JP4022703B2 - Oxygen detection agent for application - Google Patents
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- JP4022703B2 JP4022703B2 JP29539298A JP29539298A JP4022703B2 JP 4022703 B2 JP4022703 B2 JP 4022703B2 JP 29539298 A JP29539298 A JP 29539298A JP 29539298 A JP29539298 A JP 29539298A JP 4022703 B2 JP4022703 B2 JP 4022703B2
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Description
【０００１】
【発明の属する技術分野】
本発明は酸素の有無を色調の変化で表示する酸素検知剤に関する。更に詳しくは、片面に粘着面を有するテープ状であって、これを適宜の長さに切断し、該粘着面を脱酸素剤包装体又は包装容器の内部に貼付して用いる貼付用酸素検知剤に関する。
【０００２】
【従来の技術】
酸素検知剤（酸素インジケーターとも表現される。）は、食品等の包装容器内の酸素濃度を酸素の有無を検知するものであり、特に、脱酸素包装した際に酸素が充分に除かれていることを色調の変化により表示するものである。酸素検知剤として、錠剤状に成形したもの、紙、糸、脱脂綿、樹脂成形体等の多孔質物に酸素検知組成物溶液を含浸したもの、紙またはフィルムの表面に酸素検知組成物を塗布または印刷した物等が提案されている。この酸素検知剤は、そのままの形態、あるいはプラスチック積層フィルムに包装された状態で、主に脱酸素剤による食品等の品質保持の分野で広く実用化されている。
【０００３】
また、これら酸素検知剤を脱酸素剤包装体に固定すること、または脱酸素剤を適用した商品が包装される包装容器内部に固定することにも種々の利点があるために、上記酸素検知剤を接着剤や両面テープで固定される方法が提案され、かつ実用化されている。近年では主に脱酸素剤包装袋への貼付を前提とした酸素検知剤の構成も開示されている。
【０００４】
例えば、特開昭６４−６６５６１号公報には、合成紙の少なくとも一方の面に酸素インジケーター層が設けられた酸素インジケーターが開示されている。実開平４−３９８０号公報には、脱酸素剤袋に酸素検知剤シートを接着剤または両面テープで貼付け一体型とした脱酸素剤包装袋が提案されている。しかしながら、これらの公報には食品等の被保存物に含まれる水分や油分が酸素検知剤に浸透し、変色機能が損なわれる場合に対する効果的な防止策が開示されていない。
【０００５】
また、特開平８−２８２７４０号公報には脱酸素剤包装袋／両面テープ／検知剤シート／透明フィルムをこの順に重ね合わせる方法によって得られた脱酸素剤一体型酸素検知剤が提案されている。しかしながら、この方法は、両面テープを使用するため、高価なものになる、離型紙が廃棄物として発生する、切断性が悪い、厚みが大きくなり柔軟性が悪い等の問題がある。また、この酸素検知剤シート及び透明フィルムを切断したときに、その端部から水分や油分が検知剤シート全体に浸透して色調の異常を示すことがある等の実用上の問題があった。
【０００６】
さらに、本発明者らの検討によれば、脱酸素剤を使用し食品等を包装保存した際、包装容器内の酸素濃度の減少に対して酸素検知剤の変色が遅れることがしばしばある。すなわち、酸素検知剤の変色が酸素濃度の変化に迅速に対応していないことになり、食品包装管理上、不都合であるという問題がある。
【０００７】
【発明が解決しようとする課題】
本発明では、従来の貼付用検知剤が有する上記のような耐水耐油性や厚みの問題あるいはコストの問題を解決して、実用範囲が広くかつ変色性能に優れた貼付用酸素検知剤を開発することを目的とする。特に、酸素濃度の変化に対応して速やかに変色する貼付用酸素検知剤及びその適用物品を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明は、非通気性かつ非透湿性のテープ状基材に、酸素検知組成物等の雰囲気検知剤が塗布、印刷又は含浸等の手段により添着されたテープ状酸素検知剤（１）と、（１）より幅が広く少なくとも一部分が透明で片面に粘着層を有するプラスチック製片面粘着テープ（２）から成り、（１）の酸素検知組成物添着面全体が実質的に空隙なく粘着されているテープ状貼付用酸素検知剤、換言すれば、酸素検知剤の添着面の実質的に全てが前記粘着テープ（２）により塞がれているテープ状貼付用酸素検知剤に関する。
【０００９】
本発明では、（１）が、テープ状基材の片面に酸素検知組成物を塗布又は印刷したものであり、且つ（２）の幅方向のほぼ中央に（１）が、（１）の酸素検知組成物面と（２）の粘着層が接するように粘着されていることが好ましい。
【００１０】
また、本発明では、（１）が、非透湿性や非通気性など外部から遮断される特性を持つプラスチックフィルム又は合成紙の片面に複数個の酸素検知組成物が一定間隔或いは所定間隔で塗布又は印刷されたものであることが好ましい。また本発明では、（２）の非粘着面に離型剤が塗布されていることが好ましい。
また本発明は、上記のテープ状貼付用酸素検知剤が適宜の長さに切断されて成る貼付用酸素検知剤に関する。
【００１１】
本発明は、上記の貼付用酸素検知剤が包装容器内部に貼付されて成ることを特徴とする酸素検知剤付き包装容器に関する。また本発明は、上記の貼付用酸素検知剤が脱酸素剤包装体表面に直接貼付された脱酸素剤包装体に関する。
【００１２】
また本発明は、上記のテープ状貼付用酸素検知剤と脱酸素剤等の雰囲気調節剤の連包体とを連続的に貼り付けた後、貼り付けたままの状態で脱酸素剤連包体を１個づつに分かれるよう切り離すことを特徴とする酸素検知剤が貼付された脱酸素剤包装体の製造方法に関する。
【００１３】
本発明でテープ状とは、幅に対して長さが長く、厚みが幅より薄い状態を言う。本発明の貼付用酸素検知剤は、厚みは好ましくは２ｍｍ以下より好ましくは０．５ｍｍ以下であり、幅は３ｍｍ以上３０ｍｍ以下が好ましい。長さは貼付時に適宜の寸法に切断して使用されるので特に規定されないが、貼付用酸素検知剤の製造コストと使用時のコストを最小に保持するためには、連続加工できる少なくとも数十ｍ以上の長さであることが好ましい。
【００１４】
本発明のテープ状貼付用酸素検知剤は、テープ状酸素検知剤とプラスチック製片面粘着テープ（以後、片面粘着テープと称する場合がある）から成り、極めてシンプルな構成故に生産性が高く低コスト化が可能であり、しかも使用時の操作性も高いため、酸素検知剤としてのトータルコストを低くできる。更には、片面粘着テープは、そのほぼ中央部分でテープ状酸素検知剤の酸素検知組成物面を密封し、両端寄り部分で粘着貼付するとの単純化された層構成を採用しているために、薄く柔軟性に富む上に酸素検知剤としての変色性能や耐水耐油性に優れていて、高湿度の過酷な使用条件下においても性能劣化することなく本来の酸素検知性能が発揮される。また柔軟性に優れることから、脱酸素剤包装袋や食品包装容器等の凹凸のある面や剛性の小さい面にも良好な貼り付け性が発揮される。また使用時に離型紙などの廃棄物が一切発生せず、使い勝手が良い。
【００１５】
尚、使用時には、本発明の酸素検知剤は片面粘着テープによりその表面が覆われ、反対面はテープ状基材により密閉され外部雰囲気から隔離されるが、驚くべきことに、酸素検知組成物が雰囲気に直接接している従来型の酸素検知剤よりも雰囲気中の酸素濃度の減少に対する変色応答速度が速い。その機構は明らかでないが、片面粘着テープは、酸素検知性能劣化の要因となる過度の水分吸収を防止し、雰囲気ガスを適度に透過する機能を果たし、また、酸素検知剤を隙間なく密閉して検知剤成分の外部への移行を防止することが関係しているものと推定される。
【００１６】
【発明の実施の形態】
図１は、本発明の貼付用酸素検知剤の幅方向の断面図であり、（１）がテープ状酸素検知剤、（２）が片面粘着テープである。片面粘着テープは（３）のプラスチックフィルムの片面に（４）の粘着剤が全面に塗布または積層されている。この片面粘着テープの幅方向のほぼ中央に、片面粘着テープの幅Ｂより小さい幅Ａを有するテープ状酸素検知剤が（４）の粘着剤によって（３）に固定されている。幅Ｂより幅Ａが小さいことにより、テープ状酸素検知剤の両側に粘着剤可着部Ｃ及びＣ'が残り、この部分で脱酸素剤包装体などの被着体に貼付される。ＣとＣ'は被着体への貼付能力が失われない限り、必ずしも同じ寸法である必要はない。
【００１７】
本発明に用いられるプラスチック製片面粘着テープは、プラスチックフィルムの片面に粘着剤が塗布または積層されているものである。プラスチックフィルムの材質としては、ポリエチレン、ポリプロピレン、ポリエステル、ポリアミド、ポリカーボネート、セルロースアセテート、セロハン等があげられるが、透明性、柔軟性、強度等の面から、延伸ポリプロピレン及びポリエステルが好ましい。プラスチックフィルムの厚みは実用的な強度と柔軟性があれば特に問わないが、１０〜１００ミクロンが好ましい。プラスチックフィルムは無色透明でも、酸素検知剤の色変化を見やすくするために適宜着色した透明のものでも良い。更に酸素検知剤の色変化が判るように一部分を透明のまま残し、他の部分に隠蔽の文字や絵文字等の情報表示をしたり、酸素検知剤色調を判別しやすくする目的で適宜の色調での印刷を施しても良い。また、プラスチックフィルムの酸素透過度は５０〜３０００ｃｃ／ｍ2・ｄａｙ・ａｔｍが好ましい。透湿度は、５０ｇ／ｍ2・ｄａｙ以下が好ましい。
【００１８】
粘着剤としては合成ゴム系、天然ゴム系、アクリル系、シリコン系等既存のものを用いることができる。好ましくは、粘着剤はプラスチックフィルム片面全体に塗布又は積層される。この際、粘着剤の種類と厚みは、酸素検知剤に用いる色素が染着したり色素の変色を阻害したりしないこと、透明性に優れること、安全衛生性に優れること、被着体に対する適度な接着性が得られること等を考慮して適宜選択すればよい。プラスチックフィルムへの粘着加工方法は、粘着剤をエマルジョンとして又は溶剤で希釈して塗布後乾燥する方法、粘着剤を押し出し積層する方法、フィルム化した粘着剤を離型紙から転写する方法等、公知の方法が用いられる。
【００１９】
このようにして得られた片面粘着テープの幅はテープ状酸素検知剤の幅より大きく、図１に示すＣ及びＣ'の幅が確保できれば良いが、取り扱い性やコストの点から３〜５０ｍｍが好ましく、５〜３０ｍｍが特に好ましい。また、図１のＣ及びＣ'の幅は各々１〜５ｍｍが好ましい。また紙管等に巻かれた片面粘着テープを巻き出す際に少ない抵抗で円滑に巻き出しが可能になるので、非粘着面側にシリコン系、アルキッド樹脂系等の離型剤を塗布することが好ましい。
【００２０】
テープ状酸素検知剤とは、テープ状基材に酸素検知組成物を添着したものであり、酸素検知組成物が周囲雰囲気の酸素濃度に応じて変色することにより酸素の有無を表示する。酸素検知組成物としては、アントラキノン系、インジゴ系、チアジン系、硫化染料等の還元剤によって色変化を示す染料、アルカリ金属又はアルカリ土類金属の水酸化物や塩等のアルカリ性物質、及び還元糖類等の還元剤を必須成分とする組成物が好ましく用いられる。これらの必須成分に、必要に応じて、溶媒、還元剤によって変色しない染料又は顔料、水溶性高分子、バインダー樹脂等を組み合わせて添加し、テープ状基材に添着する。添着方法としては、塗布、印刷又は含浸等の各方法が例示される。
【００２１】
高湿度の過酷な条件下でも高い酸素検知性能を発揮するためにテープ状酸素検知剤としては、非通気性かつ非透湿性の合成紙又はフィルムの片面に実質的に水分を含まない酸素検知組成物を塗布又は印刷したものが好ましく用いられる。
テープ状基材としては、非通気性かつ非透湿性の合成紙又はフィルム等が用いられる。例えば、ポリエチレン、ポリプロピレン、ポリエステル、ポリアミド、ポリカーボネート、セルロースアセテート、セロハン等があげられるが、透明性、柔軟性、強度等の面から、延伸ポリプロピレン又はポリエステルが好ましい。テープ状基材の厚みは実用的な強度と柔軟性があれば特に問わないが、１０〜１００ミクロンが好ましい。また、テープ状基材の酸素透過度は５０〜３０００ｃｃ／ｍ2・ｄａｙ・ａｔｍが好ましく、透湿度は５０ｇ／ｍ2・ｄａｙ以下が好
ましい。
【００２２】
テープ状基材は、酸素検知剤の色変化を見やすくするために、不透明又は適宜着色したものが好ましい。更に酸素検知剤の色変化が判るように一部分を透明のまま残し、他の部分に隠蔽の文字や絵文字等の情報表示をしたり、酸素検知剤色調を判別しやすくする目的で適宜の色調での印刷を施しても良い。
テープ状酸素検知剤の幅は２〜２０ｍｍが好ましい。狭すぎると見にくくなり、広すぎるとコスト高となり、かつ取り扱いにも不便になる。また厚みは柔軟性及び美観上、１ｍｍ以下が好ましく、０．５ｍｍ以下が特に好ましい。
【００２３】
テープ状酸素検知剤を片面粘着テープと組み合わせた際に、テープ長さ方向に色変化部を連続化しても良いが、色変化の判別をしやすくするためにテープ長さ方向で色変化部と変化しない部分とを交互に存在させることが好ましい。図２〜図４に好ましいパターンを例示した。図２は、全面が透明な片面粘着テープと酸素検知組成物をドット状に連続配置したテープ状酸素検知剤とを組み合わせたものである。図３は、長さ方向に連続した透明部を有する片面粘着テープと酸素検知組成物を縞状に配置したテープ状酸素検知剤とを組み合わせたものである。図４は、長さ方向に間欠的に透明部を有する片面粘着テープと全面に酸素検知組成物を配置したテープ状酸素検知剤とを組み合わせたものである。尚、本発明はこれ等の例示に制限されるものではない。
【００２４】
本発明のテープ状の貼付用酸素検知剤は、片面粘着テープの幅方向中央寄りにテープ状酸素検知剤が酸素検知組成物面全体と粘着層がすきまなく粘着されているものであり、例えば数十ｍ以上のテープが紙管に巻き付けられた形状をしている。幅方向中央寄りとは、図１においてＣとＣ'が被着体への十分な貼付能力が得られる幅を与える位置である。
【００２５】
片面粘着テープの粘着面に粘着層が形成されているために、テープ状酸素検知剤の酸素検知組成物面と片面粘着テープは、粘着層により実質的に空隙なく粘着される。酸素検知組成物面と片面粘着テープの粘着層の間に、両者が粘着していないこと等による空隙があると、脱酸素剤を使用し食品等を包装保存する際、包装容器内の酸素濃度の変化に対して酸素検知剤の変色が遅れることがある。
【００２６】
このテープ状貼付用酸素検知剤を適宜の長さに切断して個々の貼付用酸素検知剤とし、食品の脱酸素包装等の用途で包材や脱酸素剤に貼り付けて使用する。或いは、テープ状酸素検知剤と片面粘着テープのそれぞれを例えば数十ｍ以上の長尺で巻き取っておき、両者を同時に巻き出して重ね合わせ、直後に被着物に貼り付けて使用することもできる。
【００２７】
特に、貼付用酸素検知剤が貼付された脱酸素剤包装体は、食品を脱酸素包装する際に便利に使用される。この貼付用酸素検知剤が貼付された脱酸素剤包装体を製造する方法としては、テープ状貼付用酸素検知剤と脱酸素剤連包体とを連続的に貼り付けた後、貼り付けたままの状態で脱酸素剤連包体を１個づつの脱酸素剤包装体に分かれるよう切り離す方法が、コストが低く合理的である。
【００２８】
また、貼付用酸素検知剤を包装容器内部に貼付して、酸素検知剤付き包装容器としてもよい。例えば、包装容器内の皿、仕切りなどの構造物又は包装材料に、酸素検知剤が片面粘着テープ側から視認できるように貼付する。
【００２９】
図５には、図３に示す貼付用酸素検知剤が貼付された脱酸素剤包装体の一例を示す。また、図６に、図２の貼付用酸素検知剤が貼付された脱酸素剤包装体の一例を示す。いずれの酸素検知剤とも、テープ状酸素検知剤が図１に示したＡの部分でプラスチック製片面粘着テープに貼着され、ＣとＣ'の部分で脱酸素剤包装体に貼着される。
【００３０】
【実施例】
以下に実施例により本発明を詳しく説明するが、本発明はこれによって限定されるものではない。尚、実施例における酸素検知剤の色調は、(株)ＧＥ企画センター発行の色調見本（カラーセレクター）の色調番号で示している。色調番号の説明を表１に示した。
【００３１】
【表１】
実施例１
〔酸素検知組成物の調製〕
アルカリ性物質として水酸化マグネシウム微粉末、還元剤としてフルクトース、還元剤によって変色する色素としてメチレンブルー（C.I.Basic Blue 9）を含有し、その他にバインダー樹脂としてエチルセルロース、還元剤により変色しない色素としてフロキシン（C.I.Acid Red 92 ）、溶剤として水−メタノールを含有するインキを調合した。
【００３３】
〔テープ状酸素検知剤の作成〕
ポリプロピレン系合成紙（王子製紙(株)製商品名ユポ、厚み７０ミクロン）を基材とし、その片面に、線幅５ｍｍ、線間隔５ｍｍ、版深８０ミクロンの斜めストライプ版２ロール及び版深４０ミクロンのベタ版１ロールをこの順にセットしたグラビア印刷機を用い、ストライプ版で上記酸素検知組成物インキ、ベタ版でオ−バ−プリント剤（サーモライトＰ）を印刷した。印刷品の水分は１０５℃７０分の加熱減量法で０．５％以下であり、実質的に水分は残留していなかった。この印刷物を５ｍｍ幅にスリットし、１００ｍ巻きのロール状としてテープ状酸素検知剤を得た。印刷部分のインキ厚みは２０ミクロンであった。
【００３４】
〔片面粘着テープの作成〕
裏印刷を施した延伸ポリプロピレンフィルム（厚み４０ミクロン）の片面全面に粘着剤としてアクリル系粘着剤を塗工し、反対面全面にシリコン系の離型剤を塗工した後１２ｍｍ幅にスリットし、３インチ紙管に１００ｍ巻き取り、幅方向中央部に４ｍｍ幅の長さ方向に連続した透明部を有し、その他の部分に灰緑色地に白文字の印刷を施した片面粘着テープを得た。
【００３５】
〔テープ状貼付用酸素検知剤の作成〕
上下２組の巻き出しロールとガイド及び巻き取りロールからなる装置に上記テープ状酸素検知剤と上記片面粘着テープをかけ、それぞれ巻き出しながら片面粘着テープの幅方向ほぼ中央部に、テープ状酸素検知剤が酸素検知組成物と粘着面が接して重なるよう、位置を合わせて巻き取りロールの３インチ紙管に１００ｍ巻き取り、図３に示すような構成のテープ状貼付用酸素検知剤を得た。この貼付用酸素検知剤の色変化は、空気中でCS21-04（紺色）であり、脱酸素剤によって酸素濃度０．１％以下にした雰囲気下ではCS26-04（赤色）であった。
【００３６】
〔酸素検知剤が貼付された脱酸素剤包装体の作成及び保管〕
複数の巻き出しロール、ガイド、圧着ロール、厚み検知ロール、カッターからなる貼付装置を用いて、脱酸素剤ロール状連包体（三菱瓦斯化学(株)製商品名エージレスＳＡ−１００Ｒ）を巻き出して導入し、その片面に上記のテープ状貼付用酸素検知剤を重ねて圧着ロールで貼り付けた後、厚み検知ロールに連動するカッターで脱酸素剤包装体を１包ずつ切り離し、酸素検知剤が貼付された脱酸素剤包装体を得た。更にこのものを１００個づつ、ガスバリア性積層フィルム（ＫＯＮ／ＰＥ）製の平袋（２２０×３００ｍｍ）に入れ、内部の空気を抜いて袋口をヒートシールした。このものを１５℃の温調倉庫に保管した。
【００３７】
〔測定１．酸素検知剤変色速度テスト〕
保管前及び保管１ヶ月後の酸素検知剤が貼付された脱酸素剤包装体について、１包をガスバリア袋（１８０×２５０ｍｍ）に空気５００ｍｌ及び８０％ＲＨ調湿液を含浸した脱脂綿とともに密封し、経時的に袋内ガスを少量ずつサンプリングして東レ(株)製酸素分析計を用いて酸素濃度を測定するとともに酸素検知剤の色調を観察した。結果を表２に示した。
【００３８】
〔測定２．食品実装テスト〕
保管前の酸素検知剤が貼付された脱酸素剤包装体をドーナツ２個とともにガスバリア袋（１８０×２５０ｍｍ）にヒートシールで密封し、２５℃の室内に保存した。経時的に酸素検知剤の色調を観察しつつ、保存１ヶ月後に袋を開封し、酸素検知剤の色変化を観察した。結果を表３に示した。
【００３９】
実施例２
片面粘着テープとして、延伸ポリプロピレンの代わりに延伸ポリエステルフィルム(厚さ４０ミクロン)を用いたこと以外は実施例１と同様にしてテープ状酸素検知剤を作成し、酸素検知剤が貼付された脱酸素剤包装体を得た。これを使って、実施例１と同様にして測定１、測定２を行った。結果を表２、表３に示した。
【００４０】
実施例３
片面粘着テープの粘着剤として、アクリル系粘着剤の代わりに合成ゴム系粘着剤を用いたこと以外は実施例１と同様にしてテープ状酸素検知剤を作成し、酸素検知剤が貼付された脱酸素剤包装体を得た。これを使って、実施例１と同様にして測定１、測定２を行った。結果を表２、表３に示した。
【００４１】
比較例１
実施例１で用いた貼付装置に、実施例１で作成したテープ状酸素検知剤と５ｍｍ幅の両面テープとを供給し、テープ状酸素検知剤の非印刷側と導入した脱酸素剤連包体の片面とを両面テープで貼着した後、厚み検知ロールに連動するカッターで脱酸素剤包装体を１包ずつ切り離し、テープ状酸素検知剤が両面テープで固定された脱酸素剤包装体を得た。これを使って、実施例１と同様にして測定１、測定２を行った。結果を表２、表３に示した。
【００４２】
比較例２
ポリプロピレン系合成紙の代わりに耐水耐油紙（中越パルプ(株)製商品名ＷＯＰ、厚さ８０ミクロン）を用いたこと以外は実施例１と同様にしてテープ状酸素検知剤を作成し、これを使用したこと以外は比較例１と同様にしてテープ状酸素検知剤が両面テープで固定された脱酸素剤包装体を作成し、これを用いて測定１、測定２を行った。結果を表２、表３に示した。
【００４３】
【表２】
【表３】
測定１の結果（表２）から、実施例１では、保管前、保管後ともに袋内酸素濃度０．１％到達後速やかに酸素検知剤は色調CS26-04に達し、色調薄れもないことから、本発明の貼付用酸素検知剤は優れた酸素濃度指示機能を有しかつ保存安定性にも優れていることが判る。これに対し、比較例１及び２では保管前であっても酸素検知剤の変色速度に遅れが見られた他、保管後では変色速度の遅れが顕著になると共に色調が薄れ判別しにくくなった。これは脱酸素剤包装体の有する湿度（９７％ＲＨ／２５℃）により、酸素検知組成物に劣化を生じたためと考えられた。特に非透湿性のテープ状酸素検知剤を使用したものが、透湿性のものより良い性能を示したことから、透湿による厚み方向の色素移動が性能変化の一要因となっていると推定された。
【００４６】
また、測定２の結果（表３）から、片面粘着テープを用いない比較例ではドーナツの油分又は水分により、酸素検知剤の色調異常が生じ、開封して空気に触れた際にも青色への復色が不十分で色の濃さも薄いのに対し、本発明の実施例では良好に色調を保持し、開封後も変色性能を保持していることが判る。
【００４７】
実施例４
実施例１のテープ状貼付用酸素検知剤ロールを市販の事務用テープディスペンサー（コクヨ(株)製商品名Ｔ−Ｍ１２）に装着し、事務用粘着テープと同様に適宜の長さに手で引き出し切断することを繰り返したが、全く問題なく任意の長さの貼付用酸素検知剤を切り出すことができた。１ｃｍの長さに切り出した貼付用酸素検知剤をポリスチレン製皿（１５０×１１０ｃｍ）の裏面に貼付し、皿上に脱酸素剤包装体（三菱瓦斯化学(株)製商品名エージレスＦＸ−３０）とチーズたら７０ｇを入れた後、ガスバリア性袋（１５０×２００ｍｍ）に入れ、袋口をヒートシールした。このとき、酸素検知剤の色調はCS21-04であった。このものを５℃の恒温槽中に保管したところ、翌日、袋内酸素濃度は０．０２％まで低下しており、酸素検知剤の色調はCS26-04に変化していた。
【００４８】
更に袋に縫い針でピンホール１個を開け、その翌日、袋内酸素濃度を測定すると０．４％まで上昇していた。このとき検知剤色調はCS24-04に変化し、袋体の異常を検知することができた。更に２日後、袋内酸素濃度は１２％まで上昇しており、これに対応して検知剤の色調はCS22-04に変化していた。尚、袋内酸素濃度の測定には、少量の袋内ガスをサンプリングし、ガスクロマトグラフを用いて分析した。本発明の貼付用酸素検知剤は、脱酸素剤を適用した食品包装容器に異常が起き脱酸素状態が損なわれると忠実にそれを反映して色調が変化することが判った。
【００４９】
【発明の効果】
本発明の貼付用酸素検知剤によれば、脱酸素剤による包装容器内の酸素濃度の変化に対応して酸素検知剤が速やかに変色し、酸素濃度の減少を時間遅れを伴うことなく目視により容易に検知することができるという効果を達成する。
また、本発明の貼付用酸素検知剤を貼付した脱酸素剤は、包装容器内の酸素濃度の変化に対応して酸素検知剤が速やかに変色し、酸素濃度の変化を時間遅れを伴うことなく目視により容易に検知することができるという機能を付加した脱酸素剤として、食品等の保存に好適に使用される。
【００５０】
本発明の貼付用酸素検知剤は、構成がシンプルなので低コストで製造でき、かつ一般の片面粘着テープと同様の薄く柔軟性に富むテープ状とすることができるため、単純な器具で任意の長さに切断して使用できるほか、機械的に自動連続製造、切断、貼付を行うこともでき、極めて使い勝手に優れる。また柔軟性に優れることから、脱酸素剤包装袋や食品包装容器等の凹凸のある面や剛性の小さい面にも良好な貼り付け性が発揮される。また使用時に離型紙などの廃棄物が発生せず、使い勝手が良い。
【００５１】
更に本発明の貼付用酸素検知剤は、水分や油分の多い環境下でも色調の異常を示すことがなく、脱酸素剤包装体上又は包装容器内部に貼付した状態で在庫しても色調、変色速度の劣化がなく、酸素検知剤として優れた性能を有するので、食品等の脱酸素包装品質管理に安心して利用できる。また、酸素濃度を色調で表示でき、変色速度性能に優れ、色調の安定性や耐水耐油性にも優れることを利用して、脱酸素包装以外にも各種物品の包装、各種装置の安全管理等の用途に市販の粘着テープあるいはラベル、ワッペンと同様の手軽さで使用することが可能である。
【図面の簡単な説明】
【図１】本発明のテープ状貼付用酸素検知剤の一例の断面図である。
【図２】本発明のテープ状貼付用酸素検知剤のデザインの一例を示す見取り図である。
【図３】本発明のテープ状貼付用酸素検知剤のデザインの一例を示す見取り図である。
【図４】本発明のテープ状貼付用酸素検知剤のデザインの一例を示す見取り図である。
【図５】本発明の貼付用酸素検知剤が貼付された脱酸素剤包装体の一例を示す平面図である。
【図６】本発明の貼付用酸素検知剤が貼付された脱酸素剤包装体の一例を示す平面図である。
【符号の説明】
１ テープ状酸素検知剤
２ 片面粘着テープ
３ プラスチックフィルム
４ 粘着剤[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oxygen detector that displays the presence or absence of oxygen by a change in color tone. More specifically, it is in the form of a tape having an adhesive surface on one side, which is cut into an appropriate length, and the adhesive surface is used by sticking the adhesive surface inside the oxygen absorber package or packaging container. About.
[0002]
[Prior art]
An oxygen detector (also expressed as an oxygen indicator) detects the presence or absence of oxygen based on the oxygen concentration in a packaging container such as food, and in particular, oxygen is sufficiently removed when deoxidized and packaged. This is displayed by a change in color tone. As an oxygen detector, a product molded into a tablet, a porous material such as paper, thread, absorbent cotton, or a resin molded body impregnated with an oxygen detection composition solution, or an oxygen detection composition is applied or printed on the surface of paper or film. Proposed items have been proposed. This oxygen detection agent has been widely put into practical use in the field of maintaining the quality of foods and the like mainly using an oxygen scavenger, in the form as it is or packaged in a plastic laminated film.
[0003]
In addition, there are various advantages in fixing these oxygen detectors to the oxygen absorber package or in the packaging container in which the product to which the oxygen absorber is applied is packaged. Has been proposed and put to practical use. In recent years, a configuration of an oxygen detection agent mainly premised on sticking to an oxygen scavenger packaging bag is also disclosed.
[0004]
For example, Japanese Patent Application Laid-Open No. 64-66561 discloses an oxygen indicator in which an oxygen indicator layer is provided on at least one surface of a synthetic paper. Japanese Utility Model Laid-Open No. 4-3980 has proposed an oxygen scavenger packaging bag in which an oxygen detection agent sheet is attached to an oxygen scavenger bag with an adhesive or a double-sided tape. However, these publications do not disclose an effective preventive measure against a case where moisture or oil contained in an object to be preserved such as food penetrates into the oxygen detector and the discoloration function is impaired.
[0005]
Japanese Patent Application Laid-Open No. 8-282740 proposes an oxygen detector integrated oxygen detector obtained by a method in which an oxygen absorber packaging bag / double-sided tape / detector sheet / transparent film is superposed in this order. However, since this method uses a double-sided tape, there are problems such that it becomes expensive, release paper is generated as waste, cutting property is poor, thickness is large, and flexibility is poor. In addition, when the oxygen detector sheet and the transparent film are cut, there is a practical problem such that moisture or oil may permeate the entire detector sheet from the end portion to show an abnormal color tone.
[0006]
Furthermore, according to the study by the present inventors, when foods are packaged and stored using an oxygen scavenger, discoloration of the oxygen detector is often delayed with respect to a decrease in oxygen concentration in the packaging container. That is, the discoloration of the oxygen detector does not respond quickly to the change in oxygen concentration, which is inconvenient in food packaging management.
[0007]
[Problems to be solved by the invention]
In the present invention, the oxygen detection agent for patch having a wide practical range and excellent color change performance is solved by solving the above problems of water resistance, oil resistance, thickness and cost of the conventional patch detection agent. For the purpose. In particular, it is an object of the present invention to provide an oxygen detector for sticking that quickly changes color in response to a change in oxygen concentration and an article to which the oxygen detector is applied.
[0008]
[Means for Solving the Problems]
The present invention relates to a tape-like oxygen detector (1) in which an atmosphere detector such as an oxygen detector composition is attached to a non-breathable and moisture-impermeable tape-like substrate by means such as coating, printing or impregnation; (1) It is made of a plastic single-sided adhesive tape (2) that is wider and at least partially transparent and has an adhesive layer on one side, and the entire oxygen-sensing composition-attached surface of (1) is adhered substantially without voids. The present invention relates to a tape-like oxygen detection agent for sticking, in other words, a tape-like oxygen detection agent for sticking, in which substantially all of the attachment surface of the oxygen detection agent is closed by the adhesive tape (2).
[0009]
In the present invention, (1) is obtained by applying or printing an oxygen detection composition on one side of a tape-like substrate, and (1) is the oxygen of (1) at the center in the width direction of (2). It is preferable that the detection composition surface and the adhesive layer (2) are adhered so as to contact each other.
[0010]
Further, in the present invention, (1) is that a plurality of oxygen detection compositions are applied at regular intervals or at predetermined intervals on one side of a plastic film or synthetic paper having a property of being blocked from the outside, such as moisture permeability and air permeability. Or it is preferable that it is what was printed. Moreover, in this invention, it is preferable that the mold release agent is apply | coated to the non-adhesive surface of (2).
The present invention also relates to a sticking oxygen detection agent obtained by cutting the tape-like sticking oxygen detection agent into an appropriate length.
[0011]
The present invention relates to a packaging container with an oxygen detecting agent, characterized in that the above-mentioned oxygen detecting agent for pasting is stuck inside a packaging container. The present invention also relates to an oxygen scavenger package in which the above-mentioned oxygen detector for patch is directly pasted on the surface of the oxygen scavenger package.
[0012]
The present invention also provides a deoxidant package in a state where the tape-like oxygen detector for sticking and a continuous package of an atmosphere control agent such as a deoxidizer are continuously pasted. It is related with the manufacturing method of the oxygen-absorbing agent package body to which the oxygen detection agent stuck, characterized in that the oxygen detecting agent is separated.
[0013]
In the present invention, the tape shape means a state in which the length is longer than the width and the thickness is thinner than the width. The oxygen detector for sticking of the present invention preferably has a thickness of 2 mm or less, more preferably 0.5 mm or less, and a width of 3 mm or more and 30 mm or less. The length is not particularly specified because it is cut into an appropriate dimension at the time of application, but it can be continuously processed at least several tens of meters in order to keep the manufacturing cost and the cost of use of the oxygen detector for application to a minimum. It is preferable that it is the above length.
[0014]
The oxygen detection agent for tape-like application of the present invention comprises a tape-like oxygen detection agent and a plastic single-sided adhesive tape (hereinafter sometimes referred to as a single-sided adhesive tape), and has a very simple structure, resulting in high productivity and low cost. In addition, since the operability at the time of use is high, the total cost as an oxygen detector can be reduced. Furthermore, since the single-sided adhesive tape employs a simplified layer structure in which the oxygen-sensing composition surface of the tape-like oxygen detector is sealed at its substantially central portion and adhesively stuck at both end portions. In addition to being thin and flexible, it has excellent discoloration performance and water / oil resistance as an oxygen detection agent, and exhibits its original oxygen detection performance without deterioration even under severe usage conditions at high humidity. Moreover, since it is excellent in a softness | flexibility, favorable sticking property is exhibited also on the surface with unevenness | corrugation, such as an oxygen absorber packaging bag, a food packaging container, or a surface with small rigidity. In addition, no waste such as release paper is generated at the time of use, and it is easy to use.
[0015]
In use, the surface of the oxygen detector of the present invention is covered with a single-sided adhesive tape, and the opposite surface is sealed with a tape-like substrate and isolated from the external atmosphere. The color change response speed with respect to the decrease in the oxygen concentration in the atmosphere is faster than that of a conventional oxygen detector directly in contact with the atmosphere. Although the mechanism is not clear, single-sided adhesive tape functions to prevent excessive moisture absorption, which causes deterioration in oxygen detection performance, and to properly permeate atmospheric gas. It is presumed to be involved in preventing the detection agent component from being transferred to the outside.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a cross-sectional view in the width direction of the oxygen detector for sticking of the present invention, wherein (1) is a tape-like oxygen detector and (2) is a single-sided adhesive tape. In the single-sided adhesive tape, the adhesive (4) is applied or laminated on one side of the plastic film (3). A tape-like oxygen detecting agent having a width A smaller than the width B of the single-sided adhesive tape is fixed to (3) by the adhesive (4) at substantially the center in the width direction of the single-sided adhesive tape. Since the width A is smaller than the width B, the adhesive adhering portions C and C ′ remain on both sides of the tape-shaped oxygen detector, and these portions are affixed to an adherend such as an oxygen scavenger package. C and C ′ do not necessarily have the same dimensions as long as the ability to stick to the adherend is not lost.
[0017]
The plastic single-sided adhesive tape used in the present invention is one in which an adhesive is applied or laminated on one side of a plastic film. Examples of the material of the plastic film include polyethylene, polypropylene, polyester, polyamide, polycarbonate, cellulose acetate, cellophane, and the like. From the viewpoint of transparency, flexibility, strength, and the like, stretched polypropylene and polyester are preferable. The thickness of the plastic film is not particularly limited as long as it has practical strength and flexibility, but is preferably 10 to 100 microns. The plastic film may be colorless and transparent, or a transparent film appropriately colored to make the color change of the oxygen detector easy to see. Furthermore, leave the part transparent so that the color change of the oxygen detector can be seen, display information such as concealed characters and pictograms in other parts, and make it easy to distinguish the oxygen detector color tone. May be printed. Moreover, the oxygen permeability of the plastic film is 50 to 3000 cc / m. 2 · Day · atm is preferred. Moisture permeability is 50g / m 2 -Day or less is preferable.
[0018]
As the pressure-sensitive adhesive, existing ones such as synthetic rubber type, natural rubber type, acrylic type, and silicon type can be used. Preferably, the pressure-sensitive adhesive is applied or laminated on the entire surface of the plastic film. At this time, the type and thickness of the pressure-sensitive adhesive are such that the dye used for the oxygen detector does not stain or inhibit discoloration of the dye, is excellent in transparency, is excellent in safety and hygiene, and is appropriate for the adherend. May be selected as appropriate in consideration of obtaining good adhesiveness. Adhesive processing methods for plastic film include known methods such as a method in which an adhesive is diluted as an emulsion or a solvent and then dried, a method in which an adhesive is extruded and laminated, a method in which a filmed adhesive is transferred from a release paper, and the like. The method is used.
[0019]
The width of the single-sided adhesive tape thus obtained is larger than the width of the tape-like oxygen detector, and it is sufficient if the widths of C and C ′ shown in FIG. 1 can be ensured. Preferably, 5 to 30 mm is particularly preferable. Further, the widths of C and C ′ in FIG. In addition, when unwinding a single-sided adhesive tape wound around a paper tube, etc., it can be smoothly unwound with little resistance, so it is possible to apply a release agent such as silicon or alkyd resin to the non-adhesive side preferable.
[0020]
The tape-like oxygen detector is a tape-like base material attached with an oxygen-sensing composition, and the presence or absence of oxygen is indicated by changing the color of the oxygen-sensing composition according to the oxygen concentration in the surrounding atmosphere. Examples of the oxygen detection composition include anthraquinone series, indigo series, thiazine series, dyes that change color with a reducing agent such as sulfur dyes, alkaline substances such as hydroxides or salts of alkali metals or alkaline earth metals, and reducing sugars. A composition containing a reducing agent such as an essential component is preferably used. If necessary, these essential components are added in combination with a solvent, a dye or pigment that does not change color with a reducing agent, a water-soluble polymer, a binder resin, and the like, and are attached to a tape-like substrate. Examples of the attaching method include each method such as coating, printing or impregnation.
[0021]
In order to exhibit high oxygen detection performance even under severe conditions of high humidity, as a tape-like oxygen detection agent, an oxygen detection composition containing substantially no moisture on one side of a non-breathable and non-breathable synthetic paper or film What applied or printed the thing is used preferably.
As the tape-like substrate, non-breathable and moisture-impermeable synthetic paper or film is used. For example, polyethylene, polypropylene, polyester, polyamide, polycarbonate, cellulose acetate, cellophane, and the like can be mentioned. From the viewpoint of transparency, flexibility, strength, and the like, stretched polypropylene or polyester is preferable. The thickness of the tape-shaped substrate is not particularly limited as long as it has practical strength and flexibility, but is preferably 10 to 100 microns. The oxygen permeability of the tape-like substrate is 50 to 3000 cc / m. 2 -Day-atm is preferable, and the water vapor transmission rate is 50 g / m. 2 ・ Day or less is preferred
Good.
[0022]
The tape-like substrate is preferably opaque or appropriately colored in order to make the color change of the oxygen detector easy to see. Furthermore, leave the part transparent so that the color change of the oxygen detector can be seen, display information such as concealed characters and pictograms in other parts, and make it easy to distinguish the oxygen detector color tone. May be printed.
The width of the tape-shaped oxygen detector is preferably 2 to 20 mm. If it is too narrow, it will be difficult to see, if it is too wide it will be expensive and inconvenient to handle. Further, the thickness is preferably 1 mm or less, particularly preferably 0.5 mm or less, from the viewpoint of flexibility and aesthetics.
[0023]
When a tape-like oxygen detector is combined with a single-sided adhesive tape, the color change part may be continuous in the tape length direction, but the color change part in the tape length direction is easy to distinguish the color change. It is preferable that portions that do not change exist alternately. A preferable pattern is illustrated in FIGS. FIG. 2 is a combination of a single-sided adhesive tape whose entire surface is transparent and a tape-shaped oxygen detection agent in which an oxygen detection composition is continuously arranged in dots. FIG. 3 is a combination of a single-sided pressure-sensitive adhesive tape having a transparent portion continuous in the length direction and a tape-like oxygen detector having an oxygen-sensing composition arranged in stripes. FIG. 4 is a combination of a single-sided adhesive tape having a transparent portion intermittently in the length direction and a tape-like oxygen detector having an oxygen detection composition disposed on the entire surface. The present invention is not limited to these examples.
[0024]
The tape-like oxygen detector for sticking of the present invention is one in which the entire surface of the oxygen-sensing composition and the adhesive layer are adhered tightly to the center of the single-sided adhesive tape in the width direction. A tape of 10 m or more is wound around a paper tube. The center in the width direction is a position where C and C ′ in FIG. 1 give a width that provides a sufficient pasting ability to the adherend.
[0025]
Since the pressure-sensitive adhesive layer is formed on the pressure-sensitive adhesive surface of the single-sided pressure-sensitive adhesive tape, the oxygen-sensing composition surface of the tape-shaped oxygen detector and the single-sided pressure-sensitive adhesive tape are adhered to each other substantially without a gap by the pressure-sensitive adhesive layer. If there is a gap between the oxygen detection composition surface and the adhesive layer of the single-sided adhesive tape, the oxygen concentration in the packaging container when storing food using an oxygen scavenger, etc. Discoloration of the oxygen detection agent may be delayed with respect to the change of.
[0026]
The tape-like oxygen detector for sticking is cut into an appropriate length to obtain individual oxygen detectors for sticking, and is used by being attached to a packaging material or oxygen absorber for uses such as deoxidation packaging of food. Alternatively, each of the tape-shaped oxygen detector and the single-sided adhesive tape can be wound up in a long length of, for example, several tens of meters, and both can be unwound at the same time, overlapped, and immediately attached to the adherend.
[0027]
In particular, the oxygen scavenger package to which the oxygen detecting agent for affixing is affixed is conveniently used when food is deoxygenated and packaged. As a method for producing the oxygen scavenger package with the oxygen detecting agent attached, the tape-like oxygen detecting agent and the oxygen scavenger package are continuously attached, and are then attached. In this state, the method of separating the oxygen scavenger continuous package so as to be separated into one oxygen scavenger package is low in cost and reasonable.
[0028]
Moreover, it is good also as a packaging container with an oxygen detection agent by sticking the oxygen detection agent for sticking inside a packaging container. For example, the oxygen detecting agent is attached to a structure such as a dish or partition in a packaging container or a packaging material so that the oxygen sensing agent can be visually recognized from the single-sided adhesive tape side.
[0029]
FIG. 5 shows an example of an oxygen scavenger package to which the oxygen detecting agent for application shown in FIG. 3 is attached. FIG. 6 shows an example of an oxygen scavenger package to which the oxygen detection agent for application shown in FIG. 2 is attached. In any of the oxygen detectors, the tape-like oxygen detector is attached to the plastic single-sided adhesive tape at the portion A shown in FIG. 1, and attached to the oxygen absorber package at the portions C and C ′.
[0030]
【Example】
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. The color tone of the oxygen detecting agent in the examples is indicated by the color tone number of the color tone sample (color selector) issued by GE Planning Center. The explanation of the tone number is shown in Table 1.
[0031]
[Table 1]
Example 1
(Preparation of oxygen sensing composition)
Contains magnesium hydroxide fine powder as an alkaline substance, fructose as a reducing agent, methylene blue (CI Basic Blue 9) as a colorant that changes with a reducing agent, ethyl cellulose as a binder resin, and Phloxine (CIAcid Red 92 as a colorant that does not change with a reducing agent) ), An ink containing water-methanol as a solvent was prepared.
[0033]
[Preparation of tape-shaped oxygen detector]
Polypropylene synthetic paper (trade name YUPO manufactured by Oji Paper Co., Ltd., thickness of 70 microns) is used as a base material, and on one side, two rolls of diagonal stripe plate with a line width of 5 mm, a line interval of 5 mm, and a plate depth of 80 microns and a plate depth of 40 Using a gravure printing machine in which one roll of a micron solid plate was set in this order, the oxygen detection composition ink was printed on a stripe plate, and an overprinting agent (thermolite P) was printed on a solid plate. The moisture content of the printed product was 0.5% or less by the heating loss method at 105 ° C. for 70 minutes, and substantially no moisture remained. This printed material was slit to a width of 5 mm to obtain a tape-shaped oxygen detector as a roll of 100 m. The ink thickness of the printed part was 20 microns.
[0034]
[Creation of single-sided adhesive tape]
Apply an acrylic adhesive as an adhesive to the entire surface of one side of a stretched polypropylene film (thickness 40 microns) that has been printed on the back, and then apply a silicone mold release agent to the entire opposite surface and slit it to a width of 12 mm. A single-sided adhesive tape having a transparent portion continuous in the length direction of 4 mm width at the center in the width direction and having a transparent portion continuous in the length direction with a width of 4 mm was obtained on the 3 inch paper tube, and white letters were printed on the grayish green background. .
[0035]
[Preparation of oxygen detector for tape application]
The tape-shaped oxygen detector and the single-sided adhesive tape are applied to an apparatus consisting of two sets of upper and lower unwinding rolls, a guide, and a take-up roll. The tape was attached to a 3-inch paper tube of a take-up roll for 100 m so that the agent overlapped with the oxygen-sensing composition in contact with the adhesive surface, and a tape-like oxygen sensing agent for tape application having a structure as shown in FIG. 3 was obtained. . The color change of the oxygen detector for sticking was CS21-04 (dark blue) in the air, and CS26-04 (red) in an atmosphere in which the oxygen concentration was reduced to 0.1% or less with an oxygen scavenger.
[0036]
[Preparation and storage of oxygen scavenger package with oxygen detector]
Using a sticking device composed of a plurality of unwinding rolls, guides, pressure-bonding rolls, thickness detection rolls, and cutters, an oxygen scavenger roll-shaped continuous package (trade name Ageless SA-100R manufactured by Mitsubishi Gas Chemical Co., Ltd.) is unwound. The oxygen detection agent for tape application is overlaid on one side and attached with a pressure roll, and then the oxygen scavenger package is separated one by one with a cutter interlocking with the thickness detection roll. An attached oxygen scavenger package was obtained. Further, 100 pieces of each were put into flat bags (220 × 300 mm) made of a gas barrier laminate film (KON / PE), the air inside was vented, and the bag mouth was heat sealed. This was stored in a temperature-controlled warehouse at 15 ° C.
[0037]
[
About the oxygen scavenger package with the oxygen detection agent attached before storage and after 1 month of storage, one package is sealed with absorbent cotton impregnated with 500 ml of air and 80% RH humidity control liquid in a gas barrier bag (180 × 250 mm), Over time, the gas in the bag was sampled little by little, the oxygen concentration was measured using an oxygen analyzer manufactured by Toray Industries, Inc., and the color tone of the oxygen detector was observed. The results are shown in Table 2.
[0038]
[
The oxygen scavenger package to which the oxygen detector before storage was attached was sealed in a gas barrier bag (180 × 250 mm) with two donuts by heat sealing and stored in a room at 25 ° C. While observing the color tone of the oxygen detector over time, the bag was opened after one month of storage, and the color change of the oxygen detector was observed. The results are shown in Table 3.
[0039]
Example 2
A tape-like oxygen detector was prepared in the same manner as in Example 1 except that a stretched polyester film (thickness 40 microns) was used instead of stretched polypropylene as a single-sided adhesive tape, and deoxygenated with an oxygen detector attached. An agent package was obtained. Using this,
[0040]
Example 3
A tape-like oxygen detector was prepared in the same manner as in Example 1 except that a synthetic rubber adhesive was used instead of an acrylic adhesive as the adhesive for the single-sided adhesive tape, and the oxygen detector was affixed. An oxygen agent package was obtained. Using this,
[0041]
Comparative Example 1
The tape-shaped oxygen detector prepared in Example 1 and a double-sided tape having a width of 5 mm are supplied to the sticking device used in Example 1, and the non-printing side of the tape-shaped oxygen detector and the introduced oxygen scavenger continuous package are introduced. After sticking one side of the tape with a double-sided tape, the oxygen scavenger package is cut off one by one with a cutter interlocking with the thickness detection roll to obtain the oxygen scavenger package with the tape-shaped oxygen detector fixed with the double-sided tape. It was. Using this,
[0042]
Comparative Example 2
A tape-shaped oxygen detector was prepared in the same manner as in Example 1 except that water-resistant and oil-resistant paper (trade name WOP manufactured by Chuetsu Pulp Co., Ltd., thickness 80 microns) was used instead of polypropylene synthetic paper. Except that it was used, a oxygen scavenger package in which a tape-like oxygen detector was fixed with a double-sided tape was prepared in the same manner as in Comparative Example 1, and
[0043]
[Table 2]
[Table 3]
From the results of measurement 1 (Table 2), in Example 1, the oxygen detector reached the color tone CS26-04 immediately after reaching the oxygen concentration in the bag of 0.1% both before and after storage, and there was no color fading. It can be seen that the oxygen detector for patch of the present invention has an excellent oxygen concentration indicating function and is excellent in storage stability. On the other hand, in Comparative Examples 1 and 2, there was a delay in the color change rate of the oxygen detection agent even before storage, and after storage, the color change rate was significantly delayed and the color tone faded, making it difficult to determine. . This was considered due to the deterioration of the oxygen detection composition due to the humidity (97% RH / 25 ° C.) of the oxygen scavenger package. In particular, those using non-breathable tape-like oxygen detectors showed better performance than those with moisture permeability, and it is estimated that dye movement in the thickness direction due to moisture permeation contributed to the performance change. It was.
[0046]
In addition, from the result of measurement 2 (Table 3), in the comparative example not using the single-sided adhesive tape, an abnormal color tone of the oxygen detector occurs due to the oil content or moisture of the donut, and when it is opened and touched with air, it turns blue. It can be seen that the color recovery is inadequate and the color intensity is thin, while the embodiment of the present invention maintains a good color tone and maintains the color-changing performance after opening.
[0047]
Example 4
The oxygen detection agent roll for tape attachment of Example 1 was mounted on a commercially available office tape dispenser (trade name T-M12 manufactured by KOKUYO Co., Ltd.) and pulled out by hand to an appropriate length in the same manner as the office adhesive tape. The cutting was repeated, but an oxygen detecting agent of any length could be cut out without any problem. An oxygen detector for sticking cut to a length of 1 cm is pasted on the back of a polystyrene dish (150 × 110 cm), and an oxygen scavenger package (trade name AGELESS FX-30, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on the dish. After adding 70 g of cheese, it was put in a gas barrier bag (150 × 200 mm) and the bag mouth was heat-sealed. At this time, the color tone of the oxygen detector was CS21-04. When this was stored in a 5 ° C. constant temperature bath, the oxygen concentration in the bag dropped to 0.02% the next day, and the color tone of the oxygen detector changed to CS26-04.
[0048]
Further, one pinhole was opened in the bag with a sewing needle, and the oxygen concentration in the bag was measured the next day, and it was increased to 0.4%. At this time, the color of the detection agent changed to CS24-04, and the abnormality of the bag could be detected. Two more days later, the oxygen concentration in the bag increased to 12%, and the color tone of the detection agent changed to CS22-04 correspondingly. For measuring the oxygen concentration in the bag, a small amount of the gas in the bag was sampled and analyzed using a gas chromatograph. It has been found that the oxygen detector for patch of the present invention faithfully reflects the color tone when an abnormality occurs in the food packaging container to which the oxygen absorber is applied and the oxygen absorber state is impaired.
[0049]
【The invention's effect】
According to the oxygen detector for sticking of the present invention, the oxygen detector rapidly discolors in response to a change in oxygen concentration in the packaging container due to the oxygen absorber, and the decrease in oxygen concentration is visually observed without a time delay. The effect that it can be easily detected is achieved.
Further, the oxygen scavenger attached with the oxygen detector for application of the present invention quickly changes color in response to a change in oxygen concentration in the packaging container, and the change in oxygen concentration is not accompanied by a time delay. As an oxygen scavenger to which a function that can be easily detected visually is added, it is suitably used for storage of foods and the like.
[0050]
Since the oxygen detector for sticking of the present invention has a simple structure, it can be produced at low cost, and can be formed into a thin and flexible tape similar to a general single-sided adhesive tape. In addition to being able to be cut, it can also be used for automatic continuous manufacturing, cutting and pasting, making it extremely easy to use. Moreover, since it is excellent in a softness | flexibility, favorable sticking property is exhibited also on the surface with unevenness | corrugation, such as an oxygen absorber packaging bag, a food packaging container, or a surface with small rigidity. In addition, no waste such as release paper is generated during use, making it easy to use.
[0051]
Furthermore, the oxygen detection agent for application of the present invention does not exhibit abnormal color tone even in an environment with a lot of moisture or oil, and even if it is stocked on the oxygen scavenger package or inside the packaging container, the color tone or discoloration Since there is no deterioration in speed and it has excellent performance as an oxygen detector, it can be used with peace of mind in quality control of deoxidized packaging of foods and the like. In addition to deoxygenation packaging, various items can be packaged and various devices can be safely managed by utilizing the fact that oxygen concentration can be displayed in color tone, excellent color-changing speed performance, and excellent color stability and water / oil resistance. It can be used with the same ease as a commercially available adhesive tape, label, or emblem.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of an example of an oxygen detecting agent for tape application according to the present invention.
FIG. 2 is a sketch showing an example of the design of a tape-like oxygen detector for sticking of the present invention.
FIG. 3 is a sketch showing an example of the design of the oxygen detecting agent for tape-like application of the present invention.
FIG. 4 is a sketch showing an example of the design of the oxygen detecting agent for tape-like application of the present invention.
FIG. 5 is a plan view showing an example of an oxygen scavenger package to which the oxygen detection agent for application of the present invention is applied.
FIG. 6 is a plan view showing an example of an oxygen scavenger package to which the oxygen detection agent for application of the present invention is applied.
[Explanation of symbols]
1 Tape-like oxygen detector
2 single-sided adhesive tape
3 Plastic film
4 Adhesive
Claims (9)
（１）より幅が広く少なくとも一部分が透明で片面に粘着層を有するプラスチック製片面粘着テープ（２）とから成り、
テープ状酸素検知剤（１）の酸素検知組成物添着面全体が片面粘着テープ（２）によって実質的に空隙なく粘着されているテープ状貼付用酸素検知剤。A tape-like oxygen detector (1) in which an oxygen-sensing composition is attached to a non-breathable and moisture-impermeable tape-like substrate;
(1) A plastic single-sided adhesive tape (2) having a wider width and at least a part of which is transparent and has an adhesive layer on one side,
A tape-like oxygen detector for sticking, wherein the entire oxygen-sensing composition-attached surface of the tape-like oxygen detector (1) is adhered to the single-sided adhesive tape (2) substantially without voids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29539298A JP4022703B2 (en) | 1997-10-17 | 1998-10-16 | Oxygen detection agent for application |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-285667 | 1997-10-17 | ||
| JP28566797 | 1997-10-17 | ||
| JP29539298A JP4022703B2 (en) | 1997-10-17 | 1998-10-16 | Oxygen detection agent for application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11190729A JPH11190729A (en) | 1999-07-13 |
| JP4022703B2 true JP4022703B2 (en) | 2007-12-19 |
Family
ID=26555982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29539298A Expired - Fee Related JP4022703B2 (en) | 1997-10-17 | 1998-10-16 | Oxygen detection agent for application |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4022703B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180114923A (en) | 2016-02-19 | 2018-10-19 | 가부시키가이샤 도키와 산교 | The oxygen detecting composition and the oxygen detecting element |
| KR20190057551A (en) * | 2017-11-20 | 2019-05-29 | 한국생산기술연구원 | Hazardous gas detection kit package and harmful gas detection method using the kit package |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003029786A1 (en) * | 2001-10-03 | 2003-04-10 | University Of Western Sydney | Detection and measurement of oxygen permeation across a film |
| JP4422466B2 (en) * | 2003-02-07 | 2010-02-24 | パウダーテック株式会社 | Article quality control method and oxygen detector used therefor |
| US7921798B2 (en) | 2004-08-06 | 2011-04-12 | Powdertech Co., Ltd. | Oxygen detector sheet and oxygen detecting agent using the same, and method for manufacturing oxygen detector sheet |
| JP4816907B2 (en) * | 2006-01-06 | 2011-11-16 | 凸版印刷株式会社 | Ink composition for oxygen indicator, oxygen indicator using the same, and packaging material containing oxygen indicator |
| JP4888055B2 (en) * | 2006-10-30 | 2012-02-29 | 凸版印刷株式会社 | Oxidation prevention method for film containing easily oxidizable substance |
| EP3012629A4 (en) * | 2013-06-21 | 2017-03-22 | Mitsubishi Gas Chemical Company, Inc. | Oxygen-detecting multilayered body, and oxygen-detecting packaging material and oxygen-scavenger package using said oxygen-detecting multilayered body |
-
1998
- 1998-10-16 JP JP29539298A patent/JP4022703B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180114923A (en) | 2016-02-19 | 2018-10-19 | 가부시키가이샤 도키와 산교 | The oxygen detecting composition and the oxygen detecting element |
| KR20190057551A (en) * | 2017-11-20 | 2019-05-29 | 한국생산기술연구원 | Hazardous gas detection kit package and harmful gas detection method using the kit package |
| KR102029730B1 (en) * | 2017-11-20 | 2019-10-08 | 한국생산기술연구원 | Hazardous gas detection kit package and harmful gas detection method using the kit package |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11190729A (en) | 1999-07-13 |
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