JP2008096375A - Oxygen indicator and packaging material - Google Patents
Oxygen indicator and packaging material Download PDFInfo
- Publication number
- JP2008096375A JP2008096375A JP2006281190A JP2006281190A JP2008096375A JP 2008096375 A JP2008096375 A JP 2008096375A JP 2006281190 A JP2006281190 A JP 2006281190A JP 2006281190 A JP2006281190 A JP 2006281190A JP 2008096375 A JP2008096375 A JP 2008096375A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen indicator
- oxygen
- cyclic olefin
- sealant layer
- redox dye
- 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
Links
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 133
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Abstract
Description
本発明は、食品や医薬品などの内容物が包装されている包装体内の酸素の有無を検知するための酸素インジケーターと酸素インジケーター機能を有する包装材料、さらに詳しくは、酸素インジケーターの一部を構成する酸素インジケーター部に内在する酸化還元色素の溶出が防止できると共に、従来の酸素インジケーターにおいて酸化還元色素の溶出が原因で引き起こされていた色調異常をも防止できるようにした、酸素の有無を目視で確実に検知でき、しかも安全性の高い酸素インジケーターと酸素インジケーター機能を有する包装材料に関するものである。 The present invention relates to an oxygen indicator for detecting the presence or absence of oxygen in a package in which contents such as foods and pharmaceuticals are packaged, and a packaging material having an oxygen indicator function, and more specifically, a part of the oxygen indicator. Elution of redox dyes inherent in the oxygen indicator can be prevented, and abnormal color tone caused by redox dye elution in conventional oxygen indicators can also be prevented. The present invention relates to a packaging material having a highly safe oxygen indicator and an oxygen indicator function.
酸素はその反応性の高さから食品や医薬品などを酸化し、その有効成分を変性させたり、品質を劣化させることが知られている。このため、食品や医薬品などの包装体への収納に際しては、酸素吸収剤を共存させることにより、食品や医薬品などの内容物の酸化を防止するようにしている。そして、この酸素吸収剤の収納に際しては、酸素の吸収状況や包装体のピンホール、シール不良などに起因する酸素の進入を検知するための酸素インジケーターを同包しているのが一般的である。 Oxygen is known to oxidize foods and pharmaceuticals due to its high reactivity, denatures its active ingredients and degrades its quality. For this reason, when storing foods and pharmaceuticals in a package, an oxygen absorber is allowed to coexist to prevent oxidation of contents such as foods and pharmaceuticals. When storing the oxygen absorbent, it is common to enclose an oxygen indicator for detecting oxygen ingress due to oxygen absorption status, pinholes in the package, sealing failure, etc. .
現在、このような酸素インジケーターとしては、酸化還元色素、還元剤、バインダー樹脂などを主剤とするインジケーター組成物から構成されるインジケーター部を有するものが数多く使用されている。このような酸素インジケーターは、酸化還元色素が還元型と酸化型とで異なる色調を呈する性質を酸素の有無の検知に利用したものである。そして、酸化還元色素としてはメチレンブルーが広く用いられている。このメチレンブルーを用いた酸素インジケーターは、脱酸素の環境下では還元剤の働きによって還元型、すなわち無色を呈し、酸素の存在下では酸化されて青色を呈するようになっており、色相の変化で周辺の酸素の有無を検知できるようになっている。 Currently, many oxygen indicators having an indicator portion composed of an indicator composition mainly composed of a redox dye, a reducing agent, a binder resin and the like are used. Such an oxygen indicator utilizes the property that the redox dye exhibits different colors between the reduced type and the oxidized type for detecting the presence or absence of oxygen. Methylene blue is widely used as the redox dye. This oxygen indicator using methylene blue is reduced by the action of the reducing agent in the deoxygenated environment, that is, colorless, and is oxidized to blue in the presence of oxygen. The presence or absence of oxygen can be detected.
このチアジン系色素の一つであるメチレンブルーが酸化還元色素として用いられている酸素インジケーターにおいては、メチレンブルーの染色性が強く、酸素インジケーター部を担持する基材フィルムなどを通って包装体内に同包されている内容物側へと移行し、内容物を汚染するといった問題を抱えている。特に、包装体に高温滅菌処理などが施されて酸素インジケーターが高温の雰囲気に晒されると、その傾向が顕著になる。 In the oxygen indicator in which methylene blue, one of these thiazine dyes, is used as a redox dye, methylene blue has a strong dyeing property and is enclosed in a package through a base film carrying the oxygen indicator portion. It has a problem of moving to the contents side and contaminating the contents. In particular, when the package is subjected to a high temperature sterilization treatment and the oxygen indicator is exposed to a high temperature atmosphere, the tendency becomes remarkable.
このような問題に対処するには、酸素インジケーターに含まれている酸化還元色素の移行が防止できるように、酸素インジケーター自体を小袋などに入れたり、フィルムで包んでから食品や医薬品などと共に包装体内に収納する手法が取られてきている。しかしながら、この方法では、酸素インジケーターの小袋などへの収納や、包装した酸素インジケーターの包装体への投入などに係る一連の作業が煩雑で、コストが余分にかかるといった新たな問題が発生している。 To deal with these problems, the oxygen indicator itself can be placed in a sachet or wrapped in a film and then packaged together with food, medicine, etc. to prevent the redox dye contained in the oxygen indicator from migrating. The method of storing in the case has been taken. However, this method has a new problem in that a series of operations related to storing the oxygen indicator in a small bag or the like and putting the packaged oxygen indicator into the package is complicated and costs are increased. .
一方、上記した構成の酸素インジケーターが高温の状態に晒されて酸化還元色素が酸素インジケーターから溶出し、その他の部材と接触することにより色調異常を引き起こすことも問題点として指摘されている。要するに、酸素インジケーターが酸素のない環境に置かれている場合でも酸化還元色素の還元色が維持できず、酸化色を呈してしまうことがある。これは、例えば、溶出してしまった酸化還元色素が包装体を構成する酸素バリアフィルムの酸素バリア処理面まで浸透していき、その部分で凝集物などと接触することにより酸化色を呈する現象であると考えられている。 On the other hand, it has been pointed out as a problem that the oxygen indicator having the above-described configuration is exposed to a high temperature state, and the redox dye is eluted from the oxygen indicator and causes an abnormal color tone by contacting with other members. In short, even when the oxygen indicator is placed in an oxygen-free environment, the redox color of the redox dye cannot be maintained and may exhibit an oxidized color. This is, for example, a phenomenon in which the redox dye that has been eluted penetrates to the oxygen barrier treatment surface of the oxygen barrier film that constitutes the package, and exhibits an oxidation color when it comes into contact with aggregates or the like at that portion. It is thought that there is.
これまでにも接着剤やインキ中の低分子量成分の溶出を防止し、溶出に起因する問題点を解消しようとする試みが種々なされている（例えば、特許文献１参照。）。しかしこれらはいずれも室温下での使用を前提としたものである。しかも、高温滅菌処理や高温加熱調理が加えられた場合においても染色性の極めて強いメチレンブルーなどの酸化還元色素を溶出させないようにし、溶出に伴う色調異常をも阻止できるようにしたものではなかった。
本発明は以上のような状況に鑑みなされたもので、酸素インジケーター部を構成する酸素インジケーター組成物中の酸化還元色素や低分子量物質の成分が溶出せず、近接して置かれている他の物質を汚染しないようにした、安全衛生性の高い酸素インジケーターおよび酸素インジケーター機能を有する包装材料を提供するものである。また、本発明は、酸化還元色素がインジケーター部から溶出することがなく、それが置かれている周辺の酸素濃度が０％に維持されていれば、例え高温に晒されたとしても酸化還元色素の還元色が維持でき、色調異常などを起こすことのない、酸素インジケーターと酸素インジケーター機能を有する包装材料を提供するものである。 The present invention has been made in view of the situation as described above, and does not elute the components of the redox dye and low molecular weight substance in the oxygen indicator composition constituting the oxygen indicator part, and is placed in close proximity. It is an object of the present invention to provide an oxygen indicator with high safety and hygiene and a packaging material having an oxygen indicator function so as not to contaminate substances. Further, the present invention provides that the redox dye does not elute from the indicator part, and the redox dye can be used even if it is exposed to a high temperature as long as the oxygen concentration around the redox dye is maintained at 0%. The present invention provides a packaging material having an oxygen indicator and an oxygen indicator function that can maintain a reduced color of the above and does not cause abnormal color tone.
上記問題点を解決すべくなされ、請求項１記載の発明は、基材の少なくとも片面に、酸化還元色素と還元剤とバインダー樹脂と溶媒とを少なくとも含有する酸素インジケーター組成物からなる酸素インジケーター部が設けられていると共に、この酸素インジケーター部を覆うように、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層のいずれかが少なくとも積層されて設けられていることを特徴とする酸素インジケーターである。 In order to solve the above-mentioned problems, the invention according to claim 1 is characterized in that an oxygen indicator part comprising an oxygen indicator composition containing at least a redox dye, a reducing agent, a binder resin and a solvent is provided on at least one side of a substrate. And a sealant layer containing a cyclic olefin copolymer or a blend polymer of a cyclic olefin copolymer and a polyolefin resin, or a cyclic olefin ring-opening polymer or a hydrogenated product thereof, so as to cover the oxygen indicator portion. Alternatively, the oxygen indicator is characterized in that at least one of the sealant layers containing a blend polymer of them and a polyolefin resin is provided by being laminated.
また、請求項２記載の発明は、請求項１記載の酸素インジケーターにおいて、前記酸化還元色素はチアジン系色素であることを特徴とする。 The invention according to claim 2 is the oxygen indicator according to claim 1, wherein the redox dye is a thiazine dye.
さらにまた、請求項３記載の発明は、請求項２記載の酸素インジケーターにおいて、前記チアジン系色素はメチレンブルーであることを特徴とする。 Furthermore, the invention according to claim 3 is the oxygen indicator according to claim 2, wherein the thiazine colorant is methylene blue.
さらにまた、請求項４記載の発明は、請求項１乃至３のいずれかに記載の酸素インジケーターにおいて、前記シーラント層は多層構成であり、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層のいずれかがその中間層として積層されていることを特徴とする。 Furthermore, the invention according to claim 4 is the oxygen indicator according to any one of claims 1 to 3, wherein the sealant layer has a multilayer structure, and a cyclic olefin copolymer or a blend polymer of a cyclic olefin copolymer and a polyolefin resin. Or a hydrogenated product of a cyclic olefin or a hydrogenated product thereof, or a sealant layer containing a blend polymer of these and a polyolefin resin, is laminated as an intermediate layer. To do.
さらにまた、請求項５記載の発明は、請求項１乃至４のいずれかに記載の酸素インジケーターをその一部に具備していることを特徴とする包装材料である。 Furthermore, the invention according to claim 5 is a packaging material characterized in that the oxygen indicator according to any one of claims 1 to 4 is included in a part thereof.
請求項１および４記載に係る発明によれば、シーラント層は、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層のいずれかを少なくとも有する層であるので、酸素インジケーター部中の酸化還元色素や低分子量物質などの溶出を防ぐことができる。また、酸化還元色素の溶出が高温度下でも確実に防げるが故に、従来の酸素インジケーターで発生していた酸化還元色素の溶出に伴う無酸素状態での酸化色の呈色現象（色調異常）を引き起こすことがなくなる。 According to the inventions according to claims 1 and 4, the sealant layer is a cyclic olefin copolymer, a sealant layer containing a blend polymer of a cyclic olefin copolymer and a polyolefin resin, a cyclic olefin ring-opening polymer, or hydrogenation thereof. Therefore, it is possible to prevent elution of redox dyes and low molecular weight substances in the oxygen indicator portion. In addition, since the elution of redox dyes can be reliably prevented even at high temperatures, the color change phenomenon (color tone abnormality) in the oxygen-free state associated with the elution of redox dyes, which has occurred with conventional oxygen indicators, is prevented. No longer cause.
また、請求項２および３に係る発明によれば、酸化還元色素が還元型での溶出が顕著であるフェノチアジン環を有する酸化還元色素であるにも拘わらず、酸素インジケーター部からの溶出が防げ、還元状態と酸化状態における色調の変化を正確に表示できるようになる。 In addition, according to the inventions according to claims 2 and 3, although the redox dye is a redox dye having a phenothiazine ring that is remarkably eluted in a reduced form, elution from the oxygen indicator portion can be prevented, A change in color tone between the reduced state and the oxidized state can be accurately displayed.
請求項５に係る発明によれば、高温滅菌処理や高温加熱調理などにより高温が加えられた後でも酸素インジケーター機能を維持し、酸素検知を正確に行うことができ、包装袋や包装容器などの包装体を構成するための包装材料として好適に用いられる。 According to the invention according to claim 5, the oxygen indicator function can be maintained even after high temperature is applied by high temperature sterilization treatment or high temperature heat cooking, and oxygen detection can be accurately performed. It is suitably used as a packaging material for constituting a package.
以下、本発明の最良の実施の形態を説明する。 The best mode of the present invention will be described below.
本発明の酸素インジケーターは、前述したように、基材の少なくとも片面に、酸化還元色素と還元剤とバインダー樹脂と溶媒とを少なくとも含有する酸素インジケーター組成物からなる酸素インジケーター部が設けられていると共に、この酸素インジケーター部を覆うように、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層のいずれかが少なくとも積層されて設けられていることを特徴とするものである。 As described above, the oxygen indicator of the present invention is provided with an oxygen indicator portion made of an oxygen indicator composition containing at least a redox dye, a reducing agent, a binder resin, and a solvent on at least one surface of a substrate. A sealant layer containing a cyclic olefin copolymer or a blend polymer of a cyclic olefin copolymer and a polyolefin resin, or a cyclic olefin ring-opening polymer or a hydrogenated product thereof, or a polyolefin resin so as to cover the oxygen indicator portion Any one of the sealant layers containing the blend polymer is provided by being laminated at least.
一方、本発明の包装材料は、上記した構成の酸素インジケーターをその一部に具備してなるものである。すなわち、包装袋や包装容器などの包装体を構成する包装材料であって、その一部に、酸化還元色素と還元剤とバインダー樹脂と溶媒とを少なくとも含有する酸素インジケーター組成物からなる酸素インジケーター部が設けられていると共に、この酸素インジケーター部を覆うように、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層のいずれかが少なくとも積層されて設けられているものである。 On the other hand, the packaging material of the present invention comprises the oxygen indicator having the above-described configuration in a part thereof. That is, a packaging material that constitutes a packaging body such as a packaging bag or packaging container, and an oxygen indicator portion comprising an oxygen indicator composition containing at least a redox dye, a reducing agent, a binder resin, and a solvent. And a sealant layer containing a cyclic olefin copolymer, a blend polymer of a cyclic olefin copolymer and a polyolefin resin, or a cyclic olefin ring-opening polymer or a hydrogenated product thereof so as to cover the oxygen indicator portion Or a sealant layer containing a blend polymer of them and a polyolefin resin is provided by being laminated at least.
本発明に使用される酸化還元色素は、酸化状態と還元状態で異なる色相を呈する色素であれば、いずれのものも採用することができる。具体的にはメチレンブルーの他、ニューメチレンブルー、トルイジンブルー、チオニンアセテート、ニュートラルレッド、インジゴカルミン、インジゴスルフォン酸カリウム塩、サフラニンＴ、フェノサフラニン、カプリブルー、ナイルブルー、ジフェニルアミン、ジフェニルアミンスルホン酸、キシレンシアノール、ニトロジフェニルアミン、フェロイン、ニトロフェロイン、Ｎ−フェニルアントラニル酸などが使用できる。特にフェノチアジン環を有するチアジン系色素は、還元型での溶出が顕著であるが、後述するシーラント層が設けられているので、酸素インジケーター部からの溶出を心配する必要がない。 As the redox dye used in the present invention, any dye may be adopted as long as it exhibits a different hue in the oxidized state and the reduced state. Specifically, in addition to methylene blue, neutral methylene blue, toluidine blue, thionine acetate, neutral red, indigo carmine, indigo sulfonic acid potassium salt, safranin T, phenosafranine, capri blue, nile blue, diphenylamine, diphenylamine sulfonic acid, xylene cyanol , Nitrodiphenylamine, ferroin, nitroferroin, N-phenylanthranilic acid and the like can be used. In particular, thiazine dyes having a phenothiazine ring are remarkably eluted in a reduced form, but since a sealant layer described later is provided, there is no need to worry about elution from the oxygen indicator portion.
また、本発明に使用される還元剤は、高温下での長期間の保存、あるいは高温滅菌処理などにより高温が加えられた場合でも確実に還元作用を発現する還元剤であれば、いずれのものも採用することができる。ただし、熱により分解するものは、還元色を維持できないなどの不具合を抱えるため、好ましくない。還元剤として好ましいものは、ローズマリ
ー抽出物の他、トコフェロール、ケルセチンやアントシアニン、茶カテキンなどのポリフェノール、没食子酸誘導体、コーヒー酸やフェルラ酸、グルタチオンなどのアミノ酸、β−カロチンやリコピンなどのカロテノイド類などである。また、Ｎ−メチルジエタノールアミンなどヒドロキシル基を有するアミノアルコール類の一部も好適に使用することができる。前記した酸化還元色素とこれらの還元剤の組み合わせは非常に重要であり、加熱滅菌処理などによる高温加熱に対する耐性を十分に考慮する必要がある。また、その使用量は上記酸化還元色素１重量部に対して、１〜１００重量部程度が好ましい。
In addition, the reducing agent used in the present invention is any reducing agent that reliably exhibits a reducing action even when a high temperature is applied due to long-term storage at high temperature or high-temperature sterilization treatment. Can also be adopted. However, those that decompose by heat are not preferred because they have problems such as being unable to maintain a reduced color. Preferred reducing agents include rosemary extract, polyphenols such as tocopherol, quercetin and anthocyanin, tea catechin, gallic acid derivatives, amino acids such as caffeic acid, ferulic acid and glutathione, and carotenoids such as β-carotene and lycopene. Etc. Moreover, some amino alcohols which have hydroxyl groups, such as N-methyldiethanolamine, can also be used conveniently. The combination of the above-described redox dye and these reducing agents is very important, and it is necessary to sufficiently consider resistance to high-temperature heating due to heat sterilization treatment or the like. The amount used is preferably about 1 to 100 parts by weight with respect to 1 part by weight of the redox dye.
一方、バインダー樹脂は、酸素インジケーター組成物を構成する酸化還元色素、還元剤、溶媒を基材上に固着するために用いられる。好ましく用いられるバインダー樹脂としては、エチルセルロース、ヒドロキシルエチルセルロース、セルロースアセテートなどのセルロース誘導体やブチラール樹脂、アセタール樹脂、親水基を導入したポリエステル樹脂、その他にアクリル樹脂、ウレタン−ウレア樹脂、ウレタン樹脂などを挙げることができる。特に酸化還元色素の溶解性と高温下での長期保存性、あるいはボイル・レトルトなどの高温滅菌処理や加熱調理などにおける高温加熱による影響を考慮し、耐熱性を有する水性樹脂を使用することが好ましい。 On the other hand, the binder resin is used for fixing the redox dye, the reducing agent, and the solvent constituting the oxygen indicator composition on the substrate. Preferred binder resins include cellulose derivatives such as ethyl cellulose, hydroxylethyl cellulose, cellulose acetate, butyral resins, acetal resins, polyester resins having hydrophilic groups introduced, acrylic resins, urethane-urea resins, urethane resins, etc. Can do. In particular, it is preferable to use an aqueous resin having heat resistance in consideration of the solubility of the redox dye and long-term storage at high temperatures, or the effects of high-temperature heating in high-temperature sterilization treatment such as boiling and retort and cooking. .
上記バインダー樹脂は、トルエン、キシレン、メチルエチルケトン、酢酸エチルなどに代表される有機系溶剤、水、メタノール、エタノール、イソプロピルアルコールなどに代表される水系溶剤に溶解あるいは分散させて使用される。これら溶剤は単独で、また複数の溶剤を混合して用いればよい。 The binder resin is used by being dissolved or dispersed in an organic solvent typified by toluene, xylene, methyl ethyl ketone, ethyl acetate or the like, or an aqueous solvent typified by water, methanol, ethanol, isopropyl alcohol or the like. These solvents may be used alone or as a mixture of a plurality of solvents.
このような各成分を混練してなる酸素インジケーター組成物で構成される酸素インジケーター部からの酸化還元色素の溶出防止と色素溶出に伴う色調異常を阻止するために積層されるシーラント層は、具体的には、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層のいずれかを少なくとも有する層である。 The sealant layer laminated in order to prevent the redox dye from eluting from the oxygen indicator part composed of the oxygen indicator composition formed by kneading each of these components and to prevent the abnormal color tone associated with the dye elution Contains a sealant layer containing a cyclic olefin copolymer, or a blend polymer of a cyclic olefin copolymer and a polyolefin resin, or a ring-opening polymer of a cyclic olefin or a hydrogenated product thereof, or a blend polymer of these and a polyolefin resin. It is a layer having at least one of the sealant layers.
このシーラント層は多層構成であることが望ましく、例えば、上記したような構成のシーラント層を中間層とし、その両面側に低密度ポリエチレン、直鎖状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、無延伸ポリプロピレンなどのポリオレフィン樹脂からなる薄膜層を積層した多層シーラント層であることがより好ましい。 The sealant layer preferably has a multilayer structure. For example, the sealant layer having the above-described structure is used as an intermediate layer, and low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, A multilayer sealant layer in which thin film layers made of polyolefin resin such as unstretched polypropylene are laminated is more preferable.
本発明に用いる環状オレフィンコポリマーの環状オレフィン成分としては、例えばシクロペンテンまたはその誘導体、シクロヘキセンまたはその誘導体、シクロヘプテンまたはその誘導体、シクロオクテンまたはその誘導体、シクロノネンまたはその誘導体、シクロデセンまたはその誘導体、ビシクロ［２．２．１］ヘプト−２−エンまたはその誘導体、テトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンまたはその誘導体、ヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］−４−ヘプタデセンまたはその誘導体、オクタシクロ［８．８．０．１2,9．１4,7．１11,10．１13,16．０3,8．０12,17］−５−ドコセンまたはその誘導体、ペンタシクロ［６．６．１．１3,6．０2,7．０9,14］−４ヘキサデセンまたはその誘導体、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］−４−ペンタデセンまたはその誘導体、ヘプタシクロ［８．７．０．１2,9．１4,7．１11,17．０3,8．０12,16 ］−５−エイコセンまたはその誘導体、ヘプタシクロ［８．８．０．１2,9．１4,7．１11,16．０3,8．０12,17］−５−ヘンエイコセンまたはその誘導体、トリシクロ［４．４．０．１2,5］−３−ウンデセンまたはその誘導体、トリシクロ［４．３．０．１2,5］−３−デセンまたはその誘導体、トリシクロ［４．３．０．１2,5］−３，７−デカジエンまたはその誘導体、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］−４，１０−ペンタデカジエンまたはその誘導体、ペンタシクロ［４．７．０．１2,5．０8,13．１9,12］−３−ペンタデセンまたはその誘導体、ヘプタシクロ［７．８．０．１3,6．０2,7．１10,17．０11,16．１12,15］−４−エイコセンまたはその誘導体、ノナシクロ［９．１０．１．１4,7．０3,8．０2,10．０12,21．１13,20．０14,19．１15,19］−５−ペンタセコンまたはその誘導体などを挙げることができる。これらの環状オレフィン成分の１成分或いは２成分以上とα−オレフィン、好ましくはエチレン、プロピレン、ブテン、１−ヘキセンや４−メチル−１−ペンテンなどとの共重合体を環状オレフィンコポリマーとして用いることができる。 Examples of the cyclic olefin component of the cyclic olefin copolymer used in the present invention include cyclopentene or a derivative thereof, cyclohexene or a derivative thereof, cycloheptene or a derivative thereof, cyclooctene or a derivative thereof, cyclononene or a derivative thereof, cyclodecene or a derivative thereof, and bicyclo [2. 2.1] hept-2-ene or a derivative thereof, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene or a derivative thereof, hexacyclo [6.6.1.1 3,6 . 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene or derivatives thereof, octacyclo [8.8.0.1 2,9. 1 4,7 . 1 11,10 . 1 13,16 . 0 3,8 . 0 12,17 ] -5-docosene or a derivative thereof, pentacyclo [6.6.1.1 3,6 . 0 2,7 . 0 9,14 ] -4 hexadecene or a derivative thereof, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] -4-pentadecene or derivatives thereof, heptacyclo [8.7.0.1 2,9. 1 4,7 . 1 11,17 . 0 3,8 . 0 12,16 ] -5-eicosene or a derivative thereof, heptacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,16 . 0 3,8 . 0 12,17 ] -5- heneicosene or a derivative thereof, tricyclo [4.4.0.1 2,5 ] -3-undecene or a derivative thereof, tricyclo [4.3.0.1 2,5 ] -3- Decene or a derivative thereof, tricyclo [4.3.0.1 2,5 ] -3,7-decadiene or a derivative thereof, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] 4,10 penta decadiene, or a derivative thereof, pentacyclo [4.7.0.1 2,5. 0 8,13 . 1 9,12 ] -3-pentadecene or a derivative thereof, heptacyclo [7.8.0.1 3,6 . 0 2,7 . 1 10,17 . 0 11,16 . 1 12,15] -4-eicosene or derivatives thereof, Nonashikuro [9.10.1.1 4, 7. 0 3,8 . 0 2,10 . 0 12,21 . 1 13,20 . 0 14,19 . 1 15,19 ] -5-pentasecone or a derivative thereof. A copolymer of one or more of these cyclic olefin components and an α-olefin, preferably ethylene, propylene, butene, 1-hexene, 4-methyl-1-pentene, etc., may be used as the cyclic olefin copolymer. it can.
さらに、ビシクロ［２．２．１］ヘプト−２−エンまたはその誘導体、テトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンまたはその誘導体、ヘキサシクロ［６．６．１．１3,6．１10,13．０2,7．０9,14］−４−ヘプタデセンまたはその誘導体、オクタシクロ［８．８．０．１2,9．１4,7．１11,10．１13,16．０3,8．０12,17］−５−ドコセンまたはその誘導体、ペンタシクロ［６．６．１．１3,6．０2,7．０9,14］−４ヘキサデセンまたはその誘導体、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］−４−ペンタデセンまたはその誘導体、ヘプタシクロ［８．７．０．１2,9．１4,7．１11,17．０3,8．０12,16］−５−エイコセンまたはその誘導体、ヘプタシクロ［８．８．０．１2,9．１4,7．１11,16．０3,8．０12,17］−５−ヘンエイコセンまたはその誘導体、トリシクロ［４．４．０．１2,5］−３−ウンデセンまたはその誘導体、トリシクロ［４．３．０．１2,5］−３−デセンまたはその誘導体、トリシクロ［４．３．０．１2,5］−３，７−デカジエンまたはその誘導体、ペンタシクロ［６．５．１．１3,6．０2,7．０9,13］−４，１０−ペンタデカジエンまたはその誘導体、ペンタシクロ［４．７．０．１2,5．０3,13．１9,12］−３−ペンタデセンまたはその誘導体、ヘプタシクロ［７．８．０．１3,6．０2,7．１10,17．０11,16．１12,15］−４−エイコセンまたはその誘導体、ノナシクロ［９．１０．１．１4,7．０3,8．０2,10．０12,21．１13,20．０14,19．１15,19］−５−ペンタセコンまたはその誘導体などの開環物及びその水素添加物も環状オレフィン成分として挙げることができる。そして、これらの環状オレフィンの１成分或いは２成分以上と、α−オレフィン、好ましくはエチレン、プロピレン、１−ブテン、１−ヘキセンや４−メチル−１−ペンテンなどとの共重合体を環状オレフィンコポリマーとして用いることができる。 Further, bicyclo [2.2.1] hept-2-ene or a derivative thereof, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene or a derivative thereof, hexacyclo [6.6.1.1 3,6 . 1 10,13 . 0 2,7 . 0 9,14] -4-heptadecene or derivatives thereof, octacyclo [8.8.0.1 2,9. 1 4,7 . 1 11,10 . 1 13,16 . 0 3,8 . 0 12,17 ] -5-docosene or a derivative thereof, pentacyclo [6.6.1.1 3,6 . 0 2,7 . 0 9,14 ] -4 hexadecene or a derivative thereof, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] -4-pentadecene or derivatives thereof, heptacyclo [8.7.0.1 2,9. 1 4,7 . 1 11,17 . 0 3,8 . 0 12,16 ] -5-eicosene or a derivative thereof, heptacyclo [8.8.0.1 2,9 . 1 4,7 . 1 11,16 . 0 3,8 . 0 12,17 ] -5- heneicosene or a derivative thereof, tricyclo [4.4.0.1 2,5 ] -3-undecene or a derivative thereof, tricyclo [4.3.0.1 2,5 ] -3- Decene or a derivative thereof, tricyclo [4.3.0.1 2,5 ] -3,7-decadiene or a derivative thereof, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] 4,10 penta decadiene, or a derivative thereof, pentacyclo [4.7.0.1 2,5. 0 3,13 . 1 9,12 ] -3-pentadecene or a derivative thereof, heptacyclo [7.8.0.1 3,6 . 0 2,7 . 1 10,17 . 0 11,16 . 1 12,15] -4-eicosene or derivatives thereof, Nonashikuro [9.10.1.1 4, 7. 0 3,8 . 0 2,10 . 0 12,21 . 1 13,20 . 0 14,19 . 1 15,19 ] -5-Pentacene or a ring-opened product such as a derivative thereof and a hydrogenated product thereof can also be mentioned as the cyclic olefin component. A copolymer of one or more of these cyclic olefins and an α-olefin, preferably ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, or the like is used as a cyclic olefin copolymer. Can be used as
上記したシーラント層を構成する環状オレフィンコポリマーの成分において、共重合させているエチレン成分などのα−オレフィン成分に由来する構造単位は、４０〜９５モル％の範囲、環状オレフィン成分に由来する構造単位は、５〜６０モル％程度の範囲が適当である。また、開環重合体や開環共重合体の場合は環状オレフィン成分に由来する構造単位は化学量論的には２５乃至５０モル%となり、上記範囲に含まれる。ガラス転移温度は６０〜１６０℃程度のものが望まれるが、シーラント層を成膜する際の押出し成膜適性とボイル・レトルト殺菌処理などにおける耐高温性などを考慮すると、好ましくは８０〜１４０℃程度である。 In the components of the cyclic olefin copolymer constituting the sealant layer, the structural unit derived from the α-olefin component such as the ethylene component being copolymerized is in the range of 40 to 95 mol%, the structural unit derived from the cyclic olefin component. Is suitably in the range of about 5-60 mol%. In the case of a ring-opening polymer or a ring-opening copolymer, the structural unit derived from the cyclic olefin component is stoichiometrically 25 to 50 mol%, and is included in the above range. A glass transition temperature of about 60 to 160 ° C. is desired, but preferably 80 to 140 ° C. in consideration of extrusion film forming suitability when forming a sealant layer and high temperature resistance in boil / retort sterilization treatment. Degree.
シーラント層を構成するブレンドポリマーに用いられるポリオレフィン樹脂としては、低密度ポリエチレン、直鎖状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレもしくはポリプロピレンなどを挙げることができる。そして、上記環状オレフィンコポリマーとのブレンド比率は接着性、酸化還元色素や低分子量物質の溶出防止を考慮して適宜設定すればよい。具体的には、環状オレフィンコポリマーのブレンド比率は重量比で３０〜９５％程度である。また、高温加熱時にも酸素還元色素や低分子量物質の溶出を抑えるようにするには、ホモあるいはブロックタイプのポリプロピレンが好適に使用されるが、ホモタイプの方がより好ましい。 Examples of the polyolefin resin used in the blend polymer constituting the sealant layer include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and polypropylene. And the blend ratio with the said cyclic olefin copolymer should just be suitably set in consideration of adhesiveness, the elution reduction prevention of a redox pigment and a low molecular weight substance. Specifically, the blend ratio of the cyclic olefin copolymer is about 30 to 95% by weight. In order to suppress the elution of oxygen reducing dyes and low molecular weight substances even when heated at a high temperature, homo- or block-type polypropylene is preferably used, but the homo-type is more preferable.
一方、上記した構成のシーラント層や多層シーラント層の厚さは、酸素インジケーター部に内在する酸化還元色素の種類や熱処理温度などを考慮して適宜設定すればよいが、酸
化還元色素の溶出防止と的確な色調表示の観点から、環状オレフィンコポリマーまたは、環状オレフィンコポリマーとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層、或いは環状オレフィンの開環重合体またはその水素添加体、またはそれらとポリオレフィン樹脂とのブレンドポリマーを含有するシーラント層の厚さが５μｍから６０μｍ程度であることが好ましい。
On the other hand, the thickness of the sealant layer or the multilayer sealant layer having the above-described structure may be appropriately set in consideration of the kind of the redox dye inherent in the oxygen indicator part, the heat treatment temperature, etc. From the viewpoint of accurate color indication, a sealant layer containing a cyclic olefin copolymer or a blend polymer of a cyclic olefin copolymer and a polyolefin resin, a ring-opening polymer of a cyclic olefin or a hydrogenated product thereof, or a polyolefin resin thereof. The thickness of the sealant layer containing the blend polymer is preferably about 5 to 60 μm.
他方、酸素インジケーター部を設ける基材としては、酸素インジケーター部を構成する酸素インジケーター組成物と反応せず、しかもそこに含まれている酸化還元色素の呈色性を阻害しないものであれば特に制限されるものではない。具体的には、紙、合成紙、不織布、または合成樹脂フィルムなどが用いられる。また、厚さ１２μｍ程度のＰＥＴフィルムや、このＰＥＴフィルムにバリア層として酸化珪素や酸化アルミニウムなどからなる薄膜を蒸着したものや、アルミニウム箔を積層した酸素バリアフィルムも好適に用いられる。 On the other hand, the base material on which the oxygen indicator part is provided is not particularly limited as long as it does not react with the oxygen indicator composition constituting the oxygen indicator part and does not inhibit the coloration of the redox dye contained therein. Is not to be done. Specifically, paper, synthetic paper, non-woven fabric, or synthetic resin film is used. Further, a PET film having a thickness of about 12 μm, a film obtained by depositing a thin film made of silicon oxide, aluminum oxide or the like as a barrier layer on this PET film, or an oxygen barrier film in which an aluminum foil is laminated are also preferably used.
このような基材の少なくとも片面に酸素インジケーター組成物を用いて酸素インジケーター部を設けるに当たっては、印刷法やコーティング法が用いられる。印刷方法としては凸版印刷法、凹版印刷法、オフセット印刷法、スクリーン印刷法などが利用でき、またコーティング法としては、ロールコーティング、スプレーコーティング、ディップコーティング、ベタコーティングなどが用いられる。 When providing an oxygen indicator part using an oxygen indicator composition on at least one side of such a substrate, a printing method or a coating method is used. As a printing method, a relief printing method, an intaglio printing method, an offset printing method, a screen printing method, and the like can be used. As a coating method, roll coating, spray coating, dip coating, solid coating, and the like are used.
酸素インジケーター組成物中には、必要に応じて界面活性剤や分散剤、消泡剤、さらには酸化還元色素以外に別途、着色剤などが添加されていてもよい。酸素インジケーター組成物中にこれらを添加することにより、組成物の安定性や速乾性、酸素インジケーター部の視認性を向上させることができる。また、上記酸素インジケーター組成物は２液型に調整してもよい。例えば、少なくとも色素とバインダー樹脂からなるＡ液と還元剤とバインダー樹脂からなるＢ液を印刷直前に混合して使用する２液型のインキにすることにより、インキ組成物の保存安定性を向上させることができる。 In the oxygen indicator composition, a colorant or the like may be separately added in addition to the surfactant, the dispersant, the antifoaming agent, and the oxidation-reduction pigment as necessary. By adding these components to the oxygen indicator composition, the stability and quick drying property of the composition and the visibility of the oxygen indicator portion can be improved. Moreover, you may adjust the said oxygen indicator composition to a 2 liquid type. For example, the storage stability of the ink composition is improved by forming a two-component ink that is used by mixing at least the liquid A composed of a dye and a binder resin and the liquid B composed of a reducing agent and a binder resin immediately before printing. be able to.
さらには基材との密着強度の改善や酸化還元色素の退色防止を目的に、酸素インジケーター組成物からなる酸素インジケーター部の上下にアンカーコート層やオーバーコート層が設けられていてもよい。この際に使用できるコーティング剤としては、酸素を透過し、かつ基材との密着性が良いもの、また紫外線吸収材料を含有するものなどを挙げることができるが、必ずしもこれらのものに限定するものではなく、酸化還元色素の発色を妨げないものであれば特に制限なく用いることができる。 Furthermore, an anchor coat layer or an overcoat layer may be provided above and below the oxygen indicator portion made of the oxygen indicator composition for the purpose of improving the adhesion strength with the base material and preventing the redox dye from fading. Examples of the coating agent that can be used in this case include those that transmit oxygen and have good adhesion to the base material, and those that contain an ultraviolet absorbing material, but are not necessarily limited to these. Instead, any material that does not interfere with the color development of the redox dye can be used without particular limitation.
以上、本発明の酸素インジケーターについて説明したが、酸素インジケーターを一部に具備する本発明の包装材料は、上述した構成のインジケーター部を一部に具備してなる包装用の材料であって、これにより作製される包装袋や包装容器などの包装体内の酸素の有無を的確に検知し、例え高温滅菌処理や高温過熱調理などにより高温が加えられたとしても酸化還元色素の溶出がない。従って、酸化還元色素の溶出に伴う色調異常を起こすこともない。 As described above, the oxygen indicator of the present invention has been described. However, the packaging material of the present invention partially including the oxygen indicator is a packaging material partially including the indicator portion having the above-described configuration. The presence or absence of oxygen in the packaging body such as a packaging bag or packaging container produced by the method is accurately detected, and even if a high temperature is applied by high-temperature sterilization treatment or high-temperature overheating cooking, the redox dye does not elute. Accordingly, there is no occurrence of color tone abnormality associated with elution of the redox dye.
以下に本発明の実施例について、具体的に説明する。本発明はこれに限定されるものではない。 Examples of the present invention will be specifically described below. The present invention is not limited to this.
まず、下記各成分をペイントコンディショナーにより微細分散させて酸素インジケーター組成物（インキ組成物）を得た。 First, the following components were finely dispersed with a paint conditioner to obtain an oxygen indicator composition (ink composition).
＜酸素インジケーター組成物の組成＞
メチレンブルー ・・・・・１．８重量部
ローズマリー抽出物（三菱化学フーズ株式会社製：ＲＭ−２１Ａベース）
・・・・・７．２重量部
水性アクリル樹脂 ・・・・・５．０重量部
メタノール ・・・・４３．０重量部
水 ・・・・４３．０重量部。
<Composition of oxygen indicator composition>
Methylene blue: 1.8 parts by weight rosemary extract (Mitsubishi Chemical Foods, Inc .: RM-21A base)
... 7.2 parts by weight aqueous acrylic resin ... 5.0 parts by weight methanol ... 43.0 parts by weight water ... 43.0 parts by weight.
次に、酸化アルミニウムの蒸着薄膜を有する酸素バリアフィルム（厚さ１２μｍ）の酸化アルミニウム蒸着薄膜上に、前記工程で調肉した酸素インジケーターインキを使用してグラビア印刷の２度刷り（使用したグラビア版：２００線、セル深さ３０μｍ）により酸素インジケーター部を設けた。インキ薄膜は室温で１２時間乾燥させた。 Next, on the aluminum oxide vapor-deposited thin film of the oxygen barrier film (thickness 12 μm) having the aluminum oxide vapor-deposited thin film, the gravure printing was performed twice using the oxygen indicator ink prepared in the above process (the gravure plate used). : 200 lines, cell depth 30 μm) to provide an oxygen indicator part. The ink thin film was dried at room temperature for 12 hours.
続いて、酸素インジケーター部を覆うように、ホモタイプポリプロピレンからなるシーラント層（厚さ２０μｍ）／トリシクロ［４．３．０．１2,5］−３，７−デカジエンの開環重合体の水素添加体からなる中間シーラント層（厚さ２０μｍ）／ホモタイプポリプロピレンからなるシーラント層（厚さ２０μｍ）の３層構成の多層シーラント層［合計の厚さ６０μｍ］をウレタン系２液硬化型接着剤を使用したドライラミネート法により積層させ、本発明の実施例１に係る包装材料を得た。この包装材料を用いて製袋を行った後、得られた包装袋中に酸素吸収剤を入れ、しかる後に窒素置換して密封した。 Subsequently, a hydrogen of a ring-opening polymer of a sealant layer (thickness 20 μm) / tricyclo [4.3.0.1 2,5 ] -3,7-decadiene made of homotype polypropylene so as to cover the oxygen indicator part. A multilayer sealant layer [total thickness 60 μm] consisting of an intermediate sealant layer (thickness 20 μm) made of an additive / a sealant layer (thickness 20 μm) made of a homotype polypropylene is a urethane-based two-component curable adhesive. Lamination was performed by the dry laminating method used to obtain a packaging material according to Example 1 of the present invention. After making a bag by using this packaging material, an oxygen absorbent was put into the obtained packaging bag, and then nitrogen-substituted was sealed.
酸素バリアフィルムの酸化アルミニウムの蒸着薄膜と酸素インジケーター部との間にポリエチレンテレフタレートフィルム（厚さ１２μｍ）介在させた以外は実施例１と同様な方法で、実施例２に係る本発明の包装材料を得た。次に、この包装材料を用いて製袋を行った後、得られた包装袋中に酸素吸収剤を入れ、しかる後に窒素置換して密封した。 The packaging material of the present invention according to Example 2 was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film (thickness: 12 μm) was interposed between the vapor deposited aluminum oxide thin film of the oxygen barrier film and the oxygen indicator part. Obtained. Next, after making a bag using this packaging material, an oxygen absorbent was put into the obtained packaging bag, and then nitrogen-substituted was sealed.
酸化アルミニウムの蒸着薄膜を有する酸素バリアフィルム（厚さ１２μｍ）の酸化アルミニウムの蒸着薄膜上に、実施例１で用いた酸素インジケーターインキを使用してグラビア印刷の２度刷り（使用したグラビア版：２００線、セル深さ３０μｍ）により酸素インジケーター部を設けた。インキ薄膜は室温で１２時間乾燥させた。 Gravure printing was performed twice using the oxygen indicator ink used in Example 1 on the aluminum oxide vapor deposition thin film of the oxygen barrier film (thickness 12 μm) having the aluminum oxide vapor deposition thin film (gravure plate used: 200 The oxygen indicator portion was provided by a line and a cell depth of 30 μm. The ink thin film was dried at room temperature for 12 hours.
続いて、酸素インジケーター部を覆うように、無延伸ポリプロピレンからなる単層シーラント層（厚さ６０μｍ）をウレタン系２液硬化型接着剤を使用したドライラミネート法により積層させ、比較のための実施例３に係る包装材料を得た。この包装材料を用いて製袋を行った後、得られた包装袋中に酸素吸収剤を入れ、しかる後に窒素置換して密封した。 Subsequently, a single-layer sealant layer (thickness 60 μm) made of unstretched polypropylene was laminated by a dry laminating method using a urethane-based two-component curable adhesive so as to cover the oxygen indicator portion, and an example for comparison A packaging material according to 3 was obtained. After making a bag by using this packaging material, an oxygen absorbent was put into the obtained packaging bag, and then nitrogen-substituted was sealed.
酸素バリアフィルムの酸化アルミニウムの蒸着薄膜と酸素インジケーター部との間にポリエチレンテレフタレートフィルム（厚さ１２μｍ）を介在させた以外は実施例３と同様な方法で、比較のための実施例４に係る包装材料を得た。次に、この包装材料を用いて製袋を行った後、得られた包装袋中に酸素吸収剤を入れ、しかる後に窒素置換して密封した。 Packaging according to Example 4 for comparison in the same manner as in Example 3 except that a polyethylene terephthalate film (thickness 12 μm) is interposed between the evaporated thin film of aluminum oxide of the oxygen barrier film and the oxygen indicator part Obtained material. Next, after making a bag using this packaging material, an oxygen absorbent was put into the obtained packaging bag, and then nitrogen-substituted was sealed.
酸素インジケーター部と無延伸ポリプロピレンからなる単層シーラントフィルムの間にポリエチレンテレフタレートフィルム（厚さ１２μｍ）を介在させた以外は実施例３と同様な方法で、比較のための実施例５に係る包装材料を得た。次に、この包装材料を用いて製袋を行った後、得られた包装袋中に酸素吸収剤を入れ、しかる後に窒素置換して密封し
た。
A packaging material according to Example 5 for comparison in the same manner as in Example 3 except that a polyethylene terephthalate film (thickness 12 μm) is interposed between the oxygen indicator portion and a single-layer sealant film made of unstretched polypropylene. Got. Next, after making a bag using this packaging material, an oxygen absorbent was put into the obtained packaging bag, and then nitrogen-substituted was sealed.
続いて、上記各実施例に係る包装袋に対して下記試験１、２、３を行い、色調の変化や酸化還元色素の溶出、浸透状況をレトルト処理後と２週間経過後のそれぞれにおいて観察した。 Subsequently, the following tests 1, 2, and 3 were performed on the packaging bags according to the above examples, and changes in color tone, elution of redox dye, and penetration were observed after retorting and after two weeks. .
［試験１］
各包装袋に対して１２１℃−３０ｍｉｎのレトルト処理を行い、酸素インジケーター部の色調の変化を観察した。結果を表１に示す。
[Test 1]
Each packaging bag was subjected to a retort treatment at 121 ° C. for 30 minutes, and the change in the color tone of the oxygen indicator portion was observed. The results are shown in Table 1.
２週間の保存試験終了後の各包装袋をすべて開封し大気下に放置し、酸素インジケーター部における酸化色への回復状況を確認した。酸化色を呈した酸素インジケーター部の断面を光学顕微鏡にて観察し、色素の溶出と浸透の状況を観察した。結果を表２に示す。
Each packaging bag after the completion of the storage test for 2 weeks was opened and allowed to stand in the atmosphere, and the state of recovery to the oxidized color in the oxygen indicator portion was confirmed. The cross section of the oxygen indicator part exhibiting an oxidized color was observed with an optical microscope, and the state of elution and penetration of the dye was observed. The results are shown in Table 2.
包装袋に蒸留水を１００ｍｌ充填した後、ヘッドスペース（２０ｍｌ）の部分に脱酸素剤を貼り付けた。３日後、包材袋内の酸素濃度が０％になったのを確認してから脱酸素剤を切り離し、包装袋に対して１２１℃−３０ｍｉｎのレトルト処理を施して、色素の溶出状況を観察した。色素溶出があれば、蒸留水が青く染まるため、目視で容易に確認することができる。結果を表３に示す。
After filling the packaging bag with 100 ml of distilled water, an oxygen scavenger was attached to the head space (20 ml). Three days later, after confirming that the oxygen concentration in the packaging bag became 0%, the oxygen scavenger was cut off, and the packaging bag was subjected to a retort treatment at 121 ° C. for 30 minutes, and the elution state of the dye was observed. did. If there is dye elution, the distilled water is dyed blue, so it can be easily confirmed visually. The results are shown in Table 3.
また、表２より明らかなように、実施例３および４のようにシーラント層が無延伸ポリプロピレンからなる場合、酸素還元色素は包装袋の内部にまで到達し、内容物を汚染する危険性があることが分かった。一方、実施例５のように酸素インジケーター部とシーラント層の間にポリエチレンフタレートからなる層が介在している場合、色素の一部が外側の酸素バリアフィルムの処理面まで浸透し、還元色が維持できなかった。 Further, as is apparent from Table 2, when the sealant layer is made of unstretched polypropylene as in Examples 3 and 4, the oxygen reducing dye reaches the inside of the packaging bag and there is a risk of contaminating the contents. I understood that. On the other hand, when a layer made of polyethylene phthalate is interposed between the oxygen indicator portion and the sealant layer as in Example 5, a part of the dye penetrates to the treated surface of the outer oxygen barrier film, and the reduced color is maintained. could not.
さらに、表３より明らかなように、実施例１および２に係る包装材料は色素の溶出を完全に防止しており、還元状態と酸化状態における色調の表示が的確に行われていた。 Further, as apparent from Table 3, the packaging materials according to Examples 1 and 2 completely prevented the elution of the pigment, and the color tone in the reduced state and the oxidized state was accurately displayed.
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| JP2015140192A (en) * | 2014-01-28 | 2015-08-03 | 凸版印刷株式会社 | Packaging bag with oxygen indicator |
| JP2016147691A (en) * | 2015-02-12 | 2016-08-18 | 凸版印刷株式会社 | Packaging bag |
| US10989666B2 (en) | 2015-03-24 | 2021-04-27 | Mitsubishi Gas Chemical Company, Inc. | Oxygen detecting agent composition, and molded article, sheet, packaging material for oxygen scavenger, and oxygen scavenger using the same |
| JP2018080927A (en) * | 2016-11-14 | 2018-05-24 | 凸版印刷株式会社 | Oxygen indicator |
| JP2019077505A (en) * | 2019-02-15 | 2019-05-23 | 凸版印刷株式会社 | Packaging bag |
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