JP2003145615A - Polyester container and its production method - Google Patents
Polyester container and its production methodInfo
- Publication number
- JP2003145615A JP2003145615A JP2001349916A JP2001349916A JP2003145615A JP 2003145615 A JP2003145615 A JP 2003145615A JP 2001349916 A JP2001349916 A JP 2001349916A JP 2001349916 A JP2001349916 A JP 2001349916A JP 2003145615 A JP2003145615 A JP 2003145615A
- Authority
- JP
- Japan
- Prior art keywords
- cyclic trimer
- container
- polyester
- content
- molding
- 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 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 67
- 239000013638 trimer Substances 0.000 claims abstract description 67
- 238000000465 moulding Methods 0.000 claims abstract description 43
- 229920001225 polyester resin Polymers 0.000 claims abstract description 38
- 239000004645 polyester resin Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 238000009998 heat setting Methods 0.000 claims description 32
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 230000037396 body weight Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 230000006866 deterioration Effects 0.000 abstract description 7
- 239000007790 solid phase Substances 0.000 abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 39
- 239000005020 polyethylene terephthalate Substances 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- -1 polyethylene terephthalate Polymers 0.000 description 24
- 239000002994 raw material Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000000071 blow moulding Methods 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000011109 contamination Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012809 cooling fluid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 239000003570 air Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 101100160821 Bacillus subtilis (strain 168) yxdJ gene Proteins 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GGHTWSNOKADVAG-UHFFFAOYSA-N butan-1-olate germanium(4+) Chemical compound [Ge+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] GGHTWSNOKADVAG-UHFFFAOYSA-N 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
- 238000000748 compression moulding Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture 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
- 238000013021 overheating Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエチレンテレ
フタレートに代表されるポリエステル樹脂から成るの延
伸成形により得られたポリエステル容器及びその製造方
法に関するものであり、より詳細には、環状三量体の成
形金型表面への移行、即ち金型汚れが有効に防止され、
金型汚れに起因する表面光沢性や透明性の低下が有効に
抑制されたポリエステル容器及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester container made of a polyester resin represented by polyethylene terephthalate and obtained by stretch molding, and a method for producing the same. More specifically, it relates to molding of a cyclic trimer. Transfer to the mold surface, that is, mold contamination is effectively prevented,
The present invention relates to a polyester container in which a decrease in surface gloss and transparency due to mold stain is effectively suppressed, and a method for producing the same.
【０００２】[0002]
【従来の技術】ポリエチレンテレフタレート（ＰＥＴ）
の如きポリエステル樹脂から成る延伸成形により得られ
たポリエステル容器は、優れた透明性や表面光沢性を有
すると共に、ボトル等の容器に必要な耐衝撃性、剛性、
ガスバリヤー性をも有しており、各種飲料等の液体用容
器として広く使用されている。一方、上記のようなポリ
エステル容器は、耐熱性に劣るという欠点を有してお
り、特に内容物を熱間充填する用途に使用される場合に
は、延伸成形後に熱固定（ヒートセット）することが必
要である。熱固定の方法としては、例えば、特公昭６０
−５６６０６号公報に記載されているように、延伸ブロ
ー成形により得られる成形品を成形ブロー金型から取り
出した後、熱固定用の金型内に保持して熱固定を行なう
方法（ツーモールド法）や、特公昭５９−６２１６号公
報に開示されているように、ブロー成形型中で延伸ブロ
ー成形と同時に熱固定を行なう方法（ワンモールド法）
などが代表的な方法として知られている。2. Description of the Related Art Polyethylene terephthalate (PET)
Polyester container obtained by stretch molding consisting of polyester resin such as, while having excellent transparency and surface gloss, shock resistance, rigidity required for containers such as bottles,
It also has a gas barrier property and is widely used as a container for liquids such as various beverages. On the other hand, the polyester container as described above has a drawback that it is inferior in heat resistance, and particularly when it is used for the purpose of hot filling the contents, it should be heat-set (heat set) after stretch molding. is necessary. As a method of heat fixing, for example, Japanese Patent Publication Sho 60
As described in JP-A-56606, a method of performing heat setting by taking out a molded product obtained by stretch blow molding from a molding blow mold and then holding it in a heat fixing mold (two-mold method). ) Or a method of heat-setting at the same time as stretch blow molding in a blow molding die as disclosed in JP-B-59-6216 (one-mold method).
Etc. are known as typical methods.
【０００３】[0003]
【発明が解決しようとする課題】ところで、上記のよう
に熱固定されたポリエステル容器では、原料のポリエチ
レンテレフタレート中に含まれる環状三量体成分に起因
して、成形金型に金型汚れを生じ、この結果、容器表面
の平滑性が損なわれ、表面光沢性の低下（即ち、肌荒
れ）や透明性の低下という問題を生じていた。このた
め、原料ポリエステル樹脂として、このような環状三量
体成分含量が著しく抑制されたものを使用することが提
案されている。例えば、特公平７−６４９２０号公報に
は、環状三量体成分含量が０．５重量％以下のポリエチ
レンテレフタレートを用いてポリエステル容器を製造す
ることが記載されている。By the way, in the polyester container which is heat-fixed as described above, due to the cyclic trimer component contained in the raw material polyethylene terephthalate, the mold is contaminated by the mold. As a result, the smoothness of the surface of the container is impaired, and problems such as a decrease in surface gloss (that is, rough skin) and a decrease in transparency occur. Therefore, it has been proposed to use, as the raw material polyester resin, one in which the content of the cyclic trimer component is remarkably suppressed. For example, Japanese Examined Patent Publication No. 7-64920 describes manufacturing a polyester container using polyethylene terephthalate having a cyclic trimer component content of 0.5% by weight or less.
【０００４】しかしながら、環状三量体成分含量が著し
く抑制されたポリエチレンテレフタレートを使用するこ
とは、確かに金型汚れ及びそれに起因する問題を解決す
るには有効であるが、反面、経済性の点で不満足なもの
となってしまう。即ち、上記のような環状三量体成分含
量が著しく抑制されたポリエチレンテレフタレート（以
下、ハイグレードＰＥＴと呼ぶことがある）は、通常の
溶融重合法により得られるＰＥＴについて、更に熱水処
理や固相重合を行なうことにより得られるものであり、
この結果原料コストが増大してしまうという欠点があ
る。However, the use of polyethylene terephthalate in which the content of the cyclic trimer component is remarkably suppressed is certainly effective in solving the mold stain and the problems resulting therefrom, but on the other hand, it is economical. Will be unsatisfactory. That is, polyethylene terephthalate (hereinafter sometimes referred to as high-grade PET) in which the content of the cyclic trimer component is remarkably suppressed is the PET obtained by an ordinary melt polymerization method, which is further treated with hot water or solidified. It is obtained by carrying out phase polymerization,
As a result, there is a drawback that the raw material cost increases.
【０００５】従って本発明は、環状三量体成分含量を抑
制するための熱水処理や固相重合等を行うことなく得ら
れたポリエステル樹脂から延伸成形され、しかも金型汚
れやそれに起因する表面光沢性や透明性の低下が有効に
防止されたポリエステル容器及びその製造方法を提供す
ることにある。Therefore, the present invention is stretch-molded from a polyester resin obtained without performing hot water treatment or solid-phase polymerization for suppressing the content of cyclic trimer components, and further, the mold stains and the surface caused by the stain are obtained. It is an object of the present invention to provide a polyester container in which deterioration of gloss and transparency is effectively prevented and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、環状三
量体含量低減化の熱水処理をしていないポリエステル樹
脂から成る延伸成形により得られたポリエステル容器で
あって、クロロホルム抽出によって測定される容器表面
に分布する環状三量体量が４５０ｎｇ／ｃｍ２以上であ
り、且つ密度法による結晶化度が３０％以上であること
を特徴とするポリエステル容器が提供される。本発明に
よれば更に、環状三量体含量低減化の熱水処理をしてい
ないポリエステル樹脂を一次成形体に成形し、次いで該
一次成形体を延伸温度で延伸成形し、延伸成形後の容器
壁を熱固定した後に成形金型から取り出すことから成る
ポリエステル容器の製造方法において、前記熱固定時間
を３．０秒以下に設定することを特徴とするポリエステ
ル容器の製造方法が提供される。According to the present invention, there is provided a polyester container obtained by stretch molding of a polyester resin which has not been subjected to hydrothermal treatment for reducing the cyclic trimer content, and which is measured by chloroform extraction. The polyester container is characterized in that the amount of cyclic trimer distributed on the container surface is 450 ng / cm 2 or more, and the crystallinity by the density method is 30% or more. According to the present invention, further, a polyester resin not subjected to hydrothermal treatment for reducing the cyclic trimer content is molded into a primary molded body, and then the primary molded body is stretch-molded at a stretching temperature, and a container after stretch-molding is formed. A method for producing a polyester container, which comprises heat-fixing a wall and then taking it out from a molding die, wherein the heat-setting time is set to 3.0 seconds or less.
【０００７】本発明において、ポリエステル容器の延伸
成形に使用するポリエステル樹脂は、その環状三量体含
量が０．２５乃至０．７重量％の範囲にあることが好ま
しい。また、本発明において、一次成形体の延伸成形及
び熱固定は、ワンモールド法により行なわれるが、その
ライン速度、即ち、成形金型当たりの単位時間での容器
成形個数は、１０本／分以上とすることが好適である。In the present invention, the polyester resin used for stretch molding of the polyester container preferably has a cyclic trimer content of 0.25 to 0.7% by weight. Further, in the present invention, the stretch molding and heat setting of the primary molded body are carried out by a one-mold method, but the line speed, that is, the number of containers formed per unit time per molding die is 10 pieces / minute or more. Is preferred.
【０００８】即ち、本発明は、ポリエステル容器におい
て、環状三量体含量低減化の熱水処理がされていないポ
リエステル樹脂を容器の延伸成形に用い、クロロホルム
抽出によって測定される容器表面に分布する環状三量体
量が４５０ｎｇ／ｃｍ２以上であり、且つ密度法による
結晶化度が３０％以上とすることが重要な特徴である。
従来公知の延伸成形されたポリエステル容器では、例え
ば、環状三量体含量が０．５重量％以下のものが使用さ
れ、従って、既に述べた通り、熱水処理や固相重合等の
環状三量体含量を低減化するための処理が行なわれたも
のが使用されており、コスト高を招いていた。しかるに
本発明で用いるポリエステル樹脂は、環状体含量が従来
使用されていたものに比して多く、このことは、熱水処
理や固相重合等処理が行なわれていないものを成形用原
料として使用し得ることを意味し、また、本発明は、安
価なポリエステル樹脂を使用し得ると共に、容器表面に
分布する環状三量体の量と結晶化度を規定することによ
り、環状三量体の成形金型表面への移行、即ち金型汚れ
が有効に防止され、金型汚れに起因する表面光沢性や透
明性の低下が有効に抑制されるという顕著な利点を有し
ている。また、本発明においては、上記のようなポリエ
ステル樹脂を使用している結果、このようなポリエステ
ルからなるプリフォーム等の一次成形体を、ワンモール
ド法により延伸成形及び熱固定するに際して、熱固定時
間を３．０秒以下に設定することが重要である。即ち、
環状三量体を一定量以上含むポリエステル樹脂を用いて
延伸成形等を行なった場合には、既に述べた通り、この
環状三量体が成形金型表面に付着してしまい、この結
果、容器表面の平滑性が損なわれ、表面光沢性や透明性
が失われてしまう。しかるに本発明によれば、熱固定時
間を上記のように極めて短時間に設定することにより、
高温に保持された延伸成形体と金型との接触時間が短
く、従って、成形体表面に存在する環状三量体の成形金
型表面への移行、即ち金型汚れが有効に防止され、金型
汚れに起因する表面光沢性や透明性の低下が有効に抑制
される。That is, according to the present invention, in a polyester container, a polyester resin which has not been subjected to hydrothermal treatment for reducing the content of cyclic trimer is used for stretch molding of the container, and the cyclic resin distributed on the surface of the container measured by chloroform extraction is used. It is an important feature that the amount of trimer is 450 ng / cm 2 or more and the crystallinity by the density method is 30% or more.
In the conventionally known stretch-molded polyester container, for example, one having a cyclic trimer content of 0.5% by weight or less is used, and therefore, as described above, a cyclic trimer such as hot water treatment or solid phase polymerization is used. A product that has been subjected to a treatment for reducing body content is used, resulting in high cost. However, the polyester resin used in the present invention has a larger cyclic content than that conventionally used, which means that a material not subjected to treatment such as hot water treatment or solid-phase polymerization is used as a raw material for molding. In addition, the present invention allows the use of an inexpensive polyester resin, and the formation of a cyclic trimer by defining the amount and crystallinity of the cyclic trimer distributed on the container surface. It has a remarkable advantage that migration to the mold surface, that is, mold stain is effectively prevented, and deterioration of surface glossiness and transparency due to mold stain is effectively suppressed. In addition, in the present invention, as a result of using the polyester resin as described above, a primary molding such as a preform made of such a polyester is stretch-molded and heat-fixed by the one-mold method, and the heat-setting time is set. Is important to be set to 3.0 seconds or less. That is,
When stretch molding or the like is performed using a polyester resin containing a certain amount or more of the cyclic trimer, as described above, the cyclic trimer adheres to the molding die surface, resulting in the container surface. Smoothness is impaired, and surface gloss and transparency are lost. However, according to the present invention, by setting the heat setting time to an extremely short time as described above,
The contact time between the stretched molded body held at high temperature and the mold is short, and therefore the transfer of the annular trimer existing on the surface of the molded body to the surface of the molding die, that is, the mold stain is effectively prevented, The deterioration of surface gloss and transparency due to mold fouling is effectively suppressed.
【０００９】[0009]
【発明の実施形態】［原料ポリエステル樹脂］本発明に
おいて、原料として用いるポリエステル樹脂は、エチレ
ンテレフタレート単位を主体とするポリエチレンテレフ
タレート（ＰＥＴ）であり、環状三量体含量低減化の為
の熱水処理がされておらず、環状三量体含量が０．２重
量％以上、好ましくは０．２５乃至０．７重量％の範囲
にあるものであり、従来使用されているものに比して、
比較的多量の環状三量体を含有している。BEST MODE FOR CARRYING OUT THE INVENTION [Raw material polyester resin] In the present invention, the polyester resin used as a raw material is polyethylene terephthalate (PET) mainly comprising ethylene terephthalate units, and hot water treatment for reducing the cyclic trimer content. The content of the cyclic trimer is not less than 0.2% by weight, preferably in the range of 0.25 to 0.7% by weight.
It contains a relatively large amount of cyclic trimer.
【００１０】このようなＰＥＴは、これに限定されるも
のではないが、テレフタル酸またはそのエステル形成性
誘導体と、エチレングリコールまたはそのエステル形成
性誘導体とを主体とする原料を、触媒の存在下に液相重
合させることにより得られるものであることが好まし
い。経済的なＰＥＴの合成は、高純度のテレフタル酸
（ＴＰＡ）とエチレングリコール（ＥＧ）とを直接反応
させることにより行なわれ、通常、二つの工程に分けら
れている。即ち、第一段の工程では、ＴＰＡとＥＧとを
反応させて、ビス−β−ヒドロキシエチルテレフタレー
ト（ＢＨＴ）オリゴマーが合成され、第二段の工程で、
ＢＨＴオリゴマーからエチレングリコール（ＥＧ）を留
去して重縮合が行なわれる。Such a PET is not limited to this, but a raw material mainly containing terephthalic acid or its ester-forming derivative and ethylene glycol or its ester-forming derivative is added in the presence of a catalyst. It is preferably obtained by liquid phase polymerization. Economical PET synthesis is carried out by directly reacting high-purity terephthalic acid (TPA) with ethylene glycol (EG), which is usually divided into two steps. That is, in the first step, TPA and EG are reacted to synthesize a bis-β-hydroxyethyl terephthalate (BHT) oligomer, and in the second step,
Polyethylene is condensed by distilling off ethylene glycol (EG) from the BHT oligomer.
【００１１】第一段の工程でのＢＨＴオリゴマーの合成
は、それ自体公知の条件で行なうことができ、例えばＴ
ＰＡに対するＥＧの量を１．１〜１．５モル倍として、
ＥＧの沸点以上（例えば２２０〜２６０℃）の温度に加
熱して、１．５ｋｇ／ｃｍ２程度の加圧下に、水を系外
に留去しながらエステル化が行なわれる。この場合、Ｔ
ＰＡ自体が触媒となるので、それ自体公知のエステル化
触媒を用いることもできる。The synthesis of the BHT oligomer in the first step can be carried out under the conditions known per se, for example, T
The amount of EG with respect to PA is 1.1 to 1.5 mol times,
Esterification is carried out by heating to a temperature not lower than the boiling point of EG (for example, 220 to 260 ° C.) and distilling water out of the system under a pressure of about 1.5 kg / cm 2 . In this case, T
Since PA itself serves as a catalyst, an esterification catalyst known per se can be used.
【００１２】第二段での重縮合工程では、前記工程で得
られたＢＨＴオリゴマーにそれ自体公知の重縮合触媒を
加えた後、反応系を、例えば２２０〜２９０℃に保ちな
がら徐々に圧力を低下させ、最終的に１〜３ｍｍＨｇの
減圧下に攪拌し、生成するＥＧを系外に留去しながら反
応を進行させる。反応系の粘度によって分子量を検出
し、所定の値に達したら、生成されたＰＥＴを系外に吐
出し、冷却後、チップとする。重合触媒としては、ゲル
マニウム化合物、チタン化合物、アンチモン化合物等が
使用されるが、これらの中でも、二酸化ゲルマニウム、
ゲルマニウムテトラエトキシド、ゲルマニウムテトラブ
トキシドなどのゲルマニウム化合物が最適である。ま
た、本発明において用いる原料ポリエステル樹脂の分子
量は、これから得られるボトル等の容器の強度、耐圧
性、耐熱性等の特性に大きな影響を与える。例えば、ボ
トル等の容器では、未延伸部から高延伸部まで、延伸の
程度の異なる種々の領域が存在しているため、強度等に
優れた容器を得るためには、分子量の高いものを用いる
必要がある。このため、上記により得られるＰＥＴは、
０．７０ｄｌ／ｇ以上、特に０．７５乃至０．８０ｄｌ
／ｇの固有粘度（ＩＶ）を有していることが好ましい。In the polycondensation step in the second stage, a polycondensation catalyst known per se is added to the BHT oligomer obtained in the above step, and then the reaction system is gradually heated while maintaining the temperature at 220 to 290 ° C., for example. Then, the mixture is reduced and finally stirred under a reduced pressure of 1 to 3 mmHg, and the reaction is allowed to proceed while distilling the generated EG out of the system. The molecular weight is detected by the viscosity of the reaction system, and when it reaches a predetermined value, the produced PET is discharged out of the system, cooled, and made into chips. As the polymerization catalyst, germanium compounds, titanium compounds, antimony compounds and the like are used. Among these, germanium dioxide,
Germanium compounds such as germanium tetraethoxide and germanium tetrabutoxide are most suitable. Further, the molecular weight of the raw material polyester resin used in the present invention has a great influence on the properties such as strength, pressure resistance and heat resistance of the container such as a bottle obtained therefrom. For example, in containers such as bottles, since there are various regions with different degrees of stretching, from the unstretched portion to the highly stretched portion, in order to obtain a container having excellent strength and the like, one having a high molecular weight is used. There is a need. Therefore, the PET obtained by the above is
0.70 dl / g or more, especially 0.75 to 0.80 dl
It preferably has an intrinsic viscosity (IV) of / g.
【００１３】上記のようにして製造されるＰＥＴ系ポリ
エステル樹脂は、エステル反復単位の大部分、一般に７
０モル％以上、特に８０モル％以上をエチレンテレフタ
レート単位を占めるものが好ましく、またガラス転移点
（Ｔｇ）が５０乃至９０℃、特に５５乃至８０℃の範囲
にあり、更に融点（Ｔｍ）が２００乃至２７５℃、特に
２２０乃至２７０℃の範囲にあることが好適である。The PET-based polyester resin produced as described above contains most of the ester repeating unit, generally 7
It is preferable that the ethylene terephthalate unit accounts for 0 mol% or more, particularly 80 mol% or more, and the glass transition point (Tg) is 50 to 90 ° C., particularly 55 to 80 ° C., and the melting point (Tm) is 200. To 275 ° C., particularly 220 to 270 ° C. are preferred.
【００１４】また、本発明においては、特に容器の耐熱
圧性等の点で、ホモポリエチレンテレフタレートが好適
であるが、エチレンテレフタレート単位以外のエステル
単位を少量含む共重合ポリエステルも使用することがで
きる。このような共重合ポリエステルにおいて、テレフ
タル酸以外の二塩基酸としては、イソフタル酸、フタル
酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸；
シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；
コハク酸、アジピン酸、セバチン酸、ドデカンジオン酸
等の脂肪族ジカルボン酸；等の１種又は２種以上の組み
合わせを例示することができ、エチレングリコール以外
のジオール成分としては、プロピレングリコール、１，
４−ブタンジオール、ジエチレングリコール、１，６−
ヘキシレングリコール、シクロヘキサンジメタノール、
ビスフェノールＡのエチレンオキサイド付加物等の１種
又は２種以上が挙げられる。In the present invention, homopolyethylene terephthalate is particularly preferable in view of heat resistance and pressure resistance of the container, but a copolymerized polyester containing a small amount of ester units other than ethylene terephthalate units can also be used. In such a copolyester, dibasic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid;
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid;
Examples thereof include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedioic acid; and combinations of two or more thereof. Examples of the diol component other than ethylene glycol include propylene glycol, 1,
4-butanediol, diethylene glycol, 1,6-
Hexylene glycol, cyclohexanedimethanol,
One or more of bisphenol A ethylene oxide adducts and the like can be mentioned.
【００１５】本発明においては、前述した液状重合で得
られたＰＥＴをペレタイズし、このペレットをＰＥＴの
結晶化温度に加熱してＰＥＴの結晶化を行なう。即ち、
前述した液状重合で得られたＰＥＴは、環状三量体（以
下、ＣＴと呼ぶことがある）を多く含むが、この結晶化
処理により、内部に含有されるＣＴは外部にはみだし、
この結果、ＣＴ含有量は減少する。この結晶化温度は、
ＣＴ含有量の減少に関して最適範囲があり、一般に１０
０乃至１４０℃、特に１１５乃至１２５℃の範囲が適当
であり、また処理時間は、１００乃至１８０分間、特に
１２０乃至１５０分間が適当である。ＰＥＴペレットの
結晶化のための熱処理は、例えば加熱窒素ガス等の加熱
不活性ガスを用い、流動床または固定床で行うことがで
き、また真空加熱炉内で行なうこともできる。In the present invention, the PET obtained by the liquid polymerization described above is pelletized, and the pellets are heated to the crystallization temperature of PET to crystallize PET. That is,
The PET obtained by the liquid polymerization described above contains a large amount of cyclic trimers (hereinafter, sometimes referred to as CT), but the CT contained inside is exposed to the outside by this crystallization treatment,
As a result, the CT content is reduced. This crystallization temperature is
There is an optimum range for reducing CT content, generally 10
A range of 0 to 140 ° C., particularly 115 to 125 ° C. is suitable, and a treatment time is 100 to 180 minutes, particularly 120 to 150 minutes. The heat treatment for crystallization of PET pellets can be performed in a fluidized bed or a fixed bed using a heated inert gas such as heated nitrogen gas, or can be performed in a vacuum heating furnace.
【００１６】このようにして熱結晶化処理されたＰＥＴ
ペレットは、ＣＴ含有量が０．２重量％以上、特に０．
２５乃至０．７重量％の範囲に調整されており、本発明
では、これを成形用の原料ポリエステル樹脂として使用
する。即ち、従来のポリエステル延伸成形容器では、上
記で得られたＰＥＴペレットについて、更に熱水処理或
いは固相重合等により、更にＣＴ含有量を減少させたい
わゆるハイグレードのポリエステル樹脂を原料として使
用していた。しかるに、本発明では、上記のように、Ｃ
Ｔ含有量が従来使用されていたものに比して多く含むポ
リエステル樹脂を使用するため、ＣＴ含有量の低減化の
ための熱水処理や固相重合を行なう必要がない。即ち、
ハイグレードのポリエステル樹脂に比して、極めて安価
なポリエステル樹脂を原料として使用するものであり、
このようなポリエステル樹脂を使用できることは、本発
明の大きな利点である。PET subjected to the thermal crystallization treatment in this way
The CT content of the pellets is 0.2% by weight or more, and particularly, the CT content is 0.2.
It is adjusted to a range of 25 to 0.7% by weight, and in the present invention, this is used as a raw material polyester resin for molding. That is, in the conventional polyester stretch-molded container, the PET pellets obtained as described above are used as a raw material for a so-called high-grade polyester resin in which CT content is further reduced by hot water treatment or solid-state polymerization. It was However, in the present invention, as described above, C
Since a polyester resin containing a large amount of T content compared to that used conventionally is used, there is no need to perform hot water treatment or solid-phase polymerization for reducing the CT content. That is,
Compared to high grade polyester resin, it uses extremely cheap polyester resin as a raw material,
The ability to use such polyester resins is a major advantage of the present invention.
【００１７】［ポリエステル延伸成形容器の製造］本発
明によれば、上記のポリエステル樹脂（ＰＥＴペレッ
ト）を使用し、一次成形体を成形し、次いで、延伸金型
内で延伸成形及び熱固定を行ない、目的とするポリエス
テル延伸成形容器を製造する。以下、延伸ブロー成形法
により、二軸延伸ボトルを製造する場合を例にとって、
この製造方法を説明する。[Manufacture of polyester stretch-molded container] According to the present invention, the above-mentioned polyester resin (PET pellet) is used to mold a primary molded body, and then stretch-molded and heat-set in a stretching die. Then, the intended polyester stretch-molded container is produced. Hereinafter, by the stretch blow molding method, taking as an example the case of producing a biaxially stretched bottle,
This manufacturing method will be described.
【００１８】二軸延伸ボトルを製造するには、先ず、一
次成形体としてプリフォームを成形するが、このプリフ
ォームは、射出成形法で成形することができ、また圧縮
成形法で成形することもできる。射出成形法によりプリ
フォームを成形する場合、その条件等は特に制限される
ものではないが、一般に、２６０乃至３００℃の射出温
度、３０乃至６０ｋｇ／ｃｍ２の射出圧力で有底プリフ
ォームを成形することができる。In order to manufacture a biaxially stretched bottle, first, a preform is molded as a primary molded body. This preform can be molded by an injection molding method or a compression molding method. it can. When molding a preform by an injection molding method, the conditions and the like are not particularly limited, but in general, a bottomed preform is molded at an injection temperature of 260 to 300 ° C. and an injection pressure of 30 to 60 kg / cm 2. can do.
【００１９】上記で得られたプリフォームに耐熱性を与
えるため、通常、プリフォームに形成されている口頚部
（螺合部、嵌合部、支持リング等）を熱処理により結晶
化して白化せしめる。この熱結晶化は、前述したポリエ
チレンテレフタレートの熱結晶化温度領域、特に１４０
乃至２００℃の範囲で行なうのがよい。この場合、２軸
延伸ブロー成形完了後に、未延伸部分の口頚部を熱処理
により結晶化させ、白化させることも可能である。In order to impart heat resistance to the preform obtained above, the mouth / neck portion (screwed portion, fitting portion, support ring, etc.) formed on the preform is usually crystallized and whitened by heat treatment. This thermal crystallization is carried out by the above-mentioned thermal crystallization temperature range of polyethylene terephthalate, especially 140
It is preferable to carry out at a temperature within the range of 200 to 200 ° C. In this case, after completion of the biaxial stretch blow molding, it is possible to crystallize the mouth and neck portion of the unstretched portion by heat treatment to whiten it.
【００２０】以上のようにして得られた一次成形体であ
るプリフォームを、所定の延伸成形温度に加熱し、延伸
成形金型内でプリフォーム内に加圧流体を吹き込み、延
伸棒による軸方向引張延伸と周方向膨張延伸とを行なう
ことにより、二軸延伸ブロー成形が行なわれる。延伸成
形温度は、通常、８５〜１２５℃の温度であり、延伸成
形温度へのプリフォームの加熱は、赤外線加熱、高周波
誘導加熱、熱風加熱等の公知の手段で行なわれ、また、
射出機のプリフォームに与えた熱（即ち余熱）を利用し
て行なうこともできるし、コールドパリソンにあっては
再加熱により行なわれる。軸方向延伸倍率は、１．３乃
至３．５倍、特に１．５乃至３倍とすることが好まし
く、また、周方向延伸倍率は、２乃至５．５倍、特に３
乃至５倍程度が好適である。この場合、軸方向の延伸速
度が３．０倍／秒以上、特に４．０倍／秒以上であり、
且つ周方向の延伸速度が５．０倍／秒以上、特に６．０
倍／秒以上の高速延伸が特に好適である。更に、ブロー
成形時に吹き込む加圧流体としては、プリフォーム温度
よりも少なくとも１０℃高い温度に保持されている高温
流体を用いるのがよい。The preform, which is the primary molded body obtained as described above, is heated to a predetermined stretch molding temperature, a pressurized fluid is blown into the preform in a stretch molding die, and an axial direction is drawn by a stretch rod. Biaxial stretch blow molding is performed by performing tensile stretching and circumferential expansion. The stretch molding temperature is usually 85 to 125 ° C., and heating of the preform to the stretch molding temperature is carried out by a known means such as infrared heating, high frequency induction heating, hot air heating, and the like.
It can be carried out by utilizing the heat (that is, residual heat) given to the preform of the injection machine, or in the cold parison, it is carried out by reheating. The axial stretching ratio is preferably 1.3 to 3.5 times, particularly preferably 1.5 to 3 times, and the circumferential stretching ratio is 2 to 5.5 times, especially 3 times.
It is preferably about 5 times. In this case, the stretching speed in the axial direction is 3.0 times / second or more, particularly 4.0 times / second or more,
The stretching speed in the circumferential direction is 5.0 times / second or more, especially 6.0.
High-speed stretching of double / second or more is particularly suitable. Further, as the pressurized fluid blown at the time of blow molding, it is preferable to use a high temperature fluid kept at a temperature higher by at least 10 ° C. than the preform temperature.
【００２１】本発明においては、いわゆるワンモールド
法が使用され、延伸成形金型（ブロー金型）で２軸延伸
成形するにあたり、この金型を、前記ポリエチレンテレ
フタレートの熱結晶化温度領域に加熱保持しておく。即
ち、延伸ブロー成形されたプリフォームの器壁の外側が
金型内面と接触すると同時に、熱固定（ヒートセット）
を行なうが、この熱固定時間を３．０秒以下、特に２．
５秒以下に設定する。即ち、この熱固定時間を短縮する
ことにより、高温に保持された延伸成形ボトルの器壁表
面と加熱金型との接触時間が短くなり、この結果、器壁
表面に存在する環状三量体成分の金型表面への移行、即
ち、金型汚れが有効に防止され、金型汚れに起因するボ
トルの表面光沢性や透明性の低下を有効に抑制すること
ができる。例えば、この熱固定時間を上記範囲よりも長
く設定すると、器壁表面に存在する環状三量体成分が金
型表面に移行し付着する時間が長くなってしまうため、
金型汚れが生じ、得られるボトルの表面光沢性や透明性
が失われてしまう。また、本発明では、熱固定を上記の
ような短時間で行なうため、前述した金型温度を、短時
間での熱固定により、例えば容器壁の密度法による結晶
化度が３０％以上、特に３５％以上となるような温度領
域に保持しておくことにより、耐熱性が付与できる。即
ち、前記ポリエチレンテレフタレートの熱結晶化温度領
域の中でも特に高温側、例えば、１４０乃至１８０℃、
特に１５０乃至１６５℃の範囲に金型温度をシフトさせ
ておくことが好ましい。In the present invention, the so-called one-mold method is used, and when biaxially stretch-molding with a stretch-molding die (blow die), the die is heated and held in the thermal crystallization temperature region of the polyethylene terephthalate. I'll do it. That is, the outside of the wall of the stretch-blow-molded preform comes into contact with the inner surface of the mold, and at the same time, heat fixation (heat setting) is performed.
The heat setting time is 3.0 seconds or less, especially 2.
Set to 5 seconds or less. That is, by shortening the heat setting time, the contact time between the heating mold and the vessel wall surface of the stretch-molded bottle held at a high temperature is shortened, and as a result, the cyclic trimer component present on the vessel wall surface is reduced. Can be effectively prevented from being transferred to the mold surface, that is, the mold stain can be effectively prevented, and the deterioration of the surface gloss and transparency of the bottle due to the mold stain can be effectively suppressed. For example, if this heat setting time is set to be longer than the above range, the cyclic trimer component existing on the surface of the vessel wall will be transferred to the mold surface for a long time to adhere,
Mold stains occur and the resulting bottle loses surface gloss and transparency. Further, in the present invention, since the heat setting is carried out in a short time as described above, the mold temperature described above is applied by heat setting in a short time, for example, the crystallinity of the container wall by the density method is 30% or more, particularly The heat resistance can be imparted by keeping the temperature range of 35% or more. That is, in the thermal crystallization temperature range of the polyethylene terephthalate, particularly on the high temperature side, for example, 140 to 180 ° C.,
In particular, it is preferable to shift the mold temperature in the range of 150 to 165 ° C.
【００２２】上記のように制限された時間内での熱固定
が終了後、ブロー用加圧流体を内部冷却用流体に切り換
え、内部の冷却を行ない、冷却終了後に金型から延伸成
形及び熱固定された二次延伸成形容器（延伸ブローボト
ル）を取り出す。この冷却用流体としては、適当な温度
に冷却された各種気体、例えば−４０℃〜室温に保持さ
れた窒素、空気、炭酸ガスが好適に使用されるが、これ
以外にも、化学的不活性な液化ガス、例えば液化窒素ガ
ス、液化炭酸ガス、液化トリクロロフルオロメタンガ
ス、液化ジクロロジフルオロメタンガス、その他の液化
脂肪族炭化水素ガス等を使用することもできる。After the heat setting within the limited time is completed as described above, the blow pressurized fluid is switched to the internal cooling fluid to cool the inside, and after the cooling is completed, the mold is stretched and heat set. The secondary stretch-molded container (stretch blow bottle) thus prepared is taken out. As this cooling fluid, various gases cooled to an appropriate temperature, for example, nitrogen, air or carbon dioxide gas maintained at -40 ° C to room temperature is preferably used, but in addition to this, it is chemically inert. A liquefied gas such as liquefied nitrogen gas, liquefied carbon dioxide gas, liquefied trichlorofluoromethane gas, liquefied dichlorodifluoromethane gas, or other liquefied aliphatic hydrocarbon gas can also be used.
【００２３】上記の冷却用流体を用いての冷却時間は、
熱固定温度（金型温度）や熱固定時間によっても異なる
が、本発明では、成形金型（ブロー金型）当たりの成形
本個数で示されるライン速度が１０本個／分以上、特に
１５本個／分以上となるように冷却時間を調整するのが
よい。即ち、このような高速のライン速度で延伸成形及
び熱固定を行なうことにより、環状三量体成分を含むポ
リエステル樹脂と金型との接触時間が大幅に短縮され、
金型表面への環状三量体の移行及び付着による金型汚れ
を、一層、有効に防止することができる。The cooling time using the above cooling fluid is
In the present invention, the line speed indicated by the number of moldings per molding die (blow mold) is 10 or more, particularly 15 although it varies depending on the heat-setting temperature (mold temperature) and the heat-setting time. It is preferable to adjust the cooling time so that the number of pieces / minute or more. That is, by performing stretch molding and heat setting at such a high line speed, the contact time between the polyester resin containing the cyclic trimer component and the mold is significantly shortened,
It is possible to further effectively prevent the mold contamination due to the transfer and adhesion of the cyclic trimer on the mold surface.
【００２４】以上、本発明によるポリエステル樹脂延伸
成形容器の製法を、二軸延伸ブローボトルを例にとって
説明したが、このようなブローボトル以外にも本発明を
適用し得ることは勿論である。即ち、環状三量体含量低
減化の為の熱水処理がされていないポリエステル樹脂を
使用し、射出成形、押出成形等により一次成形体である
シート乃至フィルムを成形し、このシート等を、所定の
成形金型を用いて、真空成形、圧空成形、張出成形、プ
ラグアシスト成形等の延伸成形を行ない、ブロー成形と
同様、成形金型を熱固定温度に加熱しておくことによ
り、延伸成形と同時に熱固定を行ない、カップ容器を製
造することができる。即ち、このときの熱固定時間を、
３．０秒以下、特に２．５秒以下の短時間とすることに
より、金型表面への環状三量体の移行及び付着による金
型汚れを有効に防止することができる。また、ブロー成
形の場合と同様、成形金型当たりのライン速度を１０本
個／分以上、特に１５本個／分以上となるようにするこ
とにより、環状三量体による金型汚れを一層有効に抑制
することができる。Although the method for producing the polyester resin stretch-molded container according to the present invention has been described above by taking the biaxially stretched blow bottle as an example, it goes without saying that the present invention can be applied to other than such a blow bottle. That is, using a polyester resin that has not been subjected to hot water treatment for reducing the cyclic trimer content, a sheet or film that is a primary molded body is molded by injection molding, extrusion molding, etc. Stretch forming such as vacuum forming, pressure forming, bulging forming, plug assist forming, etc. is performed by using the forming die of No. 1, and the stretching forming is performed by heating the forming die to a heat setting temperature as in blow molding. At the same time, heat setting can be performed to manufacture a cup container. That is, the heat setting time at this time is
By setting the time to be 3.0 seconds or less, particularly 2.5 seconds or less, it is possible to effectively prevent the die contamination due to the transfer and attachment of the cyclic trimer on the die surface. Further, as in the case of blow molding, the line speed per molding die is set to 10 pieces / minute or more, and particularly 15 pieces / minute or more, so that the die contamination by the cyclic trimer is more effective. Can be suppressed.
【００２５】［ポリエステル容器］かくして得られる本
発明のポリエステル容器は、原料ポリエステル樹脂とし
て比較的多くの環状三量体を含有するものを使用してい
るため、容器表面に分布している環状三量体量をクロロ
ホルム抽出によって測定したとき、その量は、４５０ｎ
ｇ／ｃｍ２以上、特に４８０乃至６００ｎｇ／ｃｍ２の
範囲にある。しかるに、本発明のポリエステル容器は、
上記のような量の環状三量体成分を含有しているもの
の、成形金型の環状三量体成分による金型汚れが有効に
抑制されているため、表面光沢度や透明性の点で極めて
優れている。また、前述した熱固定により、密度法によ
る結晶化度は、３０％以上、特に３５％以上であり、優
れた耐熱性を示す。[Polyester Container] Since the polyester container of the present invention thus obtained contains a relatively large amount of cyclic trimer as the raw material polyester resin, the cyclic trimer distributed on the container surface is used. When the body weight was measured by chloroform extraction, the amount was 450n.
g / cm 2 or more, particularly in the range of 480 to 600 ng / cm 2 . However, the polyester container of the present invention,
Although it contains the amount of the cyclic trimer component as described above, since the mold stain due to the cyclic trimer component of the molding die is effectively suppressed, it is extremely excellent in terms of surface gloss and transparency. Are better. Further, the crystallinity by the density method is 30% or more, particularly 35% or more by the above-mentioned heat setting, and shows excellent heat resistance.
【００２６】[0026]
【実施例】本発明のポリエステル容器に用いるポリエチ
レンテレフタレートの特性値の評価、測定方法は次の方
法による。EXAMPLES The method for evaluating and measuring the characteristic values of polyethylene terephthalate used in the polyester container of the present invention is as follows.
【００２７】（１）ＰＥＴ中の環状三量体（ＣＴ）の含
有量
サンプル約１００ｍｇを精秤し、ヘキサフルオロイソプ
ロパノール（ＨＦＩＰ）約１．０ｍｌに溶解する（室温
×１６時間）。テトラヒドロフランを少しずつ混合して
行き、ポリマー分を再沈させ、濾過して全量を２５ｍｌ
に希釈後、ゲルパーミュエーションクロマトグラフィー
（ＧＰＣ）測定を行った。（ＣＴ１００％の時のピーク
面積値を基準として、含有量を算出する。）
ＧＰＣ測定条件
装 置：東ソー（株）・ＨＬＣ−８１２０ＧＰＣ
カラム：ガードカラム＋東ソー（株）・ＴＳＫ−ＧＥＬ
SuperHM-H
検出器：示差屈折計東ソー（株）・ＵＶ−８０２０
溶離液：クロロホルム(1) Content of cyclic trimer (CT) in PET About 100 mg of a sample is precisely weighed and dissolved in about 1.0 ml of hexafluoroisopropanol (HFIP) (room temperature × 16 hours). Tetrahydrofuran was mixed little by little, the polymer content was reprecipitated, and the total amount was 25 ml by filtration.
After dilution, the gel permeation chromatography (GPC) was measured. (The content is calculated based on the peak area value at the time of CT100%.) GPC measurement condition device: Tosoh Corp., HLC-8120GPC column: Guard column + Tosoh Corp., TSK-GEL
SuperHM-H Detector: Differential refractometer Tosoh Corp. UV-8020 Eluent: Chloroform
【００２８】（２）金型付着物の定量
脱脂綿にクロロホルム：ＨＦＩＰ＝１：１の混合溶液を
含ませて、金型付着物を拭き取り、この脱脂綿を濾紙を
用いて濾過し、クロロホルム・ＨＦＩＰ混合溶液で繰り
返し洗浄した。この濾液をエバポレーターで濃縮し、Ｇ
ＰＣ測定を行った。
ＧＰＣ測定条件：（１）同様(2) Quantitative amount of mold adhered cotton swab containing a mixed solution of chloroform: HFIP = 1: 1, wiped off the mold adherent, filtered the absorbent cotton with a filter paper, and mixed chloroform / HFIP. Wash repeatedly with the solution. The filtrate is concentrated with an evaporator, and G
PC measurement was performed. GPC measurement conditions: Same as (1)
【００２９】（３）容器表面に分布するＣＴ量
容器表面を定量したクロロホルム０．０７５ｍｌ／ｃｍ
２で洗い流し、その溶液を濾紙を用いて濾過し、エバポ
レーターで乾固寸前まで揮発させた。最後ジメチルホル
ムアミドで希釈し、高速液体クロマトグラフィー（ＨＰ
ＬＣ）測定を行った。所定量のＣＴを同様の方法で溶解
し定量用試料とした。
ＨＬＰＣ測定条件
装 置：東ソー（株）・ＡＳ−８０１０
カラム：東ソー（株）・ＯＤＳ−８０Ｔｓ ４．６×１５０ｍｍ
検出器：ＵＶ２５４ｍｍ
溶離液：Ａ；０．０５％リン酸含有水
Ｂ；アセトアクリル(3) CT amount distributed on the container surface Chloroform 0.075 ml / cm for quantifying the container surface
It was washed off with 2 , the solution was filtered using a filter paper, and evaporated to almost dryness with an evaporator. Finally, dilute with dimethylformamide and perform high performance liquid chromatography (HP
LC) measurement was performed. A predetermined amount of CT was dissolved by the same method to obtain a quantitative sample. HLPC measurement conditions Equipment: Tosoh Corporation / AS-8010 Column: Tosoh Corporation / ODS-80Ts 4.6 × 150 mm Detector: UV254 mm Eluent: A; 0.05% phosphoric acid-containing water B; acetoacrylic
【００３０】（４）光沢度
容器の胴壁を切り出し、外表面の光沢度を６０度鏡面で
測定した。（ＪＩＳＫ ７１０５）
装置：スガ試験機（株）・デジタル変角光沢計ＵＧＶ−
５Ｋ(4) Glossiness The body wall of the container was cut out, and the glossiness of the outer surface was measured with a 60 degree mirror surface. (JISK 7105) Device: Suga Test Instruments Co., Ltd. Digital variable angle gloss meter UGV-
5K
【００３１】（５）Ｈａｚｅ
容器の胴壁を切り出し、積分球式光線透過率測定装置で
測定した。（ＪＩＳＫ ７１０５）
装置：スガ試験機（株）・ヘーズメーターＨＧＭ−２Ｋ(5) The shell wall of the Haze container was cut out and measured with an integrating sphere type light transmittance measuring device. (JISK 7105) Device: Suga Test Instruments Co., Ltd. Haze meter HGM-2K
【００３２】（実施例１）環状三量体含有量低減化の熱
水処理をしていないポリエチレンテレフタレート樹脂
（明細書記載の方法で測定した結果、環状三量体の含有
量は０．２５重量％であった）を用いて、射出成形機に
よりプリフォームを成形し、口部結晶化した後、遠赤外
線ヒーターで過熱後延伸ブロー成形を行い、内容量約５
００ｍｌの容器を作成した。この時、成形金型当り１
７．８本／分の速度、金型の温度１５０℃、熱固定時間
２．２秒とした。また、成形は金型清掃後開始し、約４
８時間後に延伸ブロー成形されたポリエステルボトル及
び金型について前述した方法で評価を行った。(Example 1) Polyethylene terephthalate resin not subjected to hydrothermal treatment for reducing the cyclic trimer content (measured by the method described in the specification, the content of the cyclic trimer was 0.25 wt. %) Was used to mold a preform with an injection molding machine, the mouth was crystallized, and then stretch blow molding was performed after overheating with a far infrared heater, and the internal volume was about 5%.
A 00 ml container was made. At this time, 1 per molding die
The speed was 7.8 lines / minute, the mold temperature was 150 ° C., and the heat setting time was 2.2 seconds. In addition, molding starts after cleaning the mold,
After 8 hours, stretch-blow molded polyester bottles and molds were evaluated by the methods described above.
【００３３】（実施例２）上記実施例１において、環状
三量体の含有量が０．４５重量％のポリエチレンテレフ
タレート樹脂を用いた以外は、実施例１と同様の方法で
ポリエステルボトルを作成し、測定、評価を行った。Example 2 A polyester bottle was prepared in the same manner as in Example 1 except that polyethylene terephthalate resin having a cyclic trimer content of 0.45% by weight was used. , Measurement and evaluation were performed.
【００３４】（実施例３）上記実施例１において、環状
三量体の含有量が０．７０重量％のポリエチレンテレフ
タレート樹脂を用いた以外は、実施例１と同様の方法で
ポリエステルボトルを作成し、測定、評価を行った。Example 3 A polyester bottle was prepared in the same manner as in Example 1 except that polyethylene terephthalate resin having a cyclic trimer content of 0.70% by weight was used. , Measurement and evaluation were performed.
【００３５】（実施例４）上記実施例１において、環状
三量体の含有量が０．４５重量％のポリエチレンテレフ
タレート樹脂を用い、成形金型当り１０本／分の速度、
熱固定時間２．９秒とした以外は、実施例１と同様の方
法でポリエステルボトルを作成し、測定、評価を行っ
た。Example 4 In Example 1, the polyethylene terephthalate resin having a cyclic trimer content of 0.45% by weight was used, and the rate per mold was 10 / min.
A polyester bottle was prepared, measured and evaluated in the same manner as in Example 1 except that the heat setting time was 2.9 seconds.
【００３６】（比較例１）実施例１において、環状三量
体の含有量が０．４５重量％のポリエチレンテレフタレ
ート樹脂を用い、成形金型当り８．０本／分の速度、熱
固定時間４．０秒とした以外は、実施例１と同様の方法
でポリエステルボトルを作成し、測定、評価を行った。(Comparative Example 1) In Example 1, a polyethylene terephthalate resin having a cyclic trimer content of 0.45% by weight was used, and the rate per mold was 8.0 per minute, and the heat setting time was 4 times. A polyester bottle was prepared, measured and evaluated in the same manner as in Example 1 except that the time was set to 0.0 second.
【００３７】（比較例２）実施例１において、環状三量
体の含有量が０．２５重量％のポリエチレンテレフタレ
ート樹脂を用い、成形金型当り６．０本／分の速度、熱
固定時間６．７秒とした以外は、実施例１と同様の方法
でポリエステルボトルを作成し、測定、評価を行った。(Comparative Example 2) In Example 1, a polyethylene terephthalate resin having a cyclic trimer content of 0.25% by weight was used, a rate of 6.0 pieces / min per molding die, and a heat setting time of 6 A polyester bottle was prepared, measured and evaluated in the same manner as in Example 1 except that the time was set to 0.7 seconds.
【００３８】（比較例３）実施例１において、環状三量
体含有量の低減化として熱水処理を行っているポリエチ
レンテレフタレート樹脂（環状三量体の含有量は０．２
９重量％であった）を用い、成形金型当り８．０本／分
の速度、熱固定時間４．０秒とした以外は、実施例１と
同様の方法でポリエステルボトルを作成し、測定、評価
を行った。(Comparative Example 3) In Example 1, a polyethylene terephthalate resin (the content of the cyclic trimer is 0.2 is subjected to the hot water treatment to reduce the content of the cyclic trimer.
(9% by weight) was used, and a polyester bottle was prepared and measured in the same manner as in Example 1 except that the rate per mold was 8.0 and the heat setting time was 4.0 seconds. , Evaluated.
【００３９】（比較例４）実施例１において、環状三量
体含有量の低減化として熱水処理を行っているポリエチ
レンテレフタレート樹脂（環状三量体の含有量は０．２
９重量％であった）を用い、成形金型当り１０本／分の
速度、熱固定時間２．９秒とした以外は、実施例１と同
様の方法でポリエステルボトルを作成し、測定、評価を
行った。(Comparative Example 4) In Example 1, a polyethylene terephthalate resin (the content of the cyclic trimer is 0.2 is treated by the hot water treatment to reduce the content of the cyclic trimer.
Was 9% by weight), a polyester bottle was prepared, measured and evaluated in the same manner as in Example 1, except that the speed per mold was 10 per minute and the heat setting time was 2.9 seconds. I went.
【００４０】（比較例５）実施例１において、環状三量
体含有量の低減化として熱水処理を行っているポリエチ
レンテレフタレート樹脂（環状三量体の含有量は０．２
９重量％であった）を用い、成形金型当り１７．８本／
分の速度、熱固定時間２．２秒とした以外は、実施例１
と同様の方法でポリエステルボトルを作成し、測定、評
価を行った。(Comparative Example 5) In Example 1, a polyethylene terephthalate resin (the content of the cyclic trimer is 0.2 is treated by hot water treatment to reduce the content of the cyclic trimer.
Was 9% by weight), and 17.8 pieces per molding die /
Example 1 except that a speed of minutes and a heat setting time of 2.2 seconds were used.
A polyester bottle was prepared by the same method as above, and measured and evaluated.
【００４１】[0041]
【表１】
Ｎ．Ｄ．：ＧＰＣのピーク分離限界以下（注入液の濃度
が１００μｇ／ｍｌ以下）[Table 1] N. D. : Less than GPC peak separation limit (concentration of infusion solution is less than 100 μg / ml)
【００４２】この結果、樹脂中の環状三量体の含有量が
０．７０重量％と多いポリエステル容器でも、最適な熱
固定時間にする事により、外観特性であるＨａｚｅ、光
沢度において環状三量体含有量の少ない容器と見劣りし
ない事が確認された。また、金型付着物に関しても環状
三量体は確認されず、金型汚れの防止にも有効である事
も確認された。さらに、実施例と比較例４乃至５から明
らかなように、本発明においては低減化の熱水処理をし
ていないポリエステル樹脂を用いているが、従来の熱水
処理を行って環状三量体成分含量を著しく抑制したハイ
グレードＰＥＴと同等の効果が得られる事も確認され
た。尚、ポリエステル容器において、樹脂中の環状三量
体の含有量が０．２５重量％未満、又０．７重量％を越
えるポリエステル樹脂を用いる事は現実的でないため、
実施例及び比較例の何れからも除外した。As a result, even in a polyester container in which the content of the cyclic trimer in the resin is as high as 0.70% by weight, the optimum heat-setting time is used to obtain the haze and gloss of the cyclic trimer which are appearance characteristics. It was confirmed that it is not inferior to a container with a low body content. Further, regarding the deposits on the mold, no cyclic trimer was confirmed, and it was also confirmed that it was effective in preventing stains on the mold. Further, as is clear from Examples and Comparative Examples 4 to 5, in the present invention, the polyester resin which has not been subjected to the reduced hydrothermal treatment is used, but the conventional hydrothermal treatment is applied to the cyclic trimer. It was also confirmed that an effect equivalent to that of high-grade PET in which the content of components was remarkably suppressed was obtained. In a polyester container, it is not realistic to use a polyester resin in which the content of the cyclic trimer in the resin is less than 0.25% by weight or more than 0.7% by weight.
It was excluded from both Examples and Comparative Examples.
【００４３】[0043]
【発明の効果】本発明のポリエステル容器によれば、環
状三量体含量低減化の熱水処理をしていないポリエステ
ル樹脂を原料として使用しているため、この環状三量体
を抑制するための熱水処理や固相重合等を行う必要がな
く、経済的に極めて有利である。また、本発明のポリエ
ステル容器によれば、容器表面に分布する環状三量体の
量と結晶化度を規定することにより、環状三量体の成形
金型表面への移行、即ち金型汚れが有効に防止され、金
型汚れに起因する表面光沢性や透明性の低下が有効に抑
制される
また、本発明のポリエステル容器の製造方法によれば、
環状三量体含量低減化の為の熱水処理をしていないポリ
エステル樹脂を使用していながら、延伸成形と同時に熱
固定を行ない、且つ熱固定時間を３．０秒以下に短縮す
ることにより、環状三量体成分の金型表面へ移行及び付
着による金型汚れが有効に抑制されており、従って、得
られるポリエステル容器は、表面平滑性の低下の問題は
なく、表面光沢度や透明性に極めて優れている。更に
は、金型汚れが有効に防止されていることから、金型の
洗浄等による工程を短縮できるという点でも、本発明は
極めて有利である。According to the polyester container of the present invention, the polyester resin which has not been subjected to the hydrothermal treatment for reducing the cyclic trimer content is used as a raw material. It is economically extremely advantageous because there is no need to perform hot water treatment or solid phase polymerization. Further, according to the polyester container of the present invention, by defining the amount and crystallinity of the cyclic trimer distributed on the container surface, migration of the cyclic trimer to the molding die surface, that is, mold stain Effectively prevented, the deterioration of the surface gloss and transparency due to mold stain is effectively suppressed Further, according to the method for producing a polyester container of the present invention,
By using a polyester resin that has not been subjected to hydrothermal treatment for reducing the cyclic trimer content, heat setting is performed simultaneously with stretch molding, and the heat setting time is shortened to 3.0 seconds or less. Mold contamination due to migration and adhesion of the cyclic trimer component to the mold surface is effectively suppressed. Therefore, the obtained polyester container has no problem of deterioration of surface smoothness, and surface gloss and transparency. Very good. Furthermore, the present invention is extremely advantageous in that the step of cleaning the mold can be shortened because the mold is effectively prevented from being soiled.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２９Ｌ 22:00 Ｃ０８Ｌ 67:00 Ｃ０８Ｌ 67:00 Ｂ６５Ｄ 1/00 Ａ Ｃ Ｆターム(参考） 3E033 AA01 BA18 CA07 FA03 4F071 AA43 AA46 AA89 AF30 AF32 AH05 BB05 BB07 BB13 BC04 4F208 AA24 AG07 AH55 AR06 AR08 AR11 LA05 LA08 LA09 LB01 LG03 LN01 LW07 LW15 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference) B29L 22:00 C08L 67:00 C08L 67:00 B65D 1/00 ACF term (reference) 3E033 AA01 BA18 CA07 FA03 4F071 AA43 AA46 AA89 AF30 AF32 AH05 BB05 BB07 BB13 BC04 4F208 AA24 AG07 AH55 AR06 AR08 AR11 LA05 LA08 LA09 LB01 LG03 LN01 LW07 LW15
Claims (5)
いないポリエステル樹脂から成る延伸成形により得られ
たポリエステル容器であって、クロロホルム抽出によっ
て測定される容器表面に分布する環状三量体量が４５０
ｎｇ／ｃｍ２以上であり、且つ密度法による結晶化度が
３０％以上であることを特徴とするポリエステル容器。1. A polyester container obtained by stretch molding of a polyester resin which has not been subjected to hydrothermal treatment for reducing the content of cyclic trimer, wherein the cyclic trimer distributed on the surface of the container is measured by chloroform extraction. Body weight is 450
A polyester container having a ng / cm 2 or more and a crystallinity by a density method of 30% or more.
０．２５乃至０．７重量％の範囲にある請求項１に記載
のポリエステル容器。2. The polyester container according to claim 1, wherein the content of cyclic trimer in the polyester resin is in the range of 0.25 to 0.7% by weight.
いないポリエステル樹脂を一次成形体に成形し、次いで
該一次成形体を延伸温度で延伸成形し、延伸成形後の容
器壁を熱固定した後に成形金型から取り出すことから成
るポリエステル容器の製造方法において、 前記熱固定時間を３．０秒以下に設定することを特徴と
するポリエステル容器の製造方法。3. A polyester resin which has not been subjected to hydrothermal treatment for reducing the content of cyclic trimer is molded into a primary molded body, and then the primary molded body is stretch-molded at a stretching temperature to form a container wall after stretch-molding. A method for producing a polyester container, which comprises taking out from a molding die after heat setting, wherein the heat setting time is set to 3.0 seconds or less.
量％のポリエステル樹脂を使用する請求項３に記載のポ
リエステル容器の製造方法。4. The method for producing a polyester container according to claim 3, wherein a polyester resin having a cyclic trimer content of 0.25 to 0.7% by weight is used.
一次成形体の延伸成形及び熱固定を行う請求項３に記載
のポリエステル容器の製造方法。5. The method for producing a polyester container according to claim 3, wherein the primary molding is stretch-molded and heat-set at a rate of 10 pieces / minute or more per molding die.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001349916A JP4069614B2 (en) | 2001-11-15 | 2001-11-15 | Polyester container manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001349916A JP4069614B2 (en) | 2001-11-15 | 2001-11-15 | Polyester container manufacturing method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007122171A Division JP4544264B2 (en) | 2007-05-07 | 2007-05-07 | Polyester container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003145615A true JP2003145615A (en) | 2003-05-20 |
| JP4069614B2 JP4069614B2 (en) | 2008-04-02 |
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ID=19162515
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001349916A Expired - Lifetime JP4069614B2 (en) | 2001-11-15 | 2001-11-15 | Polyester container manufacturing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005171081A (en) * | 2003-12-11 | 2005-06-30 | Toyo Seikan Kaisha Ltd | Polyester resin for compression molding, and preform and polyester container composed of the same |
-
2001
- 2001-11-15 JP JP2001349916A patent/JP4069614B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005171081A (en) * | 2003-12-11 | 2005-06-30 | Toyo Seikan Kaisha Ltd | Polyester resin for compression molding, and preform and polyester container composed of the same |
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| Publication number | Publication date |
|---|---|
| JP4069614B2 (en) | 2008-04-02 |
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