JP2009035286A - Synthetic resin vessel excellent in barrier property - Google Patents

Synthetic resin vessel excellent in barrier property Download PDF

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Publication number
JP2009035286A
JP2009035286A JP2007200125A JP2007200125A JP2009035286A JP 2009035286 A JP2009035286 A JP 2009035286A JP 2007200125 A JP2007200125 A JP 2007200125A JP 2007200125 A JP2007200125 A JP 2007200125A JP 2009035286 A JP2009035286 A JP 2009035286A
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barrier
amorphous nylon
barrier layer
synthetic resin
layer
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JP5148199B2 (en
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Kazuhiko Shimizu
一彦 清水
Masahiro Sukai
昌弘 須貝
Hiromi Shimura
博美 志村
Masato Suzuki
正人 鈴木
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Yoshino Kogyosho Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic resin vessel with excellent barrier properties, which prevents a barrier layer from being whitened or forming a patchy pattern, even in the application of retort sterilization. <P>SOLUTION: This PET bottle includes a base material layer 11 which is composed of PET and which forms the basic shape of a bottle body, and the barrier layer 12 which has a gas permeability lower than the base material layer 11. The barrier layer 12 contains amorphous nylon with a metaxylylene-isophthalamide structure. A copolymer of meta-xylylenediamine and an isophthalic acid is used for the amorphous nylon, and the rate of the content of the amorphous nylon in the barrier layer 12 is set to be in the range of 20-30 wt.%. Additionally, a meta-xylylene group-containing polyamide is used as a barrier material which constitutes the barrier layer together with the amorphous nylon. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、合成樹脂からなる基材層と、この基材層よりも気体透過性の低いバリア層とを有する、バリア性に優れた合成樹脂製容器に関するものである。   The present invention relates to a synthetic resin container having excellent barrier properties, comprising a base material layer made of a synthetic resin and a barrier layer having a lower gas permeability than the base material layer.

PET(ポリエチレンテレフタレート)ボトルに代表される合成樹脂製容器は、僅かながらも酸素や炭酸ガス等を透過させることが知られており、これを防止することを目的に、PET樹脂からなる基材層に、ガスバリア層を積層したものが提案されている(例えば、特許文献1参照。)。
特開2007−8582号公報
Synthetic resin containers represented by PET (polyethylene terephthalate) bottles are known to allow slight permeation of oxygen, carbon dioxide, etc., and a base material layer made of PET resin for the purpose of preventing this. In addition, a structure in which a gas barrier layer is laminated has been proposed (see, for example, Patent Document 1).
JP 2007-8582 A

しかしながら、ガスバリア層を積層した従来の合成樹脂製容器に、例えば、蒸気や加圧熱水を利用して100度を超える加熱を30分程度行う、いわゆるレトルト殺菌を行うと、バリア層に白濁や斑模様が生じる場合がある。   However, when a so-called retort sterilization is performed on a conventional synthetic resin container in which a gas barrier layer is laminated, for example, by using steam or pressurized hot water for about 30 minutes, the barrier layer becomes cloudy. Spotted patterns may occur.

こうした白濁や斑模様の発生は、容器そのものの機能には何ら問題ないものの、外観不良となるため、極力抑えられることが好ましい。   The occurrence of such white turbidity or mottled pattern is not adversely affected by the function of the container itself, but the appearance is poor.

本発明の解決すべき課題は、バリア性に優れた合成樹脂製容器にレトルト殺菌を行うと、バリア層に白濁や斑模様が生じることにあり、
本発明の目的とするところは、レトルト殺菌を行った場合でも、バリア層に白濁や斑模様が生じないバリア性に優れた合成樹脂製容器を提供することにある。
The problem to be solved by the present invention is that when a retort sterilization is performed on a synthetic resin container excellent in barrier properties, white turbidity and a spotted pattern are generated in the barrier layer.
An object of the present invention is to provide a synthetic resin container excellent in barrier properties that does not cause white turbidity or spots on the barrier layer even when retort sterilization is performed.

本発明である、バリア性に優れた合成樹脂製容器は、合成樹脂からなる基材層と、この基材層よりも気体透過性の低いバリア層とを有する、バリア性を有する合成樹脂製容器において、バリア層に、メタキシリレンイソフタラミド構造を有する非晶性ナイロンを含有させたことを特徴とするものである。   The synthetic resin container having excellent barrier properties according to the present invention has a base material layer made of synthetic resin and a barrier resin layer having a barrier property having a gas permeability lower than that of the base material layer. In the present invention, the barrier layer contains amorphous nylon having a metaxylylene isophthalamide structure.

本発明において、メタキシリレンイソフタラミド構造を有する非晶性ナイロンとしては、例えば、メタキシレンジアミンとイソフタル酸との共重合体が挙げられる。   In the present invention, examples of the amorphous nylon having a metaxylylene isophthalamide structure include a copolymer of metaxylenediamine and isophthalic acid.

また、バリア層における非晶性ナイロンの含有率は、20重量パーセント以上、30重量パーセント以下の範囲であることが好ましい。   Moreover, it is preferable that the content rate of the amorphous nylon in a barrier layer is the range of 20 weight% or more and 30 weight% or less.

具体例としては、バリア層が、本発明に係る非晶性ナイロンと、基材層を構成する材質よりも気体透過性の低いバリア材とからなる場合、これらの混合率(重量比)が、
バリア材:本発明に係る非晶性ナイロン=80:20〜70:30
となることが好ましい。
As a specific example, when the barrier layer is composed of amorphous nylon according to the present invention and a barrier material having lower gas permeability than the material constituting the base material layer, the mixing ratio (weight ratio) thereof is:
Barrier material: Amorphous nylon according to the present invention = 80: 20 to 70:30
It is preferable that

更に、本発明に係るバリア材としては、メタキシレン基含有ポリアミドが挙げられる。   Furthermore, examples of the barrier material according to the present invention include a metaxylene group-containing polyamide.

更に、本発明によれば、基材層をポリエチレンテレフタレートで構成し、バリア層を、前記非晶性ナイロンと、前記メタキシレン基含有ポリアミドと、コバルト錯体から構成することもできる。   Furthermore, according to this invention, a base material layer can be comprised with a polyethylene terephthalate, and a barrier layer can also be comprised from the said amorphous nylon, the said metaxylene group containing polyamide, and a cobalt complex.

本発明によれば、バリア層に、メタキシリレンイソフタラミド構造を有する非晶性ナイロンを含有させたことで、バリア性に優れた合成樹脂製容器として用い、それをレトルト殺菌しても、バリア層には白濁や斑模様が発生しない。即ち、本発明によれば、レトルト殺菌に伴う外観不良を生じることなく、バリア性に優れた合成樹脂製容器を提供することができる。   According to the present invention, by including amorphous nylon having a metaxylylene isophthalamide structure in the barrier layer, it is used as a container made of synthetic resin having excellent barrier properties, and even if it is sterilized by retort, There is no cloudiness or mottled pattern on the barrier layer. That is, according to this invention, the synthetic resin container excellent in barrier property can be provided, without producing the external appearance defect accompanying retort sterilization.

具体的には、本発明に係る非晶性ナイロンとして、メタキシレンジアミンとイソフタル酸との共重合体を用いれば、白濁や斑模様の防止に有効である。   Specifically, if a copolymer of metaxylenediamine and isophthalic acid is used as the amorphous nylon according to the present invention, it is effective in preventing white turbidity and spots.

しかも、本発明によれば、バリア層における非晶性ナイロンの含有率を、20重量パーセント以上、30重量パーセント以下の範囲とすれば、白濁や斑模様の防止に特に有効である。   In addition, according to the present invention, if the content of amorphous nylon in the barrier layer is in the range of 20 weight percent or more and 30 weight percent or less, it is particularly effective for preventing white turbidity and spots.

更に、バリア材が、メタキシレン基含有ポリアミドとした場合、白濁や斑模様の防止に優れた効果を奏する。   Furthermore, when the barrier material is a metaxylene group-containing polyamide, it has an excellent effect in preventing white turbidity and mottled patterns.

以下、図面を参照して、本発明の一形態を詳細に説明する。   Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings.

図1は、本発明に従うPETボトル1を一部断面で示す側面図である。   FIG. 1 is a side view showing a PET bottle 1 according to the present invention in partial cross section.

ボトル1は、図1に示すように、口部2、ネック3、肩部4、胴部5及び底部6よりなる。更に詳細には、ボトル1は、図1の領域Xに示すように、ボトル本体の基本形状を形作るPET(ポリエチレンテレフタレート)からなる2つの基材層11の間に、この基材層11よりも気体透過性の低いバリア層12が介在する積層ボトルである。   As shown in FIG. 1, the bottle 1 includes a mouth portion 2, a neck 3, a shoulder portion 4, a trunk portion 5, and a bottom portion 6. In more detail, as shown in the region X of FIG. 1, the bottle 1 is interposed between two base material layers 11 made of PET (polyethylene terephthalate) that forms the basic shape of the bottle body. It is a laminated bottle in which a barrier layer 12 having low gas permeability is interposed.

バリア層12は、基材層11を構成するPETよりも気体透過性の低いバリア材に、メタキシリレンイソフタラミド構造を有する非晶性ナイロン(以下、「非晶性ナイロン」という。)を含有させたものである。   The barrier layer 12 is made of amorphous nylon having a metaxylylene isophthalamide structure (hereinafter referred to as “amorphous nylon”) as a barrier material having a lower gas permeability than PET constituting the base material layer 11. It is contained.

バリア材としてはメタキシレン基含有ポリアミドが挙げられ、例えば、メタキシレンジアミンとアジピン酸との共重合体により構成される。   Examples of the barrier material include a metaxylene group-containing polyamide, and the barrier material is made of, for example, a copolymer of metaxylenediamine and adipic acid.

これに対し、非晶性ナイロンとしては、例えば、メタキシレンジアミンとイソフタル酸との共重合体が挙げられる。   On the other hand, examples of amorphous nylon include a copolymer of metaxylenediamine and isophthalic acid.

また、本発明において、バリア層12における非晶性ナイロンの含有率は、20重量パーセント以上、30重量パーセント以下の範囲であることが好ましい。   In the present invention, the content of amorphous nylon in the barrier layer 12 is preferably in the range of 20 weight percent or more and 30 weight percent or less.

即ち、バリア層12におけるこれらの混合率(重量比)が、
バリア材:非晶性ナイロン=80:20〜70:30
となることが好ましい。
That is, the mixing ratio (weight ratio) in the barrier layer 12 is
Barrier material: amorphous nylon = 80: 20-70: 30
It is preferable that

本発明によれば、バリア層12に、非晶性ナイロンを含有させたことで、バリア性に優れたPETボトルとして用い、それをレトルト殺菌しても、バリア層12には白濁や斑模様が発生しない。即ち、本発明によれば、レトルト殺菌に伴う外観不良を生じることなく、バリア性に優れたPETボトルを提供することができる。   According to the present invention, since the amorphous nylon is contained in the barrier layer 12, it is used as a PET bottle having excellent barrier properties, and even if it is sterilized by retort, the barrier layer 12 has white turbidity or spots. Does not occur. That is, according to the present invention, it is possible to provide a PET bottle excellent in barrier properties without causing an appearance defect associated with retort sterilization.

即ち、本形態のように、バリア層12に含有させる非晶性ナイロンとして、メタキシレンジアミンとイソフタル酸との共重合体を用いれば、白濁や斑模様の防止に有効である。   That is, as in this embodiment, if a copolymer of metaxylenediamine and isophthalic acid is used as the amorphous nylon contained in the barrier layer 12, it is effective in preventing white turbidity and spots.

しかも、本形態のように、バリア層12における非晶性ナイロンの含有率を、20重量パーセント以上、30重量パーセント以下の範囲とすれば、白濁や斑模様の防止に特に有効である。   Moreover, when the amorphous nylon content in the barrier layer 12 is in the range of 20 weight percent or more and 30 weight percent or less as in the present embodiment, it is particularly effective for preventing white turbidity and mottled patterns.

更に、バリア層12の主成分であるバリア材が、メタキシレン基含有ポリアミドとした場合、白濁や斑模様の防止に優れた効果を奏する。   Furthermore, when the barrier material which is the main component of the barrier layer 12 is a metaxylene group-containing polyamide, it has an excellent effect in preventing white turbidity and mottled patterns.

なお、ボトルの層構成は、これに限定されるものではなく、基材層とガスバリア層との少なくとも二層構成であればよい。また、ガスバリア層のみでボトルを形成してもよい。   The layer structure of the bottle is not limited to this, and it may be at least a two-layer structure including a base material layer and a gas barrier layer. Moreover, you may form a bottle only with a gas barrier layer.

以下、図1のボトル(内容量500ml)をレトルト殺菌したときを例として、本発明の実施例と、その比較例との試験データを示す。なお、レトルト殺菌は、124度の蒸気を利用して20分程度加熱する方法を選択している。   Hereinafter, the test data of the Example of this invention and its comparative example are shown by taking as an example the case of retort sterilizing the bottle of FIG. For retort sterilization, a method of heating for about 20 minutes using steam at 124 degrees is selected.

Figure 2009035286
Figure 2009035286

比較例1は、PETのみからなる単層ボトルである。   Comparative Example 1 is a single layer bottle made of only PET.

一方、比較例2は、バリア層12を、メタキシレン基含有ポリアミドを主成分とするバリア材樹脂(MXD6 三菱ガス化学株式会社製造)と、非晶性ナイロン(Grivory HB FE7103 EMS社製造)とを、90:10で混合した混合物で構成したものである。尚、バリア層12に遷移金属触媒(コバルト錯体)を添加して、酸素吸収機能を付与している。   On the other hand, in Comparative Example 2, the barrier layer 12 is made of a barrier material resin (MXD6 manufactured by Mitsubishi Gas Chemical Co., Ltd.) mainly composed of a metaxylene group-containing polyamide and amorphous nylon (manufactured by Grivory HB FE7103 EMS). , 90:10. A transition metal catalyst (cobalt complex) is added to the barrier layer 12 to provide an oxygen absorption function.

また、比較例3は、比較例2と同様のバリア材樹脂と、非晶性ナイロンとの混合比率を65:35としたものであり、更に、比較例4は、実施例1と同様のバリア材樹脂と、非晶性ナイロンとの混合比率を60:40としたものである。   In Comparative Example 3, the mixing ratio of the same barrier material resin as in Comparative Example 2 and amorphous nylon was set to 65:35. Further, in Comparative Example 4, the same barrier as in Example 1 was used. The mixing ratio of the material resin and amorphous nylon is 60:40.

これに対し、実施例1は、比較例2と同様のバリア材樹脂と、非晶性ナイロンとの混合比率を80:20としたものである。また、実施例2は、比較例2と同様のバリア材樹脂と、非晶性ナイロンとの混合比率を75:25としたものであり、更に、実施例3は、比較例2と同様のバリア材樹脂と、非晶性ナイロンとの混合比率を70:30としたものである。   On the other hand, in Example 1, the mixing ratio of the same barrier material resin as in Comparative Example 2 and amorphous nylon is set to 80:20. In Example 2, the mixing ratio of the barrier material resin similar to Comparative Example 2 and amorphous nylon was set to 75:25. Further, Example 3 was the same barrier as Comparative Example 2. The mixing ratio of the material resin and amorphous nylon is 70:30.

上述の試験結果からも明らかなように、比較例1、実施例1〜3はいずれも、外観的な問題は生じなかったのに対し、比較例2〜4では、外観的な問題を生じるに至った。即ち、各実施例を参酌すれば、バリア層12におけるバリア材樹脂と非晶ナイロンとの混合率(重量比)を、
バリア材樹脂:非晶性ナイロン=80:20〜70:30
とすることが好適であることが明らかである。
As is clear from the test results described above, neither Comparative Example 1 nor Examples 1 to 3 caused an appearance problem, whereas Comparative Examples 2 to 4 caused an appearance problem. It came. That is, if each example is taken into consideration, the mixing ratio (weight ratio) of the barrier material resin and amorphous nylon in the barrier layer 12 is:
Barrier material resin: Amorphous nylon = 80: 20 to 70:30
It is clear that it is suitable.

本発明容器は、ボトルに限らず、内容物の品質保持が目的とされる容器であれば、様々な形態の容器に採用することができる。   The container of the present invention is not limited to a bottle, and can be used in various forms of containers as long as the purpose is to maintain the quality of contents.

本発明に従うPETボトル1を一部断面で示す側面図である。It is a side view which shows the PET bottle 1 according to this invention in a partial cross section.

符号の説明Explanation of symbols

1 PETボトル
2 口部
3 ネック部
4 肩部
5 胴部
6 底部
11 基材層
12 ガスバリア層
DESCRIPTION OF SYMBOLS 1 PET bottle 2 Mouth part 3 Neck part 4 Shoulder part 5 Trunk part 6 Bottom part
11 Base material layer
12 Gas barrier layer

Claims (5)

合成樹脂からなる基材層と、この基材層よりも気体透過性の低いバリア層とを有する、バリア性に優れた合成樹脂製容器において、
バリア層に、メタキシリレンイソフタラミド構造を有する非晶性ナイロンを含有させたことを特徴とする、バリア性に優れた合成樹脂製容器。
In a synthetic resin container having an excellent barrier property, having a base material layer made of a synthetic resin and a barrier layer having a lower gas permeability than the base material layer,
A synthetic resin container excellent in barrier properties, characterized in that amorphous nylon having a metaxylylene isophthalamide structure is contained in the barrier layer.
請求項1において、メタキシリレンイソフタラミド構造を有する非晶性ナイロンが、メタキシレンジアミンとイソフタル酸との共重合体であることを特徴とする、バリア性に優れた合成樹脂製容器。   The synthetic resin container having excellent barrier properties according to claim 1, wherein the amorphous nylon having a metaxylylene isophthalamide structure is a copolymer of metaxylenediamine and isophthalic acid. 請求項1又は2において、バリア層における非晶性ナイロンの含有率が、20重量パーセント以上、30重量パーセント以下の範囲であることを特徴とする、バリア性に優れた合成樹脂製容器。   3. The synthetic resin container having excellent barrier properties according to claim 1, wherein the content of amorphous nylon in the barrier layer is in the range of 20 weight percent or more and 30 weight percent or less. 請求項1乃至3のいずれか一項において、バリア層は、前記非晶性ナイロンと、基材層を構成する材質よりも気体透過性の低いバリア材とからなり、
このバリア材は、メタキシレン基含有ポリアミドであることを特徴とする、バリア性に優れた合成樹脂製容器。
In any one of Claims 1 thru | or 3, a barrier layer consists of the said amorphous nylon and the barrier material whose gas permeability is lower than the material which comprises a base material layer,
The barrier material is a metaxylene group-containing polyamide, and is a synthetic resin container excellent in barrier properties.
請求項4において、基材層は、ポリエチレンテレフタレートにより構成され、バリア層は、前記非晶性ナイロンと、前記メタキシレン基含有ポリアミドと、コバルト錯体から構成されていることを特徴とする、バリア性に優れた合成樹脂製容器。   5. The barrier property according to claim 4, wherein the base material layer is composed of polyethylene terephthalate, and the barrier layer is composed of the amorphous nylon, the metaxylene group-containing polyamide, and a cobalt complex. Excellent synthetic resin container.
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EP2261124A1 (en) * 2008-03-31 2010-12-15 Yoshino Kogyosyo Co., Ltd. Container made of synthetic resin having excellent barrier properties
JP2018507147A (en) * 2015-02-10 2018-03-15 カーディフ グループ ナームローゼ ベンノートシャープ Barrels for CO2-containing beverages and their use
WO2019208501A1 (en) * 2018-04-24 2019-10-31 三菱瓦斯化学株式会社 Multilayered body and multilayered container
WO2019208500A1 (en) * 2018-04-24 2019-10-31 三菱瓦斯化学株式会社 Multilayered body and multilayered container
CN111511647A (en) * 2017-12-28 2020-08-07 株式会社吉野工业所 Synthetic resin container, preform, and method for manufacturing synthetic resin container
US12017433B2 (en) 2018-04-24 2024-06-25 Mitsubishi Gas Chemical Company, Inc. Multilayered article and multilayered container

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