JP2007003259A - Oxygen detector composition. - Google Patents
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- JP2007003259A JP2007003259A JP2005181604A JP2005181604A JP2007003259A JP 2007003259 A JP2007003259 A JP 2007003259A JP 2005181604 A JP2005181604 A JP 2005181604A JP 2005181604 A JP2005181604 A JP 2005181604A JP 2007003259 A JP2007003259 A JP 2007003259A
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Abstract
【課題】 酸素の有無あるいは濃度を色の変化により識別する光および熱に対して安定性が改良された酸素検知剤組成物を提供する。
【解決手段】 シクロデキストリン類、可逆変色性有機色素および還元剤を含む酸素検知剤組成物。
【選択図】 無PROBLEM TO BE SOLVED: To provide an oxygen detector composition having improved stability against light and heat for identifying the presence or concentration of oxygen by color change.
An oxygen detector composition comprising cyclodextrins, a reversible color-changing organic dye and a reducing agent.
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Description
本発明は酸素検知剤組成物に関する。より詳しくは酸素の有無あるいは濃度を色の変化により識別でき、しかも光および熱に対して安定な酸素検知剤組成物に関するものである。本発明の酸素検知剤組成物は、粉末状、錠剤状、紙状、布状、糸状又はインキとして使用できる。 The present invention relates to an oxygen detector composition. More specifically, the present invention relates to an oxygen detector composition that can identify the presence or concentration of oxygen by color change and is stable against light and heat. The oxygen detector composition of the present invention can be used as a powder, tablet, paper, cloth, thread, or ink.
従来より、酸化還元により可逆的に色が変わる可変性有機色素を利用した酸素検知剤が提案されている。例えば、チアジン染料あるいはアジン染料、オキサジン染料などの有機色素と還元剤とからなる固形状の酸素検知剤が開示されている（特許文献１および特許文献２）。また、チアジン染料等と還元性糖類とアルカリ性物質とを樹脂溶液中に溶解もしくは分散させた酸素インジケーターインキ組成物が知られている（特許文献３）。市販の錠剤型酸素検知剤（登録商標エージレスアイ、三菱瓦斯化学（株）製）および酸素検知機能を有するインキ組成物を塗布した酸素検知体（登録商標ペーパーアイ、三菱瓦斯化学（株）製）は、透明な包装容器内の酸素濃度が０．１容量％未満の無酸素状態であることを簡便に色変化で示す機能製品であり、脱酸素剤（登録商標エージレス、三菱瓦斯化学（株）製）と共に食品の鮮度保持および医療医薬品の品質保持等に使用されている。 Conventionally, oxygen detectors using variable organic dyes that change color reversibly by oxidation-reduction have been proposed. For example, solid oxygen detectors composed of thiazine dyes, azine dyes, oxazine dyes and other organic pigments and reducing agents are disclosed (Patent Documents 1 and 2). Also known is an oxygen indicator ink composition in which a thiazine dye or the like, a reducing saccharide, and an alkaline substance are dissolved or dispersed in a resin solution (Patent Document 3). Commercially available tablet-type oxygen detector (registered trademark Ageless Eye, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and an oxygen detector coated with an ink composition having an oxygen detection function (registered trademark Paper Eye, manufactured by Mitsubishi Gas Chemical Co., Ltd.) Is a functional product that simply shows a color change that the oxygen concentration in the transparent packaging container is less than 0.1% by volume, and is an oxygen scavenger (registered trademark AGELESS, Mitsubishi Gas Chemical Co., Ltd.) And used for maintaining the freshness of food and the quality of medical drugs.
しかしながら、従来の酸素検知剤は、耐光性および保存安定性が不十分で、光照射下では退色したり変色機能が低下することがあり、また、高温下では褐色化したり変色機能が低下することがあるため、鮮明な色彩を長期間維持するためには遮光下かつ低温下で保存しなければならない欠点を有していた。特にこの傾向は酸素検知インキを塗布した酸素検知体の場合に顕著であった。
近年、層状ケイ酸塩の層間に有機色素を挿入することにより耐光性と保存安定性が大幅に改善された酸素検知剤組成物（特許文献４）および酸素検知インキ組成物（特許文献５）が開発されている。また、酸素検知体は、空気下から無酸素状態に置かれた際に迅速に変色する変色応答性が要求される。
However, conventional oxygen detectors have insufficient light resistance and storage stability, and may fade or discolor under light irradiation, and may brown or discolor under high temperatures. Therefore, in order to maintain a vivid color for a long period of time, it has a disadvantage that it must be stored under light shielding and at a low temperature. This tendency was particularly remarkable in the case of an oxygen detector coated with an oxygen detection ink.
In recent years, an oxygen detection agent composition (Patent Document 4) and an oxygen detection ink composition (Patent Document 5), in which light resistance and storage stability are greatly improved by inserting an organic dye between layers of a layered silicate, Has been developed. In addition, the oxygen detector is required to have a color change responsiveness that quickly changes color when placed in an oxygen-free state from under air.
本発明の目的は、耐光性および保存安定性に優れ、かつ応答性に優れた実用性に優れた酸素検知体を提供することにある。 An object of the present invention is to provide an oxygen detector excellent in light resistance and storage stability and excellent in responsiveness and practicality.
本発明者らは、前記従来技術の問題点に鑑み鋭意研究を行った結果、包接化合物の使用によって、耐光性と保存安定性に優れ、かつ雰囲気が無酸素状態に変化した際の変色応答性に優れることを見出し本発明に到達した。
すなわち、本発明は、シクロデキストリン類、可逆変色性有機色素および還元剤を含む酸素検知剤組成物に関するものである。さらに、前記酸素検知剤組成物を担体に担持させてなる酸素検知剤、前記酸素検知剤を打錠してなる酸素検知剤錠剤前記酸素検知剤組成物を紙、布または糸に含ませてなる酸素検知体、前記酸素検知剤組成物を含有する酸素検知インキ及び該酸素検知インキを塗布または印刷した酸素検知体に関するものである。
As a result of diligent research in view of the problems of the prior art, the inventors of the present invention are excellent in light resistance and storage stability due to the use of an inclusion compound, and the color change response when the atmosphere is changed to an oxygen-free state. As a result, the present invention has been found.
That is, the present invention relates to an oxygen detector composition containing cyclodextrins, a reversible color-changing organic dye and a reducing agent. Further, an oxygen detector formed by supporting the oxygen detector composition on a carrier, an oxygen detector tablet formed by compressing the oxygen detector, and the oxygen detector composition contained in paper, cloth or thread. The present invention relates to an oxygen detector, an oxygen detector ink containing the oxygen detector composition, and an oxygen detector applied or printed with the oxygen detector ink.
本発明は、シクロデキストリン類を使用することを特徴とする。シクロデキストリン類が種々の化合物を包接して安定化又は機能化を促す場合があることは知られている。しかしながら、少なくとも可逆変色性有機色素がシクロデキストリン類に包接された複合体を形成する本発明の構成によって、耐光性・保存安定性と変色応答性という互いに矛盾する機能を両立させる酸素検知剤組成物が提供されることは、予想し難い発見であった。 The present invention is characterized by using cyclodextrins. It is known that cyclodextrins may include various compounds to promote stabilization or functionalization. However, the composition of the present invention that forms a complex in which at least a reversible color-changing organic dye is encapsulated in cyclodextrins allows the oxygen detector composition to achieve both contradictory functions of light resistance, storage stability and color change responsiveness. It was an unexpected discovery that things were offered.
本発明によれば、光および熱に対して比較的安定な酸素検知剤が提供される。
本発明の酸素検知剤は、形状が粉末状、錠剤、布または糸に含浸させたもの、または、これを含有する酸素検知インキを塗布または印刷したものとして、また、透明あるいは半透明な固形状のものとして、食品の保存および医療医薬品の品質保持の分野において極めて高い価値を有する。
According to the present invention, an oxygen detector that is relatively stable to light and heat is provided.
The oxygen detection agent of the present invention is a powder, tablet, cloth or thread impregnated, or coated or printed with an oxygen detection ink containing the same, or a transparent or translucent solid As such, it has extremely high value in the field of food preservation and quality maintenance of medical drugs.
本発明で用いられるシクロデキストリン類とは、環状オリゴ糖である。クラウンエーテルのように包接能を有する化合物の一種で、環の内部に分子を取り込むことができる。シクロデキストリンは環の外部は親水性で、内部は疎水性という特異的な構造をつくっているため、様々な分子を取り込んで包接化合物を形成することができる。 The cyclodextrins used in the present invention are cyclic oligosaccharides. It is a kind of compound having an inclusion ability such as crown ether, and can incorporate molecules inside the ring. Since cyclodextrin has a specific structure in which the outside of the ring is hydrophilic and the inside is hydrophobic, it can incorporate various molecules to form an inclusion compound.
シクロデキストリンは、疎水空洞内に化合物を取り込み、薬物の物理化学的性質を改善することができるため、食品、化粧品、臨床検査薬、繊維、樹脂など多方面で利用されている。特に化合物がゲスト化合物の場合、シクロデキストリンとの包接複合体の形成により、温度、湿度、酸素、光などに不安定な分子を安定化させたり、水に溶けにくい化合物の溶解性の改善のために汎用されている。 Cyclodextrins are used in various fields such as foods, cosmetics, clinical diagnostics, fibers, and resins because they can incorporate compounds into hydrophobic cavities and improve the physicochemical properties of drugs. In particular, when the compound is a guest compound, formation of an inclusion complex with cyclodextrin stabilizes molecules unstable to temperature, humidity, oxygen, light, etc., and improves the solubility of compounds that are difficult to dissolve in water. Because it is universal.
シクロデキストリンは、高度に選択的な酵素的合成によって製造されることが一般的である。シクロデキストリンは、一般にドーナツ形状の環をなす６個、７個または８個のグルコースモノマーからなり、グルコースの個数に応じて各々α-シクロデキストリン、β-シクロデキストリンまたはγ-シクロデキストリンと呼ばれる。グルコースモノマーの特異的な結合によって、シクロデキストリンが剛性を有する円錐台分子構造をとり、その内部に一定の体積の空洞が形成される。この内部空間がシクロデキストリンの重要な構造的特徴であり、この構造によって数々の分子と錯体を形成することができる。錯体を形成する分子は、シクロデキストリンの内部空間に少なくとも部分的に嵌合し、包接化合物を形成できる大きさでなければならない。 Cyclodextrins are generally produced by highly selective enzymatic synthesis. The cyclodextrin is generally composed of 6, 7 or 8 glucose monomers forming a donut-shaped ring, and is called α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin depending on the number of glucoses. Due to the specific binding of glucose monomer, cyclodextrin takes a rigid truncated cone molecular structure, and a certain volume of cavity is formed inside. This internal space is an important structural feature of cyclodextrins, and this structure can form complexes with numerous molecules. The molecules forming the complex must be sized to at least partially fit into the interior space of the cyclodextrin and form an inclusion compound.
本発明で用いられる可逆変色性有機色素は、分子内に動きやすいπ電子を有する長い共役二重結合系を含んでいる芳香族化合物であって、酸化還元により可逆的に色彩が変わる酸化還元可変性有機色素である。本発明の可変性有機色素として、酸化還元指示薬、あるいはチアジン染料、アジン染料、オキサジン染料、インジゴイド染料、チオインジゴイド染料などが好適に用いられる。例えば、メチレンブルー、ニューメチレンブルー、メチレングリーン、バリアミンブルーＢ、ジフェニルアミン、フェロイン、カプリブルー、サフラニンＴ、インジゴ、インジゴカルミン、インジゴ白、インジルビンなどが挙げられる。好ましくは、メチレンブルーに代表されるチアジン染料である。可逆変色性有機色素に組み合わせて、不変性有機色素等の非変色性着色剤を使用することもできる。これにより色調の変化を分かりやすくすることができる。 The reversible color-changing organic dye used in the present invention is an aromatic compound containing a long conjugated double bond system having a π-electron that moves easily in the molecule, and its redox-variable color changes reversibly by redox. Organic dye. As the variable organic coloring matter of the present invention, a redox indicator, a thiazine dye, an azine dye, an oxazine dye, an indigoid dye, a thioindigoid dye, or the like is preferably used. For example, methylene blue, new methylene blue, methylene green, barrier amine blue B, diphenylamine, ferroin, capri blue, safranin T, indigo, indigo carmine, indigo white, indirubin and the like can be mentioned. Preferred is a thiazine dye typified by methylene blue. In combination with the reversible color-changing organic dye, a non-color-changing colorant such as an unmodified organic dye can also be used. This makes it easy to understand the change in color tone.
本発明で用いられる還元剤は、酸素濃度が大気中より低い条件下で上記の有機色素を還元する化合物であって、例えば、グルコース、フルクトース、キシロースなどの単糖類、マルトースなどの還元性二糖類、アスコルビン酸およびその塩、亜ジチオン酸およびその塩、システインおよびその塩などが挙げられる。 The reducing agent used in the present invention is a compound that reduces the above-mentioned organic dye under conditions where the oxygen concentration is lower than in the atmosphere, for example, monosaccharides such as glucose, fructose, and xylose, and reducing disaccharides such as maltose. , Ascorbic acid and its salt, dithionic acid and its salt, cysteine and its salt and the like.
還元剤の還元活性を高めるために、更に、塩基性物質を加えることが望ましい場合がある。塩基性物質としては、水酸化ナトリウム、水酸化カリウム、水酸化カルシウムなどの水酸化塩や炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸水素ナトリウムなどの炭酸塩などが選択できる。 In order to enhance the reducing activity of the reducing agent, it may be desirable to further add a basic substance. As the basic substance, a hydroxide salt such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or a carbonate salt such as sodium carbonate, potassium carbonate, calcium carbonate or sodium bicarbonate can be selected.
本発明の酸素検知剤おいて、シクロデキストリン類、可逆変色性有機色素及び還元剤の配合比は、シクロデキストリン類１重量部に対して、可逆変色性有機色素は、０．００１重量部〜１００重量部、好ましくは、０．００５〜５０重量部、より好ましくは、０．０１重量部〜１０重量部である。還元剤は、シクロデキストリン類１重量部に対して、０．０１重量部〜１０００重量部、好ましくは、０．１重量部〜５００重量部である。塩基性物質は、還元剤１重量部に対して、０．００１重量部〜１０００重量部、好ましくは、０．０１重量部〜５００重量部である。 In the oxygen detector of the present invention, the compounding ratio of the cyclodextrins, the reversible color-changing organic dye and the reducing agent is 0.001 part by weight to 100 parts by weight of the reversible color-changing organic dye with respect to 1 part by weight of the cyclodextrins. Parts by weight, preferably 0.005 to 50 parts by weight, more preferably 0.01 to 10 parts by weight. A reducing agent is 0.01 weight part-1000 weight part with respect to 1 weight part of cyclodextrins, Preferably, it is 0.1 weight part-500 weight part. The basic substance is 0.001 to 1000 parts by weight, preferably 0.01 to 500 parts by weight with respect to 1 part by weight of the reducing agent.
本発明の酸素検知剤組成物を担体に含浸させることにより、形状が粉末状である酸素検知剤粉粒体を得ることができる。担体としては、各種の無機物粉粒体が使用でき、特に塩基性無機物が好ましい。さらに、本発明の酸素検知剤組成物を担体に含浸させた後、これを打錠することで、錠剤形状とすることができる。本発明の酸素検知剤組成物のアルカリ性水溶液を糸・紙・布などに含浸することにより、フィルム状、シート状、糸状形態にすることができる。 By impregnating the carrier with the oxygen detector composition of the present invention, an oxygen detector powder granule having a powder shape can be obtained. As the carrier, various inorganic powders can be used, and basic inorganic substances are particularly preferable. Furthermore, after impregnating the carrier with the oxygen detector composition of the present invention, it is tableted to form a tablet. By impregnating an alkaline aqueous solution of the oxygen detector composition of the present invention into yarn, paper, cloth, etc., it can be made into a film form, a sheet form, or a thread form.
本発明により、耐光性および保存安定性に優れ、かつ酸素濃度低下に対する応答性にも優れた酸素検知体が提供される。本発明の酸素検知体は、食品の保存および医療医薬品の品質保持等の無酸素保存分野において極めて高い利用価値を有する。 The present invention provides an oxygen detector that is excellent in light resistance and storage stability and excellent in response to a decrease in oxygen concentration. The oxygen detector of the present invention has extremely high utility value in the field of oxygen-free storage such as food preservation and quality maintenance of medical drugs.
以下、本発明を実施例によって詳細に説明する。
実施例１
γ−シクロデキストリン０．２０ｇ、可逆変色性有機色素メチレンブルー０.０１ｇおよびＤ−（＋）−グルコース１.０ｇが溶解している水溶液１０ｍＬを炭酸マグネシウム粉末２５ｇに混合し、含浸させ、青色粉末状の酸素検知剤を得た。
この青色粉末状の酸素検知剤を用いて以下の変色試験を行った。すなわち、市販の脱酸素剤（商品名：エージレスＳＡ、三菱瓦斯化学（株）製）とともにガスバリア性容器内に密封保存し、ジルコニア式酸素濃度計を用いて容器内酸素濃度を追跡した。容器内酸素濃度が０．１容量％未満の脱酸素雰囲気になってから１時間以内に、酸素検知剤は無酸素状態を示す白色になり、開封による空気曝露により速やかに再び青色になった。繰り返しこの操作を行ったところ、この色調変化は、酸素濃度により可逆的であり、酸素検知剤は繰り返し使用できた。
Hereinafter, the present invention will be described in detail by way of examples.
Example 1
10 g of an aqueous solution in which 0.20 g of γ-cyclodextrin, 0.01 g of the reversible color-changing organic dye methylene blue and 1.0 g of D-(+)-glucose are mixed with 25 g of magnesium carbonate powder, impregnated, and blue powder An oxygen detector was obtained.
The following discoloration test was performed using this blue powdery oxygen detector. That is, it was hermetically stored in a gas barrier container together with a commercially available oxygen scavenger (trade name: Ageless SA, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the oxygen concentration in the container was traced using a zirconia oxygen analyzer. Within 1 hour after the oxygen concentration in the container was less than 0.1% by volume, the oxygen detector became white indicating anoxic conditions and quickly turned blue again by air exposure by opening. When this operation was repeated, the color tone change was reversible depending on the oxygen concentration, and the oxygen detector could be used repeatedly.
実施例２
シクロデキストリン混合物（商品名：セルデックスＴＢ−５０、日本食品化工（株））０．４５ｇ、メチレンブルー０.０３ｇ、非変色性有機色素フロキシン０.０２ｇおよびキシロース２.５ｇが溶解している水溶液１５ｍＬを炭酸マグネシウム５０ｇに混合し、含浸させた後、錠剤型に成形し、青紫色錠剤型の酸素検知剤を得た。
Example 2
15 mL of an aqueous solution in which 0.45 g of a cyclodextrin mixture (trade name: Celdex TB-50, Nippon Shokuhin Kako Co., Ltd.), 0.03 g of methylene blue, 0.02 g of the non-discoloring organic dye Phloxine and 2.5 g of xylose are dissolved. Was mixed with 50 g of magnesium carbonate and impregnated, and then formed into a tablet shape to obtain a blue-violet tablet-type oxygen detector.
この青紫色錠剤型の酸素検知剤を用いて実施例１と同様の変色試験を行った。ガスバリア性容器内が酸素濃度０．１容量％未満の脱酸素雰囲気にってから１時間以内に、酸素検知剤は無酸素状態を示すピンク色になり、開封による空気曝露により速やかに再び青色になった。繰り返しこの操作を行ったところ、この色調変化は、酸素濃度により可逆的であり、酸素検知剤は繰り返し使用できた。 A discoloration test similar to that of Example 1 was performed using this blue-violet tablet type oxygen detector. Within one hour after the inside of the gas barrier container is in a deoxygenated atmosphere with an oxygen concentration of less than 0.1% by volume, the oxygen detection agent turns pink indicating anoxic conditions, and quickly turns blue again by air exposure by opening. became. When this operation was repeated, the color tone change was reversible depending on the oxygen concentration, and the oxygen detector could be used repeatedly.
実施例３
γ−シクロデキストリン０．２０ｇ、メチレンブルー０.０１ｇおよびＤ−（＋）−グルコース１.０ｇが溶解している水溶液５ｍＬに水酸化ナトリウム水溶液を混合してｐＨ１１．０に調整した混合液を得た後、濾紙に含浸させ青色シート状の酸素検知剤を得た。
Example 3
An aqueous solution of sodium hydroxide was mixed with 5 mL of an aqueous solution in which 0.20 g of γ-cyclodextrin, 0.01 g of methylene blue and 1.0 g of D-(+)-glucose were dissolved to obtain a mixed solution adjusted to pH 11.0. Thereafter, the filter paper was impregnated to obtain a blue sheet-shaped oxygen detector.
得られた青色シート状の酸素検知剤の光照射劣化加速試験を行った。すなわち、得られた酸素検知剤に、蛍光灯を光源とする５０００ルクスの可視光を２５℃、６０％ＲＨ、空気下にて照射し、可視分光光度計で有機色素成分の濃度変化を追跡することにより耐光性を評価した。蛍光灯照射６時間後も極大吸収波長約６５０ｎｍから計測されたメチレンブルー濃度は、全く減少していなかった。すなわち、本発明の酸素検知剤は、光照射下でも劣化しにくい酸素検知剤であった。 The obtained blue sheet-shaped oxygen detector was subjected to a light irradiation deterioration acceleration test. That is, the obtained oxygen detector is irradiated with 5000 lux of visible light using a fluorescent lamp as a light source at 25 ° C. and 60% RH in the air, and the concentration change of the organic dye component is traced by a visible spectrophotometer. The light resistance was evaluated. Even after 6 hours of fluorescent lamp irradiation, the methylene blue concentration measured from the maximum absorption wavelength of about 650 nm did not decrease at all. That is, the oxygen detector of the present invention was an oxygen detector that hardly deteriorates even under light irradiation.
比較例１
シクロデキストリン類を使用することなく、メチレンブルー０．０１ｇおよびＤ−（＋）−グルコース１．０ｇが溶解している水溶液５ｍＬに水酸化ナトリウム水溶液を混合してｐＨ１１．０に調整した混合液を得た後、濾紙に含浸させた青色シート状の酸素検知剤を得た。
Comparative Example 1
Without using cyclodextrins, an aqueous solution of sodium hydroxide was mixed with 5 mL of an aqueous solution in which 0.01 g of methylene blue and 1.0 g of D-(+)-glucose were dissolved to obtain a mixed solution adjusted to pH 11.0. After that, a blue sheet-shaped oxygen detector impregnated in the filter paper was obtained.
比較例１にて得られた青色シート状の酸素検知剤に、実施例３と同様に蛍光灯を光源とする５０００ルクスの可視光を２５℃、６０％ＲＨ、空気下にて照射して光照射劣化加速試験を行った。蛍光灯照射開始６時間後、極大吸収波長約６５０ｎｍから計測されたメチレンブルー濃度は、５０％減少していた。すなわち、従来型の酸素検知剤は、光照射により色素成分が劣化した。 The blue sheet-shaped oxygen detector obtained in Comparative Example 1 was irradiated with 5000 lux of visible light using a fluorescent lamp as a light source in the same manner as in Example 3 at 25 ° C., 60% RH in the air. An irradiation deterioration acceleration test was conducted. Six hours after the start of fluorescent lamp irradiation, the methylene blue concentration measured from the maximum absorption wavelength of about 650 nm was reduced by 50%. That is, in the conventional oxygen detector, the pigment component was deteriorated by light irradiation.
実施例４
実施例３にて得られた青色シート状の酸素検知剤を用いて、６０℃、６０％ＲＨ、脱酸素雰囲気下における加熱劣化加速試験を行った。すなわち、得られたフィルム状の酸素検知剤をガスバリア性容器内が酸素濃度０.１容量％未満の脱酸素雰囲気に密封し、６０℃、６０％ＲＨ下に保管し、耐熱性を評価した。評価は、保管試料を空気下に戻した後、可視分光光度計を用いて有機色素成分の濃度変化を追跡した。加熱劣化加速試験開始３日後も極大吸収波長６５０ｎｍから計測されたメチレンブルー濃度は、全く減少していなかった。すなわち、本発明の酸素検知剤は、熱によっても劣化しにくい酸素検知剤であった。
Example 4
Using the blue sheet-shaped oxygen detector obtained in Example 3, a heat deterioration acceleration test was performed at 60 ° C., 60% RH, in a deoxygenated atmosphere. That is, the obtained film-shaped oxygen detector was sealed in a deoxygenated atmosphere with an oxygen concentration of less than 0.1% by volume in a gas barrier container, and stored at 60 ° C. and 60% RH to evaluate heat resistance. In the evaluation, after the stored sample was returned to the air, the concentration change of the organic dye component was followed using a visible spectrophotometer. The methylene blue concentration measured from the maximum absorption wavelength of 650 nm was not reduced at all even 3 days after the start of the heat deterioration acceleration test. That is, the oxygen detector of the present invention is an oxygen detector that is not easily deteriorated by heat.
比較例２
比較例１で得られた青色シート状の酸素検知剤を用いて、実施例４と同様に６０℃、６０％ＲＨ、脱酸素雰囲気下に保管し、加熱劣化加速試験を行った。評価は、保管試料を空気下に戻した後、可視分光光度計を用いて有機色素成分の濃度変化を追跡した。エージレスアイＣの極大吸収波長６５０ｎｍから計測されたメチレンブルー濃度は、３日後２０％減少した。すなわち、従来型の酸素検知剤は、熱により色素成分が劣化した。
Comparative Example 2
Using the blue sheet-shaped oxygen detector obtained in Comparative Example 1, it was stored in a 60 ° C., 60% RH, deoxygenated atmosphere in the same manner as in Example 4, and a heat deterioration acceleration test was performed. In the evaluation, after the stored sample was returned to the air, the concentration change of the organic dye component was followed using a visible spectrophotometer. The methylene blue concentration measured from the maximum absorption wavelength of 650 nm of Ageless Eye C decreased by 20% after 3 days. That is, in the conventional oxygen detector, the dye component was deteriorated by heat.
実施例５
ヒドロキシプロピル化β−シクロデキストリン（商品名：ＨＰ−β−シクロデキストリン、日本食品化工（株）製）１０．０ｇ、メチレンブルー１．０ｇをグリセリン１００ｇに混合した後に、Ｌ−（＋）−アスコルビン酸１．８ｇを加えて混合し、青色の酸素検知インキ顔料を得た。
Example 5
After mixing 10.0 g of hydroxypropylated β-cyclodextrin (trade name: HP-β-cyclodextrin, manufactured by Nippon Shokuhin Kako Co., Ltd.) and 1.0 g of methylene blue into 100 g of glycerin, L-(+)-ascorbic acid 1.8 g was added and mixed to obtain a blue oxygen detecting ink pigment.
この酸素検知インキ顔料と、ロジンのペンタエリスリトールエステル３．８ｇ、プロピレングリコールモノエチルエーテル１．３ｇ、ミネラルスピリット１．３ｇ、粘土２．０ｇを混合して酸素検知インキとした。この酸素検知インキを用いて青色の絵文字を上質紙にスクリーン印刷し、印刷物を、脱酸素剤エージレスＳＡＰＥ（三菱瓦斯化学（株）製）および含水綿布と共に、透明な気体非透過性プラスチック袋に密封した。８時間後、袋内雰囲気の酸素濃度は０．１容量％未満になったが、その約１時間後に青色絵文字は無酸素状態を示す無色になり、開封による空気曝露後５分以内に元の青色に戻った。本発明の酸素検知インク顔料の印刷適性と反復的酸素検知能を有することが示された。 This oxygen detection ink pigment was mixed with 3.8 g of rosin pentaerythritol ester, 1.3 g of propylene glycol monoethyl ether, 1.3 g of mineral spirit, and 2.0 g of clay to obtain an oxygen detection ink. This oxygen detection ink is used to screen-print blue pictograms on high-quality paper, and the printed matter is sealed in a transparent gas-impermeable plastic bag together with oxygen scavenger AGELESS SAPE (Mitsubishi Gas Chemical Co., Ltd.) and water-containing cotton cloth. did. After 8 hours, the oxygen concentration in the atmosphere in the bag became less than 0.1% by volume, but after about 1 hour, the blue pictograms became colorless indicating anoxic conditions, and within 5 minutes after exposure to air by opening It returned to blue. The oxygen sensing ink pigments of the present invention have been shown to have printability and repetitive oxygen sensing capabilities.
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| JP2008088201A (en) * | 2006-09-29 | 2008-04-17 | Toppan Printing Co Ltd | Oxygen indicator ink and packaging material using the same |
| CN102053087A (en) * | 2009-10-28 | 2011-05-11 | 保德科技股份有限公司 | Oxygen detector and method for manufacturing oxygen detector |
| WO2013021868A1 (en) * | 2011-08-09 | 2013-02-14 | パウダーテック株式会社 | Oxygen sensing agent, method for producing oxygen sensing agent, and oxygen sensing aqueous solution |
| JP2013040925A (en) * | 2011-07-21 | 2013-02-28 | Powdertech Co Ltd | Oxygen detecting agent and oxygen detecting solution |
| CN104777162A (en) * | 2015-04-17 | 2015-07-15 | 深圳九星印刷包装集团有限公司 | Color change indicating device |
| CN105136789A (en) * | 2015-09-04 | 2015-12-09 | 齐齐哈尔大学 | Color-change indicator used for detecting oxygen, synthesizing method thereof, oxygen sensor and preparation method of oxygen sensor |
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| JP2008088201A (en) * | 2006-09-29 | 2008-04-17 | Toppan Printing Co Ltd | Oxygen indicator ink and packaging material using the same |
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| CN105136789A (en) * | 2015-09-04 | 2015-12-09 | 齐齐哈尔大学 | Color-change indicator used for detecting oxygen, synthesizing method thereof, oxygen sensor and preparation method of oxygen sensor |
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