JPS5845229A - Preparation of polyester chip for blow molding - Google Patents
Preparation of polyester chip for blow moldingInfo
- Publication number
- JPS5845229A JPS5845229A JP14245881A JP14245881A JPS5845229A JP S5845229 A JPS5845229 A JP S5845229A JP 14245881 A JP14245881 A JP 14245881A JP 14245881 A JP14245881 A JP 14245881A JP S5845229 A JPS5845229 A JP S5845229A
- Authority
- JP
- Japan
- Prior art keywords
- phase polymerization
- solid
- chips
- temperature
- polyethylene terephthalate
- 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
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は中空成形用ポリエステルチップの製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing polyester chips for blow molding.
さらに詳しくは、本発明は透明性に優れ、ポリマ中に含
有しているアセトアルデヒドが少く、特に食品容器用途
に適した中空成形用ポリエステルチップの製造法に関す
る1、ポリエステル、特にポリエチレンテレフタレート
は優れた物理的性質、化学的性質を有している弧繊維、
フィルム、プラスチック成形分野などで広く使用されて
いる。More specifically, the present invention relates to a method for producing polyester chips for blow molding that have excellent transparency, contain little acetaldehyde, and are particularly suitable for food container applications.1. Polyester, especially polyethylene terephthalate, has excellent physical properties. Arc fibers with physical and chemical properties,
Widely used in film and plastic molding fields.
従来プラスチック中空成形品向は樹脂としては、主とし
てポリ塩化ビニルが用いられてきたが、近年衛生問題に
よシ特に食品向は中空成形容器の分野でその使用が制限
を受けるようになってきた。Conventionally, polyvinyl chloride has been mainly used as the resin for plastic blow-molded products, but in recent years its use has been restricted due to sanitary issues, particularly in the field of blow-molded containers for food products.
一方、ポリエチレンテレ7タレートは前述の通り優れた
諸%性を有しているにもかかわらず中空成形分野、特に
食品容器分野への進出が十分でなかった。この原因は、
主にポリマの溶融時の粘度が低いことおよび極めて結晶
化が速く、得られる製品が白化しやすいこと並びに製品
中にアセトアルデヒドが残存することにあった。これら
の問題のうち前二者に対しては成形技術の観点から各種
の改良がなされ一応ポリ塩化ビニルの代替としての機能
をもつようになったが、依然として、ポリエチレンテレ
フタレートには、アセトアルデヒドを含有するため充填
物の味や臭いが変化しやすいという欠点がある。このポ
リエチレンテレフタレート中のアセトアルデヒド全減少
せしめ、中空成形用として十分な溶融粘度が得られるよ
う重合度を上昇せしめる方法として、具体的には減圧あ
るいは不活性気体流通下190℃以上、融点以下の温度
で数時間乃至数十時間処理する、いわゆる同相重合法が
知られている。On the other hand, although polyethylene tere-7 tallate has excellent percent properties as mentioned above, it has not been sufficiently penetrated into the blow molding field, particularly in the food container field. The cause of this is
The main problems were that the viscosity of the polymer when melted was low, crystallization was extremely rapid, the resulting product was prone to whitening, and acetaldehyde remained in the product. Regarding the first two of these problems, various improvements have been made from the perspective of molding technology, and it has come to function as a substitute for polyvinyl chloride, but polyethylene terephthalate still contains acetaldehyde. Therefore, there is a drawback that the taste and odor of the filling are likely to change. As a method for completely reducing the acetaldehyde in this polyethylene terephthalate and increasing the degree of polymerization so as to obtain a sufficient melt viscosity for blow molding, specifically, the method is to increase the degree of polymerization at a temperature of 190°C or higher and below the melting point under reduced pressure or inert gas flow. A so-called in-phase polymerization method is known in which the treatment is carried out for several hours to several tens of hours.
このうちで高温不活性気流下で行なう同相重合法はチッ
プの処理が連続的に行なえるfcめ経済性、生産性に優
れている利点がある。Among these, the in-phase polymerization method, which is carried out under a high-temperature inert gas flow, has the advantage of being excellent in economical efficiency and productivity because it allows chips to be processed continuously.
しかしながら、尚温不活性気流下で行なう固相重合法は
、ポリエチレンテレフタレート中のアセトアルデヒド全
十分に減少せしめ重合度の上昇が十分に行なわれるよう
な条件下ではチップ間でのブロッキングや融着が起りや
すく、安定したチップの処理ができにくい欠点がある。However, in the solid phase polymerization method carried out under a still-temperature inert gas flow, blocking and fusion between chips may occur under conditions where all the acetaldehyde in polyethylene terephthalate is sufficiently reduced and the degree of polymerization is sufficiently increased. The drawback is that it is difficult to process chips easily and stably.
特に溶液へイス10チ以下の中空成形用ポリエチレンテ
レフタレートチップは通常のポリエチレンテレフタレー
トチップに比べ前記傾向が著しい。本発明者らは溶液ヘ
イズ10%以下のポリエチレンテレフタレートについて
、ポリマー中のアセトアルデヒドを減少せしめ、高品質
の中空成形品を効率よく製造することのできるチップに
変換する方法について鋭意検討した結果、効果の顕著な
本発明に到達した。In particular, polyethylene terephthalate chips for blow molding with a solution height of 10 inches or less exhibit this tendency more markedly than ordinary polyethylene terephthalate chips. The present inventors have conducted intensive studies on a method for converting polyethylene terephthalate with a solution haze of 10% or less into chips that can reduce acetaldehyde in the polymer and efficiently produce high-quality hollow molded products. We have arrived at the remarkable invention.
即ち、本発明は、溶液ヘイズが10%以下のポリエチレ
ンテレフタレートチップ全固相重合せしめるに際し、該
チップ會、同相重合温度より低いが該温度を20℃は下
まわらない温度範囲で結晶化度が少なくとも50%に達
するまで熱処理して後、不活性気流下に移動床式同相重
合装置内で連続的に同相重合せしめることを特徴とする
中空成形用ポリエステルチップの製造法全提供するもの
である。That is, in the present invention, when carrying out all-solid phase polymerization of polyethylene terephthalate chips having a solution haze of 10% or less, the crystallinity of the chips is at least within a temperature range lower than the same phase polymerization temperature but not lower than the same temperature by 20°C. The present invention provides a complete method for producing polyester chips for blow molding, which comprises heat-treating the polyester chips until they reach 50% and then subjecting them to continuous homopolymerization in a moving bed type homopolymerization apparatus under an inert gas flow.
本発明に用いられるポリエチレンテレフタレートとは、
エチレンテレフタレート単位が少くとも85モルチ、好
ましくFi90モル優以上のものでありテレフタル酸と
エチレングリコールとのエステル化反応後、またはテレ
フタル酸の低級アルキルエステルとエチレンクリコール
とのエステル交換反応援、得うれるビスジオールエステ
ルおよび/またはその低重合体を重合触媒、たとえば従
来公知のアンチモン化合物、ゲルマニウム化合物、チタ
ン化合物の一糧以上、の存在下に筒温、高真空下にて重
縮合せしめることによって得られるものでらって、テレ
フタル酸残基以外のジカルボン酸残基またはジオール残
基が少i7に存在してもよい。テレフタル酸残基以外の
ジカルボン酸残基としてはイソフタル酸、フタル酸、2
,6−ナフタリンジカルボン酸、トリメリット酸、ピロ
メリット酸、アジピン酸、5−ナトリウムスルホイソフ
タル酸などの残基がある。The polyethylene terephthalate used in the present invention is
The ethylene terephthalate units are at least 85 mol, preferably more than 90 mol Fi, and obtained after esterification reaction of terephthalic acid and ethylene glycol or transesterification reaction between lower alkyl ester of terephthalic acid and ethylene glycol. The bisdiol ester and/or its low polymer are polycondensed in the presence of a polymerization catalyst, such as one or more of conventionally known antimony compounds, germanium compounds, and titanium compounds, at a cylinder temperature under high vacuum. A small amount of dicarboxylic acid residue or diol residue other than terephthalic acid residue may be present in i7. Dicarboxylic acid residues other than terephthalic acid residues include isophthalic acid, phthalic acid, 2
, 6-naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid, adipic acid, and 5-sodium sulfoisophthalic acid.
5−
またジオール成分としてはエチレングリコ−羨が主体で
あるが他のグリコールを少量併用してもよい。この例と
しては、プロピレングリコール、トリメチレングリコー
ル、テトラメチレンクリコール、ネオペンチルグリコー
ル、シクロヘキサンジメタツール、ジエチレングリコー
ルなどが挙げられる。5-Although the diol component is mainly ethylene glycol, small amounts of other glycols may be used in combination. Examples include propylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, cyclohexane dimetatool, diethylene glycol, and the like.
一方、ポリエステル中空成形品に優れた透明性を付与す
るためには浴融重縮合時に用いられる各種エステル交換
触媒、エステル化触媒、重縮合触媒、リン系着色防止剤
等の触媒残渣に起因して生成するいわゆる内部粒子を含
まないか含んでも微細で極少量のものが好ましい。On the other hand, in order to impart excellent transparency to polyester blow molded products, it is necessary to reduce Preferably, it does not contain so-called internal particles, or even if it does contain them, they are fine and in very small quantities.
かかる観点から本発明方法に供するポリエチレンテレフ
タレートは溶液ヘイズが10%以下、好ましくは5%以
下、であることを要する〇
本発明において溶液ヘイズ扛、ポリエチレンテレフタレ
ー)4.5fk四塩化エタン/フエノールのVrs混合
溶媒30CC6−
に加え102℃で1時間攪拌、溶解後冷却し該溶液を石
英ガラス製厚み20mのセルに採取し、積分球式HTR
メーター5EP−H−2型(日本精密光学製)によりヘ
イズ値を測定し、−で表わしたものでおる。From this point of view, the polyethylene terephthalate used in the method of the present invention must have a solution haze of 10% or less, preferably 5% or less. Added to Vrs mixed solvent 30CC6-, stirred at 102℃ for 1 hour, cooled after dissolving, collected the solution into a 20m thick cell made of quartz glass, and transferred to an integrating sphere type HTR.
The haze value was measured using a meter 5EP-H-2 (manufactured by Nippon Seimitsu Kogaku) and is expressed as -.
本発明方法に供するf6液ヘイズ10%以下のポリエチ
レンテレフタレートは極度粘度が0.5以上0.72以
下、特に0.53以上0.68Ji下のものが好ましく
用いられる。The polyethylene terephthalate having an F6 liquid haze of 10% or less to be used in the method of the present invention preferably has an extreme viscosity of 0.5 or more and 0.72 or less, particularly 0.53 or more and 0.68Ji or less.
このような要件を満足するポリエチレンテレ7タレート
ブレボリマーテツプカζ同相重合に先だって、固相重合
温度以下でかつ該温度t−20℃、好ましくFi15℃
以上下まわらない温度範囲で少なくとも50%の結晶化
度が得られるよう熱処理される。熱処理雰囲気は、空気
中、不活性ガス中、高真空下のいずれも適用できる。ま
たチップの攪拌の有無は特に限定されない。熱処理温度
が本発明で規定する下限値以下になると、たとえ熱処理
で結晶化度が50%以上になっても次の移動床式連続固
相重合装置内でチップ同志のブロッキングが起こ9、安
定した排出d4可能となる。また結晶化度が50−未満
の場合は該同相重合装置内で激しい融着を起こす。Prior to homopolymerization of polyethylene tere-7-talate brevolimer ζ that satisfies these requirements, the temperature is below the solid phase polymerization temperature and the temperature is t-20°C, preferably Fi15°C.
Heat treatment is performed to obtain a crystallinity of at least 50% within a temperature range not exceeding 50%. The heat treatment atmosphere may be air, inert gas, or under high vacuum. Moreover, whether or not the chips are stirred is not particularly limited. When the heat treatment temperature falls below the lower limit specified in the present invention, even if the degree of crystallinity becomes 50% or more through heat treatment, blocking of the chips with each other occurs in the next moving bed continuous solid phase polymerization apparatus9, resulting in stability. Ejection d4 becomes possible. If the crystallinity is less than 50, severe fusion occurs in the same phase polymerization apparatus.
また、固相重合温度鉱通常190C以上である力ζチッ
プ中のアセトアルデヒド含量を効率よく低下させるため
に該温度を高めに設定することが好まし込。Further, in order to efficiently reduce the acetaldehyde content in the solid phase polymerization temperature, which is usually 190C or higher, in the chip, it is preferable to set the temperature at a high temperature.
本発明でいうポリエチレンテレフタレートの結晶化度は
密度より求めたものである。密度の測定は密度勾配管法
にょ夛求めたものであシ、軽液として舊−ベブタン、重
液として四塩化炭素を連続的に混合し用いた。密度より
結晶化度を求めるには下式を用いる。。The crystallinity of polyethylene terephthalate as used in the present invention is determined from the density. The density was determined using a density gradient tube method, using a continuous mixture of bebutane as a light liquid and carbon tetrachloride as a heavy liquid. The following formula is used to determine the degree of crystallinity from the density. .
ただし、Pは試料の密度、 p、は非晶部の密度1.3
35(t/cd)pcは結晶部の密度1.+55(r/
j)前述の通り、溶液ヘイズが105GJ%下のポリエ
チレンテレフタレートチップを固相重合する前に、同相
重合温度以下でかつ該温度を20℃下まわらない温度範
囲で少なくとも50チの結晶化度が得られる保熱処理を
行ない、しかる後不活性気流化に移動床式固相重合装置
内で固相重合せしめることにより、効率的な固相重合が
実施でき、中空成形用に著効を示すチップが得られるの
である。However, P is the density of the sample, p is the density of the amorphous part 1.3
35 (t/cd) pc is the density of the crystal part 1. +55(r/
j) As mentioned above, before solid-phase polymerizing polyethylene terephthalate chips with a solution haze of 105 GJ%, a crystallinity of at least 50 GJ is obtained within a temperature range below the in-phase polymerization temperature and not less than 20 °C below said temperature. By carrying out heat retention treatment, followed by solid phase polymerization in a moving bed type solid phase polymerization apparatus under inert gas flow, efficient solid phase polymerization can be carried out, and chips that are highly effective for blow molding can be obtained. It will be done.
本発明方法に供するポリエチレンテレフタレートプレポ
リマーは通常50〜300ppmのアセトアルデヒドを
含有しているが、本発明方法に供することにより、極限
粘度i0.05以上上昇させ、アセトアルデヒド含有蓋
f3ppm未満に減少させることができ、味覚変化が少
なく、透明性等のF4t?!I注にすぐれた尚品質の中
空成形品を得ることかり能となる。The polyethylene terephthalate prepolymer used in the method of the present invention usually contains 50 to 300 ppm of acetaldehyde, but by subjecting it to the method of the present invention, it is possible to increase the intrinsic viscosity i by 0.05 or more and reduce the acetaldehyde content to less than 3 ppm. F4t? ! It is possible to obtain a hollow molded product with excellent quality.
尚このようにして得られたチップを用いる中空成形は、
射出成形、押出成形等の従来絢知の溶融成形技術に従が
って行なわれうる。In addition, the blow molding using the chips obtained in this way is as follows:
It can be carried out according to conventional melt molding techniques such as injection molding and extrusion molding.
9−
以下実施例1挙げ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。9- The present invention will be specifically explained below with reference to Example 1, but the present invention is not limited to these Examples.
実施例において、ポリエチレンテレフタレート中のアセ
トアルデヒド含量は液体窒素中でポリエチレンテレフタ
レート全微粉砕して、この粉末を島津製作所製、4CM
型ガスクロマトグラフィーによシ165℃に加熱し標準
に対する生成ピークを比べて遊離し友アセトアルデヒド
′Mを求めることにより測定した。また、極限粘度はO
−クロロフェノール溶媒を用い25℃で測定した。成形
品の透明性は厚み3閤の射出角板についてASTM−D
−1003−59TK準じてヘイズ會測定した。In the examples, the acetaldehyde content in polyethylene terephthalate was determined by pulverizing the entire polyethylene terephthalate in liquid nitrogen and converting this powder into 4CM manufactured by Shimadzu Corporation.
The mixture was heated to 165° C. by gas chromatography, and the produced peak was compared with that of a standard to determine the amount of free acetaldehyde M. Also, the intrinsic viscosity is O
- Measured at 25°C using chlorophenol solvent. The transparency of the molded product is ASTM-D for an injection square plate with a thickness of 3 mm.
The haze was measured according to -1003-59TK.
実施例
テレフタル酸ジメチル150重量部、エチレングリコー
ル92重蓋部、酢酸マグネシウム0.135重譬部全混
合し窒素気流下において145〜225℃でメタノール
を留出しなからエ10−
ステル交換反応を行なった。引きつづき反応物を重縮合
反応器に移しメチルアンドホスフェ−)0.0451i
i部、重合触媒として二酸化ゲルマニウム0.03重量
部を加えて系内を徐々に減圧昇温し最終的に285℃、
0.21Hfで2時間50分重縮合金行ない極限粘度0
.55、溶液ヘイズ0.9チ、含有アセトアルデヒドl
l 8ppmの平均長さ3■、長径3.0■、短径2
.0閣の円柱状ポリエチレンテレフタレートチップを得
た。Example: 150 parts by weight of dimethyl terephthalate, 92 parts by weight of ethylene glycol, and 0.135 parts by weight of magnesium acetate were mixed together and methanol was distilled off at 145 to 225°C under a nitrogen stream, followed by an ester exchange reaction. Ta. Subsequently, the reactants were transferred to a polycondensation reactor and 0.0451i of methyl and phosphate was added.
Part i, 0.03 parts by weight of germanium dioxide as a polymerization catalyst was added, and the system was gradually heated to 285°C under reduced pressure.
Polycondensation alloy was processed at 0.21Hf for 2 hours and 50 minutes, and the intrinsic viscosity was 0.
.. 55, Solution haze 0.9, Contains acetaldehyde 1
l 8ppm average length 3■, major axis 3.0■, minor axis 2
.. A cylindrical polyethylene terephthalate chip of zero size was obtained.
該チップは150℃の熱風下で1時間処理された後、1
95℃窒素気流下で2.5時間処理され結晶化度52%
のチップを得た。The chips were treated under hot air at 150°C for 1 hour, and then
Processed for 2.5 hours at 95°C under nitrogen flow, crystallinity 52%
got a tip.
引きつづき該結晶化チップは、はとんど冷却されること
なく、加熱窒素が下部よシ吹き込まれ上部に排出されチ
ップは上部から連続的に供給され下部よシ排出される構
造AT!−する移動床式連続同相重合基において205
℃で20時間の滞留時間をも′:)様処理したが塔内で
のポリマ融着、ブロッキングは全く認められなかった。Subsequently, the crystallized chips are not cooled at all, and heated nitrogen is blown from the bottom and discharged to the top, and the chips are continuously supplied from the top and discharged from the bottom. Structure AT! -205 in a moving bed continuous homopolymerizable group
Even though the treatment was carried out for a residence time of 20 hours at .degree. C., no polymer fusion or blocking was observed in the column.
得られたポリマは極限粘度0.80、含1アセトアルデ
ヒド1pptyhでう飢該チップを用いた射出角板のヘ
イズは1.5sで透明性に優れたものであった。The obtained polymer had an intrinsic viscosity of 0.80, contained 1 pptyh of 1-acetaldehyde, had a haze of 1.5 s, and was excellent in transparency.
実験例
各種ポリマについて実施例と同様の方法で熱処理条件を
変東したポリマの特注を表−1に示す。Experimental Examples Table 1 shows custom-made polymers in which the heat treatment conditions were changed in the same manner as in the examples for various polymers.
実験JfI&1 、4 、5I/′i本発明の範囲によ
るもので移動床式連続固相重合塔内での融着を起こすこ
となく固相重合後のチップ中に含有されるアセトアルデ
ヒドもlp声以下と良好で射出成形板の透明性も優れて
いることがわかった。Experiments JfI & 1, 4, 5I/'i According to the scope of the present invention, acetaldehyde contained in chips after solid-phase polymerization was reduced to less than LP without causing fusion in a moving-bed continuous solid-phase polymerization tower. It was found that the transparency of the injection molded plate was also excellent.
実験A2は熱処理温度が本発明の範囲1越えるもので、
実験43は結晶化度が十分上昇しないものである。いず
れも固相重合塔内で激しい融着を起こした。In Experiment A2, the heat treatment temperature exceeded the range of the present invention by 1.
In Experiment 43, the degree of crystallinity did not increase sufficiently. In both cases, severe fusion occurred within the solid phase polymerization tower.
実験A7tj:ポリマの溶液ヘイズ、熱処理条件、結晶
化度が本発明の範囲を越えるものであシボリマの溶液へ
イズが高ければ熱処理条件が不十分でも塔内融Nを起こ
さないが、射出成形品の透明性に劣ることがわかる。Experiment A7tj: The solution haze, heat treatment conditions, and crystallinity of the polymer are beyond the scope of the present invention.If the solution haze of the shiborima is high, even if the heat treatment conditions are insufficient, in-column melting N will not occur, but injection molded products It can be seen that the transparency is inferior.
実験A6も同様、射出成形品の透明性に劣ることがわか
る。Similarly, in Experiment A6, it can be seen that the injection molded product was inferior in transparency.
13−13-
Claims (1)
チップを固相重合せしめるに際し、該チップを、同相重
合温度より低いが該卑度會20℃は下まわらない温度範
囲で結晶化度が少なくとも5otsに達するまで熱処理
して後、不活性気流下に移動床式固相重合装置内で連続
的に固相重合せしめることを特徴とする中空成形用ポリ
エステルテップの製造法。When solid-phase polymerizing polyethylene terephthalate chips with a liquid haze of 10% or less, the chips are subjected to solid phase polymerization at a temperature lower than the homopolymerization temperature but not lower than the base temperature of 20°C until the degree of crystallinity reaches at least 5 ots. A method for producing a polyester tep for blow molding, which comprises heat-treating and then continuously solid-phase polymerizing it in a moving bed type solid-phase polymerization apparatus under an inert air flow.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14245881A JPS5845229A (en) | 1981-09-11 | 1981-09-11 | Preparation of polyester chip for blow molding |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14245881A JPS5845229A (en) | 1981-09-11 | 1981-09-11 | Preparation of polyester chip for blow molding |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5845229A true JPS5845229A (en) | 1983-03-16 |
Family
ID=15315779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14245881A Pending JPS5845229A (en) | 1981-09-11 | 1981-09-11 | Preparation of polyester chip for blow molding |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5845229A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58176212A (en) * | 1982-04-09 | 1983-10-15 | Teijin Ltd | Polyester for molding and its production |
JPS63137822A (en) * | 1986-11-29 | 1988-06-09 | Kureha Chem Ind Co Ltd | Extrusion molding method for polyphenylene sulfide |
JPH0230512A (en) * | 1988-07-21 | 1990-01-31 | Ueno Hiroshi | Thermally fixed oriented polyester hollow vessel and its manufacture |
JP2006150957A (en) * | 2004-11-05 | 2006-06-15 | Toyobo Co Ltd | Manufacturing method for polyester preform and manufacturing method for polyester stretch-molded object |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54149792A (en) * | 1978-05-12 | 1979-11-24 | Bepex Corp | Solid phase polymerization method of polyethylene terephthalate |
-
1981
- 1981-09-11 JP JP14245881A patent/JPS5845229A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54149792A (en) * | 1978-05-12 | 1979-11-24 | Bepex Corp | Solid phase polymerization method of polyethylene terephthalate |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58176212A (en) * | 1982-04-09 | 1983-10-15 | Teijin Ltd | Polyester for molding and its production |
JPS63137822A (en) * | 1986-11-29 | 1988-06-09 | Kureha Chem Ind Co Ltd | Extrusion molding method for polyphenylene sulfide |
JPH0230512A (en) * | 1988-07-21 | 1990-01-31 | Ueno Hiroshi | Thermally fixed oriented polyester hollow vessel and its manufacture |
JP2006150957A (en) * | 2004-11-05 | 2006-06-15 | Toyobo Co Ltd | Manufacturing method for polyester preform and manufacturing method for polyester stretch-molded object |
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