JPH05309648A - Multi-layer vessel and its manufacture - Google Patents
Multi-layer vessel and its manufactureInfo
- Publication number
- JPH05309648A JPH05309648A JP4116139A JP11613992A JPH05309648A JP H05309648 A JPH05309648 A JP H05309648A JP 4116139 A JP4116139 A JP 4116139A JP 11613992 A JP11613992 A JP 11613992A JP H05309648 A JPH05309648 A JP H05309648A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- resin
- container
- parison
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
- B29C45/1643—Making multilayered or multicoloured articles having a "sandwich" structure from at least three different materials or with at least four layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/081—Specified dimensions, e.g. values or ranges
- B29C2949/0811—Wall thickness
- B29C2949/0817—Wall thickness of the body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
- B29C2949/0872—Weight
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は２軸延伸ブローされた多
層容器およびその製造方法に関するものであり、更に詳
しくは透明性、ガスバリア−性、層間接着性、及び機械
的強度に優れた多層容器とその製造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 biaxially stretch-blown multilayer container and a method for producing the same, and more particularly to a multilayer container excellent in transparency, gas barrier property, interlayer adhesion and mechanical strength. And its manufacturing method.
【０００２】[0002]
【従来の技術】従来、炭酸飲料等の清涼飲料、果汁飲
料、ビール、日本酒等の酒類、調味料、油、化粧品、洗
剤などの容器として、ガラスが広く使用されてきたが、
ガラス容器は製造コスト、取扱い、安全性の面での欠点
を有している。これらの欠点を解消するためにガラス容
器からプラスチック容器への転換が進んでいる。特に透
明性が要求される炭酸飲料、調味料、果汁飲料、洗剤、
化粧品等の分野でポリエチレンテレフタレート（以下、
ＰＥＴと略記する）を主体とした樹脂からなる２軸配向
した容器が広く採用されている。2. Description of the Related Art Conventionally, glass has been widely used as a container for soft drinks such as carbonated drinks, fruit juice drinks, beer, liquors such as sake, seasonings, oils, cosmetics, detergents, etc.
Glass containers have drawbacks in terms of manufacturing cost, handling and safety. In order to eliminate these drawbacks, conversion from glass containers to plastic containers is in progress. Carbonated drinks, seasonings, fruit juice drinks, detergents, which require transparency in particular,
In the field of cosmetics, polyethylene terephthalate (hereinafter,
Biaxially oriented containers made of a resin mainly composed of PET) are widely used.
【０００３】しかし、熱可塑性ポリエステル樹脂からな
る２軸配向した容器も万全の性能を有している訳ではな
く、特に充填する内容物がガスバリアー性を高度に要求
する飲料品である場合には、その酸素および炭酸ガスに
対するガスバリアー性が不十分であった。ガスバリアー
性を改善するために、熱可塑性ポリエステル樹脂とガス
バリアー性樹脂であるメタキシリレン基含有ポリアミド
樹脂（以下、ＭＸナイロンと略記する）の２種類の樹脂
からなり、ＰＥＴを表面層にＭＸナイロンを中央層とし
た３層構造とした発明が特開昭第５７ー１２８５１６号
公報、特開昭第５７ー１２８５２０号公報、および特開
昭第５９ー９７１９１号公報に開示されている。However, a biaxially oriented container made of a thermoplastic polyester resin does not have perfect performance, and particularly when the content to be filled is a beverage requiring a high gas barrier property. However, its gas barrier property against oxygen and carbon dioxide was insufficient. In order to improve gas barrier properties, it is composed of two types of resins, a thermoplastic polyester resin and a gas-barrier resin, a metaxylylene group-containing polyamide resin (hereinafter abbreviated as MX nylon), and PET is used with MX nylon as a surface layer. Inventions having a three-layer structure with a central layer are disclosed in JP-A-57-128516, JP-A-57-128520, and JP-A-59-97191.
【０００４】[0004]
【発明が解決しようとする課題】上記の方法では、たし
かにガスバリアー性の特性が満足できるが、一般にガス
バリアー性樹脂とポリエチレンテレフタレート層間の接
着性が小さいため、落下や打撃等の機械的な力が加えら
れた場合、ポリエチレンテレフタレート樹脂層とガスバ
リアー性層樹脂層との間で、層間剥離を起こしやすいと
いう欠点を抱えていた。層間剥離を起こした容器は、、
その部分が複数のフィルムに分離するため幾分白く見
え、外観上好ましくない。In the above method, the gas barrier property is certainly satisfied, but since the adhesive property between the gas barrier resin and the polyethylene terephthalate layer is generally small, mechanical force such as dropping or hitting may occur. In the case of addition of the above-mentioned, there was a drawback that delamination is likely to occur between the polyethylene terephthalate resin layer and the gas barrier layer resin layer. Containers that have undergone delamination,
Since the part is separated into a plurality of films, it looks somewhat white, which is not preferable in appearance.
【０００５】[0005]
【課題を解決するための手段】本願の発明者等は、ガス
バリアー性を有し、同時に層間剥離を起こし難い多層容
器の開発について鋭意研究した結果、上記性能を同時に
満足する新規な容器およびその製造方法を見出し、本発
明に到達した。すなわち本発明は、熱可塑性樹脂Ａおよ
び熱可塑性樹脂Ｂを使用して製造した多層容器であり、
該容器の口部開口端部が熱可塑性樹脂Ａの単層構造より
なり、胴部肉薄部分は熱可塑性樹脂Ａの単層部分と熱可
塑性樹脂Ａと熱可塑性樹脂Ｂの多層部分とからなる多層
容器、および該容器の前駆体であるパリソンであり、そ
の製造方法として、熱可塑性樹脂Ａおよび熱可塑性樹脂
Ｂを、それぞれ専用の射出シリンダーから射出し、かつ
最初に熱可塑性樹脂Ａを、次に熱可塑性樹脂Ａと熱可塑
性樹脂Ｂの同時射出と熱可塑性樹脂Ａの単独射出とを交
互に繰り返し、最後に熱可塑性樹脂Ａを射出する方法を
提供するものである。The inventors of the present application have earnestly studied the development of a multilayer container having a gas barrier property and at the same time hardly causing delamination. The present invention has been achieved by finding a manufacturing method. That is, the present invention is a multi-layer container manufactured using a thermoplastic resin A and a thermoplastic resin B,
The mouth opening end of the container has a single-layer structure of thermoplastic resin A, and the thin-walled portion of the body is a multi-layer including a single-layer portion of thermoplastic resin A and a multi-layer portion of thermoplastic resin A and thermoplastic resin B. A container and a parison which is a precursor of the container, and as a method for producing the same, a thermoplastic resin A and a thermoplastic resin B are respectively injected from dedicated injection cylinders, and first the thermoplastic resin A and then the thermoplastic resin A are injected. It is intended to provide a method of alternately repeating simultaneous injection of thermoplastic resin A and thermoplastic resin B and individual injection of thermoplastic resin A, and finally injecting thermoplastic resin A.
【０００６】なお、以後熱可塑性樹脂Ａと熱可塑性樹脂
Ｂを、それぞれ樹脂Ａ、樹脂Ｂということがある。Incidentally, hereinafter, the thermoplastic resin A and the thermoplastic resin B may be referred to as resin A and resin B, respectively.
【０００７】本発明で使用しうる樹脂Ａとしては、機械
的強度、透明性および成形性の点から熱可塑性ポリエス
テル樹脂が例示できるが、なかでもポリエチレンテレフ
タレートを主体とした熱可塑性ポリエステル樹脂がこれ
らの性能をすべて満足する点から特に好ましい。The resin A which can be used in the present invention can be exemplified by a thermoplastic polyester resin in view of mechanical strength, transparency and moldability. Among them, a thermoplastic polyester resin mainly composed of polyethylene terephthalate is used. It is particularly preferable from the viewpoint of satisfying all the performances.
【０００８】熱可塑性ポリエステル樹脂とは、通常酸成
分 の８０モル％以上、好ましくは９０モル％以上がテ
レフタル酸であり、グリコール成分の８０モル％以上、
好ましくは９０％以上がエチレングリコールであるポリ
エステルを意味し、残部の他の酸成分としては、イソフ
タル酸、ジフェニルエーテル−４，４−ジカルボン酸、
ナフタレン−１，４または２，６−ジカルボン酸、アジ
ピン酸、セバシン酸、デカン−１，１０−ジカルボン
酸、ヘキサヒドロテレフタル酸を、また、他のグリコ−
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、ネオペンチルグリコール、ジエチレングリ
コール、シクロヘキサンジメタノール、２，２−ビス
（４−ヒドロキシエトキシフェニル）プロパン等を例示
することができる。The thermoplastic polyester resin is usually 80 mol% or more, preferably 90 mol% or more of the acid component is terephthalic acid, and 80 mol% or more of the glycol component.
Preferably 90% or more means a polyester in which ethylene glycol is used, and the remaining other acid components include isophthalic acid, diphenyl ether-4,4-dicarboxylic acid,
Naphthalene-1,4 or 2,6-dicarboxylic acid, adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, hexahydroterephthalic acid and also other glyco-
Examples of the component include propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyethoxyphenyl) propane and the like.
【０００９】更に、オキシ酸としてＰ−オキシ安息香酸
等を含有するポリエステル樹脂も例示することができ
る。これらの熱可塑性ポリエステル樹脂の固有粘度は、
0.55以上が適当であり、好ましくは0.65〜1.4 である。
固有粘度が0.55未満では、多層パリソンを透明な非晶状
態で得ることは困難であるほか、得られる容器の機械的
強度も不十分である。Further, a polyester resin containing P-oxybenzoic acid or the like as the oxyacid can be exemplified. The intrinsic viscosity of these thermoplastic polyester resins is
0.55 or more is suitable, and preferably 0.65 to 1.4.
When the intrinsic viscosity is less than 0.55, it is difficult to obtain the multilayer parison in a transparent amorphous state, and the mechanical strength of the obtained container is insufficient.
【００１０】本発明で使用しうる樹脂Ｂ、すなわち酸
素、炭酸ガス等のガスバリアー性に優れた熱可塑性樹脂
としては、ＭＸナイロン、エチレン・酢ビ共重合体、ポ
リアクリロニトリル共重合体、ポリ塩化ビニリデン樹脂
等が例示できるが、なかでも高湿度におけるガスバリア
ー性の点からＭＸナイロンが特に好ましい。Resin B which can be used in the present invention, that is, a thermoplastic resin having excellent gas barrier properties against oxygen, carbon dioxide, etc., is MX nylon, ethylene / vinyl acetate copolymer, polyacrylonitrile copolymer, polychlorinated resin. Although vinylidene resin and the like can be exemplified, MX nylon is particularly preferable from the viewpoint of gas barrier property at high humidity.
【００１１】ＭＸナイロンとは、メタキシリレンジアミ
ン単独、またはメタキシリレンジアミンおよび全量の30
％以下のパラキシリレンジアミンを含む混合キシリレン
ジアミンと炭素数6 〜10のα，ω−直鎖脂肪属ジカルボ
ン酸とから得られる構成単位を少なくとも70モル％以上
含有する重合体を意味する。これらの重合体の例として
は、ポリメタキシリレンアジパミド（以下「Ｎ−ＭＸＤ
６」と略記する）、ポリメタキシリレンセバカミド、ポ
リメタキシリレンスペラミド等のような単独重合体、メ
タキシリレン／パラキシリレンスペラミド共重合体のよ
うな共重合体およびこれらの単独もしくは共重合体を例
示できる。MX nylon means metaxylylenediamine alone, or metaxylylenediamine and the total amount of 30
% Of para-xylylenediamine and a polymer containing at least 70 mol% or more of a constituent unit obtained from a mixed xylylenediamine containing 6% or less of para-xylylenediamine and an α, ω-linear aliphatic dicarboxylic acid having 6 to 10 carbon atoms. Examples of these polymers include polymethaxylylene adipamide (hereinafter "N-MXD").
6 "), homopolymers such as polymeta-xylylene sebacamide, polymeta-xylylene speramide and the like, copolymers such as meta-xylylene / para-xylylene speramide copolymer, and homopolymers or copolymers thereof. An example is coalescence.
【００１２】さらに、上記単独もしくは共重合体の原料
の一部を、ヘキサメチレンジアミンのような脂肪属ジア
ミン、ピペラジンのような脂環式ジアミン、パラ−ビス
−（２−アミノエチル）ベンゼンのような芳香族ジアミ
ン、テレフタル酸のような芳香族ジカルボン酸、ε−カ
プロラクタムのようなω−アミノカルボン酸、パラ−ア
ミ安息香酸のような芳香族アミノカルボン酸で置き換え
た物も例示することができる。Further, a part of the raw material of the above homopolymer or copolymer may be used as an aliphatic diamine such as hexamethylenediamine, an alicyclic diamine such as piperazine, or para-bis- (2-aminoethyl) benzene. And aromatic dicarboxylic acids such as terephthalic acid, ω-aminocarboxylic acids such as ε-caprolactam, and aromatic aminocarboxylic acids such as para-amibenzoic acid may be used. ..
【００１３】また、これらの重合体に例えばナイロン6
、ナイロン66、ナイロン610 、ナイロン11等の重合体
を含有させてもよい。上記のＭＸナイロンの相対粘度
は、1.5以上であり、好ましくは2.0 〜4.0 である。Further, for example, nylon 6 can be added to these polymers.
Polymers such as nylon 66, nylon 610, and nylon 11 may be contained. The MX nylon has a relative viscosity of 1.5 or more, preferably 2.0 to 4.0.
【００１４】本発明で使用する樹脂としては、樹脂Ａと
してＰＥＴ、樹脂ＢとしてＭＸナイロンの組み合わせが
最も好ましい。この組み合わせが最も好ましい理由とし
ては、樹脂の持つ透明性、機械的強度、射出成形性、延
伸ブロー成形性、およびガスバリアー性のすべてにおい
て優れている為である。The resin used in the present invention is most preferably a combination of PET as the resin A and MX nylon as the resin B. The reason why this combination is most preferable is that the resin has excellent transparency, mechanical strength, injection moldability, stretch blow moldability, and gas barrier property.
【００１５】本発明においては、必要に応じて樹脂Ａお
よび／または樹脂Ｂの樹脂層に、着色剤、紫外線吸収
剤、耐電防止剤、酸化防止剤、滑剤、核剤等を本発明の
目的を損なわない範囲内で使用することができる。In the present invention, a colorant, an ultraviolet absorber, an antistatic agent, an antioxidant, a lubricant, a nucleating agent, etc. may be added to the resin layer of the resin A and / or the resin B, if necessary. It can be used within a range that does not impair it.
【００１６】本発明において、実用的な多層容器の胴部
肉厚は、200 〜 800μ、好ましくは250 〜 600μの範囲
である。In the present invention, the practical wall thickness of the multi-layer container is in the range of 200 to 800 μ, preferably 250 to 600 μ.
【００１７】ガスバリアー性と層間接着性の双方を兼ね
備えるためには、本発明の多層容器の胴部における樹脂
Ａの単層構造の部分に対する樹脂Ａと樹脂Ｂの多層構造
の部分の割合は３０％以上、好ましくは３０％以上であ
る。また、胴部における多層部分の数は、ボトルの形状
により異なるが、２か所以上、好ましくは４か所以上で
ある。In order to have both gas barrier properties and interlayer adhesion properties, the ratio of the multi-layer structure portion of resin A and resin B to the single-layer structure portion of resin A in the body of the multi-layer container of the present invention is 30. % Or more, preferably 30% or more. Further, the number of multi-layer portions in the body portion is 2 or more, preferably 4 or more, though it depends on the shape of the bottle.
【００１８】図１は本発明の容器の前駆体である多層パ
リソンの射出成形装置の一例を示す模式図である。この
装置は熱可塑性樹脂の種類と同数の２本の射出シリンダ
ー、樹脂Ａ用シリンダー１、樹脂Ｂ用シリンダー２とを
有し、各々のシリンダーで溶融した樹脂Ａ、樹脂Ｂとを
ゲートを通って金型内に順次射出するものである。FIG. 1 is a schematic view showing an example of an injection molding apparatus for a multi-layer parison which is a precursor of the container of the present invention. This device has two injection cylinders of the same number as the type of thermoplastic resin, a cylinder 1 for resin A, and a cylinder 2 for resin B, and the molten resin A and resin B in each cylinder pass through a gate. It is one that is sequentially injected into the mold.
【００１９】射出シーケンスを図２に示す。上記装置に
おいて本願発明のパリソンを射出成形するには最初に樹
脂Ａを射出し、次に樹脂Ａと樹脂Ｂを同時射出と、樹脂
Ａの単独射出を必要数だけ繰り返し、最後に樹脂Ａを射
出する。The injection sequence is shown in FIG. In the above apparatus, in order to injection-mold the parison of the present invention, the resin A is first injected, then the resin A and the resin B are simultaneously injected, and the resin A alone is repeated by the required number of times, and finally the resin A is injected. To do.
【００２０】上記シーケンスにしたがって該樹脂が金型
内に順次射出される様子を図３−Ａ、図３−Ｂ、図４−
Ａおよび図４−Ｂに示す。 第１射出（図３−Ａ） まず最初に、パリソンの口部単層部および内外表面層を
形成する樹脂Ａを単独射出する。 第２射出（図３−Ｂと図４−Ａ） 次に樹脂Ａと樹脂Ｂを同時射出と樹脂Ａの単独射出を必
要数だけ繰り返す。このとき、樹脂Ａと樹脂Ｂは図１の
ゲート部断面図に示すごとく、三重環構造のゲートを、
外側を樹脂Ａが、中間を樹脂Ｂが、そして中央を樹脂Ａ
が流れる環状流となって射出される。すなわち樹脂Ｂ
は、常に同時に射出された樹脂Ａによて囲まれながらキ
ャビティの中を進んでゆくので、第１射出において口部
単層部および内外表面層を形成すべく単独射出された樹
脂Ａと接触して冷却固化することがない。この第２射出
において、樹脂Ａと樹脂Ｂの同時射出の数だけ樹脂Ｂ層
がバリソンの肉厚方向中心部付近に軸方向に断続的に並
んで形成されることになる。 第３射出（図４−Ｂ） 最後に樹脂Ａを単独射出し、ゲート部まわりを樹脂Ａ単
層として射出を終了する。この結果、図４−Ｂに示す様
な口部開口端部が樹脂Ａの単層構造よりなり、胴部肉薄
部分が樹脂Ａのみの単層構造と樹脂Ａと樹脂Ｂの３層構
造が交互に繰り返す構造よりなる多層パリソンが得られ
る。FIG. 3-A, FIG. 3-B and FIG. 4- show how the resin is sequentially injected into the mold according to the above sequence.
A and FIG. 4-B. First Injection (FIG. 3-A) First, the resin A that forms the mouth single layer portion and the inner and outer surface layers of the parison is first independently injected. Second injection (FIGS. 3-B and 4-A) Next, simultaneous injection of resin A and resin B and single injection of resin A are repeated as many times as necessary. At this time, the resin A and the resin B have a triple-ring structure gate, as shown in the sectional view of the gate portion of FIG.
Resin A on the outside, resin B on the middle, and resin A on the center
Is ejected as an annular flow. That is, resin B
Moves in the cavity while always being surrounded by the injected resin A at the same time, so that in the first injection, it comes into contact with the injected resin A to form the mouth single layer portion and the inner and outer surface layers. It does not solidify by cooling. In this second injection, the resin B layers are formed in the axial direction intermittently in the vicinity of the center portion in the thickness direction of the varison, the number of which is equal to the number of simultaneous injections of the resin A and the resin B. Third injection (FIG. 4-B) Finally, the resin A is separately injected, and the injection is completed by forming the resin A single layer around the gate portion. As a result, the mouth opening end as shown in FIG. 4-B has a single-layer structure of resin A, and the thin-walled portion of the body has a single-layer structure in which only resin A and a three-layer structure of resin A and resin B alternate. A multi-layer parison having a structure repeating in the above is obtained.
【００２１】本発明の多層容器は、パリソンを70〜130
℃の温度で、軸方向に１〜４倍、周方向に２〜７倍、面
積延伸倍率で 5〜15倍に２軸延伸して製造される。The multi-layer container of the present invention has a parison of 70 to 130.
It is produced by biaxially stretching at a temperature of ℃ 1 to 4 times in the axial direction, 2 to 7 times in the circumferential direction, and 5 to 15 times in area stretching ratio.
【００２２】本発明において、樹脂ＢとしてＭＸナイロ
ンを使用する場合、容器全体におけるＭＸナイロンの使
用割合は、使用する全樹脂量の１ないし２０重量％の範
囲で選択しえる。ここにおいてＭＸナイロンの使用割合
が１％以下ではガスバリアー性が向上せず、また、一般
にガスバリアー性樹脂は機械的物性に劣ること、必要と
するガスバリアー性能が得られる量以上であればよいこ
と等から判断してＭＸナイロンの使用割合は容器に使用
する全樹脂量の２０重量％以下あれば充分である。In the present invention, when MX nylon is used as the resin B, the proportion of MX nylon used in the entire container can be selected within the range of 1 to 20% by weight based on the total amount of the resin used. Here, when the use ratio of MX nylon is 1% or less, the gas barrier property is not improved, and generally, the gas barrier resin is inferior in mechanical properties, and it is sufficient if the amount is not less than the required gas barrier performance. Judging from this, it is sufficient that the amount of MX nylon used is 20% by weight or less of the total amount of resin used in the container.
【００２３】[0023]
【実施例】以下、実施例により本発明を更に詳細に説明
する。なお、採用した特性等の測定方法は次の通りであ
る。 (1) ポリエステル樹脂固有粘度〔η〕：フェノール／テ
トラクロロエタン＝６／４（重量比）の混合溶媒を使用
し、測定温度は３０℃である。 (2) ポリアミド樹脂相対粘度〔ηrel 〕：樹脂１ｇを９
６％硫酸１００ｍｌに溶解し温度２５℃で測定した。 (3) 曇度： 〔拡散透過率（光量／全透過量（光量）〕×１００ ＊ＪＩＳ Ｋ−６７１４（またはＡＳＴＭ Ｄ８８３−
６２Ｔ）により測定し、日本電色工業製デジタル曇度計
ＮＤＨ−２Ｄを使用した。 (4) 酸素透過率：ＡＳＴＭ Ｄ３９８５に準拠して行な
った。モダンコントロール社製OXTRAN100を使用した。 測定条件： 測定温度； ２０℃、 内側相対湿度；１００％、 外側相対湿度； ６５％、 (5) 層間接着性 水道水をボトルに満注まで充填し、２ｍの高さから落下
させた。これを５回繰り返し、ボトル多層部の剥離状態
を観察した。The present invention will be described in more detail with reference to the following examples. The method of measuring the characteristics used is as follows. (1) Polyester resin intrinsic viscosity [η]: A mixed solvent of phenol / tetrachloroethane = 6/4 (weight ratio) is used, and the measurement temperature is 30 ° C. (2) Polyamide resin relative viscosity [ηrel]: 1 g of resin is 9
It was dissolved in 100 ml of 6% sulfuric acid and measured at a temperature of 25 ° C. (3) Haze: [Diffuse transmittance (amount of light / total amount of light (amount of light)] x 100 * JIS K-6714 (or ASTM D883-
62T) and a digital haze meter NDH-2D manufactured by Nippon Denshoku Industries Co., Ltd. was used. (4) Oxygen permeability: measured according to ASTM D3985. OXTRAN100 manufactured by Modern Control was used. Measurement conditions: Measurement temperature: 20 ° C., inner relative humidity: 100%, outer relative humidity: 65%, (5) Interlayer adhesiveness A bottle of tap water was filled to the full volume and dropped from a height of 2 m. This was repeated 5 times, and the peeled state of the bottle multilayer portion was observed.
【００２４】実施例１ 樹脂Ａは、固有粘度０．７５のＰＥＴを、樹脂Ｂは、相
対粘度２．１のＮ−ＭＸＤ６（三菱瓦斯化学製、商品
名：ＭＸナイロン６００７）を使用し、図１に示した装
置を使用してパリソンの射出成形を行なった。樹脂の射
出は、最初に樹脂Ａ、次に樹脂Ａと樹脂Ｂの同時射出と
樹脂Ａ単独射出を５回交互に繰り返し、最後に樹脂Ａを
射出した。各々の射出量をキャビテ−容量に対する割合
で示すと次の通りである。最初の 樹脂Ａ ： ６０％ 同時射出での樹脂Ｂ ： ５％ 同時または単独射出での樹脂Ａ ： ２５％ 最後の樹脂Ａ ： １０％ 射出時の温度条件は次の通りである。 樹脂Ａ用射出シリンダー：２８０℃ 樹脂Ｂ用射出シリンダー：２６０℃ 金型内温度 ：２８０℃ 金型冷却水 ： １０℃ 上記射出成形により、図３の模式図に示す胴部肉厚約
４．５mmで、胴部が樹脂Ａ単層部分と樹脂Ａ／樹脂Ｂの
３層部分が軸方向に交互に繰り返した構造を有する、重
さ約５０ｇのパリソンを得た。２軸延伸ブロー成形機を
用いて、上記パリソンの表面温度が約１００℃になるま
で石英ヒーターで加熱した後、吹き込み金型内に移送
し、延伸ロッドの移送速度２０cm／sec,延伸吹き込み圧
力２０kg／cm2 の条件で２軸延伸ブロー成形し、ボトル
形状中空容器（全長：３００mm、外径：９０mmφ，内容
積：１５００ml、胴部肉厚：４００μｍ）を得た。胴部
肉薄部分の樹脂Ａ／樹脂Ｂの３層部は、平均の幅３５mm
で５か所に分割されており、円周方向にほぼ均一に分布
していた。得られたボトル形状中空容器の胴部の３層部
分における各層の厚さの比は容器外側より樹脂Ａ：樹脂
Ｂ：樹脂Ａ＝４：１：４であった。また、胴部における
樹脂Ａの単層構造の部分に対する樹脂Ａと樹脂Ｂの多層
構造の部分の割合は、約７０％であった。得られた多層
容器の酸素透過率を測定するとともに、胴部より試験片
を切り出し、曇度を測定した。また、層間接着性も調べ
た。評価結果を第１表にまとめて示した。Example 1 Resin A was PET having an intrinsic viscosity of 0.75, and Resin B was N-MXD6 (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: MX Nylon 6007) having a relative viscosity of 2.1. The parison was injection-molded using the apparatus shown in FIG. The resin was injected by first repeating resin A, then simultaneously injecting resin A and resin B and injecting resin A alone alternately five times, and finally injecting resin A. Each injection amount is shown as a ratio with respect to the cavitation capacity as follows. First resin A: 60% Resin B in simultaneous injection: 5% Resin A in simultaneous or single injection: 25% Last resin A: 10% The temperature conditions at the time of injection are as follows. Injection cylinder for resin A: 280 ° C Injection cylinder for resin B: 260 ° C Mold temperature: 280 ° C Mold cooling water: 10 ° C Body thickness of approximately 4.5mm shown in the schematic diagram of Fig. 3 by the above injection molding Thus, a parison having a weight of about 50 g was obtained, in which the body portion had a structure in which the resin A single layer portion and the resin A / resin B three layer portion were alternately repeated in the axial direction. Using a biaxial stretch blow molding machine, the parison was heated with a quartz heater until the surface temperature reached about 100 ° C., and then transferred into a blow mold, the transfer speed of the draw rod was 20 cm / sec, and the draw blow pressure was 20 kg. Biaxial stretch blow molding was carried out under the condition of / cm 2 to obtain a bottle-shaped hollow container (total length: 300 mm, outer diameter: 90 mmφ, inner volume: 1500 ml, body thickness: 400 μm). The resin A / resin B three-layer portion of the thin-walled portion has an average width of 35 mm
It was divided into 5 parts and was distributed almost uniformly in the circumferential direction. The thickness ratio of each layer in the three-layer portion of the body of the obtained bottle-shaped hollow container was resin A: resin B: resin A = 4: 1: 4 from the outside of the container. The ratio of the multi-layered structure of resin A and resin B to the single-layered structure of resin A in the body was about 70%. The oxygen permeability of the obtained multilayer container was measured, and a test piece was cut out from the body to measure the haze. The interlaminar adhesion was also examined. The evaluation results are summarized in Table 1.
【００２５】比較例１ 比較のため図１に示した２本の射出シリンダーを有する
射出成形機を用い、シリンダー１に樹脂Ａ，シリンダー
２に樹脂Ｂを充填して射出成形を行い、図４の模式図に
示す口部開口端部が単層構造で胴部全体が３層構造のパ
リソンを得た。射出シーケンスを図５に示す。使用した
樹脂は実施例１で用いた樹脂Ａ，樹脂Ｂと同じものであ
る。樹脂の射出は、樹脂Ａ，樹脂Ａと樹脂Ｂ同時，樹脂
Ａの順に順次行なった。それぞれの樹脂の射出量をキャ
ビテー容量に対する割合で示すと、次のとおりである。 最初に射出する樹脂Ａ： ６０％ 次に同時射出する樹脂Ｂ ： ５％ 同時射出する樹脂Ａ ： ２０％ 最後に射出する樹脂Ａ： １５％ 射出時の温度条件は次のとおりである。 樹脂Ａ用シリンダー ：２８０℃ 樹脂Ｂ用シリンダー ：２６０℃ 金型内温度 ：２８０℃ 冷却水温度 ： １０℃ その他の条件は実施例１と同様に行なった。得られた評
価結果を第１表に示した。COMPARATIVE EXAMPLE 1 For comparison, an injection molding machine having two injection cylinders shown in FIG. 1 was used to fill a cylinder 1 with a resin A and a cylinder 2 with a resin B to perform injection molding. A parison having a single-layer structure at the mouth opening end and a three-layer structure at the entire trunk as shown in the schematic diagram was obtained. The injection sequence is shown in FIG. The resin used is the same as the resins A and B used in Example 1. The resin was injected in the order of resin A, resin A and resin B simultaneously, and resin A in this order. The injection amount of each resin is shown below in proportion to the cavitation capacity. Resin A to be initially injected: 60% Resin B to be simultaneously injected: 5% Resin A to be simultaneously injected: 20% Resin A to be finally injected: 15% Temperature conditions at the time of injection are as follows. Cylinder for resin A: 280 ° C. Cylinder for resin B: 260 ° C. Mold temperature: 280 ° C. Cooling water temperature: 10 ° C. Other conditions were the same as in Example 1. The evaluation results obtained are shown in Table 1.
【００２６】比較例２ 比較のため図６に示した２本の射出シリンダーを有する
射出成形機を用い、シリンダー１に樹脂Ａを充填して、
ＰＥＴ単層構造のパリソンを得た。使用した樹脂は実施
例１で用いた樹脂Ａと同じものである。射出時の温度条
件は次のとおりである。 樹脂Ａ用シリンダー ：２８０℃ 金型内温度 ：２８０℃ 冷却水温度 ： １０℃ その他の条件は実施例と同様に行なった。得られた評価
結果を第１表に示した。 （以下余白）Comparative Example 2 For comparison, an injection molding machine having two injection cylinders shown in FIG. 6 was used to fill the cylinder 1 with resin A,
A parison having a PET single layer structure was obtained. The resin used is the same as the resin A used in Example 1. The temperature conditions at the time of injection are as follows. Cylinder for Resin A: 280 ° C. Mold temperature: 280 ° C. Cooling water temperature: 10 ° C. Other conditions were the same as in the example. The evaluation results obtained are shown in Table 1. (Below margin)
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】本発明によれば、多層容器の前駆体であ
るパリソンをガスバリアー層を有する多層構造にするこ
とにより、該パリソンを２軸延伸ブロー成形して得た多
層容器は、透明性、層間接着性およびガスバリアー性に
優れた性能を有する。本発明の多層容器は、透明性、ガ
スバリアー性、層間接着性、機械的強度にも優れたもの
であり従来にない画期的なものである。EFFECTS OF THE INVENTION According to the present invention, a multi-layer container obtained by biaxially stretch-blow molding the parison by forming the parison as a precursor of the multi-layer container into a multi-layer structure having a gas barrier layer is transparent. , Excellent in interlayer adhesion and gas barrier properties. The multi-layer container of the present invention is excellent in transparency, gas barrier property, interlayer adhesion and mechanical strength, and is an epoch-making thing that has never been seen before.
【図１】 本願発明に使用しうる多層パリソン射出成形
装置の一例、および第２射出においてゲート部断面を流
れる樹脂構成についてその模式図を示す。FIG. 1 is a schematic view showing an example of a multi-layer parison injection molding apparatus that can be used in the present invention, and a resin configuration that flows through a gate section in the second injection.
【図２】 本願発明における熱可塑性樹脂Ａと熱可塑性
樹脂Ｂの射出シーケンスを示す。FIG. 2 shows an injection sequence of thermoplastic resin A and thermoplastic resin B in the present invention.
【図３】 本願発明の射出シーケンスにおける第１射出
と第２射出の様子を示す。FIG. 3 shows a state of first injection and second injection in an injection sequence of the present invention.
【図４】 本願発明の射出シーケンスにおける第２射出
と第３射出の様子を示す。図４−Ｂは本願発明の多層容
器の前駆体である多層パリソンの概念図でもある。FIG. 4 shows states of second injection and third injection in the injection sequence of the present invention. FIG. 4-B is also a conceptual diagram of a multi-layer parison that is a precursor of the multi-layer container of the present invention.
【図５】 比較例２において使用したパリソン射出成形
装置の模式図を示す。FIG. 5 shows a schematic diagram of a parison injection molding apparatus used in Comparative Example 2.
【図６】 従来法（比較例）における熱可塑性樹脂Ａと
熱可塑性樹脂Ｂの射出シーケンスを示す。FIG. 6 shows an injection sequence of thermoplastic resin A and thermoplastic resin B in a conventional method (comparative example).
【図７】 図６の射出シーケンスによって製造した多層
容器の前駆体である多層パリソンの概念図を示す。FIG. 7 shows a conceptual diagram of a multilayer parison that is a precursor of a multilayer container manufactured by the injection sequence of FIG.
１ 熱可塑性樹脂Ａ ２ 熱可塑性樹脂Ｂ ３ 熱可塑性樹脂Ａ射出用シリンダー ４ 熱可塑性樹脂Ｂ射出用シリンダー ５ 金型 ６ キャビティ 1 Thermoplastic Resin A 2 Thermoplastic Resin B 3 Thermoplastic Resin A Injection Cylinder 4 Thermoplastic Resin B Injection Cylinder 5 Mold 6 Cavity
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｌ 9:00 4Ｆ 22:00 4Ｆ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B29L 9:00 4F 22:00 4F
Claims (7)
使用して製造した多層容器であり、該容器の口部開口端
部が熱可塑性樹脂Ａの単層構造よりなり、胴部肉薄部分
は熱可塑性樹脂Ａの単層部分と熱可塑性樹脂Ａと熱可塑
性樹脂Ｂの多層部分とからなる多層容器、および該容器
の前駆体であるパリソン。1. A multi-layer container manufactured by using a thermoplastic resin A and a thermoplastic resin B, wherein the mouth opening end of the container has a single layer structure of the thermoplastic resin A, and the thin-walled portion of the body is A multilayer container comprising a single layer portion of a thermoplastic resin A and a multilayer portion of a thermoplastic resin A and a thermoplastic resin B, and a parison which is a precursor of the container.
樹脂である特許請求の範囲第１項記載の多層容器、およ
び該容器の前駆体であるパリソン。2. The multilayer container according to claim 1, wherein the thermoplastic resin A is a thermoplastic polyester resin, and a parison which is a precursor of the container.
もエチレンテレフタレートを主たる繰り返し単位とした
樹脂である特許請求の範囲第２項記載の多層容器、およ
び該容器の前駆体であるパリソン。3. The multilayer container according to claim 2, wherein the thermoplastic polyester resin is a resin containing at least ethylene terephthalate as a main repeating unit, and a parison which is a precursor of the container.
た熱可塑性樹脂である特許請求の範囲第１項記載の多層
容器、および該容器の前駆体であるパリソン。4. The multilayer container according to claim 1, wherein the thermoplastic resin B is a thermoplastic resin having an excellent gas barrier property, and a parison which is a precursor of the container.
メタキシリレン基含有ポリアミド樹脂であり、メタキシ
リレン基含有ポリアミド樹脂の使用割合が、多層容器全
体の樹脂の使用量の１ないし２０重量％である特許請求
の範囲第４項記載の多層容器、および該容器の前駆体で
あるパリソン。5. A thermoplastic resin having excellent gas barrier properties is a metaxylylene group-containing polyamide resin, and the metaxylylene group-containing polyamide resin is used in an amount of 1 to 20% by weight based on the total amount of the resin used in the multilayer container. The multilayer container according to claim 4, and a parison which is a precursor of the container.
を、それぞれ専用の射出シリンダーから射出し、かつ最
初に熱可塑性樹脂Ａを、次に熱可塑性樹脂Ａと熱可塑性
樹脂Ｂの同時射出と熱可塑性樹脂Ａの単独射出とを交互
に繰り返し、最後に熱可塑性樹脂Ａを射出して得られる
パリソンを２軸延伸ブロー成形することを特徴とする多
層容器、および該容器の前駆体であるパリソンの製造方
法。6. A thermoplastic resin A and a thermoplastic resin B
From the respective dedicated injection cylinders, and first the thermoplastic resin A, then the simultaneous injection of the thermoplastic resin A and the thermoplastic resin B, and the single injection of the thermoplastic resin A are alternately repeated, and finally A multi-layer container characterized by biaxially stretch blow-molding a parison obtained by injecting a thermoplastic resin A, and a method for producing a parison which is a precursor of the container.
間部においてゲートに続く樹脂の流路が三重管構造をな
し、熱可塑性樹脂Ａと熱可塑性樹脂Ｂの同時射出のと
き、三重管の中心部および最外環状部から熱可塑性樹脂
Ａを、そして中間環状部から熱可塑性樹脂Ｂを射出する
特許請求の範囲第６項記載の多層容器および該容器の前
駆体であるパリソンの製造方法。7. A mold, an injection cylinder, or a resin flow path following a gate in a middle portion thereof has a triple pipe structure, and when the thermoplastic resin A and the thermoplastic resin B are simultaneously injected, a central portion of the triple pipe and The multilayer container according to claim 6, wherein the thermoplastic resin A is injected from the outermost annular portion, and the thermoplastic resin B is injected from the intermediate annular portion, and the method for producing the parison which is the precursor of the container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4116139A JPH05309648A (en) | 1992-05-08 | 1992-05-08 | Multi-layer vessel and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4116139A JPH05309648A (en) | 1992-05-08 | 1992-05-08 | Multi-layer vessel and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05309648A true JPH05309648A (en) | 1993-11-22 |
Family
ID=14679706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4116139A Pending JPH05309648A (en) | 1992-05-08 | 1992-05-08 | Multi-layer vessel and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05309648A (en) |
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|---|---|---|---|---|
| EP1034910A1 (en) * | 1999-03-11 | 2000-09-13 | Mitsubishi Gas Chemical Company, Inc. | Multi-layered article |
| JP2004160935A (en) * | 2002-11-15 | 2004-06-10 | Mitsubishi Gas Chem Co Inc | Multilayered container |
| JP2006306470A (en) * | 2005-04-28 | 2006-11-09 | Yoshino Kogyosho Co Ltd | Bottle with gradation pattern and preform for molding bottle |
| WO2006118067A1 (en) * | 2005-04-28 | 2006-11-09 | Yoshino Kogyosho Co., Ltd. | Bottles with gradation patterns and process for injection molding of preforms |
| JP2006334855A (en) * | 2005-05-31 | 2006-12-14 | Yoshino Kogyosho Co Ltd | Preform molding method, preform and bottle body |
| JP2006334849A (en) * | 2005-05-31 | 2006-12-14 | Yoshino Kogyosho Co Ltd | Preform manufacturing method, preform and bottle body |
| JP2006334854A (en) * | 2005-05-31 | 2006-12-14 | Yoshino Kogyosho Co Ltd | Preform molding method, preform and bottle body |
| WO2009133783A1 (en) * | 2008-04-30 | 2009-11-05 | 株式会社吉野工業所 | Multilayer bottle |
| WO2010001842A1 (en) * | 2008-06-30 | 2010-01-07 | 株式会社 吉野工業所 | Synthetic-resin laminated bottle body, injection molding device and method for forming laminated preform |
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-
1992
- 1992-05-08 JP JP4116139A patent/JPH05309648A/en active Pending
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