JPH081766A - Deeply drawn thermoformed polyester vessel - Google Patents
Deeply drawn thermoformed polyester vesselInfo
- Publication number
- JPH081766A JPH081766A JP16593594A JP16593594A JPH081766A JP H081766 A JPH081766 A JP H081766A JP 16593594 A JP16593594 A JP 16593594A JP 16593594 A JP16593594 A JP 16593594A JP H081766 A JPH081766 A JP H081766A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- sheet
- layer
- intrinsic viscosity
- vessel
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 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 16
- 238000003856 thermoforming Methods 0.000 claims abstract description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000010030 laminating Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 230000001788 irregular Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 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
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は熱成形性が良好で、特に
容器の透明性・偏肉が改良された深絞りポリエステル容
器に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deep-drawn polyester container which has good thermoformability and in particular has improved transparency and uneven thickness of the container.
【0002】[0002]
【従来の技術】飽和ポリエステル、特にポリエチレンテ
レフタレート(以下これをPETと略す)に代表される
結晶性ポリエステル樹脂は、繊維を始めとしてシート、
フィルム用ポリマーとして広く使用されているが、その
優れた耐薬品性及び低ガス透過性を生かして炭酸飲料、
ジュース、ビール等飲料用ボトル、化粧品容器、食品用
トレーなどにも応用されるようになってきた。2. Description of the Related Art A crystalline polyester resin represented by saturated polyester, particularly polyethylene terephthalate (hereinafter abbreviated as PET), is used as a sheet including fibers.
It is widely used as a polymer for films, but its excellent chemical resistance and low gas permeability make it a carbonated drink,
It has come to be applied to bottles for beverages such as juice and beer, cosmetic containers, and trays for food.
【0003】中でもA−PETと呼ばれる非晶状態のポ
リエステルシートはその優れたリサイクル性、低公害
性、食品安全性が注目され近年塩化ビニールやポリスチ
レンに替わる包装素材として急速に使用量が増大してい
る。このポリエステルシートは熱成形により食品、薬品
の容器や雑貨のブリスターパックとして使われるほか、
その優れた透明性を生かして化粧品や電気機器等を入れ
るクリヤーケースとして用いられている。Among them, the amorphous polyester sheet called A-PET has attracted attention for its excellent recyclability, low pollution and food safety, and in recent years, its amount has rapidly increased as a packaging material replacing vinyl chloride and polystyrene. There is. This polyester sheet is used as a blister pack for food and medicine containers and miscellaneous goods by thermoforming,
Utilizing its excellent transparency, it is used as a clear case in which cosmetics, electric devices, etc. are put.
【0004】従来このような飽和ポリエステルシート
は、結晶性を有しているため、熱成形時に加熱し過ぎる
と結晶化による白化現象を起こしA−PETの優れた透
明性を損なう。特にコップ状の深絞りの容器や複雑なリ
ブを有する容器を熱成形する場合には熱成形時にシート
を充分加熱して柔らかくする必要があり、未変性のポリ
エステルでは容器が曇ったりあるいは偏肉が生じ、適正
な熱成形条件幅が非常に狭いことが問題になっており改
善が望まれていた。Conventionally, since such a saturated polyester sheet has crystallinity, if it is overheated during thermoforming, a whitening phenomenon due to crystallization occurs and the excellent transparency of A-PET is impaired. In particular, when thermoforming a cup-shaped deep-drawing container or a container having a complicated rib, it is necessary to sufficiently heat the sheet to be soft during thermoforming, and unmodified polyester may cause clouding or uneven thickness of the container. However, the problem is that the appropriate range of thermoforming conditions is very narrow, and improvement has been desired.
【0005】従来よりポリエステルシートの熱成形性を
改善する方法については多くの提案がある。例えば特開
昭51−81857号公報、特開昭51−38335号
公報記載のように結晶性を阻害する成分を共重合し加熱
時の結晶化を防止する方法等がある。Conventionally, there have been many proposals for a method for improving the thermoformability of a polyester sheet. For example, as described in JP-A-51-81857 and JP-A-51-38335, there is a method of copolymerizing a component that inhibits crystallinity to prevent crystallization during heating.
【0006】しかしながら、結晶性を阻害する成分を少
量共重合する方法では熱成形性の改善効果は低く、深絞
り成形時の偏肉を改善することは困難である。又、共重
合成分を多くすることにより熱成形性は改善されるがA
−PETの有する柔軟性や耐衝撃性が損なわれ好ましく
ない。However, the method of copolymerizing a small amount of a component that impairs crystallinity has a low effect of improving thermoformability, and it is difficult to improve uneven thickness during deep drawing. Further, the thermoformability is improved by increasing the copolymerization component, but
-It is not preferable because the flexibility and impact resistance of PET are impaired.
【0007】[0007]
【発明が解決しようとする課題】本発明者等はこのよう
な従来の問題点を解決するために鋭意検討した結果、固
有粘度が0.5〜0.75であるポリエステルの少なく
とも片面に1,4−シクロヘキサンジメタノールを特定
の範囲で共重合させた固有粘度が0.5〜0.90であ
るポリエステルを積層させたポリエステルシートを深絞
り熱成形することにより得られる容器が、A−PET本
来が有する透明性や機械強度を維持し、偏肉がなくかつ
経済性に非常に優れていることを見いだし本発明に至っ
た。DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent studies to solve such conventional problems, and as a result, 1, on at least one surface of a polyester having an intrinsic viscosity of 0.5 to 0.75. A container obtained by deep drawing thermoforming a polyester sheet obtained by laminating a polyester having an intrinsic viscosity of 0.5 to 0.90, which is obtained by copolymerizing 4-cyclohexanedimethanol in a specific range, is originally A-PET. The present invention has been accomplished by maintaining the transparency and mechanical strength possessed by, having no uneven thickness and being extremely excellent in economic efficiency.
【0008】[0008]
【課題を解決するための手段】即ち本発明は(A)テレ
フタル酸を主たる成分とするジカルボン酸成分と、エチ
レングリコール0〜90モル%および1,4−シクロヘ
キサンジメタノール10〜100モル%からなるグリコ
ール成分とを縮重合せしめ、かつ固有粘度が0.5〜
0.90であるポリエステルからなる層、(B)テレフ
タル酸とエチレングリコールを縮重合せしめ、かつ固有
粘度が0.5〜0.75であるポリエステルからなる
層、から構成されるポリエステル積層体であって、該
(A)層が少なくとも片面に積層されており、かつ該
(A)層がシート全体の厚みの1〜30%の範囲にある
シートを絞り比0.8以上の深絞り熱成形をして得られ
たポリエステル容器である。That is, the present invention comprises (A) a dicarboxylic acid component containing terephthalic acid as a main component, 0 to 90 mol% of ethylene glycol and 10 to 100 mol% of 1,4-cyclohexanedimethanol. Polyglycol component is polycondensed and has an intrinsic viscosity of 0.5-
A polyester laminate comprising a polyester layer having a ratio of 0.90 and (B) a layer made of a polyester obtained by polycondensing terephthalic acid and ethylene glycol and having an intrinsic viscosity of 0.5 to 0.75. Then, a sheet in which the (A) layer is laminated on at least one side and the (A) layer is in the range of 1 to 30% of the total thickness of the sheet is subjected to deep drawing thermoforming with a drawing ratio of 0.8 or more. It is a polyester container obtained by.
【0009】本発明の主層に用いるポリエステルとはP
ETは勿論の事、テレフタル酸成分の一部をイソフタル
酸、アジピン酸、ジフェニルカルボン酸、ジフェニルエ
ーテルジカルボン酸、ジフェニルスルフォンジカルボン
酸、セバシン酸、ナフタレンジカルボン酸等の如き他の
1種以上のジカルボン酸成分へ置換し、エチレングリコ
ール成分の一部をジエチレングリコール、ヘキサメチレ
ングリコール、トリメチレングリコール、プロピレング
リコール、シクロヘキサンジメタノール、ネオペンチル
グリコール、ブチレングリコール等の如き他の1種以上
のグリコール成分で置換した共重合ポリエステルを包含
する。The polyester used for the main layer of the present invention is P
Not to mention ET, a part of the terephthalic acid component is one or more other dicarboxylic acid components such as isophthalic acid, adipic acid, diphenylcarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, sebacic acid, naphthalenedicarboxylic acid, etc. And a part of the ethylene glycol component is replaced with one or more other glycol components such as diethylene glycol, hexamethylene glycol, trimethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, butylene glycol, etc. Includes polyester.
【0010】該共重合PET中の共重合成分の総割合は
全酸成分に対して10モル%以下であることが好まし
い。又、実質的に直鎖状と見なされる範囲で三官能以上
の化合物や単官能の化合物を含んでいても良い。更に、
ポリエステル中に透明性を低下させない範囲内で熱安定
剤、流動性改善剤、紫外線吸収剤、制電剤、防曇剤等を
添加することができる。又、艶消しが必要な場合には二
酸化チタン、炭酸カルシウム、酸化鉄、カーボンブラッ
ク等の着色剤を含有することもできる。The total proportion of the copolymerization components in the copolymerized PET is preferably 10 mol% or less based on the total acid components. Further, a compound having three or more functional groups or a monofunctional compound may be contained within the range considered to be substantially linear. Furthermore,
A heat stabilizer, a fluidity improver, an ultraviolet absorber, an antistatic agent, an antifogging agent and the like can be added to the polyester within a range that does not reduce the transparency. Further, when matting is required, a coloring agent such as titanium dioxide, calcium carbonate, iron oxide or carbon black may be contained.
【0011】固有粘度は20℃に於て重量比60/40
のフェノール/テトラクロロエタン混合溶媒中での測定
で、固有粘度は0.5〜0.75が必要であり、特に好
ましくは0.6〜0.75である。0.5より小さいと
容器の機械的強度が充分でなく、特に低温時の衝撃強度
が充分でない。又、熱成形時シートがドローダウンし成
形品に偏肉やシワが生じ易く好ましくない。一方、固有
粘度が0.75を超える場合には原料のPET樹脂を固
相重合する必要があり経済性に劣る。The intrinsic viscosity is 60/40 at a weight ratio of 60/40.
When measured in a phenol / tetrachloroethane mixed solvent, the intrinsic viscosity is required to be 0.5 to 0.75, and particularly preferably 0.6 to 0.75. If it is less than 0.5, the mechanical strength of the container is insufficient, and especially the impact strength at low temperature is insufficient. Further, the sheet is drawn down during thermoforming, and uneven thickness and wrinkles are likely to occur in the molded product, which is not preferable. On the other hand, if the intrinsic viscosity exceeds 0.75, the raw material PET resin needs to be solid-phase polymerized, resulting in poor economy.
【0012】又、本発明の表面に積層させる共重合ポリ
エステルは、テレフタル酸を主たる成分とするジカルボ
ン酸成分と、エチレングリコール0〜90モル%および
1,4−シクロヘキサンジメタノール10〜100モル
%からなるグリコール成分を縮重合することにより得ら
れ、共重合させる1,4−シクロヘキサンジメタノール
の量は、好ましくは25〜35モル%である。10モル
%より少ない場合には衝撃性の改善効果が小さい。The copolymerized polyester to be laminated on the surface of the present invention comprises a dicarboxylic acid component containing terephthalic acid as a main component, 0 to 90 mol% of ethylene glycol and 10 to 100 mol% of 1,4-cyclohexanedimethanol. The amount of 1,4-cyclohexanedimethanol obtained by polycondensation of the following glycol component and copolymerized is preferably 25 to 35 mol%. If it is less than 10 mol%, the effect of improving impact resistance is small.
【0013】用いる1,4−シクロヘキサンジメタノー
ルのシスとトランスの割合は特に限定しないが、4:6
〜0:10が衝撃強度の点で良好である。固有粘度は
0.5〜0.90が必要であり、特に好ましくは0.6
0〜0.90である。固有粘度が0.50より低い場合
には最終製品の機械的強度が充分でなく、特に低温時の
衝撃強度が充分でない。また、表層の固有粘度を主層よ
りやや高くした方が熱成形品にプラグアシストの転写跡
やドラッグラインが発生し難く透明性の良好な熱成形品
が得られる。The ratio of cis and trans of 1,4-cyclohexanedimethanol used is not particularly limited, but it is 4: 6.
˜0: 10 is good in terms of impact strength. The intrinsic viscosity is required to be 0.5 to 0.90, particularly preferably 0.6
It is 0 to 0.90. When the intrinsic viscosity is lower than 0.50, the mechanical strength of the final product is insufficient, and especially the impact strength at low temperature is insufficient. Further, when the intrinsic viscosity of the surface layer is slightly higher than that of the main layer, a thermoformed product having good transparency, in which plug-assisted transfer marks and drag lines are less likely to occur in the thermoformed product, can be obtained.
【0014】絞り比(容器の深さと容器の直径との比)
が0.8を超える深絞りの熱成形品、あるいはリブ形状
の複雑なトレーを熱成形する場合には加熱時にシートを
充分柔らかくする必要があり、未改質なA−PETでは
成形品の表面に曇りが生じる。この原因はシート製膜時
のシート表面の配向したスキン層が熱成形の加熱時に結
晶化するためと考えられ、シートのごく表面層のみに特
定の組成の共重合ポリエステルを積層するのみで深絞り
性や容器の曇りが大幅に改善されることが判明した。Drawing ratio (ratio of container depth to container diameter)
When thermoforming a deep-drawing thermoformed product of more than 0.8 or a rib-shaped complex tray, it is necessary to make the sheet sufficiently soft during heating. With unmodified A-PET, the surface of the molded product is Is clouded. It is considered that this is because the oriented skin layer on the surface of the sheet during film formation crystallizes during heating during thermoforming, and it is possible to perform deep drawing only by laminating a copolyester of a specific composition only on the very surface layer of the sheet. It was found that the property and the fogging of the container were significantly improved.
【0015】シートの表面に積層させる共重合ポリエス
テルのシート全体に占める割合は1〜30%であるが、
経済性,品質の安定性の点から5〜20%が好ましい。
1%より小さい場合にはスキン層を均一にすることが困
難になる。一方、30%を超える場合には熱成形性の更
なる改善効果が小さいだけでなく高価な共重合ポリエス
テルを多量に使用するため経済的に好ましくない。The proportion of the copolyester laminated on the surface of the sheet in the whole sheet is 1 to 30%,
From the viewpoint of economy and stability of quality, 5 to 20% is preferable.
If it is less than 1%, it becomes difficult to make the skin layer uniform. On the other hand, if it exceeds 30%, not only the effect of further improving the thermoformability is small, but also a large amount of expensive copolyester is used, which is economically unfavorable.
【0016】本発明を製造するために用いるシート厚み
は特に限定しないが、通常50〜3000μmであり、
好ましくは350〜2000μmである。The sheet thickness used for producing the present invention is not particularly limited, but is usually 50 to 3000 μm,
It is preferably 350 to 2000 μm.
【0017】シートは、例えば単軸押出機、二軸ベント
式押出機の様な通常のポリエステル用エクストルーダー
により溶融押出しを行い、溶融状態の樹脂を冷却ドラム
で冷却することにより得ることが出来る。シートは結晶
化による透明性の低下を防ぐためできるだけ急冷するこ
とが好ましく、主層の結晶化度は10重量%以下(密度
1.348g/cm3 以下)、シートヘイズは5%以下
が望ましい。The sheet can be obtained by melt-extruding with a usual extruder for polyester such as a single-screw extruder or a twin-screw vent extruder, and cooling the molten resin with a cooling drum. The sheet is preferably cooled as rapidly as possible in order to prevent a decrease in transparency due to crystallization, and the crystallinity of the main layer is preferably 10% by weight or less (density 1.348 g / cm 3 or less) and the sheet haze is preferably 5% or less.
【0018】本発明を得るには、フィードブロックダ
イ、マルチマニホールドダイ等を有する公知の共押出装
置の使用が可能である。又、溶融ラミネート、ドライラ
ミネート等公知の技術により製造することもできるが、
シートの品質から共押出しが好ましい。In order to obtain the present invention, it is possible to use a known coextrusion device having a feed block die, a multi-manifold die and the like. Also, it can be manufactured by a known technique such as melt laminating or dry laminating,
Coextrusion is preferred because of the quality of the sheet.
【0019】また、製膜方法としては金属ロール間で挟
み冷却する方法(タッチロール法)や静電印加法、エア
ーナイフ法等があるが、シートの光沢性、厚み均一性の
点からタッチロール法が好ましい。Further, as a film forming method, there are a method of sandwiching and cooling between metal rolls (touch roll method), an electrostatic application method, an air knife method and the like. However, from the viewpoint of sheet glossiness and thickness uniformity, the touch roll is used. Method is preferred.
【0020】製膜時にシートを所定の幅にカットする際
に出る耳部や、熱成形後容器を打抜いたスケルトン部を
粉砕して原料として戻すインラインリサイクルがA−P
ETでは一般的に用いられるが、本発明ではシートの固
有粘度を極端に低下させない範囲内で主層へ配合するこ
とが可能である。In-line recycling is carried out by crushing the ears that appear when the sheet is cut to a predetermined width during film formation and the skeleton part punched out of the container after thermoforming and returning it as a raw material.
It is generally used in ET, but in the present invention, it can be compounded into the main layer within a range that does not extremely reduce the intrinsic viscosity of the sheet.
【0021】本発明品は、真空成形,圧空成形,熱盤成
形,プラグアシスト成形,リバースドロー成形,エアー
スリップ成形等、またはこれらを組み合わせた成形方法
の、何れの方法を用いて製造しても差し支えない。The product of the present invention may be manufactured by any of vacuum forming, pressure forming, hot plate forming, plug assist forming, reverse draw forming, air slip forming, etc., or a combination of these methods. It doesn't matter.
【0022】[0022]
【発明の効果】本発明は、透明性,機械物性,リサイク
ル性等のA−PET本来が有する特性を維持し、偏肉が
なくかつ経済性に非常に優れており、深絞りの飲料コッ
プや複雑なリブを有するトレー,ブリスターパック等に
最適である。INDUSTRIAL APPLICABILITY The present invention maintains the original properties of A-PET such as transparency, mechanical properties, and recyclability, has no uneven thickness, and is extremely excellent in economic efficiency. Optimal for trays with complex ribs, blister packs, etc.
【0023】[0023]
【実施例】以下、実施例によって本発明を更に具体的に
説明するが、本発明はこれに限定されるものではない。
尚、各特性値測定は以下の方法に従って行った。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In addition, each characteristic value measurement was performed according to the following methods.
【0024】(1)固有粘度 重量比60/40のフェノール/テトラクロロエタン混
合溶媒を用い1.0g/dlの濃度、20℃の条件で測
定した。(1) Intrinsic Viscosity A phenol / tetrachloroethane mixed solvent having a weight ratio of 60/40 was used and measured at a concentration of 1.0 g / dl and at 20 ° C.
【0025】(2)容器のヘイズ 日本電色(株)製ヘイズメーター NDH−20Dを使
用し、JIS−K−7105に準じた方法にて容器のヘ
イズ(曇価)を測定した。(2) Haze of container The haze (haze value) of the container was measured by a method according to JIS-K-7105 using a haze meter NDH-20D manufactured by Nippon Denshoku Co., Ltd.
【0026】(3)熱成形性 プラグアシスト付きの真空成形機にて直径80mm、各
絞り比の容器を作製した。完全な容器ができたものを
○,賦形は完全であるが透明性不良であるものを△,賦
形が不完全あるいは偏肉を起こしたものを×とした。(3) Thermoformability A container having a diameter of 80 mm and a drawing ratio was produced by a vacuum forming machine with plug assist. The case where a perfect container was formed was evaluated as ○, the case where the shape was complete but the transparency was poor was evaluated as △, and the case where the shape was incomplete or caused uneven thickness was evaluated as ×.
【0027】(4)熱成形条件幅 熱成形が完全に出来るシート表面温度を非接触型の赤外
線放射温度計にて測定した。熱成形可能なシート表面温
度の幅が15℃以上あるものを○,10℃以上15℃未
満のものを△,10℃未満のものを×とした。(4) Width of thermoforming conditions The sheet surface temperature at which thermoforming can be completed was measured with a non-contact type infrared radiation thermometer. A sheet having a thermoformable sheet surface temperature range of 15 ° C. or more was evaluated as ◯, a sheet having a temperature of 10 ° C. or more and less than 15 ° C. was evaluated as Δ, and a sheet having a temperature of less than 10 ° C. was evaluated as x.
【0028】(5)容器の落下強度 直径80mm×深さ80mmのカップ状の容器中に20
0gの水を入れ蓋を閉じ(かん合蓋)高さ2.5mより
コンクリート面に落下させ評価を行った。全く割れない
ものは○,割れる確率が10%以下のものは△,割れる
確率が10%より大きいものは×とした。(5) Drop strength of container 20 in a cup-shaped container having a diameter of 80 mm and a depth of 80 mm
Evaluation was carried out by adding 0 g of water and closing the lid (mating lid) and dropping it from the height of 2.5 m onto the concrete surface. Those that did not crack at all were marked with O, those with a cracking probability of 10% or less were marked with Δ, and those with a cracking probability of more than 10% were marked with X.
【0029】実施例1〜2,比較例1〜6 285℃、ベント部の真空度5mmHgの条件で二軸ベ
ント付き多層押出機を用いてTダイより溶融押出を行
い、タッチロール法にて製膜し、厚さ800μmの表1
に示す組成のシートを得た。Examples 1 to 2 and Comparative Examples 1 to 6 Melt extrusion was performed from a T die using a multi-layer extruder with a biaxial vent under conditions of 285 ° C. and a vacuum degree of a vent portion of 5 mmHg, and manufactured by a touch roll method. Membrane, 800 μm thick Table 1
A sheet having the composition shown in was obtained.
【0030】次いで、上記シートをガラス転移温度以上
融点以下に予熱し、45℃に温調した雌金型を取り付け
たプラグアシスト付き真空成形機にて直径80mm×各
絞り比(表1参照)のカップ状の容器を作製し評価を行
った。評価結果を合わせて表1に記載する。Then, the sheet was preheated to a temperature not lower than the glass transition temperature and not higher than the melting point, and the diameter of 80 mm × each drawing ratio (see Table 1) was measured by a vacuum molding machine with a plug assist equipped with a female mold whose temperature was adjusted to 45 ° C. A cup-shaped container was prepared and evaluated. The evaluation results are also shown in Table 1.
【0031】[0031]
【表1】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 B29L 22:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area B29L 22:00
Claims (1)
ジカルボン酸成分と、エチレングリコール0〜90モル
%および1,4−シクロヘキサンジメタノール10〜1
00モル%からなるグリコール成分とを縮重合せしめ、
かつ固有粘度が0.5〜0.90であるポリエステルか
らなる層、(B)テレフタル酸とエチレングリコールを
縮重合せしめ、かつ固有粘度が0.5〜0.75である
ポリエステルからなる層、から構成されるポリエステル
積層体であって、該(A)層が少なくとも片面に積層さ
れており、かつ該(A)層がシート全体の厚みの1〜3
0%の範囲にあるシートを絞り比0.8以上の深絞り熱
成形をして得られたポリエステル容器。1. A dicarboxylic acid component containing (A) terephthalic acid as a main component, 0 to 90 mol% of ethylene glycol, and 10 to 1 of 1,4-cyclohexanedimethanol.
Polycondensation with a glycol component consisting of 00 mol%,
And a layer composed of a polyester having an intrinsic viscosity of 0.5 to 0.90 and (B) a layer composed of a polyester obtained by polycondensing terephthalic acid and ethylene glycol and having an intrinsic viscosity of 0.5 to 0.75. A polyester laminate constituted, wherein the (A) layer is laminated on at least one side, and the (A) layer has a thickness of 1 to 3 of the entire sheet.
A polyester container obtained by subjecting a sheet in the range of 0% to deep drawing thermoforming with a drawing ratio of 0.8 or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16593594A JP3464531B2 (en) | 1994-06-23 | 1994-06-23 | Deep drawn thermoformed polyester container |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16593594A JP3464531B2 (en) | 1994-06-23 | 1994-06-23 | Deep drawn thermoformed polyester container |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH081766A true JPH081766A (en) | 1996-01-09 |
JP3464531B2 JP3464531B2 (en) | 2003-11-10 |
Family
ID=15821817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16593594A Expired - Lifetime JP3464531B2 (en) | 1994-06-23 | 1994-06-23 | Deep drawn thermoformed polyester container |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3464531B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5649874A (en) * | 1996-08-05 | 1997-07-22 | Marble Vision Inc. | Transparent ball with insert, and process of manufacture thereof |
JP2006082442A (en) * | 2004-09-16 | 2006-03-30 | Mitsubishi Plastics Ind Ltd | Extrusion film for deep drawing, bottom material using it and deep drawing container |
US7854225B2 (en) | 2002-11-02 | 2010-12-21 | Glaxo Group Limited | Blister package for inhalable medicament |
JP2021130491A (en) * | 2020-02-20 | 2021-09-09 | 中央化学株式会社 | Packing container and manufacturing method of packing container |
-
1994
- 1994-06-23 JP JP16593594A patent/JP3464531B2/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5649874A (en) * | 1996-08-05 | 1997-07-22 | Marble Vision Inc. | Transparent ball with insert, and process of manufacture thereof |
US7854225B2 (en) | 2002-11-02 | 2010-12-21 | Glaxo Group Limited | Blister package for inhalable medicament |
JP2006082442A (en) * | 2004-09-16 | 2006-03-30 | Mitsubishi Plastics Ind Ltd | Extrusion film for deep drawing, bottom material using it and deep drawing container |
JP4563758B2 (en) * | 2004-09-16 | 2010-10-13 | 三菱樹脂株式会社 | Coextruded film for deep drawing, bottom material using this film, and deep drawn container |
JP2021130491A (en) * | 2020-02-20 | 2021-09-09 | 中央化学株式会社 | Packing container and manufacturing method of packing container |
Also Published As
Publication number | Publication date |
---|---|
JP3464531B2 (en) | 2003-11-10 |
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