JP2001001389A - Container for liquid agent and production of stretch blow molded bottle for liquid agent - Google Patents

Container for liquid agent and production of stretch blow molded bottle for liquid agent

Info

Publication number
JP2001001389A
JP2001001389A JP17653099A JP17653099A JP2001001389A JP 2001001389 A JP2001001389 A JP 2001001389A JP 17653099 A JP17653099 A JP 17653099A JP 17653099 A JP17653099 A JP 17653099A JP 2001001389 A JP2001001389 A JP 2001001389A
Authority
JP
Japan
Prior art keywords
bottle
synthetic resin
resin layer
mouth
container
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
Application number
JP17653099A
Other languages
Japanese (ja)
Other versions
JP4065082B2 (en
Inventor
Hiroichi Mihashi
博一 三橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taisei Kako Co Ltd
Original Assignee
Taisei Kako Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Taisei Kako Co Ltd filed Critical Taisei Kako Co Ltd
Priority to JP17653099A priority Critical patent/JP4065082B2/en
Publication of JP2001001389A publication Critical patent/JP2001001389A/en
Application granted granted Critical
Publication of JP4065082B2 publication Critical patent/JP4065082B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • B29C2949/3009Preforms or parisons made of several components at neck portion partially
    • 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
    • B29C2949/302Preforms 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
    • 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
    • B29C2949/3032Preforms 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

Landscapes

  • Containers Having Bodies Formed In One Piece (AREA)
  • Packages (AREA)
  • Closures For Containers (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

PROBLEM TO BE SOLVED: To prevent the deterioration of the appearance of a bottle caused by the generation of the non-uniform peeled part between the inner and outer layers of the bottle while employing a laminated bottle in order to suppress the reduction in the transmission amt. of steam and the adsorption of a medicinal component. SOLUTION: A container comprises a bottle 4 having a body portion and a mouth portion 2 and the cap 6 attached to the mouth portion 2 of the bottle 3 in a freely detachable manner. The bottle 4 is formed by laminating inner and outer synthetic resin layers 8 made of different materials and the inner and outer synthetic resin layers 8, 9 of the body portion 3 of the bottle are preliminarily peeled over the entire periphery of the body portion in a production line.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、点眼剤用容器とし
て好適に用いることができる液剤用容器、並びに、該容
器の主たる構成要素であるボトルを延伸ブロー成形法に
より製造する方法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a container for a liquid preparation which can be suitably used as a container for eye drops, and a method for producing a bottle which is a main component of the container by a stretch blow molding method. .

【0002】[0002]

【従来の技術】例えば点眼剤などの薬液剤用ボトルとし
ては、従来より、高分子合成樹脂材料からなる延伸ブロ
ー成形品が広く用いられているとともに、射出成形ボト
ルも用いられている。特に、点眼剤等の薬液は人体に適
用されるものであるから、長期保存によって液性ができ
るだけ変化しないよう、十分な水蒸気バリア性、ガスバ
リア性が要求され、材料選定に十分な配慮がなされてい
る。
2. Description of the Related Art As a bottle for a drug solution such as an eye drop, for example, a stretch blow-molded product made of a high-molecular synthetic resin material has been widely used, and an injection-molded bottle has also been used. In particular, since chemical solutions such as eye drops are applied to the human body, sufficient water vapor barrier properties and gas barrier properties are required so that the liquid properties do not change as much as possible during long-term storage, and sufficient consideration is given to material selection. I have.

【0003】例えば、点眼剤用ボトルの成形材料として
は、PP、LDPE、HDPE又はCOP(Circle Ole
fin Polymer )などの透明なオレフィン系材料が従来よ
り用いられている。オレフィン系材料は、耐薬品性も高
く、水蒸気バリア性にも優れるため、上記のような薬液
用容器の分野においては、水蒸気透過減量に伴う薬効成
分の変化防止の観点から好ましい材料である。さらに、
オレフィン系材料は比較的柔軟な材質であるため、ボト
ル形状に制約が少なく、単純な有底円筒状のボトル形状
に成形した場合でも十分なスクイズ性(押圧による圧縮
変形性)が得られる。有底円筒状のボトル形状であれ
ば、ブロー成形後、ボトル内への薬液充填等を行う生産
ライン内で、ガイドレールによるボトルの搬送路を形成
し得るため、量産性に優れた生産システムを構築し得る
という利点がある。
[0003] For example, molding materials for bottles for eye drops include PP, LDPE, HDPE and COP (Circle Ole).
Transparent olefin materials such as fin Polymer) have been used. Olefin-based materials are high in chemical resistance and excellent in water vapor barrier properties. Therefore, in the field of chemical liquid containers as described above, they are preferable materials from the viewpoint of preventing a change in a medicinal component due to loss of water vapor transmission. further,
Since the olefin-based material is a relatively flexible material, there is little restriction on the bottle shape, and sufficient squeezability (compression deformation by pressing) can be obtained even when the olefin-based material is molded into a simple bottomed cylindrical bottle shape. If the bottle has a bottomed cylindrical shape, a bottle transport path with guide rails can be formed in the production line where the bottle is filled with a chemical solution after blow molding. It has the advantage that it can be built.

【0004】[0004]

【発明が解決しようとする課題】しかし、薬効成分や防
腐剤の中にはオレフィン系樹脂材料に吸着するもの、吸
収されるもの、或いは収着するものがある。このような
薬効成分としては、例えば、ビタミンE(PL−α−ト
コフェロール)などがあり、また、防腐剤としては、β
−フェニルエチルアルコール(β−PEA)、塩化ベン
ザルコニウム(BKC)などが挙げられる。このような
薬効成分や防腐剤を含む薬剤のための容器としては、薬
効成分や防腐剤が吸着等しないポリエステル系透明樹脂
材料が使用される。PETやPENなどのポリエステル
系樹脂は、水蒸気透過性が比較的大きいため、水蒸気透
過減量に伴う薬効成分の変化防止のために、ピロー包装
などが施される。また、その一方で、ポリエステルとの
接触を嫌う薬剤もあり、この場合はポリオレフィン系材
料が使用されるが、O2バリアー機能が不足しするた
め、この場合もピロー包装や脱酸素剤などが使用され
る。
However, some of the medicinal components and preservatives are adsorbed, absorbed, or sorbed by the olefin resin material. Such medicinal ingredients include, for example, vitamin E (PL-α-tocopherol) and the like.
-Phenylethyl alcohol (β-PEA), benzalkonium chloride (BKC) and the like. As a container for such a drug containing a medicinal ingredient or a preservative, a polyester-based transparent resin material to which the medicinal ingredient or the preservative is not adsorbed is used. Since polyester-based resins such as PET and PEN have relatively high water vapor permeability, pillow packaging or the like is applied to prevent a change in a medicinal component due to a decrease in water vapor transmission. On the other hand, there are also agents that dislike contact with polyester. In this case, a polyolefin-based material is used. However, since the O 2 barrier function is insufficient, pillow packaging and an oxygen absorber are also used in this case. Is done.

【0005】ポリエステル系材料は比較的硬い材質であ
るため、ある程度の水蒸気バリア性、ガスバリア性等を
持たせつつ点眼ボトルとして必要なスクイズ性を持たせ
るためには、扁平断面のボトル形状に設計せざるを得
ず、その容器形状の変更に応じて生産ラインの大幅な改
造が必要となる。したがって、既存の生産ラインを用い
るには、結果的に生産可能な薬品に制限が行われている
のが実情である。
[0005] Since the polyester-based material is a relatively hard material, it must be designed in a bottle shape having a flat cross section in order to provide a certain degree of water vapor barrier property and gas barrier property while providing the necessary squeezing properties as an eye drop bottle. Inevitably, the production line needs to be remodeled significantly in accordance with the change in the shape of the container. Therefore, in order to use an existing production line, the fact is that the chemicals that can be produced as a result are limited.

【0006】本発明は、薬効成分の吸着性並びに水蒸気
透過性を共に小さくし得るものでありながら、ボトル形
状の自由度を大きくして、量産性の高い生産ラインを使
用し得る液剤用容器、並びに、延伸ブロー成形ボトルの
製造方法を提供することを目的とする。
SUMMARY OF THE INVENTION The present invention provides a liquid container capable of using a production line having a high degree of freedom in mass production while increasing the degree of freedom of the bottle shape while reducing both the adsorptivity of the medicinal component and the water vapor permeability. Another object of the present invention is to provide a method for producing a stretch blow-molded bottle.

【0007】[0007]

【課題を解決するための手段】上記目的を達成するため
に、本願出願人は、胴部と口部とを有するボトルと、該
ボトルの口部に着脱自在に取付けられるキャップとを備
え、前記ボトルを、材質の異なる合成樹脂層を内外に積
層してなるものとした液剤用容器を発明した。これによ
れば、例えば、ボトル胴部の壁部の内側合成樹脂層を構
成する樹脂材料を、薬効成分の吸着性の低い飽和ポリエ
ステルとし、一方、外側合成樹脂層を構成する樹脂材料
には水蒸気バリアー性の高いポリオレフィンを用いるこ
とにより、両者の欠点を相互にカバーでき、薬効成分の
吸着性が低くかつ水蒸気バリアー性の高い薬液用容器を
提供でき、長期保存によっても薬効成分に変化が生じる
ことを防止し得る。さらに、内側合成樹脂層の飽和ポリ
エステルは薬効成分に対する保護層として機能すれば良
いから、比較的硬い飽和ポリエステル層を可及的に薄く
して、所望のスクイズ性を容易に得ることができ、ボト
ル形状の設計の自由度が増し、有底円筒状のボトルとし
て構成することができるから、量産性の高い生産ライン
を用いることができ、大量生産性、低コスト化を図るこ
とも可能である。
In order to achieve the above object, the present applicant has a bottle having a body and a mouth, and a cap detachably attached to the mouth of the bottle. We have invented a liquid container in which a bottle is formed by laminating synthetic resin layers of different materials inside and outside. According to this, for example, the resin material forming the inner synthetic resin layer of the wall portion of the bottle body is a saturated polyester having a low adsorptivity of a medicinal component, while the resin material forming the outer synthetic resin layer has water vapor. By using a polyolefin with high barrier properties, the drawbacks of both can be mutually covered, a low-absorbency of the medicinal component and a container for a medicinal solution with a high water vapor barrier property can be provided, and the medicinal component changes even after long-term storage. Can be prevented. Further, since the saturated polyester of the inner synthetic resin layer only has to function as a protective layer for the medicinal component, the relatively hard saturated polyester layer can be made as thin as possible to easily obtain a desired squeezing property, Since the degree of freedom in shape design is increased and the bottle can be configured as a cylindrical bottle with a bottom, a production line with high mass productivity can be used, and mass productivity and cost reduction can be achieved.

【0008】上記積層ボトルを用いた液剤用容器によれ
ば上述のような利点を有するものであるが、本願発明者
の実験によって、上記積層ボトルによれば次のような問
題が生じることが判明した。即ち、ボトルの成形直後
は、内側合成樹脂層と外側合成樹脂層とは、これらの構
成樹脂材料の持つ接着性により全体にわたって密着して
いるが、内側合成樹脂層の飽和ポリエステルは、外側合
成樹脂層のポリオレフィンに比して水蒸気透過性が大き
いことから、内側合成樹脂層を透過する水蒸気の気圧等
によって内側合成樹脂層と外側合成樹脂層とが部分的に
剥離され、ボトル胴部の壁部に気泡状の模様となって現
れることになる。かかる現象が生じると、その外観の劣
化によって、薬剤としての品質劣化がない場合であって
も、安全のために破棄処分となることも多く、ボトル構
造等を改善する必要がある。
Although the liquid medicine container using the above-mentioned laminated bottle has the above-mentioned advantages, the experiment by the inventor of the present application has revealed that the following problem occurs according to the above-mentioned laminated bottle. did. That is, immediately after the bottle is molded, the inner synthetic resin layer and the outer synthetic resin layer are in close contact with each other due to the adhesiveness of these constituent resin materials, but the saturated polyester of the inner synthetic resin layer is The inner synthetic resin layer and the outer synthetic resin layer are partially peeled off due to the pressure of water vapor passing through the inner synthetic resin layer because the water vapor permeability is higher than the polyolefin of the layer, and the wall of the bottle body In the form of a bubble. When such a phenomenon occurs, the bottle is often discarded for safety even if there is no deterioration in quality as a medicine due to deterioration of its appearance, and it is necessary to improve the bottle structure and the like.

【0009】上記の積層ボトルにおいて内側合成樹脂層
と外側合成樹脂層との界面に気泡状の剥離部分が生じる
のは、ポリオレフィンの接着性が低いことが原因である
と考えられる。気泡状の模様が出現することを防止する
ためには、内側合成樹脂層と外側合成樹脂層とを予め全
体にわたって剥離させておくか、若しくは、内側合成樹
脂層と外側合成樹脂層との接着力を強めれば良い。
[0009] It is considered that the formation of a bubble-like exfoliated portion at the interface between the inner synthetic resin layer and the outer synthetic resin layer in the above-mentioned laminated bottle is due to the low adhesiveness of the polyolefin. In order to prevent the appearance of a bubble-like pattern, the inner synthetic resin layer and the outer synthetic resin layer must be separated from each other in advance, or the adhesive strength between the inner synthetic resin layer and the outer synthetic resin layer. Should be strengthened.

【0010】かかる知見に基づいてなされた本発明の液
剤用容器は、胴部と口部とを有するボトルと、該ボトル
の口部に着脱自在に取付けられるキャップとを備え、前
記ボトルは、異なる合成樹脂層を内外に積層形成してな
るものであって、該ボトル胴部の内側合成樹脂層と外側
合成樹脂層との間に互いの接着性を有しないことを特徴
とするものである。これによれば、ボトルの成形直後に
おいては内側の合成樹脂層と外側の合成樹脂層が、熱成
形に起因して生ずる分子間の結合力によって接着する
が、かかるボトルの胴部の内側合成樹脂層と外側合成樹
脂層とを予め剥離させることにより互いの接着性を無く
しているので、長期保存した際でも該胴部に気泡状の模
様が出現することがなく、良好な外観を保持することが
できる。なお、ボトルの口部及び底部においても内側合
成樹脂層と外側合成樹脂層とを予め剥離させても良い
が、内側合成樹脂層と外側合成樹脂層とが相対的に回転
してしまうことを防止するために、外観に差ほど影響し
ないボトルの口部及び底部においては内側合成樹脂層と
外側合成樹脂層とを接着させておくことが好ましい。
[0010] The solution container of the present invention based on such knowledge is provided with a bottle having a body and a mouth, and a cap detachably attached to the mouth of the bottle. A synthetic resin layer is formed by laminating the inner and outer layers, wherein the inner synthetic resin layer and the outer synthetic resin layer of the bottle body have no mutual adhesiveness. According to this, immediately after the bottle is molded, the inner synthetic resin layer and the outer synthetic resin layer adhere to each other due to a bonding force between molecules generated by thermoforming. The layer and the outer synthetic resin layer are peeled off in advance so that their mutual adhesiveness is eliminated, so that even when stored for a long period of time, a bubble-like pattern does not appear on the body, and a good appearance is maintained. Can be. The inner synthetic resin layer and the outer synthetic resin layer may be peeled off at the mouth and the bottom of the bottle in advance, but the inner synthetic resin layer and the outer synthetic resin layer are prevented from relatively rotating. To this end, it is preferable to bond the inner synthetic resin layer and the outer synthetic resin layer at the mouth and bottom of the bottle, which do not significantly affect the appearance.

【0011】また、本発明の液剤用容器は、胴部と口部
とを有するボトルと、該ボトルの口部に着脱自在に取付
けられるキャップとを備え、前記ボトルは、材質の異な
る合成樹脂を内外に積層形成してなるものであって、該
ボトル胴部の壁部の内側合成樹脂層と外側合成樹脂層と
の接着性を高める添加材料が、内側合成樹脂層を構成す
る合成樹脂及び/又は外側合成樹脂層を構成する合成樹
脂中に混合されていることを特徴とするものである。こ
れによれば、添加材料の混合によってボトルの内側合成
樹脂層と外側合成樹脂層との接着力が高められているの
で、内側合成樹脂層と外側合成樹脂層とが剥離しにくく
なり、胴部に気泡状の模様が出現することが防止され
る。
The liquid medicine container of the present invention comprises a bottle having a body and a mouth, and a cap detachably attached to the mouth of the bottle, wherein the bottle is made of a synthetic resin of a different material. An additive material which is formed by laminating the inside and outside, and which enhances the adhesiveness between the inner synthetic resin layer and the outer synthetic resin layer of the wall of the bottle body, comprises synthetic resin and / or Alternatively, it is mixed in the synthetic resin constituting the outer synthetic resin layer. According to this, since the adhesive force between the inner synthetic resin layer and the outer synthetic resin layer of the bottle is increased by mixing the additive materials, the inner synthetic resin layer and the outer synthetic resin layer are less likely to be separated, and The appearance of a bubble-like pattern is prevented.

【0012】なお、上記積層ボトルは、射出成形法、ダ
イレクトブロー成形法、インジェクションブロー成形法
等の適宜の成形法によって成形し得るが、大量生産性、
コストの面を考慮すれば、異種の合成樹脂を内外に積層
した積層パリソンを用いた延伸ブロー成形によって形成
することが好ましい。
The laminated bottle can be molded by an appropriate molding method such as an injection molding method, a direct blow molding method, or an injection blow molding method.
In consideration of cost, it is preferable to form by stretch blow molding using a laminated parison in which different kinds of synthetic resins are laminated inside and outside.

【0013】上記各液剤用容器において、ボトル口部に
おいて内外の合成樹脂層を凹凸嵌合させることができ
る。例えば、射出成型機を用いて、まず、口部外周に縦
リブと横リブとを有するPET製パリソンを成形し、こ
のPET製パリソンを別の射出成形金型にインサートし
て、その外周にPPを射出成形により積層形成すること
で、内側合成樹脂層のPETと外側合成樹脂層のPPと
が口部において凹凸嵌合している構造が得られる。これ
によれば、ボトル胴部において内側合成樹脂層と外側合
成樹脂層とを予め剥離させたものでは、口部においては
内側合成樹脂層と外側合成樹脂層との間で強固な結合が
得られ、円筒状ボトルの場合であっても内側合成樹脂層
と外側合成樹脂層とが相対的に回転してしまうことがな
く、ボトル口部に螺着されるキャップの操作性が良くな
るとともに、キャップ装着時の気密性の向上が図られ
る。また、ボトルの内側合成樹脂層と外側合成樹脂層と
の接着性を高めたものでは、口部において内側合成樹脂
層と外側合成樹脂層との強固な結合が得られるので、キ
ャップの着脱を繰り返し行っても、ボトル胴部の内側合
成樹脂層と外側合成樹脂層との界面に応力が作用するこ
とを防止でき、これらが剥離することが防止される。
In each of the above liquid agent containers, the inner and outer synthetic resin layers can be fitted to each other at the mouth of the bottle. For example, using an injection molding machine, first, a PET parison having a vertical rib and a horizontal rib on the outer periphery of the mouth is molded, and this PET parison is inserted into another injection molding die, and the outer periphery is formed of PP. Are laminated by injection molding, whereby a structure is obtained in which the PET of the inner synthetic resin layer and the PP of the outer synthetic resin layer are fitted into the mouth in an uneven manner. According to this, when the inner synthetic resin layer and the outer synthetic resin layer are separated in advance at the bottle body, a strong bond is obtained between the inner synthetic resin layer and the outer synthetic resin layer at the mouth. Even in the case of a cylindrical bottle, the inner synthetic resin layer and the outer synthetic resin layer do not relatively rotate, and the operability of the cap screwed to the bottle mouth is improved, and the cap is The airtightness at the time of mounting is improved. In addition, in the case where the adhesiveness between the inner synthetic resin layer and the outer synthetic resin layer of the bottle is increased, a strong connection between the inner synthetic resin layer and the outer synthetic resin layer can be obtained at the mouth, so that the cap is repeatedly attached and detached. Even if it is performed, it is possible to prevent stress from acting on the interface between the inner synthetic resin layer and the outer synthetic resin layer of the bottle body, and prevent them from peeling off.

【0014】本発明は、上記ボトルが、その胴部にスク
イズ性を有する有底円筒状の点眼ボトルである場合に好
適に実施される。また、ボトルの内側合成樹脂層材料に
はPET(ポリエチレンテレフタレート)やPEN(ポ
リエチレンナフタレート)などの飽和ポリエステルを用
い、外側合成樹脂層材料には、PP(ポリプロピレ
ン)、PE(ポリエチレン)又はCOP(Circle Olefi
n Polymer )などのポリオレフィンを用いることが好適
である。反対に、ボトルの内側合成樹脂層材料にポリオ
レフィンを用い、外側合成樹脂層材料に飽和ポリエステ
ルを用いた場合、酸素バリアー機能の確保と、内容保香
剤等のガス成分の拡散防止作用の向上とを図ることが可
能であるとともに、この場合においても内外層間に気泡
が生じることが防止される。
The present invention is suitably carried out when the bottle is a cylindrical ophthalmic bottle having a bottom and a squeezing property on its body. Further, a saturated polyester such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) is used for the inner synthetic resin layer material of the bottle, and PP (polypropylene), PE (polyethylene) or COP ( Circle Olefi
It is preferable to use a polyolefin such as n Polymer). Conversely, when polyolefin is used for the inner synthetic resin layer material of the bottle and saturated polyester is used for the outer synthetic resin layer material, the oxygen barrier function is ensured and the effect of preventing the diffusion of gas components such as content flavoring agents is improved. In this case, it is also possible to prevent bubbles from being generated between the inner and outer layers.

【0015】また、上記液剤用容器において、更なる水
蒸気透過減量の低減を図るために、キャップは、ボトル
口部の外周側を覆うように口部に取付けられ、該キャッ
プの下端周縁部が、ボトルの外面に気密に接触している
構造にすることができる。これによれば、成形機の構造
上及び成形工程の必要性から内側合成樹脂層の上端(開
口端)に外方へ延びるフランジ部が形成され、該フラン
ジ部よりも下方で外側合成樹脂層が積層形成されている
ような場合に、水蒸気透過性の比較的大きい内側合成樹
脂層の上記フランジ部を経由して、キャップとボトル口
部との間の空間に微量ずつ水蒸気が漏れ出すことがある
が、キャップの下端周縁をボトル外面に気密的に接触さ
せておくことで、水蒸気がキャップ外へ漏れることを防
止でき、長期保存の際のキャップ下端部からの水蒸気漏
れを解消し得る。なお、キャップの構成材料としては、
水蒸気バリアー性の高い材料(例えば、ポリオレフィ
ン、金属など)を用いることが好ましいのは勿論であ
る。
In the above-mentioned liquid container, in order to further reduce the water vapor transmission loss, the cap is attached to the mouth so as to cover the outer peripheral side of the mouth of the bottle, and the lower edge of the cap has a lower peripheral edge. The structure can be in airtight contact with the outer surface of the bottle. According to this, a flange portion extending outward is formed at the upper end (opening end) of the inner synthetic resin layer due to the structure of the molding machine and the necessity of the molding step, and the outer synthetic resin layer is formed below the flange portion. In such a case that a laminate is formed, a small amount of water vapor may leak into the space between the cap and the bottle mouth via the flange portion of the inner synthetic resin layer having relatively high water vapor permeability. However, by keeping the lower peripheral edge of the cap in airtight contact with the outer surface of the bottle, water vapor can be prevented from leaking out of the cap, and water vapor leakage from the lower end of the cap during long-term storage can be eliminated. In addition, as a constituent material of the cap,
Of course, it is preferable to use a material having a high water vapor barrier property (eg, polyolefin, metal, etc.).

【0016】内側合成樹脂層と外側合成樹脂層とを予め
剥離させたボトルは、次の方法によって製造し得る。即
ち、本発明の延伸ブロー成形ボトルの製造方法は、異な
る合成樹脂を内外に積層してなる積層パリソンを製造す
る工程と、該積層パリソンをブロー成形型内で延伸ブロ
ー成形して胴部と口部とを有するボトルを成形する工程
と、該ボトル胴部の壁部の内側合成樹脂層と外側合成樹
脂層とを剥離させる工程とを含むことを特徴とするもの
である。積層パリソンの製造は、内側合成樹脂層と外側
合成樹脂層とをそれぞれ別の射出成形金型を用いて射出
成形しても良く、また、2層押出成形機によって成形す
ることもでき、その他適宜の手段によって製造できる。
The bottle in which the inner synthetic resin layer and the outer synthetic resin layer have been peeled in advance can be manufactured by the following method. That is, the method for producing a stretch blow-molded bottle of the present invention comprises the steps of producing a laminated parison by laminating different synthetic resins inside and outside, and stretching and blow molding the laminated parison in a blow mold to form a trunk and a mouth. And a step of separating the inner synthetic resin layer and the outer synthetic resin layer of the wall of the bottle body from each other. In the production of the laminated parison, the inner synthetic resin layer and the outer synthetic resin layer may be injection-molded using different injection molding dies, respectively, or may be formed by a two-layer extruder, and other suitable It can be manufactured by means of

【0017】上記製造方法において、好ましくは、内側
合成樹脂層材料を飽和ポリエステルとし、外側合成樹脂
層材料をポリオレフィンとすることができる。また、内
側合成樹脂層と外側合成樹脂層との剥離は、ボトル胴部
を外周側から押圧して弾性変形させることにより行うこ
とができ、その他の適宜の手段によって剥離させること
ができる。
In the above manufacturing method, preferably, the inner synthetic resin layer material is a saturated polyester and the outer synthetic resin layer material is a polyolefin. In addition, the inner synthetic resin layer and the outer synthetic resin layer can be peeled off by pressing the bottle body from the outer peripheral side to be elastically deformed, and can be peeled off by other appropriate means.

【0018】また、本発明の他の延伸ブロー成形ボトル
の製造方法は、飽和ポリエステルからなる内側合成樹脂
層と、α−オレフィンが添加混合されたポリオレフィン
からなる外側合成樹脂層とが積層された積層パリソンを
製造する工程と、該積層パリソンをブロー成形型内で延
伸ブロー成形して胴部と口部とを有するボトルを成形す
る工程とを含むことを特徴とするものである。これによ
れば、ポリオレフィンに接着性を高めるα−オレフィン
が添加混合されているので、ブロー成形後に内側合成樹
脂層と外側合成樹脂層との間で良好な接着性が得られ、
気泡状の模様が出現することが防止される。
In another aspect of the present invention, there is provided a method for producing a stretch blow-molded bottle, comprising a step of laminating an inner synthetic resin layer made of a saturated polyester and an outer synthetic resin layer made of a polyolefin mixed with an α-olefin. The method includes a step of manufacturing a parison and a step of forming a bottle having a body and a mouth by stretch-blowing the laminated parison in a blow mold. According to this, since the α-olefin that increases the adhesiveness is added to and mixed with the polyolefin, good adhesiveness is obtained between the inner synthetic resin layer and the outer synthetic resin layer after blow molding,
The appearance of a bubble-like pattern is prevented.

【0019】[0019]

【発明の実施の形態】以下、本発明の実施の形態を図示
実施例と共に説明する。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below with reference to the drawings.

【0020】〔第1実施形態〕図1は本発明の第1の実
施の形態に係る液剤用容器である点眼剤容器1を簡略し
て示すものであって、該容器1は、口部2及び胴部3を
有するボトル4と、該ボトル4の口部2に取付けられる
ノズル5と、口部2に着脱自在に取付けられるキャップ
6とを備えている。
[First Embodiment] FIG. 1 schematically shows an ophthalmic solution container 1 which is a container for a liquid agent according to a first embodiment of the present invention. And a bottle 4 having a body 3, a nozzle 5 attached to the mouth 2 of the bottle 4, and a cap 6 detachably attached to the mouth 2.

【0021】上記ボトル4は、その胴部3がスクイズ性
を有する有底円筒状の点眼ボトルである。したがって、
キャップ6を口部2から取り外してボトル4を上下反転
し、胴部3を外周側から指などで押圧することにより径
方向内方に弾性変形することで、ノズル5からボトル4
内の薬液を点眼することが可能である。また、ボトル4
の口部2は上部側が開口されるとともに、外周にはキャ
ップ取付用の螺旋状のネジ部7が設けられている。
The bottle 4 is a cylindrical ophthalmic bottle with a bottom having a squeezing property. Therefore,
The cap 4 is removed from the mouth 2 and the bottle 4 is turned upside down. The body 3 is elastically deformed inward in the radial direction by pressing the body 3 with a finger or the like from the outer peripheral side.
It is possible to instill the drug solution inside. In addition, bottle 4
The opening 2 has an opening on the upper side, and a helical screw portion 7 for attaching a cap is provided on the outer periphery.

【0022】また、ボトル4は、材質の異なる合成樹脂
層8,9を内外に積層形成してなるものである。かかる
積層ボトル4は、射出成形法、ダイレクトブロー成形
法、インジェクションブロー成形法等の従来公知の適宜
の方法を用いて成形することができる。本実施形態に係
るボトル4の特徴的部分は、ボトル胴部3の内側合成樹
脂層8と外側合成樹脂層9とが全周にわたって剥離され
ている点である。即ち、射出成形法や延伸ブロー成形法
等によって内外の合成樹脂層8,9を有するボトル4を
成形した時点では、成形時に樹脂が可塑化する程度に加
熱されるため、各層8,9の界面において接着性を示
す。本実施形態では、ボトルを冷却固化した後、適宜の
手段によってボトル胴部3の内層8と外層9とを剥離さ
せている。
The bottle 4 is formed by laminating synthetic resin layers 8, 9 of different materials inside and outside. Such a laminated bottle 4 can be formed using a conventionally known appropriate method such as an injection molding method, a direct blow molding method, or an injection blow molding method. A characteristic part of the bottle 4 according to the present embodiment is that the inner synthetic resin layer 8 and the outer synthetic resin layer 9 of the bottle body 3 are peeled over the entire circumference. That is, when the bottle 4 having the inner and outer synthetic resin layers 8 and 9 is formed by injection molding or stretch blow molding, the resin is heated to the extent that the resin is plasticized during molding. Shows adhesiveness. In the present embodiment, after the bottle is cooled and solidified, the inner layer 8 and the outer layer 9 of the bottle body 3 are separated by an appropriate means.

【0023】かかる剥離は、例えば、図2に示すよう
に、生産ラインの中途部にゴムローラ10を配設し、ロ
ーラ10によってボトル胴部3を径方向外方から押圧す
ることによって行うことができる。図示例では、生産ラ
イン中途部のガイドレール11の幅方向両側に、搬送方
向に複数の押圧ローラ10を配設し、各ローラ10を回
転駆動させるとともに、幅方向両側の各ローラ10の回
転数を異ならせることにより、ボトル4を回転させなが
らその胴部3の周壁部を径方向内方に圧縮変形し得るよ
うに構成している。本発明は、かかる剥離方法に限定さ
れるものではなく、適宜の方法で内層8と外層9とを剥
離させることが可能である。ボトル成形直後の内層8と
外層9との接着力は、これら各層を構成する分子間の弱
い結合力によるものであるから、上記の剥離工程を経た
後は、各層8,9は互いに接触しているに止まり、これ
らの間に互いの接着性を有しない状態となる。
Such peeling can be performed, for example, by disposing a rubber roller 10 in the middle of the production line as shown in FIG. 2, and pressing the bottle body 3 from the outside in the radial direction by the roller 10. . In the illustrated example, a plurality of pressing rollers 10 are disposed in the conveying direction on both sides in the width direction of the guide rail 11 in the middle of the production line, and each of the rollers 10 is driven to rotate. Are configured so that the peripheral wall of the body 3 can be compressed and deformed radially inward while rotating the bottle 4. The present invention is not limited to such a peeling method, and the inner layer 8 and the outer layer 9 can be peeled by an appropriate method. Since the adhesion between the inner layer 8 and the outer layer 9 immediately after the bottle molding is due to the weak bonding force between the molecules constituting these layers, the layers 8 and 9 come into contact with each other after the above-described peeling step. And there is no adhesion between them.

【0024】内側合成樹脂層8の構成材料としては、ポ
リエステル系合成樹脂材料を用いることができる。ポリ
エステルは縮合重合により合成される高分子材料であ
る。縮合重合とは、高温、真空雰囲気で2つの分子から
水やアルコールなどの低分子が取れて、徐々に分子量が
増加していく逐次重合反応である。このポリエステル
は、エステル結合という極性基を有するため、分子間に
働くファンデルワールス力が強く、一般に比較的硬質の
高分子材料として知られている。ポリエステル系合成樹
脂材料としては、ポリエステルの他、PET(ポリエチ
レンテレフタレート)やPEN(ポリエチレンナフタレ
ート)などの飽和ポリエステルが知られている。
As a constituent material of the inner synthetic resin layer 8, a polyester synthetic resin material can be used. Polyester is a polymer material synthesized by condensation polymerization. Condensation polymerization is a sequential polymerization reaction in which low molecules such as water and alcohol are removed from two molecules in a high-temperature, vacuum atmosphere, and the molecular weight gradually increases. Since this polyester has a polar group called an ester bond, Van der Waals force acting between molecules is strong, and is generally known as a relatively hard polymer material. As polyester-based synthetic resin materials, saturated polyesters such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) are known in addition to polyester.

【0025】PETは、無色透明で光沢があり、無臭性
でガスバリアー性に優れるという性質を有する。インジ
ェクションブロー成形ボトルの内層8にPETを用いる
場合には、原材料としては、例えば、IV=0.8以上
の固相重合PETレジンを用いることができる。このP
ETレジンを用いて有底筒状のパリソンを射出成形し、
該PETパリソンの外周側に後述する外側合成樹脂層9
を積層して図3に示す積層パリソン12を製造し、該積
層パリソン12をブロー成形型(図示せず)内にインサ
ートして延伸ブロー成形することによって、上記した積
層ボトル4を得ることが可能である。
PET has the properties of being colorless, transparent, glossy, odorless, and excellent in gas barrier properties. When PET is used for the inner layer 8 of the injection blow-molded bottle, for example, solid-state polymerized PET resin having an IV of 0.8 or more can be used as a raw material. This P
Injection molding of a bottomed cylindrical parison using ET resin,
An outer synthetic resin layer 9 to be described later is provided on the outer peripheral side of the PET parison.
Are laminated to produce a laminated parison 12 shown in FIG. 3, and the laminated parison 12 is inserted into a blow mold (not shown) and stretch blow-molded to obtain the laminated bottle 4 described above. It is.

【0026】ダイレクトブロー成形積層ボトルの内層8
にPETを用いる場合は、チューブ状に押し出すために
溶融PETレジンの粘度は高くなければならず、また、
ボトルを延伸していないのでPETそのものの物性も高
くなければならない。そのため、通常、小型のダイレク
トブローボトル成形には、IV=1.0以上の固相重合
PETレジンを使用する。
Inner layer 8 of direct blow molded laminated bottle
When PET is used, the viscosity of the molten PET resin must be high in order to extrude it into a tube,
Since the bottle is not stretched, the physical properties of PET itself must be high. For this reason, a solid-state polymerized PET resin having an IV of 1.0 or more is usually used for compact direct blow bottle molding.

【0027】PEN(ポリエチレンナフタレート)は、
2,6ナフタリンジカルボン酸とエチレングリコールか
らの縮合重合されたポリエステルである。このPEN
も、耐熱性、ガスバリアー性、強度が比較的高い性質を
有し、PETとほぼ同様に取り扱うことが可能である。
PEN (polyethylene naphthalate) is
It is a polyester obtained by condensation polymerization of 2,6 naphthalene dicarboxylic acid and ethylene glycol. This PEN
Also have relatively high heat resistance, gas barrier properties, and strength, and can be handled almost in the same manner as PET.

【0028】外側合成樹脂層9の構成材料としては、オ
レフィン系合成樹脂材料を用いることができ、好ましく
は、PP(ポリプロピレン)、PE(ポリエチレン)又
はCOP(Circle Orefin Polymer )などのポリオレフ
ィンを使用する。
As the constituent material of the outer synthetic resin layer 9, an olefin-based synthetic resin material can be used. Preferably, a polyolefin such as PP (polypropylene), PE (polyethylene) or COP (Circle Orefin Polymer) is used. .

【0029】PEには、大別してLDPE(低密度ポリ
エチレン)、HDPE(高密度ポリエチレン)がある
が、これらのいずれをも本発明のボトル構成材料として
用いることが可能である。
PE is roughly classified into LDPE (low-density polyethylene) and HDPE (high-density polyethylene), and any of these can be used as the bottle constituting material of the present invention.

【0030】ボトル構造の説明に戻ると、上記ボトル口
部2においては内側合成樹脂層8と外側合成樹脂層9と
が、ボトル軸方向並びに周方向への相対移動を規制する
ように凹凸嵌合している。より詳細には、内層8の口部
外周には、図4乃至図6にも示すように、周方向全周に
わたるフランジ状の横リブ13が上下一対形成されてい
るとともに、上下の横リブ13間には、周方向に間隔を
おいて複数の縦リブ14が形成されている。かかる内層
8の外面側に外層9を射出成形することで、内外層8,
9の凹凸嵌合を得ることができる。なお、ブロー成形法
によってボトル4を成形する場合には、図3に示すよう
に射出成形法により積層パリソン12を成形し、その口
部2をリップ型(図示せず)に装着してブロー成形型内
にパリソン12をインサートして延伸ブロー成形する。
なお、図示実施例では、金型構造に起因して、内層8の
上端部には外方に延びるフランジ部8aが形成され、該
フランジ部8aの下方側に外層9が積層形成されてい
る。
Returning to the description of the bottle structure, the inner synthetic resin layer 8 and the outer synthetic resin layer 9 in the bottle mouth portion 2 are fitted to each other so as to regulate relative movement in the axial and circumferential directions of the bottle. are doing. More specifically, as shown in FIGS. 4 to 6, a pair of upper and lower flange-like horizontal ribs 13 are formed on the outer periphery of the mouth of the inner layer 8 over the entire circumference in the circumferential direction. A plurality of vertical ribs 14 are formed at intervals in the circumferential direction. By injection molding the outer layer 9 on the outer surface side of the inner layer 8, the inner and outer layers 8,
Nine uneven fittings can be obtained. When the bottle 4 is molded by the blow molding method, as shown in FIG. 3, the laminated parison 12 is molded by the injection molding method, and the mouth portion 2 is attached to a lip mold (not shown) to blow mold. The parison 12 is inserted into the mold and stretch blow molded.
In the illustrated embodiment, an outwardly extending flange portion 8a is formed at the upper end of the inner layer 8 due to the mold structure, and an outer layer 9 is laminated below the flange portion 8a.

【0031】更にボトル4をインジェクションブロー成
形法により製造する実施例を挙げると、例えば、まず射
出成形機を用いて内層8を構成するPET製プリフォー
ムを成形してストックしておく。このPET製プリフォ
ームを別の金型にインサートして、その外面に外層9を
構成するPPを射出成形し、積層パリソン12を得る。
この積層パリソン12を加熱し、コールドパリソン延伸
ブロー成形機を用いてブローして、上記構造のボトル4
を得ることができる。なお、上記射出成形工程はコール
ドパリソンを成形する工程であるが、射出成形機を2台
用いてもよく、2色成形機を用いてもよく、また、射出
成形からブロー成形までを連続して行う成形機を用いる
ことも可能である。この実施例の製造方法では、ブロー
成形前のパリソンの加熱が外部加熱だけであっても、内
層のPETがPPの支えになって安定したブロー成形を
行うことも可能となる。一般的には、PETよりもPP
の法がブロー温度が高く、PPのコールドパリソンはド
ローダウンや変形が生じて安定したブロー成形を行うこ
とができないが、積層パリソンを用いることで良好なブ
ロー成形を行い得る。
Further, in an embodiment in which the bottle 4 is manufactured by the injection blow molding method, for example, first, a PET preform constituting the inner layer 8 is molded and stocked by using an injection molding machine. The PET preform is inserted into another mold, and PP constituting the outer layer 9 is injection-molded on the outer surface of the preform to obtain a laminated parison 12.
The laminated parison 12 is heated and blown using a cold parison stretch blow molding machine to form a bottle 4 having the above structure.
Can be obtained. The injection molding step is a step of molding a cold parison. However, two injection molding machines may be used, or a two-color molding machine may be used. It is also possible to use a molding machine that performs this. In the manufacturing method of this embodiment, even if the parison is heated only by external heating before blow molding, it is possible to perform stable blow molding by supporting the PET of the inner layer with PP. In general, PP rather than PET
In the method (1), the blow temperature is high, and a cold parison of PP cannot be stably blow-molded due to drawdown or deformation. However, good blow-molding can be performed by using a laminated parison.

【0032】上記ノズル5は、全体としてほぼ筒状であ
って、上下中途部に内層フランジ部8aに当接するフラ
ンジ部5aが設けられている。このフランジ部5aより
も下部側の部分は若干先絞り状の円筒形状を呈してお
り、ボトル内層8の開口部に挿入される。このノズル5
の構成材料は種々のものを用いることができるが、水蒸
気バリア性、ガスバリア性、耐薬品性の高いものが好ま
しく、例えば、ポリオレフィンを用いることが可能であ
る。
The nozzle 5 has a substantially cylindrical shape as a whole, and is provided with a flange portion 5a which comes into contact with the inner-layer flange portion 8a at an intermediate portion in the vertical direction. The portion below the flange portion 5a has a slightly tapered cylindrical shape, and is inserted into the opening of the bottle inner layer 8. This nozzle 5
Although various materials can be used as the constituent material, those having high water vapor barrier properties, gas barrier properties, and chemical resistance are preferable. For example, polyolefin can be used.

【0033】上記キャップ6は、ボトル口部2の外周側
並びに上部を覆うように口部2に取付けられるものであ
って、周壁部6aと天蓋部6bとを有する。周壁部6a
の内面には、口部2のねじ部7に係合する突起15が適
宜の箇所に設けられており、該キャップ6を口部2に対
して相対回転することによりキャップ6の着脱が行われ
る。天蓋部6bの内面には、ノズル5の先端開口をシー
ルする凹部16が設けられており、キャップ6を口部2
にねじ込むことによりノズル5先端が凹部16に密接さ
れ、ノズル5先端開口からの薬液の漏れ、並びに、水蒸
気透過を防止し得るようになっている。
The cap 6 is attached to the mouth 2 so as to cover the outer peripheral side and the upper portion of the bottle mouth 2, and has a peripheral wall 6a and a canopy 6b. Surrounding wall 6a
On the inner surface, a protrusion 15 that engages with the screw portion 7 of the mouth portion 2 is provided at an appropriate location, and the cap 6 is attached and detached by rotating the cap 6 relative to the mouth portion 2. . On the inner surface of the canopy portion 6b, a concave portion 16 for sealing the opening at the tip of the nozzle 5 is provided.
By screwing the nozzle 5 into the nozzle 5, the tip of the nozzle 5 is brought into close contact with the recess 16 so that leakage of the chemical solution from the opening of the tip of the nozzle 5 and permeation of water vapor can be prevented.

【0034】さらに、キャップ6を口部2に取付けたと
き、即ち、上記ノズル5先端が凹部16に密接されたと
きに、同時に、キャップ6の下端周縁部が、ボトル4の
外面(図示例では、ボトル4の肩部)に気密に接触する
ようになっている。これによれば、上記内層8のフラン
ジ部8aからの極微量の水蒸気透過があっても、かかる
水蒸気がキャップ6の下端部から外方に漏れ出すことを
キャップ6とボトル4との接触によって防止でき、キャ
ップ6内の空間で水蒸気を飽和させることで、それ以上
の水蒸気透過減量を防止でき、より一層の長期保存性の
向上を図りうる。
Further, when the cap 6 is attached to the mouth 2, that is, when the tip of the nozzle 5 is brought into close contact with the recess 16, the lower peripheral edge of the cap 6 is simultaneously attached to the outer surface of the bottle 4 (in the illustrated example). , The shoulder of the bottle 4). According to this, even if a very small amount of water vapor permeates from the flange portion 8 a of the inner layer 8, the water vapor is prevented from leaking outward from the lower end of the cap 6 by contact between the cap 6 and the bottle 4. By saturating water vapor in the space inside the cap 6, further reduction in water vapor transmission can be prevented, and the long-term storage property can be further improved.

【0035】〔第2実施形態〕以下、本発明の第2実施
形態について説明するが、殆どの構成は上記第1実施形
態と同様であるので同符号を付して詳細説明を省略し、
異なる構成、作用効果について説明する。
[Second Embodiment] Hereinafter, a second embodiment of the present invention will be described. However, since most of the structure is the same as that of the first embodiment, the same reference numerals are given and the detailed description is omitted.
The different configurations, functions and effects will be described.

【0036】上記第1実施形態では、ボトル4の成形
後、液剤(薬液)の充填前に予め内層8と外層9とをボ
トル胴部において剥離させたが、気泡状の剥がれを防止
するために、両層8,9を剥離させることなくこれらの
接着性を向上させることも可能である。かかる本実施形
態の液剤用容器は、胴部3と口部2とを有するボトル4
と、該ボトル4の口部2に着脱自在に取付けられるキャ
ップ6とを備え、ボトル4は、材質の異なる合成樹脂層
8,9を内外に積層形成してなるものであって、該ボト
ル胴部3の内側合成樹脂層8と外側合成樹脂層9との接
着性を高める添加材料が、内側合成樹脂層8を構成する
合成樹脂及び/又は外側合成樹脂層9を構成する合成樹
脂中に混合されているものである。
In the first embodiment, after the bottle 4 is formed, the inner layer 8 and the outer layer 9 are peeled off at the bottle body before filling with the liquid agent (chemical solution). It is also possible to improve the adhesiveness of these layers without peeling off both layers 8 and 9. The liquid medicine container according to the present embodiment includes a bottle 4 having a body 3 and a mouth 2.
And a cap 6 detachably attached to the mouth 2 of the bottle 4. The bottle 4 is formed by laminating synthetic resin layers 8, 9 of different materials inside and outside. An additive material for improving the adhesiveness between the inner synthetic resin layer 8 and the outer synthetic resin layer 9 of the part 3 is mixed with the synthetic resin forming the inner synthetic resin layer 8 and / or the synthetic resin forming the outer synthetic resin layer 9. Is what is being done.

【0037】添加材料は、内層8及び外層9を構成する
合成樹脂材料に応じて適宜選定される。例えば、内側合
成樹脂材料として飽和ポリエステルを用い、外側合成樹
脂材料としてポリオレフィンを用いる場合には、該ポリ
オレフィンに少量のα−オレフィン(例えば1−ヘキサ
ンなど)を添加混合した材料を用いて外側合成樹脂層9
を内側合成樹脂層8の外周側に積層するように射出成形
する。これにより、内層8と外層9との接着性が向上さ
れ、内層8と外層9との剥離が防止される。
The additive material is appropriately selected according to the synthetic resin material constituting the inner layer 8 and the outer layer 9. For example, when a saturated polyester is used as the inner synthetic resin material and a polyolefin is used as the outer synthetic resin material, a material obtained by adding and mixing a small amount of an α-olefin (for example, 1-hexane or the like) to the polyolefin is used. Layer 9
Is formed on the outer peripheral side of the inner synthetic resin layer 8 by injection molding. Thereby, the adhesiveness between the inner layer 8 and the outer layer 9 is improved, and the separation between the inner layer 8 and the outer layer 9 is prevented.

【0038】かかるボトル4を延伸ブロー成形によって
製造する方法としては、例えば、飽和ポリエステルから
なる内側合成樹脂層と、α−オレフィンが添加混合され
たポリオレフィンからなる外側合成樹脂層とが積層され
た積層パリソンを射出成形法により製造する工程と、該
積層パリソンをブロー成形型内で延伸ブロー成形して胴
部と口部とを有するボトルを成形する工程とを含むもの
が挙げられる。その他の適宜の方法によってボトル4を
製造し得ることは勿論である。本発明は上記各実施の形
態に限定されるものではなく、適宜設計変更し得ること
は勿論である。例えば、内層材料としてポリオレフィン
を用い、外層材料として飽和ポリエステルを用いた場合
には、ポリエステルとの接触を嫌う液剤用容器として好
適に用いることができるとともに、酸素バリアー性の向
上と、内容保香剤等のガス成分の拡散防止とを図ること
が可能である。
As a method for producing such a bottle 4 by stretch blow molding, for example, a method of laminating an inner synthetic resin layer made of a saturated polyester and an outer synthetic resin layer made of a polyolefin mixed with an α-olefin is used. The method includes a step of manufacturing a parison by an injection molding method, and a step of forming a bottle having a body and a mouth by stretch-blowing the laminated parison in a blow mold. Needless to say, the bottle 4 can be manufactured by another appropriate method. The present invention is not limited to the above embodiments, and it is needless to say that the design can be appropriately changed. For example, when a polyolefin is used as the inner layer material and a saturated polyester is used as the outer layer material, it can be suitably used as a container for a liquid agent which dislikes contact with the polyester, and has an improved oxygen barrier property and a content flavoring agent. It is possible to prevent the diffusion of gas components such as.

【0039】[0039]

【発明の効果】本発明の液剤用容器によれば、材質の異
なる合成樹脂材料を内外に積層してなる積層ボトルを用
いたので、薬効成分の吸着の低減、水蒸気透過減量の解
消等を一挙に達成できるとともに、長期保存によっても
ボトルの内外層間に気泡が生じず、外層の方が水蒸気バ
リアー性が高い場合でも胴部に気泡状の剥離現象が生じ
ることが解消される。
According to the liquid medicine container of the present invention, since a laminated bottle in which synthetic resin materials of different materials are laminated inside and outside is used, reduction of adsorption of a medicinal component, elimination of loss of water vapor transmission, etc. can be achieved at once. In addition, no bubbles are generated between the inner and outer layers of the bottle even after long-term storage, and even when the outer layer has a higher water vapor barrier property, the occurrence of a bubble-like peeling phenomenon in the body is eliminated.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明の実施の形態に係る液剤用容器の半縦断
面正面図である。
FIG. 1 is a semi-longitudinal cross-sectional front view of a liquid agent container according to an embodiment of the present invention.

【図2】同液剤用容器のボトルの内側合成樹脂層と外側
合成樹脂層との剥離方法を示す、生産ライン途中の簡略
平面図である。
FIG. 2 is a simplified plan view in the middle of a production line, showing a method of separating an inner synthetic resin layer and an outer synthetic resin layer of a bottle of the liquid agent container.

【図3】同ボトルを延伸ブロー成形法により製造する際
の積層パリソンの縦断面図である。
FIG. 3 is a longitudinal sectional view of a laminated parison when the bottle is manufactured by a stretch blow molding method.

【図4】同積層パリソンの内層合成樹脂の口部構造を示
す拡大斜視図である。
FIG. 4 is an enlarged perspective view showing a mouth structure of an inner layer synthetic resin of the laminated parison.

【図5】同液剤用容器の口部並びにキャップ取付構造を
示し、左半分は縦リブの存在しない部分の縦断面正面図
であり、右半分はキャップのみを断面で示した正面図で
ある。
FIG. 5 shows a mouth portion and a cap mounting structure of the liquid agent container, wherein the left half is a vertical sectional front view of a portion where no vertical rib is present, and the right half is a front view showing only the cap in cross section.

【図6】同液剤用容器の口部並びにキャップ取付構造を
示す、縦リブの存在する部分の縦断面図である。
FIG. 6 is a longitudinal sectional view of a portion where a vertical rib exists, showing a mouth portion and a cap mounting structure of the liquid agent container.

【符号の説明】[Explanation of symbols]

1 液剤用容器(点眼剤容器) 2 口部 3 胴部 4 ボトル(点眼ボトル) 5 ノズル 6 キャップ 8 内側合成樹脂層 9 外側合成樹脂層 12 積層パリソン 13 横リブ 14 縦リブ DESCRIPTION OF SYMBOLS 1 Liquid container (eyedrop container) 2 Mouth 3 Body 4 Bottle (Eyedrop bottle) 5 Nozzle 6 Cap 8 Inner synthetic resin layer 9 Outer synthetic resin layer 12 Laminated parison 13 Horizontal rib 14 Vertical rib

Claims (10)

【特許請求の範囲】[Claims] 【請求項1】 胴部(3)と口部(2)とを有するボト
ル(4)と、該ボトル(4)の口部(2)に着脱自在に
取付けられるキャップ(6)とを備え、前記ボトル
(4)は、材質の異なる合成樹脂層(8,9)を内外に
積層形成してなるものであって、該ボトル胴部(3)の
内側合成樹脂層(8)と外側合成樹脂層(9)との間に
互いの接着性を有しないことを特徴とする液剤用容器。
A bottle (4) having a body (3) and a mouth (2), and a cap (6) detachably attached to the mouth (2) of the bottle (4), The bottle (4) is formed by laminating synthetic resin layers (8, 9) of different materials inside and outside, and the inner synthetic resin layer (8) and the outer synthetic resin of the bottle body (3). A container for a liquid agent, which has no mutual adhesiveness with the layer (9).
【請求項2】 胴部(3)と口部(2)とを有するボト
ル(4)と、該ボトル(4)の口部(2)に着脱自在に
取付けられるキャップ(6)とを備え、前記ボトル
(4)は、材質の異なる合成樹脂層(8,9)を内外に
積層形成してなるものであって、該ボトル胴部(3)の
内側合成樹脂層(8)と外側合成樹脂層(9)との接着
性を高める添加材料が、内側合成樹脂層(8)を構成す
る合成樹脂及び/又は外側合成樹脂層(9)を構成する
合成樹脂中に混合されていることを特徴とする液剤用容
器。
2. A bottle (4) having a body (3) and a mouth (2), and a cap (6) detachably attached to the mouth (2) of the bottle (4), The bottle (4) is formed by laminating synthetic resin layers (8, 9) of different materials inside and outside, and the inner synthetic resin layer (8) and the outer synthetic resin of the bottle body (3). An additive material for improving the adhesiveness with the layer (9) is mixed in the synthetic resin constituting the inner synthetic resin layer (8) and / or the synthetic resin constituting the outer synthetic resin layer (9). Liquid container.
【請求項3】 ボトル口部(2)において内外側合成樹
脂層(8,9)がボトル軸方向並びに周方向への相対移
動を規制するように凹凸嵌合していることを特徴とする
請求項1又は2に記載の液剤用容器。
3. A method according to claim 1, wherein the inner and outer synthetic resin layers (8, 9) are fitted into the bottle mouth (2) so as to restrict relative movement in the axial direction and the circumferential direction of the bottle. Item 3. The liquid container according to Item 1 or 2.
【請求項4】 ボトル(4)は、その胴部(3)がスク
イズ性を有する有底円筒状の点眼ボトルであることを特
徴とする請求項1,2又は3に記載の液剤用容器。
4. The liquid container according to claim 1, wherein the bottle (4) is a cylindrical ophthalmic bottle with a bottom having a squeezing property.
【請求項5】 ボトル(4)の内側合成樹脂層(8)材
料が飽和ポリエステルであり、外側合成樹脂層(9)材
料がポリオレフィンであることを特徴とする請求項1乃
至4のいずれか1項に記載の液剤用容器。
5. The bottle according to claim 1, wherein the material of the inner synthetic resin layer (8) of the bottle (4) is a saturated polyester and the material of the outer synthetic resin layer (9) is a polyolefin. A container for a liquid agent according to the above item.
【請求項6】 ボトル(4)の内側合成樹脂層(8)材
料がポリオレフィンであり、外側合成樹脂層(9)材料
が飽和ポリエステルであることを特徴とする請求項1乃
至4のいずれか1項に記載の液剤用容器。
6. The bottle according to claim 1, wherein the material of the inner synthetic resin layer of the bottle is polyolefin and the material of the outer synthetic resin layer is a saturated polyester. A container for a liquid agent according to the above item.
【請求項7】 キャップ(6)は、ボトル口部(2)の
外周側を覆うように口部(2)に取付けられ、該キャッ
プ(6)の下端周縁部が、ボトル(4)の外面に気密に
接触していることを特徴とする請求項5又は6に記載の
液剤用容器。
7. A cap (6) is attached to the mouth (2) so as to cover an outer peripheral side of the bottle mouth (2), and a lower peripheral edge of the cap (6) is attached to an outer surface of the bottle (4). The liquid container according to claim 5, wherein the container is in airtight contact with the container.
【請求項8】 異なる合成樹脂を内外に積層してなる積
層パリソン(12)を製造する工程と、該積層パリソン
(12)をブロー成形型内で延伸ブロー成形して胴部
(3)と口部(2)とを有するボトル(4)を成形する
工程と、該ボトル胴部(3)の壁部の内側合成樹脂層
(8)と外側合成樹脂層(9)とを剥離させる工程とを
含むことを特徴とする液剤用延伸ブロー成形ボトルの製
造方法。
8. A process for producing a laminated parison (12) comprising different synthetic resins laminated inside and outside, and stretching and blow molding the laminated parison (12) in a blow mold to form a body (3) and a mouth. A step of molding a bottle (4) having a portion (2) and a step of peeling off the inner synthetic resin layer (8) and the outer synthetic resin layer (9) of the wall of the bottle body (3). A method for producing a stretch blow-molded bottle for a liquid agent, comprising:
【請求項9】 内側合成樹脂層(8)材料が飽和ポリエ
ステルであり、外側合成樹脂層(9)材料がポリオレフ
ィンであり、内側合成樹脂層(8)と外側合成樹脂層
(9)との剥離は、ボトル胴部(3)を外周側から押圧
して弾性変形させることにより行うことを特徴とする請
求項8に記載の液剤用延伸ブロー成形ボトルの製造方
法。
9. The separation between the inner synthetic resin layer (8) and the outer synthetic resin layer (9), wherein the material of the inner synthetic resin layer (8) is a saturated polyester and the material of the outer synthetic resin layer (9) is a polyolefin. 9. The method for producing a stretch blow-molded bottle for a liquid agent according to claim 8, wherein the step (b) is performed by pressing the bottle body (3) from the outer peripheral side to elastically deform the bottle body.
【請求項10】 飽和ポリエステルからなる内側合成樹
脂層(8)と、α−オレフィンが添加混合されたポリオ
レフィンからなる外側合成樹脂層(9)とが積層された
積層パリソン(12)を製造する工程と、該積層パリソ
ン(12)をブロー成形型内で延伸ブロー成形して胴部
(3)と口部(2)とを有するボトル(4)を成形する
工程とを含むことを特徴とする液剤用延伸ブロー成型ボ
トルの製造方法。
10. A process for producing a laminated parison (12) in which an inner synthetic resin layer (8) made of a saturated polyester and an outer synthetic resin layer (9) made of a polyolefin mixed with an α-olefin are stacked. And a step of stretch-blowing the laminated parison (12) in a blow mold to form a bottle (4) having a body (3) and a mouth (2). For manufacturing stretch blow-molded bottles.
JP17653099A 1999-06-23 1999-06-23 Liquid container and method for producing stretch blow molded bottle for liquid Expired - Lifetime JP4065082B2 (en)

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Applications Claiming Priority (1)

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Publication Number Publication Date
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JP4065082B2 JP4065082B2 (en) 2008-03-19

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JP2012100737A (en) * 2010-11-08 2012-05-31 Yoshida Industry Co Ltd Multilayer cosmetic container
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WO2013099861A1 (en) * 2011-12-27 2013-07-04 千寿製薬株式会社 Dibutylhydroxytoluene-containing preparation, and method for stabilizing dibutylhydroxytoluene
JP2014213927A (en) * 2013-04-30 2014-11-17 株式会社吉野工業所 Method for manufacturing double container and double container
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US11834226B2 (en) 2007-04-19 2023-12-05 Anheuser-Busch Inbev S.A. Integrally blow-moulded bag-in-container having interface vents opening to the atmosphere at location adjacent to bag's mouth; preform for making it; and processes for producing the preform and bag-in-container
US11890784B2 (en) 2007-04-19 2024-02-06 Anheus Er-Busch Inbev S.A. Integrally blow-moulded bag-in-container having an inner layer and the outer layer made of the same material and preform for making it

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5327873A (en) * 1976-08-24 1978-03-15 Sumitomo Chemical Co Container made from polyester resin
JPH0464440A (en) * 1990-07-03 1992-02-28 Kao Corp Multilayer plastic vessel and its manufacture
JPH04339759A (en) * 1990-12-28 1992-11-26 Yoshino Kogyosho Co Ltd Laminated bottle and manufacture thereof
JPH06345069A (en) * 1993-06-14 1994-12-20 Toyo Seikan Kaisha Ltd Laminated layer separable bottle and production thereof
JPH10249920A (en) * 1997-03-13 1998-09-22 Ishizuka Glass Co Ltd Resin container molded object and mold thereof
JPH10329855A (en) * 1997-05-30 1998-12-15 Lion Corp Dripping container

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5327873A (en) * 1976-08-24 1978-03-15 Sumitomo Chemical Co Container made from polyester resin
JPH0464440A (en) * 1990-07-03 1992-02-28 Kao Corp Multilayer plastic vessel and its manufacture
JPH04339759A (en) * 1990-12-28 1992-11-26 Yoshino Kogyosho Co Ltd Laminated bottle and manufacture thereof
JPH06345069A (en) * 1993-06-14 1994-12-20 Toyo Seikan Kaisha Ltd Laminated layer separable bottle and production thereof
JPH10249920A (en) * 1997-03-13 1998-09-22 Ishizuka Glass Co Ltd Resin container molded object and mold thereof
JPH10329855A (en) * 1997-05-30 1998-12-15 Lion Corp Dripping container

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241279A (en) * 2001-02-16 2002-08-28 Kanebo Ltd Package-containing product and method for preventing adsorption
JP2005047172A (en) * 2003-07-30 2005-02-24 Yoshino Kogyosho Co Ltd Method for blow-molding double container and blow-molded double container
US11834226B2 (en) 2007-04-19 2023-12-05 Anheuser-Busch Inbev S.A. Integrally blow-moulded bag-in-container having interface vents opening to the atmosphere at location adjacent to bag's mouth; preform for making it; and processes for producing the preform and bag-in-container
US11890784B2 (en) 2007-04-19 2024-02-06 Anheus Er-Busch Inbev S.A. Integrally blow-moulded bag-in-container having an inner layer and the outer layer made of the same material and preform for making it
JP2009101589A (en) * 2007-10-23 2009-05-14 Menicon Co Ltd Preserving laminate sheet and preserving container for solution containing cationic disinfectant ingredient
JP2011093614A (en) * 2009-09-29 2011-05-12 Toppan Printing Co Ltd Packaging container
JP2011116373A (en) * 2009-11-30 2011-06-16 Yoshino Kogyosho Co Ltd Laminated container made of synthetic resin
JP2012100737A (en) * 2010-11-08 2012-05-31 Yoshida Industry Co Ltd Multilayer cosmetic container
JP2012206736A (en) * 2011-03-29 2012-10-25 Yoshino Kogyosho Co Ltd Synthetic resin-made container
JP5580944B2 (en) * 2011-12-27 2014-08-27 千寿製薬株式会社 Dibutylhydroxytoluene-containing preparation and method for stabilizing dibutylhydroxytoluene
JPWO2013099861A1 (en) * 2011-12-27 2015-05-07 千寿製薬株式会社 Dibutylhydroxytoluene-containing preparation and method for stabilizing dibutylhydroxytoluene
TWI554285B (en) * 2011-12-27 2016-10-21 Senju Pharma Co Preparation of dibutylhydroxytoluene and dibutylhydroxytoluene
WO2013099861A1 (en) * 2011-12-27 2013-07-04 千寿製薬株式会社 Dibutylhydroxytoluene-containing preparation, and method for stabilizing dibutylhydroxytoluene
JP2014213927A (en) * 2013-04-30 2014-11-17 株式会社吉野工業所 Method for manufacturing double container and double container
WO2020116654A1 (en) * 2018-12-07 2020-06-11 藤森工業株式会社 Ophthalmic solution container
JPWO2020116654A1 (en) * 2018-12-07 2021-10-28 藤森工業株式会社 Eye drop container

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