JP3740968B2 - Method for producing biaxially stretched polyester container with whitening prevention at the bottom - Google Patents

Method for producing biaxially stretched polyester container with whitening prevention at the bottom Download PDF

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Publication number
JP3740968B2
JP3740968B2 JP2000270906A JP2000270906A JP3740968B2 JP 3740968 B2 JP3740968 B2 JP 3740968B2 JP 2000270906 A JP2000270906 A JP 2000270906A JP 2000270906 A JP2000270906 A JP 2000270906A JP 3740968 B2 JP3740968 B2 JP 3740968B2
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Prior art keywords
preform
gate
mold
injection
polyester
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JP2002079570A (en
Inventor
林  哲也
清市 浜田
周二 船橋
武史 中川
憲司 飯田
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Toyo Seikan Kaisha Ltd
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Toyo Seikan Kaisha Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/22Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/24Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/26Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/20Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
    • B29C2949/28Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3008Preforms or parisons made of several components at neck portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3012Preforms or parisons made of several components at flange portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3016Preforms or parisons made of several components at body portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/302Preforms or parisons made of several components at bottom portion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3024Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3024Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
    • B29C2949/3026Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3024Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
    • B29C2949/3026Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components
    • B29C2949/3028Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components having three or more components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3032Preforms or parisons made of several components having components being injected
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3032Preforms or parisons made of several components having components being injected
    • B29C2949/3034Preforms or parisons made of several components having components being injected having two or more components being injected
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3032Preforms or parisons made of several components having components being injected
    • B29C2949/3034Preforms or parisons made of several components having components being injected having two or more components being injected
    • B29C2949/3036Preforms or parisons made of several components having components being injected having two or more components being injected having three or more components being injected

Description

【0001】
【発明の属する技術分野】
本発明は、底部白化の防止された二軸延伸ポリエステル容器の製法に関するもので、より詳細には底部における白化や白筋の発生が防止され、外観特性に優れ、秀でた商品価値を有する二軸延伸ポリエステル容器の製法に関する。
【0002】
【従来の技術】
延伸ブロー成形容器、特にポリエステル容器は今日では一般化しており、その優れた透明性と適度なガスバリヤー性とにより、液体洗剤、シャンプー、化粧品、醤油、ソース等の液体商品の他に、ビール、コーラ、サイダー等の炭酸飲料や、果汁、ミネラルウオーター等の他の飲料容器に広く使用されている。
【0003】
ポリエステル容器の成形に際しては、ポリエステルの射出成形により、最終容器より寸法のかなり小さい且つポリエステルが非晶質である有底プリフォームをその延伸温度においてブロー金型中で軸方向に引張延伸すると共に、周方向にブロー延伸する方法が採用されている
【0004】
この有底プリフォームの形状としては、ボトルの口頚部、例えば密封用開口端、蓋係合用ネジ及び支持リング等からなる口頚部を有し且つ全体としての形状が試験管状のものが一般的である。
【0005】
ポリエチレンテレフタレートはそのガラス転移点乃至融点直下の温度範囲、一般に120乃至150℃の温度で結晶化し、球晶生成により白化する傾向を示す。ポリエステルのプリフォームへの射出成形は、金型を冷却して上記結晶化温度の通過時間を短くしポリエステルの結晶化を抑制することが行われているが、底部中心から溶融樹脂の射出を行うことから、底部が上記温度領域での経時が最も長く、従ってプリフォーム底部の中心(ゲート部)が若干白化するのを避け得ない。
【0006】
このように底部に若干の白濁のあるプリフォームを延伸ブロー成形して得られた容器の底部に若干の白濁は避けられず、容器の外観特性から必ずしも十分に満足し得るものではないと共に、びん詰め製品の購入者に、内容物のオリ状沈殿が生成し、内容物の変質が生じているのではないかという危惧を抱かせる等、商品価値を低下させる問題がある。
【0007】
プリフォーム底部の白化傾向を防止することも既に知られており、特公平5−21055号公報には、エチレンテレフタレート単位を主体とするポリエステルを側壁部が実質上非晶質の有底プリフォームに射出成形する工程と、該有底プリフォームをポリエステルの延伸温度域において二軸延伸ブロー成形する工程とからなる二軸延伸ポリエステル容器の製法において、有底プリフォーム射出金型として、底部キャビティに向けて径の増大するテーパー形状を有し、ランド長(l)が5乃至30mm及びテーパー部の傾斜角度(θ)が2乃至8度の範囲にあるゲート部を備え、ゲート部出口の径(D)と底部最大内径(D)との比(D/D)が0.10乃至0.50の範囲内にあり、底部対応キャビティ金型の曲率半径(R)が4乃至8mm及びゲート出口部分におけるキャビティ金型の曲率半径(R)が0.3乃至2.0mmの範囲内にあり、且つ最大高さ粗さ(Rmax、JISB−0601)が0.8μm以下となるように表面仕上げされた射出金型を使用して、ポリエステルの有底プリフォームへの射出成形を行うことを特徴とする底部白化の防止された二軸延伸ポリエステル容器の製法が記載されている。
【0008】
【発明が解決しようとする課題】
上記提案は、プリフォーム射出金型のゲート部の形状及び寸法を特定の範囲のものとすることにより、プリフォーム底部の白化を防止するものであるが、バルブステム付のノズルチップを用いたプリフォームの射出成形では、依然としてプリフォーム底部中心(ゲート)の白化を生じることが認められる。
【0009】
バルブステムは金型ゲート部の開閉とプリフォームゲートの切断とを行うものであり、金型ゲート部で閉じていたバルブステムがエアシリンダーにより後退し、開くと同時に射出ピストンが前進してポリエステル樹脂を金型内に射出し、射出の終期に再び閉じてプリフォームゲートの切断を行うものである。
【0010】
本発明者の研究によると、バルブステム付ノズルチップを用いた射出成形でプリフォームゲートの白化が生じる原因は、閉じた状態で金型ゲート部と接触するバルブステムが、開いた状態でノズルチップ内の溶融ポリエステル樹脂と接触して樹脂の冷却乃至徐冷が進行し、樹脂の結晶化温度領域を通過するため、結晶化が進行するためと判明した。この結晶化部分がゲート周囲のキャビティ面及びコア面に付着したものが底部の白化部であり、樹脂と共に流れたものが白筋であることも判明した。
【0011】
従って、本発明の目的は、ポリエステルを側壁部が実質上非晶質の有底プリフォームに射出成形する工程と、該有底プリフォームをポリエステルの延伸温度域で二軸延伸ブロー成形する工程とから成り、射出機としてバルブステム付ノズルチップを備えたものを用いる二軸延伸ポリエステル容器の製法において、底部白化や白筋の発生が防止された方法を提供するにある。
【0012】
【課題を解決するための手段】
本発明によれば、バルブステムを往復動可動に備えたノズルチップ付きの射出機を用いて、ポリエステルを側壁部が実質上非晶質の有底プリフォームに射出成形する工程と、該有底プリフォームをポリエステルの延伸温度域で二軸延伸ブロー成形する工程とからなる二軸延伸ポリエステル容器の製法において、射出成形する工程における有底プリフォーム射出金型として前記バルブステムと嵌合しうるストレートな円筒部と該円筒部に接続されたキャビテイに向けて径が増大するテーパー部とからなるゲート部を備え、かつプリフォームゲート切断時の円筒部の径(D)とゲート部のランド長(L)との比(D/L)が0.3乃至0.8であるものを用いることを特徴とする底部白化の防止された二軸延伸ポリエステル容器の製法が提供される。さらに、本発明においては、前記テーパー部の傾斜角度が1乃至5度の範囲にあることが好ましい。
【0013】
【発明の実施の形態】
[作用]
本発明では、従来の方法と同様に、ポリエステルを側壁部が実質上非晶質の有底プリフォームに射出成形する工程と、該有底プリフォームをポリエステルの延伸温度域で二軸延伸ブロー成形する工程とによって、二軸延伸ポリエステル容器を製造するが、最終容器における底部の白化を有底プリフォームの射出成形段階で防止するものである。
【0014】
また、プリフォーム形成用の射出機としては、バルブステム付ノズルチップを備えたものを用いるが、これに関連して、有底プリフォーム射出金型としてストレートな円筒部と該円筒部に接続されたキャビティに向けて径が増大するテーパー部とから成るゲート部を備えたものを用い、また、射出機として、前記円筒部に嵌合しうるバルブステムを往復動可能に備えたノズルチップ付きのものを用いる。
【0015】
金型ゲート部の円筒部とバルブステムとを嵌合させることは、プリフォームゲートを切断するために必須不可欠であるが、同時にこの嵌合はバルブステムを冷却し、バルブステムによる樹脂の冷却乃至徐冷と、それに基づく樹脂結晶化の原因となる。
【0016】
本発明によれば、プリフォームのゲート部の形状を細く長くすること、即ち、プリフォームゲート切断時の円筒部の径(D)とゲート部のランド長(L)との比(D/L)を0.3乃至0.8の値にすることにより、白化や白筋の原因となるバルブステムの冷却を防止し、徐冷結晶をなくすとともに、ゲート部で白化を吸収させることで、プリフォーム底部における白化や白筋の発生を有効に防止することができる。
さらに、前記テーパー部の傾斜角度が1乃至5度の範囲にすることで、より効果的に白化や白筋の発生が防止できる。
【0017】
即ち、円筒部の径(D)とゲート部のランド長(L)との比(D/L)が上記範囲を外れると、金型やバルブステムの影響により樹脂の冷却乃至徐冷が起こり、ゲート部内で白化を吸収することができず、プリフォームの底部まで白化や白筋が発生する傾向が大きくなる。
【0018】
本発明によれば、以上のように、円筒部の径とゲート部のランド長との比を一定の範囲に設定するという簡単な手段で、プリフォーム底部における白化や白筋の発生を有効に防止し、二軸延伸ブロー成型容器の外観特性を向上させ、商品価値を高めることができる。
【0019】
[射出成形装置]
本発明に用いる射出成形装置の概略構造を示す図1において、この射出金型は、キャビティ金型10とゲート金型20とを備えている。キャビティ金型10はプリフォーム胴部の外面を規定するキャビティ面11を有している。ゲート金型20はプリフォーム底部の外面を規定する底部形成用面21を有すると共に、その中心にゲート部22を有している。
図示していないが、キャビティ金型10及びゲート金型20には、その内部にこれと同軸に、コア金型が挿入されており、このコア金型(図示せず)、キャビティ金型10及びゲート金型20で規定されるキャビティ内にポリエステル樹脂が射出されてプリフォームの成形が行われる。
【0020】
一方、射出機(図示せず)の先端に取り付けられたノズルチップ30は、先端31が細められた中空円筒状であり、その軸心には中実円筒状のバルブステム32が往復動可能に設けられている。ノズルチップ30の内面とバルブステム32の外面との間には、樹脂を流動させるための樹脂通路33が形成されているが、バルブステム32が前進した状態では、ノズルチップ先端31とバルブステム32の外面とが液密状態で接触して、樹脂通路33の閉鎖が行われ、バルブステム32が後退してた状態では、樹脂通路が開放されるようになっている。
【0021】
ノズルチップ30には、樹脂通路33内の樹脂を保温するために、その外周にバンドヒーター34が設けられており、また、テーパー状の先端部31の外面には、ノズルチップ先端部31の冷却を防止するための断熱材層35が設けられている。
【0022】
ゲート金型20の底部形成用面21の反対側には、ノズルチップ30を受けるための凹部23が形成されており、バルブステム32とゲート部22とは嵌合し、ノズルチップ先端部31と凹部23とは断熱材層35を介して接触可能となっている。
【0023】
ゲート金型20及びバルブステム32の形状及び寸法を説明するための図2において、ゲート部22は、ストレートな円筒部23とこの円筒部に接続されたキャビティに向けて径が増大するテーパー部24とを備えている。また、テーパー部24の出口側は曲率部25(曲率半径:R)を介して、底部成形用面21に接触されている。
【0024】
図2に示すように、ゲート部の円筒部23は径Dと軸方向寸法Lとを有しており、一方テーパー部24は傾斜角度θと軸方向寸法Lとを有している。なお、テーパー部24の軸方向寸法とは円筒部23への付け根から、ゲート金型の底部形成用面21を含む仮想曲面までの距離を意味する。
一方、円筒部の径はD、ゲート部のランド長はLで与えられ、本発明では、D/Lを前述した0.3乃至0.8の範囲に設定するものである。
【0025】
プリフォームの射出成形の際しては、射出機(図示せず)内に溶融ポリエステルが貯留されている。射出開始に際して、バルブステム32が、エアシリンダー(図示せず)等の駆動により、図1に示す前進位置から後退し(図1において右方向に移動し)、ノズルチップ先端31が開く。
これと同時に、射出機内の射出ピストン(図示せず)が前進し(図1において右方向に移動し)、射出機内の溶融樹脂をノズルチップの樹脂通路33,ゲート部22を通して、射出型10、20内のキャビティ内に射出する。
射出成形の終了時に、バルブステム32は前進し、プリフォームゲートを切断すると共に、ノズルチップ30の先端部31を閉鎖する。
キャビティ金型10及びゲート金型20は、コア金型と共に強制水冷されており、射出溶融樹脂は非晶質状態に過冷却され、プリフォームの成形が行われる。
【0026】
本発明の方法で成形されるプリフォームの一例を示す図3において、プリフォーム40は、非晶質状態の熱可塑性ポリエステルで一体に成形されており、胴部41,閉塞底部42及び口部43を備えており、口部の外周には、支持リング44及び蓋締結用のネジ45が設けられている。
【0027】
このプリフォームにおける底部白化を防止するためには、底部を構成するポリエステルが熱結晶化温度領域を可及的に短時間で通過するようにすることが重要であり、金型ゲート部の形状を細く長くすることが、ゲート金型のゲート部からキャビティ内への樹脂の流入が容易に且つ速やかに行われ、溶融樹脂がゲート部で冷却の影響を受けないようにすることがやはり底部白化の防止に有効である。
【0028】
この目的のために、バルブステムの嵌合量は0.2乃至0.9mmの範囲内にあるのが好都合である。
また、ゲート部出口における曲率半径Rは0.5乃至2mmの範囲内にあるのがよい。
さらに、ゲート部円筒部23の長さLは、最短でバルブステムの嵌合量であるが、この嵌合量よりも長く設定して、バルブステムの嵌合量を調節自在としておくことが好ましい。
というのは、プリフォームゲートの切断性には、樹脂の種類や、射出条件によって違いがあるが、上記のゲート部円筒部の長さの設定では、ゲートの切断が確実に行われるからである。
【0029】
[ポリエステル樹脂]
本発明において、ポリエステル樹脂としては、延伸ブロー成形可能な熱可塑性ポリエステル、特にエチレンテレフタレート系熱可塑性ポリエステルが有利に使用されるが、勿論、ポリブチレンテレフタレート、ポリエチレンナフタレートなどの他のポリエステル、或いはポリカーボネートや;ポリアリレート樹脂等とのブレンド物を用いることもできる。
また、容器の材料構成は、主たる材料がポリエステルである範囲内で単層でもよく、2層以上の多層構成であってもよい。
本発明に用いるエチレンテレフタレート系熱可塑性ポリエステルは、エステル反復単位の大部分、一般に70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であり、ガラス転移点(Tg)が50乃至90℃、特に55乃至80℃で、融点(Tm)が200乃至275℃、特に220乃至270℃にある熱可塑性ポリエステルが好適である。
【0030】
ホモポリエチレンテレフタレートが耐圧性、耐熱性、耐熱圧性の点で好適であるが、エチレンテレフタレート単位以外のエステル単位の少量を含む共重合ポリエステルも使用し得る。
【0031】
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;の1種又は2種以上の組合せが挙げられ、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。
【0032】
また、エチレンテレフタレート系熱可塑性ポリエステルにガラス転移点の比較的高い、例えばポリエチレンナフタレート、ポリカーボネート或いはポリアリレート等を5%〜25%程度をブレンドした複合材を用いることができ、それにより比較的高温時の材料強度を高めることができる。
さらに、ポリエチレンテレフタレートと上記のガラス転移点の比較的高い材料とを積層化して用いることもできる。
【0033】
用いるエチレンテレフタレート系熱可塑性ポリエステルは、少なくともフィルムを形成するに足る分子量を有するべきであり、用途に応じて、射出グレード或いは押出グレードのものが使用される。その固有粘度(I.V.)は一般的に0.6乃至1.4dL/g、特に0.63乃至1.3dL/gの範囲にあるものが望ましい。
【0034】
また、本発明による容器では、上述したエチレンテレフタレート系ポリエステルを内外層とし、これを中間層として、リサイクルポリエステル層や、ガスバリアー性樹脂層、酸素吸収性樹脂層などを介在させることができる。
リサイクルポリエステル層としては、使用済みPETボトルとして回収されるポリエステル破砕品を必要により洗浄し再生したものなどが使用される。
ガスバリアー性樹脂としては、エチレンビニルアルコール共重合体、特にエチレン含有量が20乃至60モル%のエチレンビニルアルコール共重合体や、ポリアミド樹脂、特にナイロン6、ナイロン6,6、ポリキシレンアジパミド(MXD6)などが使用される。
酸素吸収剤層としては、公知の酸素吸収性樹脂組成物はいずれも使用されるが、代表的なものとして、ポリアミド樹脂、特にMXD6に遷移金属触媒、特にコバルトのカルボン酸塩を配合したものなどが使用される。
【0035】
[プリフォームの製造]
プリフォームの製造は、前述したノズルチップを備えた射出機及びゲート金型を用いる点及び底部白化を防止できる条件を用いる点を除けば、それ自体公知の条件で行うことができる。
【0036】
射出金型としては、熱伝導率が大きく、表面粗度の小さい金型を用いることが底部白化を防止する点で好ましい。
このため、金型としては銅−ベリリウム合金を用いることが好ましく、金型表面の最大高さ粗さ(Rmax、JIS B−0601)が3.2μm以下、特に0.8μm以下に表面仕上げされたものを用いるのが好ましい。
【0037】
また、射出温度及び射出圧力にも、底部白化を防止するための一定条件がある。即ち、射出する樹脂温度が高い場合には、樹脂の冷却に長い時間が必要となり、結晶化温度領域を通過する時間も長くなる。一方、樹脂温度を低くすると、成形時にシェアが増大して成形状のトラブルが発生する。
このため、射出成形温度は280乃至320℃、特に290乃至310℃の範囲が好適である。
一方、射出圧力は、60乃至130kg/cm程度が好ましい。
【0038】
また、射出金型の温度を低くすると、結晶化温度域を通過する時間を短くできるので、ゲート金型(底金型)の温度を可及的に低くすることが望ましい。一方、この温度が低すぎると、前記と同様にシェアの増大の問題が生じるので、ゲート金型(底金型)の温度を10乃至20℃に維持するのが好ましい。
【0039】
[二軸延伸ブロー成形容器の製造]
上記の方法で得られるプリフォームを延伸温度に加熱し、加熱されたプリフォームを軸方向に引っ張り延伸すると共に、圧力流体の吹き込みにより周方向にブロー延伸して、二軸延伸されたブロー成形容器とする。
この延伸ブロー成形は、一段で行ってもよく、また二段ブローと呼ばれる二段で行ってもよい。さらに、二軸延伸ブロー成形を行った容器を公知の手段で熱固定してもよい。更にまた、二段ブロー成形法では、1次ブローと2次ブローとの間に熱処理工程を設けてもよい。
【0040】
延伸ブロー成形に先立って、プリフォームを、熱風、赤外線ヒーター、高周波誘導加熱等の手段で延伸適性温度まで予備加熱する。その温度範囲は、85乃至120℃、特に95乃至110℃の範囲にあるのがよい。
【0041】
最終容器における延伸倍率は、面積倍率で4乃至10倍が適当であり、この内でも、軸方向延伸倍率を1乃至3倍とし、周方向延伸倍率を3乃至5倍とするのがよい。
軸方向延伸倍率は、プリフォーム成形品の軸方向の長さと延伸棒のストローク長とによって決定されるが、周方向の延伸倍率は、プリフォームの径と金型キャビティの径とにより決定される。
圧力流体としては、室温或いは加熱された空気や、その他のガス、例えば窒素、炭酸ガス或いは水蒸気等を使用することができ、その圧力は、通常10乃至40kg/cmゲージ、特に15乃至30kg/cmゲージの範囲にあるのがよい。
【0042】
本発明に用いるプリフォームの口部は最終容器の口部となるものであるが、この口部を、耐熱性を向上させ且つその密封精度を高めるために、熱結晶化させることができる。
必要に応じて行うプリフォームの口部の熱結晶化は、これらの部分をそれ自体公知の手段で選択的に加熱することにより行うことができる。ポリエステル等の熱結晶化は、固有の結晶化温度で顕著に生じるので、一般にプリフォームの対応する部分を、結晶化温度に加熱すればよい。加熱は、赤外線加熱或いは誘電加熱等により行うことができ、一般に延伸すべき胴部を熱源から断熱材により遮断して、選択的加熱を行うのがよい。
上記の熱結晶化は、プリフォームの延伸温度への予備加熱と同時に行っても或いは別個に行ってもよい。口部熱結晶化は、プリフォーム口部を他の部分と熱的に絶縁した状態で、一般に140乃至220℃、特に160乃至210℃の温度に加熱することにより行うことができる。プリフォーム口部の結晶化度は25%以上であるのがよい。
【0043】
本発明による容器の底部は、自立構造を有するのが好ましい。
自立型底部の一例としては、周囲の接地部と接地部から内方の部分が上に盛り上がった上底とから形成されたものが挙げられ、この上底には、底の補強の目的でリブが放射状に設けられているものであってよい。
【0044】
このタイプの自立型容器は、特許第3011058号公報に記載されているとおり、胴部と胴部の一端に設けられた口頚部と胴部の他端に設けられた閉塞底部とを備えた延伸ブロー成形用プリフォームにおいて、前記胴部は筒状乃至テーパー状であり且つ前記底部は実質上半球状であって、内面側にあっては滑らかに接続されていると共に外面側にあっては底に向けて外径の縮小するテーパー部を介して底部に接続され、該テーパー部の断面形状はストレートであり、胴部の厚み(d)と底部の厚み(d)との比(d/d)は1.1乃至1.5の範囲にある延伸ブロー成形用プリフォームを使用し、ブロー成形に際して、このプリフォームを前記半球部が底中央及び外径縮小テーパー部が底外周となるように、軸方向に引っ張り延伸すると共に周方向にブロー延伸し、ついで底中央を底打ちして、前記外径縮小テーパー部を接地部及びそれより外周の底部分とすると共に、半球部を接地部よりも内側の上底に成形することにより製造される。
【0045】
成形された容器の少なくとも胴部を、温度が110乃至170℃に保持された金型表面と接触させるか、或いは容器内に温度が200乃至300℃の加熱流体を吹き込んで、二軸配向されたポリエステルを熱固定し、耐熱性を向上させることもできる。
【0046】
自立型底部構造の他の例としては、底部の周囲に複数の足部と谷部とが交互に形成されたものを挙げることができる。
このタイプの延伸ブロー成形容器は、一般にプリフォームの第一段ブロー成形と、第一段ブロー成形品の底部、胴部及び肩部を含めた熱処理と、熱処理品の第二段ブロー成形とにより形成される。
第一段ブロー成形は前述した条件で行われる。
【0047】
第一段ブロー成形品の熱処理工程において、第一段ブロー成形品をコア金型に支持し、自転させながら、この第一段ブロー成形品の底部、胴部及び肩部を赤外線加熱体に対面させる。これにより、第一段ブロー成形品は、その底部、胴部及び肩部が赤外線加熱体の赤外線で加熱され、高さ方向及び径方向に収縮し、最終容器形状となった第二段ブロー金型に収まる形状となる。
熱処理条件は、ポリエステルの種類や第一段ブロー成形の条件によっても相違するが、一般的にいって、90乃至120℃、特に95乃至115℃の温度及び20乃至120秒間、特に30乃至90秒間の処理時間の中から、最終容器の疑似結晶の生成の程度が前述した範囲となるように定める。
【0048】
第二段ブロー成形工程においては、熱処理された成形品を、コア金型によりその首部を支持した状態で、第二段ブロー金型に挿入する。コア金型の反対側には、最終容器の底形状を規定する底金型も挿入する。割型を閉じ、熱処理品内に流体を吹き込んで、熱処理品を第二段ブロー成形し、所定の形状の最終容器に形成する。
この第二段ブロー成形では、ブローすべき熱処理品は、熱処理による結晶化で弾性率が増加しているので、高い流体圧を用いてブロー成形を行うのがよく、一般に15乃至45kg/cmの圧力を用いるのが好ましい。
第二段ブロー成形に際して、金型の温度は、5乃至135℃の温度に維持して、成形後直ちに冷却が行われるようにしてもよいし、或いは、最終成形品中に冷風等を流して冷却が行われるようにしてもよい。
【0049】
上記タイプの容器底部は、周方向に交互に配置された足部と谷部とを有するが、足部の本数を6乃至4本、特に好ましくは6乃至5本とすることが自立安定性の点で好ましい。
また、谷部は底中心部も含めて、下向きに凸の仮想曲面、例えば概略球面或いは回転楕円面に位置しているが、この曲面の曲率半径は胴部半径の0.5乃至1倍の範囲にあることが望ましい。
【0050】
【実施例】
本発明を次の実施例によりさらに説明するが、本発明は次の例に限定されるものではない。
【0051】
[実施例1]
金型ゲート部のプリフォームゲート切断時の円筒部の径D=3.00mm、ゲート部のランド長L=8.0mm(D/L=0.375)、テーパー部の角度θ=4.0度とした金型により、ポリエチレンテレフタレートを射出成形してプリフォームを作製し、それを常法によりブロー成形を行って容量500mlの二軸延伸ブローボトルを作製した。作製した容器の底部を目視して観察したところ、白化は見られなかった。
【0052】
[実施例2]
金型ゲート部のプリフォームゲート切断時の円筒部の径D=4.03mm、ゲート部のランド長L=5.09mm(D/L=0.7917)、テーパー部の角度θ=3.0度とした金型により、ポリエチレンテレフタレートを射出成形してプリフォームを作製し、それを常法によりブロー成形を行って容量500mlの二軸延伸ブローボトルを作製した。作製した容器の底部を目視して観察したところ、白化は見られなかった。
【0053】
[実施例3]
金型ゲート部のプリフォームゲート切断時の円筒部の径D=4.03mm、ゲート部のランド長L=7.0mm(D/L=0.5757)、テーパー部の角度θ=2.0度とした金型により、ポリエチレンテレフタレートを射出成形してプリフォームを作製し、それを常法によりブロー成形を行って容量500mlの二軸延伸ブローボトルを作製した。作製した容器の底部を目視して観察したところ、白化は見られなかった。
【0054】
[比較例1]
金型ゲート部のプリフォームゲート切断時の円筒部の径D=4.20mm、ゲート部のランド長L=4.49mm(D/L=0.935)とした金型により、ポリエチレンテレフタレートを射出成形してプリフォームを作製し、それを常法によりブロー成形を行って容量500mlの二軸延伸ブローボトルを作製した。作製した容器の底部を目視して観察したところ、白化が見られた。
【0055】
[比較例2]
金型ゲート部のプリフォームゲート切断時の円筒部の径D=3.00mm、ゲート部のランド長L=11.0mm(D/L=0.273)とした金型により、ポリエチレンテレフタレートを射出成形してプリフォームを作製し、それを常法によりブロー成形を行って容量500mlの二軸延伸ブローボトルを作製した。作製した容器の底部を目視して観察したところ、白化が見られた。
【0056】
【発明の効果】
本発明によれば、ポリエステルを側壁部が実質上非晶質の有底プリフォームに射出成形する工程と、該有底プリフォームをポリエステルの延伸温度域で二軸延伸ブロー成形する工程から成る二軸延伸ポリエステル容器の製法において、有底プリフォーム射出金型としてストレートな円筒部と該円筒部に接続されたキャビテイに向けて径が増大するテーパー部とからなるゲート部を備えたものを用い、射出機として前記円筒部に嵌合しうるバルブステムを往復動可動に備えたノズルチップ付きのものを用い、プリフォームゲート切断時の円筒部の径(D)とゲート部のランド長(L)との比(D/L)を0.3乃至0.8にしたことにより、容器底部における白化や白筋の発生を有効に防止し、容器の外観特性を向上させ、商品価値を高めることができる。
【図面の簡単な説明】
【図1】 本発明に用いる射出成形装置の概略構造を示す断面図である。
【図2】 本発明に用いるゲート型の形状及び寸法を示す拡大断面図である。
【図3】 プリフォームの一例の断面図である。
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a biaxially stretched polyester container in which whitening of the bottom is prevented. More specifically, whitening and white streaks are prevented from occurring at the bottom, the appearance characteristics are excellent, and the product has excellent commercial value. The present invention relates to a method for producing an axially stretched polyester container.
[0002]
[Prior art]
Stretch blow molded containers, particularly polyester containers, are now common, and due to their excellent transparency and moderate gas barrier properties, in addition to liquid products such as liquid detergents, shampoos, cosmetics, soy sauce, sauces, beer, Widely used in carbonated beverages such as cola and cider, and other beverage containers such as fruit juice and mineral water.
[0003]
When molding a polyester container, a bottomed preform that is considerably smaller in size than the final container and the polyester is amorphous is stretched in the blow mold in the axial direction at the stretching temperature by injection molding of the polyester, A method of blow-drawing in the circumferential direction is adopted. [0004]
As the shape of the bottomed preform, a bottle neck and neck portion, for example, a mouth neck portion including an opening end for sealing, a screw for engaging a lid, a support ring and the like, and the overall shape is a test tube is generally used. is there.
[0005]
Polyethylene terephthalate crystallizes in the temperature range just below its glass transition point or melting point, generally 120 to 150 ° C., and tends to whiten due to the formation of spherulites. In the injection molding of polyester into a preform, the mold is cooled to shorten the passage time of the crystallization temperature to suppress the crystallization of the polyester, but the molten resin is injected from the bottom center. Therefore, the bottom has the longest elapsed time in the above temperature region, and therefore it is inevitable that the center (gate portion) of the preform bottom is slightly whitened.
[0006]
In this way, some cloudiness is unavoidable at the bottom of the container obtained by stretch-blow molding a preform with some cloudiness at the bottom, and it is not always satisfactory from the appearance characteristics of the container. There is a problem of reducing the value of the product, such as causing the purchaser of the stuffed product to fear that the content of the precipitate is generated and the content is altered.
[0007]
It is already known to prevent the whitening tendency of the bottom of the preform, and in Japanese Patent Publication No. 5-21055, polyester having an ethylene terephthalate unit as a main component is converted into a bottomed preform having a substantially amorphous side wall. In a method for producing a biaxially stretched polyester container comprising a step of injection molding and a step of biaxially stretching blow molding the bottomed preform in a polyester stretching temperature range, the bottomed preform is directed to the bottom cavity as a bottomed preform injection mold. A gate portion having a taper shape with an increasing diameter, a land length (l) of 5 to 30 mm, and an inclination angle (θ) of the taper portion of 2 to 8 degrees. 0) and the bottom has a ratio between the maximum internal diameter (D 1) (D 0 / D 1) is in the range of 0.10 to 0.50, the bottom corresponding cavity mold radius of curvature (R 1 There is in the radius of curvature of the cavity mold (R 2) is in the range of 0.3 to 2.0mm in 4 to 8mm and the gate outlet portion, and a maximum height roughness (Rmax, JISB-0601) is 0.8μm A method for producing a biaxially stretched polyester container that prevents whitening of the bottom portion is described, wherein an injection mold having a surface finished so as to become the following is used to perform injection molding of a polyester into a bottomed preform. ing.
[0008]
[Problems to be solved by the invention]
In the above proposal, the shape and dimensions of the gate part of the preform injection mold are within a specific range to prevent whitening of the bottom of the preform. However, the above-mentioned proposal uses a nozzle tip with a valve stem. It can be seen that reinjection injection molding still results in whitening of the preform bottom center (gate).
[0009]
The valve stem opens and closes the mold gate and cuts the preform gate. The valve stem closed by the mold gate is retracted by the air cylinder, and at the same time, the injection piston moves forward to increase the polyester resin. Is injected into the mold and closed again at the end of injection to cut the preform gate.
[0010]
According to the research of the present inventor, the cause of whitening of the preform gate in the injection molding using the nozzle tip with the valve stem is that the valve stem that is in contact with the mold gate portion in the closed state is in the open state. It was found that the resin was cooled or gradually cooled in contact with the molten polyester resin and passed through the resin crystallization temperature region, so that crystallization proceeded. It was also found that the crystallized portion attached to the cavity surface and the core surface around the gate was the whitened portion at the bottom, and the one that flowed with the resin was the white streaks.
[0011]
Accordingly, an object of the present invention is to injection-mold polyester into a bottomed preform having a substantially amorphous side wall, and to perform biaxial stretch blow molding of the bottomed preform in a polyester stretching temperature range. In the manufacturing method of the biaxially stretched polyester container which uses what equipped with the nozzle tip with a valve stem as an injection machine, it is providing the method by which generation | occurrence | production of the bottom whitening and the generation | occurrence | production of a white streak was prevented.
[0012]
[Means for Solving the Problems]
According to the present invention, by using an injection machine with a nozzle tip having a valve stem that is reciprocally movable, a step of injection-molding polyester into a bottomed preform having a substantially amorphous side wall, and the bottomed In a method of producing a biaxially stretched polyester container comprising a step of biaxially stretching and molding a preform in a polyester stretching temperature range, a straight that can be fitted to the valve stem as a bottomed preform injection mold in the step of injection molding a cylindrical portion and a gate portion consisting of a tapered portion whose diameter toward the connected cavities in the cylindrical portion is increased, and the diameter of the cylindrical portion during preform gate cut (D) and a land length of the gate portion ( L) and the ratio (D / L) is a bottom anti biaxially stretched polyester container of the process of whitening, which comprises using those which are 0.3 to 0.8 is provided . Furthermore, in the present invention, it is preferable that an inclination angle of the tapered portion is in a range of 1 to 5 degrees.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
[Action]
In the present invention, as in the conventional method, the step of injection-molding polyester into a bottomed preform having a substantially amorphous side wall portion, and the bottomed preform in a biaxial stretch blow molding in the stretch temperature range of the polyester In this process, a biaxially stretched polyester container is produced, and whitening of the bottom of the final container is prevented at the injection molding stage of the bottomed preform.
[0014]
In addition, as an injection machine for forming a preform, one having a nozzle tip with a valve stem is used. In this connection, a bottomed preform injection mold is connected to a straight cylindrical portion and the cylindrical portion. A nozzle with a nozzle tip equipped with a valve stem that can be reciprocated with the cylindrical part is used as an injection machine. Use things.
[0015]
The fitting of the cylindrical part of the mold gate part and the valve stem is indispensable for cutting the preform gate. At the same time, this fitting cools the valve stem and cools the resin by the valve stem. It causes slow cooling and resin crystallization based on it.
[0016]
According to the present invention, the shape of the gate portion of the preform is made thin and long, that is, the ratio (D / L) of the diameter (D) of the cylindrical portion when cutting the preform gate and the land length (L) of the gate portion. ) Between 0.3 and 0.8 prevents the valve stem from cooling, which causes whitening and white streaks, eliminates slowly cooled crystals, and absorbs whitening at the gate. It is possible to effectively prevent whitening and white streaking at the bottom of the reform.
Furthermore, when the inclination angle of the tapered portion is in the range of 1 to 5 degrees, whitening and white streaking can be more effectively prevented.
[0017]
That is, when the ratio (D / L) of the diameter (D) of the cylindrical portion and the land length (L) of the gate portion is out of the above range, cooling or slow cooling of the resin occurs due to the influence of the mold and valve stem, Whitening cannot be absorbed in the gate portion, and the tendency of whitening and white streaking to the bottom of the preform increases.
[0018]
According to the present invention, as described above, it is possible to effectively generate whitening and white streaks at the bottom of the preform by a simple means of setting the ratio of the diameter of the cylindrical portion and the land length of the gate portion within a certain range. Preventing, improving the appearance characteristics of the biaxially stretched blow-molded container and increasing the commercial value.
[0019]
[Injection molding equipment]
In FIG. 1 showing a schematic structure of an injection molding apparatus used in the present invention, this injection mold includes a cavity mold 10 and a gate mold 20. The cavity mold 10 has a cavity surface 11 that defines the outer surface of the preform body. The gate mold 20 has a bottom forming surface 21 that defines the outer surface of the preform bottom, and a gate portion 22 at the center thereof.
Although not shown, a core mold is inserted into the cavity mold 10 and the gate mold 20 coaxially therewith, and the core mold (not shown), the cavity mold 10 and A polyester resin is injected into a cavity defined by the gate mold 20, and a preform is molded.
[0020]
On the other hand, the nozzle tip 30 attached to the tip of an injection machine (not shown) has a hollow cylindrical shape with a narrowed tip 31, and a solid cylindrical valve stem 32 can reciprocate at the axis. Is provided. A resin passage 33 for allowing the resin to flow is formed between the inner surface of the nozzle tip 30 and the outer surface of the valve stem 32. However, when the valve stem 32 is advanced, the nozzle tip tip 31 and the valve stem 32 are moved forward. The resin passage 33 is closed in a liquid-tight state, and the resin passage is opened when the valve stem 32 is retracted.
[0021]
The nozzle tip 30 is provided with a band heater 34 on its outer periphery in order to keep the resin in the resin passage 33 warm, and on the outer surface of the tapered tip portion 31, the nozzle tip tip portion 31 is cooled. A heat insulating material layer 35 is provided to prevent this.
[0022]
A concave portion 23 for receiving the nozzle tip 30 is formed on the opposite side of the bottom forming surface 21 of the gate mold 20, and the valve stem 32 and the gate portion 22 are fitted to each other, The recess 23 can be contacted via a heat insulating material layer 35.
[0023]
In FIG. 2 for explaining the shapes and dimensions of the gate mold 20 and the valve stem 32, the gate portion 22 has a straight cylindrical portion 23 and a tapered portion 24 whose diameter increases toward a cavity connected to the cylindrical portion. And. Further, the outlet side of the taper portion 24 is in contact with the bottom molding surface 21 via a curvature portion 25 (curvature radius: R).
[0024]
As shown in FIG. 2, the cylindrical portion 23 of the gate unit has a axial dimension L 1 diameter D, whereas the tapered portion 24 and an inclined angle θ and an axial dimension L 2. The axial dimension of the tapered portion 24 means the distance from the root to the cylindrical portion 23 to the virtual curved surface including the bottom forming surface 21 of the gate mold.
On the other hand, the diameter of the cylindrical portion is given by D and the land length of the gate portion is given by L. In the present invention, D / L is set in the range of 0.3 to 0.8 described above.
[0025]
During the injection molding of the preform, molten polyester is stored in an injection machine (not shown). At the start of injection, the valve stem 32 is retracted from the advanced position shown in FIG. 1 (moved rightward in FIG. 1) by driving an air cylinder (not shown) and the nozzle tip tip 31 is opened.
At the same time, an injection piston (not shown) in the injection machine moves forward (moves in the right direction in FIG. 1), and the molten resin in the injection machine passes through the resin passage 33 and the gate portion 22 of the nozzle chip, and the injection mold 10, Inject into the cavity in 20.
At the end of injection molding, the valve stem 32 moves forward to cut the preform gate and close the tip 31 of the nozzle tip 30.
The cavity mold 10 and the gate mold 20 are forcibly water-cooled together with the core mold, and the injection molten resin is supercooled to an amorphous state, and a preform is molded.
[0026]
In FIG. 3 showing an example of a preform formed by the method of the present invention, a preform 40 is integrally formed of an amorphous thermoplastic polyester, and has a body portion 41, a closed bottom portion 42, and a mouth portion 43. A support ring 44 and a screw 45 for fastening the lid are provided on the outer periphery of the mouth portion.
[0027]
In order to prevent whitening of the bottom in this preform, it is important that the polyester constituting the bottom passes through the thermal crystallization temperature region as quickly as possible. The thinning and lengthening of the bottom mold makes it easy and quick for the resin to flow into the cavity from the gate part of the gate mold, and the molten resin is not affected by cooling at the gate part. It is effective for prevention.
[0028]
For this purpose, the fitting amount of the valve stem is expediently in the range of 0.2 to 0.9 mm.
Further, the radius of curvature R at the gate portion exit is preferably in the range of 0.5 to 2 mm.
Further, the length L 1 of the gate portion cylindrical portion 23 is a fitting of the valve stem in the shortest, and set to be longer than the fitting amount, that keep the adjustable fitting of the valve stem preferable.
This is because the cutting performance of the preform gate varies depending on the type of resin and injection conditions, but the gate is reliably cut when the length of the cylindrical portion of the gate is set. .
[0029]
[Polyester resin]
In the present invention, as the polyester resin, a stretchable blow-moldable thermoplastic polyester, particularly an ethylene terephthalate thermoplastic polyester is advantageously used. Of course, other polyesters such as polybutylene terephthalate and polyethylene naphthalate, or polycarbonate A blend with a polyarylate resin or the like can also be used.
In addition, the material configuration of the container may be a single layer or a multilayer configuration of two or more layers as long as the main material is polyester.
The ethylene terephthalate-based thermoplastic polyester used in the present invention occupies most of the ester repeating units, generally 70 mol% or more, particularly 80 mol% or more of ethylene terephthalate units, and has a glass transition point (Tg) of 50 to 90. Thermoplastic polyesters having a melting point (Tm) of 200 to 275 ° C., particularly 220 to 270 ° C., at 55 ° C., in particular 55 to 80 ° C., are preferred.
[0030]
Homopolyethylene terephthalate is preferred in terms of pressure resistance, heat resistance, and heat pressure resistance, but a copolyester containing a small amount of ester units other than ethylene terephthalate units can also be used.
[0031]
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; succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc. 1 type or combination of 2 or more types of diol components other than ethylene glycol include propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexylene glycol, cyclohexane di 1 type, or 2 or more types, such as methanol and the ethylene oxide adduct of bisphenol A, are mentioned.
[0032]
Also, it is possible to use a composite material in which ethylene terephthalate thermoplastic polyester has a relatively high glass transition point, such as polyethylene naphthalate, polycarbonate or polyarylate blended in an amount of 5% to 25%. The material strength at the time can be increased.
Further, polyethylene terephthalate and the above-mentioned material having a relatively high glass transition point can be laminated and used.
[0033]
The ethylene terephthalate-based thermoplastic polyester to be used should have at least a molecular weight sufficient to form a film, and an injection grade or extrusion grade is used depending on the application. The intrinsic viscosity (IV) is generally in the range of 0.6 to 1.4 dL / g, particularly 0.63 to 1.3 dL / g.
[0034]
Further, in the container according to the present invention, the above-described ethylene terephthalate polyester can be used as an inner and outer layer, and this can be used as an intermediate layer to interpose a recycled polyester layer, a gas barrier resin layer, an oxygen-absorbing resin layer, or the like.
As the recycled polyester layer, a polyester crushed product recovered as a used PET bottle is washed and regenerated as necessary.
Examples of gas barrier resins include ethylene vinyl alcohol copolymers, particularly ethylene vinyl alcohol copolymers having an ethylene content of 20 to 60 mol%, polyamide resins, particularly nylon 6, nylon 6,6, polyxylene adipamide. (MXD6) or the like is used.
Any known oxygen-absorbing resin composition may be used as the oxygen absorbent layer, but typical examples include polyamide resins, especially MXD6 blended with transition metal catalysts, especially cobalt carboxylates, etc. Is used.
[0035]
[Preform manufacturing]
The preform can be manufactured under conditions known per se, except that the above-described injection machine equipped with the nozzle tip and the gate mold and the conditions capable of preventing whitening of the bottom are used.
[0036]
As the injection mold, it is preferable to use a mold having a large thermal conductivity and a small surface roughness in terms of preventing whitening of the bottom.
For this reason, it is preferable to use a copper-beryllium alloy as the mold, and the maximum height roughness (Rmax, JIS B-0601) of the mold surface is 3.2 μm or less, particularly 0.8 μm or less. It is preferable to use one.
[0037]
The injection temperature and injection pressure also have certain conditions for preventing bottom whitening. That is, when the resin temperature to be injected is high, a long time is required for cooling the resin, and the time for passing through the crystallization temperature region is also long. On the other hand, when the resin temperature is lowered, the share increases at the time of molding, and a molding trouble occurs.
For this reason, the injection molding temperature is preferably in the range of 280 to 320 ° C, particularly 290 to 310 ° C.
On the other hand, the injection pressure is preferably about 60 to 130 kg / cm 2 .
[0038]
Further, when the temperature of the injection mold is lowered, the time for passing through the crystallization temperature region can be shortened. Therefore, it is desirable to make the temperature of the gate mold (bottom mold) as low as possible. On the other hand, if this temperature is too low, the problem of increase in share occurs as described above. Therefore, the temperature of the gate mold (bottom mold) is preferably maintained at 10 to 20 ° C.
[0039]
[Manufacture of biaxial stretch blow molded containers]
The preform obtained by the above method is heated to a stretching temperature, the heated preform is stretched in the axial direction, blown in the circumferential direction by blowing a pressure fluid, and biaxially stretched. And
This stretch blow molding may be performed in one step, or may be performed in two steps called two-stage blow. Furthermore, you may heat fix the container which performed biaxial stretch blow molding by a well-known means. Furthermore, in the two-stage blow molding method, a heat treatment step may be provided between the primary blow and the secondary blow.
[0040]
Prior to stretch blow molding, the preform is preheated to a stretchable temperature by means of hot air, infrared heater, high frequency induction heating or the like. The temperature range is preferably in the range of 85 to 120 ° C., particularly 95 to 110 ° C.
[0041]
The draw ratio in the final container is suitably 4 to 10 times in terms of area magnification, and among these, the axial draw ratio is preferably 1 to 3 times and the circumferential draw ratio is preferably 3 to 5 times.
The axial stretch ratio is determined by the axial length of the preform and the stroke length of the stretch rod, but the circumferential stretch ratio is determined by the preform diameter and the mold cavity diameter. .
As the pressure fluid, room temperature or heated air, and other gases such as nitrogen, carbon dioxide or water vapor can be used, and the pressure is usually 10 to 40 kg / cm 2 gauge, particularly 15 to 30 kg / It should be in the range of cm 2 gauge.
[0042]
The mouth portion of the preform used in the present invention is the mouth portion of the final container, and this mouth portion can be thermally crystallized in order to improve heat resistance and increase its sealing accuracy.
The thermal crystallization of the mouth portion of the preform, which is performed as necessary, can be performed by selectively heating these portions by means known per se. Since thermal crystallization of polyester or the like occurs remarkably at a specific crystallization temperature, generally a corresponding portion of the preform may be heated to the crystallization temperature. Heating can be performed by infrared heating, dielectric heating, or the like. In general, it is preferable to perform selective heating by blocking a body portion to be stretched from a heat source with a heat insulating material.
The above thermal crystallization may be performed simultaneously with the preheating to the stretching temperature of the preform or may be performed separately. The mouth thermal crystallization can be performed by heating the preform mouth portion to a temperature of generally 140 to 220 ° C., particularly 160 to 210 ° C. in a state where the preform mouth portion is thermally insulated from other portions. The crystallinity of the preform mouth is preferably 25% or more.
[0043]
The bottom of the container according to the invention preferably has a self-supporting structure.
An example of a self-supporting bottom portion is one formed from a surrounding grounding portion and an upper bottom that is raised upward from the grounding portion, and the upper bottom includes ribs for the purpose of reinforcing the bottom. May be provided radially.
[0044]
As described in Japanese Patent No. 3011058, this type of self-supporting container has a trunk, a mouth and neck provided at one end of the trunk, and a closed bottom provided at the other end of the trunk. In the preform for blow molding, the body is cylindrical or tapered, and the bottom is substantially hemispherical, and is smoothly connected on the inner surface side and bottom on the outer surface side. connected to the bottom through the tapered portion to reduce the outer diameter towards the cross-sectional shape of the tapered portion is straight, the ratio of the trunk portion of the thickness (d 1) and the bottom of the thickness (d 2) (d 1 / d 2 ) A stretch blow molding preform having a range of 1.1 to 1.5 is used. In blow molding, the preform has the hemispherical portion at the bottom center and the outer diameter reduction taper portion at the bottom outer periphery. Pull in the axial direction so that Stretching and blow-stretching in the circumferential direction, then bottoming out the center of the bottom, making the outer diameter reduction taper part the grounding part and the bottom part of the outer periphery thereof, and the hemisphere part on the upper bottom inside the grounding part It is manufactured by molding.
[0045]
At least the body part of the molded container was brought into contact with the mold surface maintained at a temperature of 110 to 170 ° C., or a heated fluid having a temperature of 200 to 300 ° C. was blown into the container to be biaxially oriented. Polyester can be heat-set to improve heat resistance.
[0046]
Another example of the self-supporting bottom structure is a structure in which a plurality of legs and valleys are alternately formed around the bottom.
This type of stretch blow molded container is generally obtained by first stage blow molding of a preform, heat treatment including the bottom, body and shoulder of the first stage blow molded product, and second stage blow molding of the heat treated product. It is formed.
The first stage blow molding is performed under the conditions described above.
[0047]
In the heat treatment process of the first-stage blow-molded product, the first-stage blow-molded product is supported on the core mold and rotated while the bottom, body and shoulders of the first-stage blow-molded product face the infrared heater. Let As a result, the first stage blow-molded product has its bottom, body and shoulders heated by the infrared rays of the infrared heating body, and contracted in the height direction and radial direction to form a final container shape. The shape fits in the mold.
The heat treatment conditions vary depending on the type of polyester and the conditions of the first stage blow molding, but generally speaking, a temperature of 90 to 120 ° C., particularly 95 to 115 ° C., and 20 to 120 seconds, particularly 30 to 90 seconds. From the above processing time, the degree of generation of pseudo crystals in the final container is determined to be in the above-described range.
[0048]
In the second stage blow molding step, the heat-treated molded product is inserted into the second stage blow mold with the neck supported by the core mold. A bottom mold that defines the bottom shape of the final container is also inserted on the opposite side of the core mold. The split mold is closed and a fluid is blown into the heat-treated product, and the heat-treated product is second-stage blow-molded to form a final container having a predetermined shape.
In this second-stage blow molding, the heat-treated product to be blown has an increased elastic modulus due to crystallization by heat treatment, so blow molding is preferably performed using a high fluid pressure, and generally 15 to 45 kg / cm 2. It is preferable to use a pressure of
During the second stage blow molding, the temperature of the mold may be maintained at a temperature of 5 to 135 ° C. and cooling may be performed immediately after molding, or cold air or the like may be allowed to flow through the final molded product. Cooling may be performed.
[0049]
The container bottom portion of the above type has feet and valleys alternately arranged in the circumferential direction, but the number of feet is 6 to 4, particularly preferably 6 to 5 for self-supporting stability. This is preferable.
In addition, the valley portion is located on a downwardly convex virtual curved surface including the bottom center portion, for example, a substantially spherical surface or a spheroidal surface, and the curvature radius of the curved surface is 0.5 to 1 times the trunk radius. It is desirable to be in range.
[0050]
【Example】
The invention is further illustrated by the following examples, but the invention is not limited to the following examples.
[0051]
[Example 1]
The diameter D of the cylindrical portion when the preform gate of the die gate portion is cut = 3.00 mm, the land length L of the gate portion L = 8.0 mm (D / L = 0.375), and the angle θ of the taper portion = 4.0 A preform was prepared by injection-molding polyethylene terephthalate with a mold having a predetermined size, and blow molding was performed by a conventional method to prepare a biaxially stretched blow bottle having a capacity of 500 ml. When the bottom of the produced container was visually observed, no whitening was observed.
[0052]
[Example 2]
The diameter D of the cylindrical portion when the preform gate of the mold gate portion is cut is 4.03 mm, the land length L of the gate portion is 5.09 mm (D / L = 0.7917), and the angle θ of the tapered portion is 3.0. A preform was prepared by injection-molding polyethylene terephthalate with a mold having a predetermined size, and blow molding was performed by a conventional method to prepare a biaxially stretched blow bottle having a capacity of 500 ml. When the bottom of the produced container was visually observed, no whitening was observed.
[0053]
[Example 3]
Diameter of cylindrical part D = 4.03 mm at the time of cutting the preform gate of the mold gate part, Land length L of the gate part L = 7.0 mm (D / L = 0.5757), taper part angle θ = 2.0 A preform was prepared by injection-molding polyethylene terephthalate with a mold having a predetermined size, and blow molding was performed by a conventional method to prepare a biaxially stretched blow bottle having a capacity of 500 ml. When the bottom of the produced container was visually observed, no whitening was observed.
[0054]
[Comparative Example 1]
Polyethylene terephthalate is injected from a die having a cylindrical portion diameter D = 4.20 mm and a land length L = 4.49 mm (D / L = 0.935) when the preform gate of the die gate is cut. A preform was formed by molding and blow-molded by a conventional method to prepare a biaxially stretched blow bottle having a capacity of 500 ml. When the bottom of the produced container was visually observed, whitening was observed.
[0055]
[Comparative Example 2]
Polyethylene terephthalate is injected from a die with a cylindrical portion diameter D = 3.00 mm and a gate land length L = 11.0 mm (D / L = 0.273) when the preform gate of the die gate portion is cut. A preform was formed by molding and blow-molded by a conventional method to prepare a biaxially stretched blow bottle having a capacity of 500 ml. When the bottom of the produced container was visually observed, whitening was observed.
[0056]
【The invention's effect】
According to the present invention, two steps comprising the step of injection-molding polyester into a bottomed preform having substantially non-crystalline side walls and the step of biaxially stretching blow-molding the bottomed preform in the stretch temperature range of the polyester. In the method for producing an axially stretched polyester container, a bottomed preform injection mold having a straight cylindrical portion and a gate portion including a tapered portion whose diameter increases toward the cavity connected to the cylindrical portion is used. The injection machine is equipped with a nozzle tip equipped with a valve stem that can be reciprocally moved and fitted to the cylindrical part. The diameter of the cylindrical part (D) and the land length (L) of the gate part when the preform gate is cut. The ratio (D / L) to 0.3 to 0.8 effectively prevents whitening and white streaking at the bottom of the container, improves the appearance characteristics of the container, and increases the commercial value. Can.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a schematic structure of an injection molding apparatus used in the present invention.
FIG. 2 is an enlarged cross-sectional view showing the shape and dimensions of a gate mold used in the present invention.
FIG. 3 is a cross-sectional view of an example of a preform.

Claims (2)

バルブステムを往復動可動に備えたノズルチップ付きの射出機を用いて、ポリエステルを側壁部が実質上非晶質の有底プリフォームに射出成形する工程と、該有底プリフォームをポリエステルの延伸温度域で二軸延伸ブロー成形する工程とからなる二軸延伸ポリエステル容器の製法において、射出成形する工程における有底プリフォーム射出金型として前記バルブステムと嵌合しうるストレートな円筒部と該円筒部に接続されたキャビテイに向けて径が増大するテーパー部とからなるゲート部を備え、かつプリフォームゲート切断時の円筒部の径(D)とゲート部のランド長(L)との比(D/L)が0.3乃至0.8であるものを用いることを特徴とする底部白化の防止された二軸延伸ポリエステル容器の製法。 Using an injection machine with a nozzle tip equipped with a valve stem that can move reciprocally, a step of injection-molding polyester into a bottomed preform having substantially non-crystalline side walls, and stretching the bottomed preform with polyester In a method for producing a biaxially stretched polyester container comprising a step of biaxially stretching blow molding in a temperature range, a straight cylindrical portion that can be fitted to the valve stem as a bottomed preform injection mold in the step of injection molding and the cylinder A ratio of the diameter (D) of the cylindrical portion at the time of cutting the preform gate and the land length (L) of the gate portion (L) (with a tapered portion whose diameter increases toward the cavity connected to the portion) A method for producing a biaxially stretched polyester container in which whitening of the bottom is prevented , wherein a material having a D / L) of 0.3 to 0.8 is used . 前記テーパー部の傾斜角度が1乃至5度の範囲にあることを特徴とする請求項1記載の底部白化の防止された二軸延伸ポリエステル容器の製法。2. The method for producing a biaxially stretched polyester container with white bottom prevented according to claim 1, wherein an inclination angle of the tapered portion is in a range of 1 to 5 degrees.
JP2000270906A 2000-09-07 2000-09-07 Method for producing biaxially stretched polyester container with whitening prevention at the bottom Expired - Fee Related JP3740968B2 (en)

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US11130271B2 (en) 2016-02-19 2021-09-28 Nissei Asb Machine Co., Ltd. Blow molding device and blow molding method
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