 to 24 mol under a nitrogen stream.
The transesterification reaction was carried out at 0'C. Next, adipic acid, antimony trioxide 400ppm (based on polymer)
, 10,100 pp of trimethyl phosphate to polymer] was added to carry out esterification. After esterification, 2
The temperature was raised to 80°C and polycondensation was performed under reduced pressure to produce polyester. Using this polyester, 270
It was melted at °C and extruded through a T-die to obtain an unstretched film with a thickness of 180 μm.
該フィルムを予熱した上で縦方向に１．２倍延伸し、次
いで横方向に４倍延伸し４０μｍの厚さの延伸フィルム
を得た。The film was preheated and stretched 1.2 times in the machine direction, and then stretched 4 times in the cross direction to obtain a stretched film with a thickness of 40 μm.
このフィルムをＰＥＴボトルで実装テストしたところ表
１に示す如く、低温収縮性に優れ、シワ。When this film was tested on a PET bottle, as shown in Table 1, it had excellent low-temperature shrinkability and no wrinkles.
白化、収縮斑等が全くなく密着性が良好で外観上も優れ
た高品質のシュリンクフィルムが得られた。A high-quality shrink film with no whitening, shrinkage spots, etc., good adhesion, and excellent appearance was obtained.
〈比較例１〜９〉
実施例と同様の方法により、表１に記載した割合でジカ
ルボン酸成分及びジオール成分を配合しポリエステルを
製造し、製膜、延伸を行った。<Comparative Examples 1 to 9> Polyesters were produced by blending dicarboxylic acid components and diol components in the proportions shown in Table 1 in the same manner as in Examples, and film formation and stretching were performed.
Claims (1)
酸成分として、テレフタル酸を９５〜６０ｍｏｌ％、イ
ソフタル酸を５〜３０ｍｏｌ％、アジピン酸を０〜１０
ｍｏｌ％含み、ジオール成分として、エチレングリコー
ルを９５〜７０ｍｏｌ％、２，２−ジブチル−１，３−
プロパンジオールまたは２−エチル−２−ブチル−１，
３−プロパンジオールを５〜３０ｍｏｌ％含み、かつ７
５℃グリセリン浴中３０秒での該フィルムの熱収縮率が
、縦方向または横方向のうちのいずれか一方向において
４０％以上であることを特徴とするポリエステル系シュ
リンクフィルム。(1) The polyester constituting the film contains 95 to 60 mol% of terephthalic acid, 5 to 30 mol% of isophthalic acid, and 0 to 10 mol% of adipic acid as dicarboxylic acid components.
Contains 95 to 70 mol% of ethylene glycol as a diol component, 2,2-dibutyl-1,3-
propanediol or 2-ethyl-2-butyl-1,
Contains 5 to 30 mol% of 3-propanediol, and 7
A polyester shrink film characterized in that the heat shrinkage rate of the film after 30 seconds in a 5°C glycerin bath is 40% or more in either the machine direction or the transverse direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28987890A JPH04164929A (en) | 1990-10-27 | 1990-10-27 | Shrink polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28987890A JPH04164929A (en) | 1990-10-27 | 1990-10-27 | Shrink polyester film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04164929A true JPH04164929A (en) | 1992-06-10 |
Family
ID=17748942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28987890A Pending JPH04164929A (en) | 1990-10-27 | 1990-10-27 | Shrink polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04164929A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08192464A (en) * | 1995-01-19 | 1996-07-30 | Kanebo Ltd | Polyester heat-shrinkable film |
| JP2002293896A (en) * | 2001-03-29 | 2002-10-09 | Kanebo Ltd | Polyester resin |
| JP2002347720A (en) * | 2001-05-28 | 2002-12-04 | C I Kasei Co Ltd | Heat-shrinkable film and packaging method |
| JP4712993B2 (en) * | 2000-06-12 | 2011-06-29 | 大和製罐株式会社 | Low specific gravity polyester resin |
| JP2015193755A (en) * | 2014-03-31 | 2015-11-05 | 三井化学株式会社 | Polyester resin, film and molded product |
-
1990
- 1990-10-27 JP JP28987890A patent/JPH04164929A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08192464A (en) * | 1995-01-19 | 1996-07-30 | Kanebo Ltd | Polyester heat-shrinkable film |
| JP4712993B2 (en) * | 2000-06-12 | 2011-06-29 | 大和製罐株式会社 | Low specific gravity polyester resin |
| JP2002293896A (en) * | 2001-03-29 | 2002-10-09 | Kanebo Ltd | Polyester resin |
| JP4713000B2 (en) * | 2001-03-29 | 2011-06-29 | 大和製罐株式会社 | Polyester resin |
| JP2002347720A (en) * | 2001-05-28 | 2002-12-04 | C I Kasei Co Ltd | Heat-shrinkable film and packaging method |
| JP2015193755A (en) * | 2014-03-31 | 2015-11-05 | 三井化学株式会社 | Polyester resin, film and molded product |
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