JPH10307192A - Chemical time indicator - Google Patents
Chemical time indicatorInfo
- Publication number
- JPH10307192A JPH10307192A JP13292897A JP13292897A JPH10307192A JP H10307192 A JPH10307192 A JP H10307192A JP 13292897 A JP13292897 A JP 13292897A JP 13292897 A JP13292897 A JP 13292897A JP H10307192 A JPH10307192 A JP H10307192A
- Authority
- JP
- Japan
- Prior art keywords
- reagent
- chamber
- solution
- dissolving
- partition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Measurement Of Unknown Time Intervals (AREA)
Abstract
(57)【要約】 (修正有)
【目的】任意の場所に設置でき、明瞭な色調変化によっ
て経過時間が容易に認識されるる時間−温度積算値管理
用ケミカルタイムインジケーターおよび途中経過を観測
できる段階的表示ケミカルタイムインジケーターを提供
する。
【構成】特定の溶解能を有する試薬に溶解可能な隔壁で
2室以上に仕切られた容器に特定の溶解能を有する試薬
および該試薬で発色する検知試薬を収容する。
【効果】隔壁が溶解するまで発色反応等の色調変化が起
きないため、設定した時間経過超過の有無が極めて明確
に視覚化される。
(57) [Summary] (Corrected) [Purpose] Can be installed in any place, and the time can be easily recognized by a clear change in color tone. Provide a chemical time indicator to display the target. A container divided into two or more chambers by a partition wall dissolvable in a reagent having a specific solubility contains a reagent having a specific solubility and a detection reagent which develops a color with the reagent. [Effect] Since there is no change in color tone such as a coloring reaction until the partition walls are dissolved, whether or not the set time has passed is clearly visualized.
Description
【0001】[0001]
【産業上の利用分野】本発明は、一定温度以下で一定期
間保存する物品の品質を保存時間と保存温度の両面から
管理するための簡易な表示装置であり、例えば、生鮮食
料品等の鮮度管理、賞味期限の管理、医薬品等の有効期
限管理、農作物の発芽・開花管理、調理時間の管理等の
分野に有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a simple display device for managing the quality of articles stored at a certain temperature or lower for a certain period of time from both the storage time and the storage temperature. It is useful in fields such as management, expiration date management, expiration date management of pharmaceuticals, germination and flowering management of agricultural products, and management of cooking time.
【0002】[0002]
【従来の技術】経過時間の計測にはストップウォッチな
どの機械式または電気式のタイマーが利用されている。
より長期的経過時間の計測には、カレンダーに印を付け
るなどの記憶に頼る方法や、化学反応による発色または
変色を応用したケミカルタイムインジケーターが使用さ
れている。ケミカルタイムインジケーターには、pH指
示薬とアルカリ性物質および保湿剤を紙または不織布に
しみ込ませ空気中の炭酸ガスの吸収により色調が変化す
るもの(特公平4−66518)、微細多孔性の裏面の
着色層が熱可塑性ゴムの浸透によって視覚化するもの
(特開昭56−13338)、ロイコ塩基からなる熱的
に不活性な化合物と化学線照で活性化された酸を生成す
る感光性化合物からなる時間−温度指示材料(特開昭6
2−163965)、さらに第1層:シアニン染料およ
びカルボキシル基/フェノール基を有する油溶性樹脂、
第2層:pH7以上の樹脂からなるエマルジョン、第3
層:水またはアルコールで溶解する吸湿高分子からなる
変色性計時インジケーター(特開平5−12696
9)、またラジカル発生剤とラジカル反応性色素をそれ
ぞれ担持した層をスペーサーを介して非接触状態とし外
圧を加えて2つの層を接触させ計時を開始する時間表示
材料(特開平9−54174)等が考案されている。脂
肪膜と色素を保持したスライド状物質であって、細菌汚
染により脂質膜が溶解し色変化する食品鮮度状態表示器
(特開平8−15251)および熱揮発性殺虫剤の残存
薬剤量を色で表示するもの(特開昭58−50192
0)もケミカルタイムインジケーターの一種とみなされ
る。2. Description of the Related Art A mechanical or electric timer such as a stopwatch is used to measure elapsed time.
In order to measure the long-term elapsed time, a method relying on memory such as marking a calendar, or a chemical time indicator applying color development or discoloration due to a chemical reaction is used. The chemical time indicator includes a pH indicator, an alkaline substance, and a humectant which are impregnated into paper or non-woven fabric, and change the color tone by absorbing carbon dioxide gas in the air (Japanese Patent Publication No. 4-66518). Is visualized by penetration of a thermoplastic rubber (Japanese Patent Application Laid-Open No. 56-13338), a time consisting of a thermally inactive compound comprising a leuco base and a photosensitive compound which produces an acid activated by actinic radiation. -Temperature indicating material (Japanese Unexamined Patent Publication No.
2 -163965), and a first layer: an oil-soluble resin having a cyanine dye and a carboxyl group / phenol group,
Second layer: emulsion composed of resin having a pH of 7 or more, third layer
Layer: discoloration time indicator consisting of a hygroscopic polymer soluble in water or alcohol (JP-A-5-12696)
9) A time display material in which the layers each carrying a radical generator and a radical reactive dye are brought into a non-contact state via a spacer and an external pressure is applied to bring the two layers into contact with each other and start time measurement (Japanese Patent Application Laid-Open No. 9-54174). Etc. have been devised. A food-like state indicator (JP-A-8-15251), which is a slide-like substance holding a fat film and a pigment, which dissolves and changes the color of the lipid film due to bacterial contamination. What to display (Japanese Patent Application Laid-Open No. 58-50192)
0) is also considered as a kind of chemical time indicator.
【0003】[0003]
【発明が解決しようとする問題点】機械式または電気式
のタイマーは、時間計測の絶対的な正確性に優れるが、
構造が複雑なため振動や湿気の多い場所に設置すること
はできない。またこれらのタイマーは比較的高価であ
り、多種類の物品を別々に管理する目的で多数のタイマ
ーを同時に設置することは、経済的負担が大きい。時間
計測の絶対的正確性は、温度など設置場所の環境変化の
影響を受けやすい物品の保存管理において、ある程度必
要であるものの、必ずしも十分ではない。一般に、傷み
やすい物品には、有効期限と保存温度が付記されてお
り、この温度を超えた環境に物品が置かれれば、たとえ
有効期限内であっても品質は低下してしまう。従って、
有効期限を有する物品の管理は、単なる経過時間ではな
く、時間と温度の積算量(時間−温度積算値という)を
管理することが重要である。品質低下の多くは、一種の
化学的反応によってもたらされるとみなせ、化学的反応
を利用したケミカルタイムインジケーターは、時間−温
度積算値を表示すものである。ケミカルタイムインジケ
ーターは、時間計測の絶対的正確性はないものの、物品
の保存管理の手段として機械式タイマーより利用価値が
高い。しかし、これまでのケミカルタイムインジケータ
ーは、必ずしも広く利用されているとは言いがたい。例
えば、外気の流通を必要とするものや光照射を必要とす
るものは、自ずと設置場所の制限を受ける。さらに共通
の問題として、変色が緩慢なため、どの時点が計時終了
なのかの判断しにくい点が指摘されていた。Problems to be Solved by the Invention A mechanical or electric timer is excellent in absolute accuracy of time measurement,
Due to its complex structure, it cannot be installed in places with high levels of vibration or humidity. In addition, these timers are relatively expensive, and it is economically burdensome to install a large number of timers simultaneously for the purpose of separately managing various types of articles. Absolute accuracy of time measurement is necessary, but not always sufficient, in storage management of articles that are susceptible to changes in the environment of the installation location such as temperature. In general, an expiration date and a storage temperature are added to a perishable article, and if the article is placed in an environment exceeding this temperature, the quality will deteriorate even within the expiration date. Therefore,
It is important to manage an article having an expiration date, not just an elapsed time, but to manage an integrated amount of time and temperature (referred to as a time-temperature integrated value). Most of the quality deterioration can be considered to be caused by a kind of chemical reaction, and a chemical time indicator using a chemical reaction displays a time-temperature integrated value. Although the chemical time indicator is not absolutely accurate in measuring time, it is more valuable than a mechanical timer as a means of storing and managing articles. However, the conventional chemical time indicators are not necessarily widely used. For example, a device that requires circulation of outside air or a device that requires light irradiation is naturally subject to restrictions on installation locations. Furthermore, it has been pointed out that a common problem is that it is difficult to determine which time point has reached the end of timekeeping due to slow discoloration.
【0004】[0004]
【問題点を解決するための手段】本発明の目的は、時間
−温度積算値の管理を容易に行うための、小容積で管理
対象物に貼付させることも可能でかつ外部を汚染しない
密閉構造を有し、設定した時間経過直後にほぼ瞬時に変
色して判定しやすいケミカルタイムインジケーターを提
供することにある。また、経過時間の中間段階も認識で
きる段階的表示ケミカルタイムインジケーターも提供す
ることである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a sealed structure that can be attached to an object to be managed with a small volume and that does not contaminate the outside, so that the time-temperature integrated value can be easily managed. And to provide a chemical time indicator which changes color almost instantly immediately after a set time has elapsed and is easy to determine. It is another object of the present invention to provide a gradual display chemical time indicator capable of recognizing an intermediate stage of the elapsed time.
【0005】本発明におけるケミカルタイムインジケー
ターの基本形態は、溶解室と変色室の2つの室を有する
密閉容器からなる。2つの室は隣接しその隔壁の一部ま
たは全体は特定の溶解能を有する試薬(溶解試薬)によ
って溶解する材質により構成されている(以下この隔壁
を溶解壁という)。溶解室は、溶解試薬を含んだ液体
(溶解液)で満たされ、変色室は、溶解液の混入を検知
するための試薬(検知試薬)を含んだ液体(検知液)で
満たされている。検知試薬の反応結果を知るために、容
器全体又は検知室の一部は、透明部分(以下透明窓とい
う)を有する。時間−温度積算値の測定は、溶解室に注
入された溶解液が溶解壁と接触した時点に開始する。溶
解壁は、溶解液によって徐々に溶解し、時間−温度積算
値が一定量を超えると溶解壁は変色室側まで溶解し溶解
室と変色室が連通する。変色室へ浸出した溶解液と検知
試薬が反応して生じる発色または色調変化を透明窓より
観察する。検知試薬は溶解液によって変色する成分が含
まれていれば液体である必要はなく固体でもかまわな
い。The basic form of the chemical time indicator according to the present invention comprises a closed container having two chambers, a dissolution chamber and a discoloration chamber. The two chambers are adjacent to each other, and a part or the whole of the partition is made of a material that can be dissolved by a reagent having a specific solubility (dissolution reagent) (hereinafter, the partition is referred to as a dissolution wall). The dissolution chamber is filled with a liquid (dissolution liquid) containing a dissolution reagent, and the discoloration chamber is filled with a liquid (detection liquid) containing a reagent (detection reagent) for detecting contamination of the dissolution liquid. In order to know the reaction result of the detection reagent, the entire container or a part of the detection chamber has a transparent portion (hereinafter, referred to as a transparent window). The measurement of the time-temperature integrated value starts when the lysis solution injected into the lysis chamber comes into contact with the lysis wall. The dissolving wall is gradually dissolved by the dissolving solution, and when the integrated value of time and temperature exceeds a certain amount, the dissolving wall dissolves to the discoloration chamber side and the dissolution chamber communicates with the discoloration chamber. The color development or change in color tone caused by the reaction between the solution leached into the color changing chamber and the detection reagent is observed through the transparent window. The detection reagent need not be a liquid but may be a solid, as long as it contains a component that changes color depending on the solution.
【0006】溶解壁の溶解するまでの時間は、開始時の
溶解液の量、溶解試薬の濃度および溶解壁の厚さによっ
て、あらかじめ決定できる。溶解液の量、溶解試薬の濃
度を一定とし、溶解壁の厚さを薄くすれば短い時間の計
測を行うことができ、溶解壁をより厚くすることで、よ
り長い時間を計測することができる。いずれの場合も、
溶解液の量および溶解試薬の濃度は、溶解壁を十分溶解
するに足る過剰量が必要である。逆に溶解壁の厚さ形状
を一定とし溶解液の量または溶解試薬の濃度を変えるこ
とによって溶解時間を決定することもできる。[0006] The time until the dissolution of the dissolving wall can be determined in advance by the amount of the dissolving solution at the start, the concentration of the dissolving reagent, and the thickness of the dissolving wall. If the amount of the lysis solution and the concentration of the lysis reagent are fixed and the thickness of the lysis wall is reduced, measurement can be performed in a short time, and by making the lysis wall thicker, a longer time can be measured. . In either case,
The amount of the lysing solution and the concentration of the lysing reagent need to be in excess to sufficiently dissolve the lysing wall. Conversely, the dissolution time can be determined by keeping the thickness of the dissolution wall constant and changing the amount of the dissolution solution or the concentration of the dissolution reagent.
【0007】基本形態における時間計測は、溶解室に溶
解液を注入することで開始される。溶解室の一部に開栓
可能な注入口を設けておけば溶解液の注入及び注入後に
溶解室を密閉することが容易にできる。必要量の溶解液
を使い捨てのスポイトまたは注射用シリンジに充填した
注入器具を別途用意することにより注入作業はさらに容
易となる。溶解液をケミカルタイムインジケーター内の
溶解室と異なる室に収容しておき、計測開始時に溶解液
を溶解室へ移送する方法は、必要な構成要素が一体化さ
れるうえ、溶解液と接触する危険性がないため、より好
ましい。溶解液を収容する室を溶解室に隣接させ、2室
間の隔壁を溶解液に耐性の材質からなる薄膜とする。こ
の隔壁は、外部から圧力をかけることで破ることができ
るが、溶解液を収容した室の隔壁の対辺にあらかじめ突
起を設けておけば、指で対辺を強く押すことにより、突
起が隔壁を突き破り溶解液の移送が容易に達成できる。
溶解室が空室の場合、溶解室の空気が残って溶解壁と溶
解液の接触面積が減るため、溶解室の容積を可能な限り
小さくしなければならない。また溶解壁を溶解せずかつ
溶解液の溶解能を阻害しない液体(希釈液という)をあ
らかじめ溶解室に収容しておけば、溶解室内に空気は残
らない。溶解液は希釈されるが、溶解液の濃度を高めて
おけば支障はない。[0007] The time measurement in the basic mode is started by injecting a lysis solution into a lysis chamber. If an injection port which can be opened is provided in a part of the dissolution chamber, the dissolution chamber can be easily sealed after the injection of the dissolution solution and the injection. The injection operation is further facilitated by separately preparing an injection device in which a required amount of the dissolving solution is filled in a disposable dropper or a syringe for injection. The solution is stored in a chamber different from the dissolution chamber in the chemical time indicator, and the solution is transferred to the dissolution chamber at the start of measurement. It is more preferable because there is no property. The chamber containing the solution is adjacent to the solution chamber, and the partition between the two chambers is a thin film made of a material resistant to the solution. This partition can be broken by applying pressure from the outside, but if a projection is provided in advance on the opposite side of the partition of the chamber containing the solution, the projection can break through the partition by strongly pressing the opposite side with a finger. Transfer of the lysis solution can be easily achieved.
When the dissolution chamber is empty, the volume of the dissolution chamber must be reduced as much as possible because air in the dissolution chamber remains and the contact area between the dissolution wall and the dissolution liquid decreases. If a liquid (referred to as a diluent) that does not dissolve the dissolving wall and does not impair the dissolving ability of the dissolving solution is stored in the dissolving chamber in advance, no air remains in the dissolving chamber. The lysis solution is diluted, but there is no problem if the concentration of the lysis solution is increased.
【0008】ケミカルタイムインジケーターは、時間計
測中の温度変化も結果に反映させるものであるから、溶
解試薬、検知試薬および溶解壁材質のいずれも突発的高
温に耐性でかつ反応は温度依存性でなくてはならない。
生分解性の樹脂原料であるポリ乳酸は、フィルムや繊維
または容器などの加工品として供給されており、耐熱性
や強度は実用に支障はないもののアルカリ性溶液に比較
的速やかに溶解する性質を有する。これを溶解壁とし、
溶解液に水酸化ナトリウムまたは水酸化カリウム水溶液
を使用すれば上記の条件を満たす組み合わせとなる。こ
の場合の検知試薬には、塩基性pH指示薬であるフェノ
ールフタレイン、チモールブルーなどが使用できる。特
にフェノールフタレインは、中性で無色、アルカリ性で
赤色を呈するため反応終了の認識性が高い。アルカリ性
水溶液の溶解液にマグネシウム検出薬でありアルカリに
易溶なキシリジルブルーを加え、検知液には本来は検知
されるべき微量の塩化マグネシウムを含む水溶液を使用
する組み合わせも、赤から赤紫への顕著な変色で認識し
やすい。隔壁にアルミニウム箔などの金属、溶解液に酸
性溶液、検知試薬をメチルオレンジ、メチルレッド等の
酸性pH指示薬とする組み合わせも使用できる。しか
し、酸による金属の溶解は水素ガスの発生を伴うため、
ごく薄い金属箔として短時間用のインジケーターとする
か、隔壁のごく一部にのみ金属を使用する、あるいは容
器の密封を避けるなどの注意が必要となる。[0008] Since the chemical time indicator reflects the temperature change during the time measurement in the result, all of the lysis reagent, the detection reagent and the material of the lysis wall are resistant to a sudden high temperature and the reaction is not temperature-dependent. must not.
Polylactic acid, which is a biodegradable resin material, is supplied as processed products such as films, fibers, or containers, and has the property of dissolving relatively quickly in an alkaline solution, although heat resistance and strength do not hinder practical use. . This is the melting wall,
If an aqueous solution of sodium hydroxide or potassium hydroxide is used for the solution, a combination satisfying the above conditions is obtained. In this case, a basic pH indicator such as phenolphthalein or thymol blue can be used as the detection reagent. In particular, phenolphthalein is neutral and colorless, and alkaline and red, and thus has high recognition of the completion of the reaction. A combination of an aqueous solution containing a trace amount of magnesium chloride, which should be detected, is added to the solution of the alkaline aqueous solution by adding xylidyl blue, which is a magnesium detector and easily soluble in alkali, from red to purple-red. The remarkable discoloration makes it easy to recognize. A combination of a metal such as an aluminum foil for the partition, an acidic solution for the dissolving solution, and an acidic pH indicator such as methyl orange or methyl red as the detection reagent can also be used. However, dissolution of metal by acid involves generation of hydrogen gas,
Care must be taken, such as using a very thin metal foil as an indicator for a short time, using a metal only for a very small part of the partition wall, or avoiding sealing of the container.
【0009】隔壁にニトロセルロースフィルム、溶解液
にアセトンとエタノールの等量混液を使用し、検知液に
アルコール易溶性の色素懸濁液を用いた場合は、色素が
アルコールに溶解して色調が変化することから識別でき
る。いずれの場合も隔壁が存在する限り検知試薬が関わ
る反応は一切進行しないため、設定した経過時間以前、
以後の判定は極めて容易である。本発明のケミカルタイ
ムインジケーターでは、検知試薬による変色を判定基準
としない方法も可能である。例えばあらかじめ色素を溶
解させた溶解液を使用し、変色室には検出液を使用せず
希釈液のみを充填しておくと、経時的な隔壁の崩壊によ
り色素が拡散し着色面積が増大することから、アルコー
ル温度計のように長さで経過時間を判定することができ
る。When a nitrocellulose film is used for the partition walls, an equal volume mixture of acetone and ethanol is used for the dissolving solution, and a dye suspension that is readily soluble in alcohol is used for the detection solution, the color changes due to the dissolution of the dye in alcohol. Can be identified. In any case, the reaction involving the detection reagent does not proceed at all as long as the partition wall is present.
Subsequent determination is very easy. With the chemical time indicator of the present invention, a method is also possible in which discoloration due to the detection reagent is not used as a criterion. For example, if a dissolving solution in which the dye is dissolved in advance is used, and the discoloration chamber is filled with only the diluent without using the detection solution, the dye is diffused due to the temporal collapse of the partition walls, and the colored area increases. Thus, the elapsed time can be determined by the length as in an alcohol thermometer.
【0010】上記とは逆に、特定の試薬に溶解する材質
からなる小容器に検知試薬を封入しておき、溶解液を本
体である大容器に収容しておくことで、さらに簡便なケ
ミカルタイムインジケーターとすることができる。例え
ば、容量数ml以下のポリ乳酸を材質とする容器にフェ
ノールフタレインを封入し、溶解液であるNaOH溶液
を日常的に使用する透明プラスチック容器に収めれば完
成する。時間計測の開始は、透明プラスチック容器にポ
リ乳酸容器を投げ込むだけでよい。Contrary to the above, the detection time is sealed in a small container made of a material soluble in a specific reagent, and the lysis solution is stored in a large container as a main body, so that the chemical time can be further simplified. It can be an indicator. For example, phenolphthalein is sealed in a container made of polylactic acid having a capacity of several ml or less, and a NaOH solution, which is a dissolving solution, is placed in a transparent plastic container that is used daily. To start the time measurement, simply throw the polylactic acid container into the transparent plastic container.
【0011】基本形態では1つだけ存在する変色室を、
複数設けることにより段階的な時間計測を行うことが出
来る。変色室を連続して隣接させそれぞれの隔壁を溶解
壁とすれば、溶解室に注入した溶解液は、溶解室に隣接
する変色室(以下第1変色室という)との間の溶解壁が
溶解する。溶解が進み第1変色室に溶解液が拡散し変色
する。溶解試薬は第1変色室の容積分だけ希釈された濃
度になる。その濃度がさらに溶解壁を溶かすのに十分な
濃度であれば第1変色室に隣接する次の変色室(以下第
2変色室という)との間の溶解壁が溶解し始める。すな
わち溶解室と第1変色室とを合わせた領域が溶解室とし
て作用する。第1変色室と第2変色室の間の溶解壁が第
2変色室まで溶解すると、溶解液は第2変色室まで拡散
し第2変色室が変色する。同様にして第3、第4の変色
室を設ければ時間経過とともに多段階の変色が起こり段
階的な時間計測を行うことが出来る。溶解液中の溶解試
薬の濃度は、あらかじめ全ての溶解壁を溶解することか
可能な程度の高濃度とする必要があるが、それぞれの段
階の濃度における溶解壁の厚さを調整すれば、各段階に
おいて自由な時間設定を行うことが可能である。変色状
態を観察するための透明窓は、すべての変色室に設置し
ておくことが必要である。In the basic form, there is only one discoloration chamber,
By providing a plurality of them, stepwise time measurement can be performed. If the discoloration chambers are continuously adjacent to each other and the partition walls are used as dissolution walls, the dissolution liquid injected into the dissolution chamber dissolves in the dissolution wall between the discoloration chamber adjacent to the dissolution chamber (hereinafter referred to as the first discoloration chamber). I do. The dissolution proceeds and the solution is diffused into the first discoloration chamber and discolored. The lysis reagent has a concentration diluted by the volume of the first color changing chamber. If the concentration is sufficient to further dissolve the dissolution wall, the dissolution wall between the next discoloration chamber adjacent to the first discoloration chamber (hereinafter referred to as the second discoloration chamber) starts to dissolve. That is, the combined area of the melting chamber and the first color changing chamber functions as a melting chamber. When the dissolution wall between the first color changing chamber and the second color changing chamber dissolves to the second color changing chamber, the solution diffuses to the second color changing chamber and the second color changing chamber changes color. Similarly, if the third and fourth discoloration chambers are provided, multi-stage discoloration occurs with the passage of time, and stepwise time measurement can be performed. The concentration of the lysis reagent in the lysis solution needs to be high enough to dissolve all the lysis walls in advance, but if the thickness of the lysis wall at each concentration is adjusted, each Free time settings can be made in the stages. Transparent windows for observing the discoloration state must be installed in all discoloration rooms.
【0012】設定時間経過後の変色は、溶解液が変色室
に入った時点で色が変化すればよく、無色から着色へ、
着色から無色へ、着色から他の色への変色、着色の深色
化の何れでもよい。また検知試薬を使用せず、全ての変
色室内で希釈されても認識するに十分な濃度の色素試薬
を含む溶解液を使用する方法でもよい。溶解壁の片側の
成分の作用だけでなく、両側の成分が接触し双方の成分
同志の作用により変色させてもよい。計時終了前後で変
色室が、外観的に明らかな変化をするならば、どのよう
な方法でもかまわない。変色は計時終了前後で素早く行
われるのを原則とするが、緩やかな変化が必要な場合に
は、溶解壁の断面積を小さくして溶解液の拡散が緩慢に
おこるようにすればよい。溶解壁が完全に溶解した時点
を計時終了時点に設定してあれば、計時終了間際の変色
室の緩慢な色調変化から計時終了が近いことを知ること
が出来る。また逆により速く変色を行わせるためには、
溶解室を加圧状態にしたり、変色室を減圧状態にしてお
けばよい。溶解壁に穴が開くと、2室の圧力差によって
急激に2液は混合しほぼ瞬時に変色させることができ
る。The discoloration after the lapse of the set time may be changed as long as the color changes when the solution enters the discoloration chamber.
Any of discoloration from coloring to colorless, coloring to another color, and deepening of coloring may be used. Further, a method may be used in which a solution containing a dye reagent having a concentration sufficient for recognition even when diluted in all the color changing chambers is used without using the detection reagent. In addition to the action of the components on one side of the melting wall, the components on both sides may come into contact with each other and discolor by the action of both components. Any method may be used as long as the discoloration chamber undergoes a clear change in appearance before and after the end of timing. In principle, the discoloration is carried out quickly before and after the end of the time measurement. However, if a gradual change is required, the cross-sectional area of the dissolving wall may be reduced so that the diffusion of the dissolving solution occurs slowly. If the time when the melting wall is completely melted is set as the end of the timekeeping, it is possible to know that the end of the timekeeping is near from the gradual change in the color tone of the discoloration chamber immediately before the end of the timekeeping. To make the color change faster,
The dissolution chamber may be pressurized or the discoloration chamber may be depressurized. When a hole is formed in the dissolution wall, the two liquids are rapidly mixed due to the pressure difference between the two chambers, and the color can be changed almost instantaneously.
【0013】本発明のケミカルタイムインジケーター
は、1.溶解室と、変色室(溶解室と変色室は共通でも
よい)が隣接し、その境界の全体または一部が溶解壁と
して作用する。2.溶解室内の、溶解試薬が計時開始後
に溶解壁と接している。3.溶解成分は計時終了時点に
て溶解壁と接している。4.溶解液中の溶解試薬は、溶
解壁が変色室側(多段階タイプでは最終の変色室)まで
溶解するのに十分な濃度である。5.溶解液は、溶解壁
が変色室側(多段階タイプでは最終の変色室)まで溶解
するのに十分な量である。6.検知試薬の量は変色させ
る領域の変色が十分に認識できる量である。7.検知試
薬は、溶解壁が次の部屋へ通じるまで溶解した時点で変
色する領域があればどの部屋にあってもよい(2成分の
相互作用により変色してもよい)。8.溶解壁は設定さ
れた時間の経過後、変色室へ通じるまで溶解するだけの
厚さを持つ。9.容器主要部の材質は溶解液によって溶
解されないものであり、密閉性が要求される場合におい
ては溶解液、検知液(希釈液)を内部に包括し密閉性を
保つための機械的強度をもつだけの厚さを有する。1
0.変色状態が観察できるような透明窓が設けてある。
以上の条件を満たせばどのような形状であってもよい。The chemical time indicator of the present invention comprises: The dissolution chamber and the discoloration chamber (the dissolution chamber and the discoloration chamber may be common) are adjacent to each other, and all or a part of the boundary acts as a dissolution wall. 2. The lysis reagent in the lysis chamber is in contact with the lysis wall after the start of the timing. 3. The dissolved component is in contact with the dissolved wall at the end of the timing. 4. The lysis reagent in the lysis solution is at a concentration sufficient for the lysis wall to dissolve to the side of the discoloration chamber (the final discoloration chamber in the case of the multi-stage type). 5. The amount of the lysing solution is sufficient to dissolve the dissolving wall to the discoloration chamber side (the final discoloration chamber in the multi-stage type). 6. The amount of the detection reagent is such that the discoloration in the discolored area can be sufficiently recognized. 7. The detection reagent may be in any room as long as there is a region that changes color when the dissolution wall dissolves until it reaches the next room (it may change color due to the interaction of two components). 8. After a set time, the melting wall has a thickness enough to melt until it reaches the discoloration chamber. 9. The material of the main part of the container is not dissolved by the dissolving liquid, and when sealing is required, it only has the mechanical strength to cover the dissolving solution and the detection liquid (diluent) inside and maintain the sealing. Having a thickness of 1
0. A transparent window is provided so that the discolored state can be observed.
Any shape may be used as long as the above conditions are satisfied.
【0014】[0014]
【発明の実施の形態】図1は本発明におけるケミカルタ
イムインジケーターの基本形態の一例を示すものであ
り、同図において1は2つの部屋を持つ容器本体、2は
溶解室、3は変色室、4は溶解壁である。容器本体1は
透明で溶解液に耐性な合成樹脂からなる。溶解室2には
溶解壁4を溶解する成分を含んだ溶解液が注入される。
変色室には溶解液を検出する検知試薬を含んだ検知液が
満たされている。溶解液、溶解壁4、検知液の一例とし
ては、溶解液に水酸化ナトリウム水溶液、水酸化カリウ
ム水溶液等のアルカリ性溶液、検知液にフェノールフタ
レイン等のpH指示薬、溶解壁4にはポリ乳酸等のアル
カリ下で溶解する材質があげられる。溶解室2に溶解液
が注入された時点から計時が開始され、一定時間経過
後、溶解壁の溶解が変色室側まで進むと溶解液が変色室
に進入し色の変化がおこる。前記の水酸化ナトリウム溶
液とフェノールフタレイン溶液の組み合わせにおいては
計測時間経過後、無色から赤色に変化する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an example of a basic form of a chemical time indicator according to the present invention, in which 1 is a container body having two rooms, 2 is a melting room, 3 is a discoloration room, 4 is a dissolution wall. The container body 1 is made of a synthetic resin that is transparent and resistant to a solution. A dissolving solution containing a component for dissolving the dissolving wall 4 is injected into the dissolving chamber 2.
The color changing chamber is filled with a detection solution containing a detection reagent for detecting the lysis solution. Examples of the dissolving solution, the dissolving wall 4, and the detecting solution include an alkaline solution such as an aqueous solution of sodium hydroxide and potassium hydroxide as the dissolving solution, a pH indicator such as phenolphthalein as the detecting solution, and polylactic acid as the dissolving wall 4. And materials that dissolve under alkaline conditions. Time measurement is started from the time when the dissolving solution is injected into the dissolving chamber 2, and after a certain period of time, when the dissolving of the dissolving wall proceeds to the discoloring chamber side, the dissolving solution enters the discoloring chamber and changes color. In the combination of the sodium hydroxide solution and the phenolphthalein solution, the color changes from colorless to red after the elapse of the measurement time.
【0015】この形態の具体的な1例と作成手順を示
す。容器本体1を透明ポリ塩化ビニールのパイプ(内径
10mm、厚さ1mm、高さ20mm) 、溶解壁4をポリ乳酸
の円盤(外径10.2mm、厚さ0.5mm)、容器本体1
の天面および底をポリ塩化ビニールの円盤(外径10.
2mm、厚さ1mm)とする。溶解壁の円盤を容器本体に水
平に、容器本体中央(高さ10mm)まで圧入する。底部
となる部分を上にして垂直に立て、検知液としてフェノ
ールフタレイン液(100mlの水にフェノールフタレ
イン1%を含んだエタノール溶液を2〜3滴加えたも
の)を約0.7ml入れ、底部の円盤を容器本体のパイ
プの淵の部分と段差がない状態まで水平に圧入する。容
器本体を上下反対にし、溶解液として5N−NaOH溶
液を0.7ml注入し天面部の円盤を低部の円盤と同様
に圧入する。計時は5N−NaOH溶液を注入した時点
から開始される。A specific example of this embodiment and a preparation procedure will be described. The container body 1 is made of a transparent polyvinyl chloride pipe (inner diameter 10 mm, thickness 1 mm, height 20 mm), the melting wall 4 is made of a polylactic acid disk (outer diameter 10.2 mm, thickness 0.5 mm), the container body 1
The top and bottom are made of a PVC disc (outside diameter 10.
2 mm, thickness 1 mm). The disk of the melting wall is pressed into the container body horizontally to the center (height: 10 mm) of the container body. Stand vertically with the bottom part up, add about 0.7 ml of phenolphthalein solution (100 ml of water and 2-3 drops of ethanol solution containing 1% phenolphthalein), Press the bottom disk horizontally until there is no step with the edge of the pipe of the container body. The container body is turned upside down, 0.7 ml of 5N-NaOH solution is injected as a dissolving solution, and the disk on the top is press-fitted in the same manner as the lower disk. The timing is started from the time when the 5N-NaOH solution is injected.
【0016】図2は溶解液室を一体化したタイムインジ
ケーターの一例であり、図3は、その経時的な色調変化
を模したものである。図2において1は3室に仕切られ
た容器本体、2は溶解室、3は変色室、4は溶解室と変
色室の隔壁の一部としての溶解壁、5は溶解液室、6は
溶解液室と溶解室を隔てる薄膜の隔壁、7は薄膜6を破
るための突起部、8は容器本体の一部であり突起部7の
根元部分にある可動部である。容器本体1は透明でかつ
溶解液に耐性の合成樹脂からなり、溶解室3は溶解壁の
溶解能を有せずかつ溶解液の溶解能を妨げない希釈液で
満たされ、変色室3は溶解液と反応し変色する検知試薬
を含んだ検知液で満たされ、溶解室2と変色室3の間に
は溶解液によって溶解される溶解壁4があり、その厚さ
は設定時間後に2室が連通するように調整されている。
溶解液室5には希釈液によって希釈された状態で十分に
溶解壁を溶解することが可能な濃度の溶解試薬を含んだ
溶解液で満たされ、薄膜6は軟質の合成樹脂、突起部7
は硬質の合成樹脂、可動部8は柔軟性、弾力性のある合
成樹脂からなっている。FIG. 2 shows an example of a time indicator in which the solution chamber is integrated, and FIG. 3 simulates the color change over time. In FIG. 2, 1 is a container body divided into three chambers, 2 is a dissolution chamber, 3 is a discoloration chamber, 4 is a dissolution wall as a part of a partition between the dissolution chamber and the discoloration chamber, 5 is a dissolution liquid chamber, and 6 is a dissolution chamber. A thin film partition separating the liquid chamber and the dissolving chamber, 7 is a projection for breaking the thin film 6, and 8 is a movable part at the root of the projection 7 which is a part of the container body. The container body 1 is made of a synthetic resin that is transparent and resistant to the dissolving solution. The dissolving chamber 3 is filled with a diluent that does not have the dissolving ability of the dissolving wall and does not hinder the dissolving ability of the dissolving solution. There is a dissolving wall 4 filled with a detecting solution containing a detecting reagent which reacts with and discolors with the solution, and is dissolved by the dissolving solution between the dissolving chamber 2 and the discoloring chamber 3. It has been adjusted to communicate.
The lysis solution chamber 5 is filled with a lysis solution containing a lysis reagent having a concentration capable of sufficiently dissolving the lysis wall in a state diluted with the diluting solution.
Is a hard synthetic resin, and the movable portion 8 is made of a flexible and elastic synthetic resin.
【0017】時間計測開始時に、可動部8を突起部7が
薄膜6を突き破るまで押し込む(図3−A)。可動部8
は内圧および弾力性によって元にもどり薄膜6に穴が開
いた状態となる。溶解液室8中の溶解液は溶解室2へ拡
散して、希釈液により希釈された状態で溶解壁4に接触
する(図3−B)。溶解壁4の溶解が溶解室2側から変
色室3側へ向かって進行する(図3−C)。設定した時
間が経過し溶解壁4が変色室3側まで溶解すると溶解室
2と変色室3が連通し、溶解液と検知液が接触して変色
が起こり設定した時間を超過したことが認識される(図
3−D)。At the start of time measurement, the movable part 8 is pushed in until the projection 7 breaks through the thin film 6 (FIG. 3A). Movable part 8
Returns to its original state due to the internal pressure and elasticity, and the thin film 6 is opened. The lysis solution in the lysis solution chamber 8 diffuses into the lysis chamber 2 and contacts the lysis wall 4 in a state diluted with the diluent (FIG. 3-B). The dissolution of the dissolution wall 4 proceeds from the dissolution chamber 2 side to the discoloration chamber 3 side (FIG. 3-C). When the set time has elapsed and the dissolving wall 4 has melted to the discoloration chamber 3 side, the dissolution chamber 2 and the discoloration chamber 3 communicate with each other. (FIG. 3-D).
【0018】この溶解液室を一体化した形態の具体的な
1例と作成手順を示す。容器本体1は、硬質透明ポリ塩
化ビニールのパイプ(内径10mm、厚さ1mm、高さ20
mm)、溶解壁4をポリ乳酸の円盤(外径10.2mm、厚
さ0.5mm)、容器本体1の底を硬質ポリ塩化ビニール
の円盤(外径10.2mm、厚さ1mm)、薄膜6を軟質塩
化ビニール性の円盤(外径11mm、厚さ0.1mm)、溶
解液室5の周囲壁を硬質透明ポリ塩化ビニールのパイプ
(内径10mm、厚さ1mm、高さ5mm)、可動部8を軟質
ポリ塩化ビニールの円盤(外径12mm、厚さ1mm)、突
起部7を硬質ポリ塩化ビニールの円柱で片側が円錐状に
尖っている形状(円柱外径2mm、円錐部長さ2mm、全長
4mm)とする。容器本体1への溶解壁4の挿入、検知液
(フェノールフタレイン液)を入れ、底部を圧入するま
では前記基本形態と同様である。A specific example of a form in which the solution chamber is integrated and a preparation procedure will be described. The container body 1 is made of a hard transparent PVC pipe (inner diameter 10 mm, thickness 1 mm, height 20).
mm), the dissolution wall 4 is a polylactic acid disk (outside diameter 10.2 mm, thickness 0.5 mm), the bottom of the container body 1 is a hard polyvinyl chloride disk (outside diameter 10.2 mm, thickness 1 mm), a thin film 6 is a soft vinyl chloride disk (outer diameter 11 mm, thickness 0.1 mm), the surrounding wall of the solution chamber 5 is a hard transparent polyvinyl chloride pipe (inner diameter 10 mm, thickness 1 mm, height 5 mm), movable part Reference numeral 8 denotes a soft PVC disk (outer diameter 12 mm, thickness 1 mm), and protrusion 7 is a rigid PVC column having a conical point on one side (cylinder outer diameter 2 mm, cone length 2 mm, full length 4 mm). It is the same as the above-described basic mode until the dissolving wall 4 is inserted into the container body 1, the detection liquid (phenol phthalein liquid) is filled, and the bottom is press-fitted.
【0019】溶解液室5は、以下の手順で作成する。可
動部8の中央に突起部7の円錐状でない側を垂直に接着
剤(例えばテトラヒドロフラン系接着剤)を用いて接着
する。さらに、溶解液室5外壁用のパイプを、接着した
突起部7が内側になる様に、また可動部8の円周と、同
パイプの円周が一致する様に接着剤で接着する。接着部
が乾燥後これを開口部(外周パイプの接着していない
側)を上にして、溶液5N−NaOH水溶液0.3ml
を入れた後、薄膜6の円の中心がパイプの中心とほぼ一
致するようにして乗せ、超音波溶着機でリング状に溶着
する。溶着部周辺に溶解液がこぼれていないことを確認
する(こぼれている場合は拭き取り、洗浄等して外の溶
解液を取り去る)。前記底部をつけた容器本体1を、底
部を上にして置き、水0.7mlを入れたのち、この組
立てた溶解液室5を薄膜6を下にして両パイプの外周が
一致する様に上から重ねたのち超音波溶着機で溶着す
る。The solution chamber 5 is created in the following procedure. The non-conical side of the protrusion 7 is vertically bonded to the center of the movable portion 8 using an adhesive (for example, a tetrahydrofuran-based adhesive). Further, a pipe for the outer wall of the solution chamber 5 is bonded with an adhesive such that the bonded projection 7 is on the inside, and the circumference of the movable section 8 and the circumference of the pipe coincide. After the adhesive portion has dried, place the opening (the side where the outer peripheral pipe is not adhered) up with 0.3 ml of a solution 5N-NaOH aqueous solution.
, The thin film 6 is placed so that the center of the circle is substantially coincident with the center of the pipe, and the thin film 6 is welded in a ring shape by an ultrasonic welding machine. Check that the solution is not spilled around the welded area (if spilled, wipe off, wash, etc. to remove the outside solution). The bottomed container main body 1 is placed with the bottom facing up, 0.7 ml of water is put therein, and the assembled solution chamber 5 is placed on the thin film 6 down so that the outer circumferences of both pipes coincide. And then welded with an ultrasonic welding machine.
【0020】図4は、段階的時間計測を行うタイムイン
ジケーターの一例であり、図5は、その経時的変化を表
したものである。図4において、9は5室を有する容器
本体、10は溶解室、11、18、20はそれぞれ第
1、第2、第3変色室、12、17、19はそれぞれ第
1、第2、第3溶解壁、13は溶解液室、14は溶解液
室と溶解室の境界にある薄膜、15は突起部、16は可
動部を表す。材質の性状については前項と同様である
が、溶解液室内には、全ての溶解壁を溶解することが可
能な量以上の溶解試薬を含んだ溶解液を、それぞれの変
色室には検知液を(第1変色室3に含まれる検知試薬が
容器全体を変色するに十分な量ならば、第2変色室18
および、第3変色室20は希釈液で満たしてもよい)そ
れぞれの溶解壁は、それぞれが溶解し始める時の条件に
おいて、それぞれに設定された時間経過において次の変
色室まで溶解するだけの厚さを有する。FIG. 4 shows an example of a time indicator for performing stepwise time measurement, and FIG. 5 shows the change over time. In FIG. 4, 9 is a container body having five chambers, 10 is a dissolution chamber, 11, 18, and 20 are first, second, and third color changing chambers, respectively, 12, 17, and 19 are first, second, and second, respectively. 3 dissolving wall, 13 is a dissolving chamber, 14 is a thin film at the boundary between the dissolving chamber and the dissolving chamber, 15 is a projection, and 16 is a movable part. The properties of the materials are the same as in the previous section, except that the lysis solution chamber contains a lysis solution containing a lysis reagent in an amount that can dissolve all the lysis walls, and the discoloration chamber contains a detection solution. (If the amount of the detection reagent contained in the first discoloration chamber 3 is sufficient to discolor the entire container, the second discoloration chamber 18
The third discoloring chamber 20 may be filled with a diluent.) Each dissolving wall has a thickness sufficient to dissolve to the next discoloring chamber after a lapse of a set time under the condition when each dissolution starts. Having
【0021】可動部16を押して突起部15により薄膜
14を突き破った時点から1番目の計時が開始する。1
番目の設定時間が経過すると第1溶解壁12は第1変色
室11側まで溶解し溶解液と検知液が混合して、溶解液
室13、溶解室10、第1変色室11が変色する(図5
−A)。続いて第2溶解壁17が溶解しはじめ2番目の
計時を開始する。隔壁17溶解の設定時間が経過すると
第2変色室18まで変色する(図5−B)。同様にして
3番目の設定時間が経過すると第3変色室20が変色し
計時終了となる。この例では3段階の時間設定だが、第
4、第5、、、の変色室、溶解壁を追加することによ
り、さらに多段階の計時を行うことができる。The first time measurement starts when the movable portion 16 is pushed and the thin film 14 is pierced by the projection 15. 1
After the elapse of the second set time, the first dissolving wall 12 dissolves to the first discoloring chamber 11 side, the dissolving liquid and the detection liquid are mixed, and the dissolving liquid chamber 13, the dissolving chamber 10, and the first discoloring chamber 11 are discolored ( FIG.
-A). Subsequently, the second dissolution wall 17 begins to dissolve, and a second timing is started. When the set time for dissolution of the partition walls 17 has elapsed, the color changes to the second color changing chamber 18 (FIG. 5-B). Similarly, when the third set time elapses, the third color changing chamber 20 changes color and the time measurement ends. In this example, the time is set in three stages. However, by adding the fourth, fifth,... Discoloration chambers and dissolving walls, the time can be measured in multiple stages.
【0022】この多段階を計時するタイプの具体例と作
成方法を示す。溶解液室13は前記溶解液室を一体化し
た形状と同様作成する。容器本体9は透明硬質塩化ビニ
ール(内径10mm、厚さ1mm、高さ10mm)4本と、底
部を硬質ポリ塩化ビニールの円盤(外径10.2mm、厚
さ1mm)から成り、溶解壁12,17,19はポリ乳酸
の円盤(外径10.2mm、厚さ0.1mm)3枚とする。
底部を容器本体に前述と同様に圧入する。開口部を上に
し検知液としてフェノールフタレイン液を0.7ml入
れ溶解壁12,17,19用の円盤を中心がパイプの中
心とほぼ一致するようにして乗せ、その上にさらにもう
1つの容器本体9用のパイプを外周が一致する様に載せ
上部から超音波振動を与え溶着させる。同様にして検知
液の注入、超音波溶着を繰り返し、最後に溶解液室を超
音波溶着して容器本体9とする。A specific example of the type for measuring the time of the multi-step and a method of preparing the time will be described. The solution chamber 13 is formed similarly to the shape in which the solution chamber is integrated. The container body 9 is composed of four transparent hard vinyl chlorides (inner diameter 10 mm, thickness 1 mm, height 10 mm) and a hard polyvinyl chloride disk (outer diameter 10.2 mm, thickness 1 mm). 17 and 19 are three polylactic acid disks (outer diameter 10.2 mm, thickness 0.1 mm).
Press the bottom into the container body as before. 0.7 ml of phenolphthalein solution as a detection liquid is placed with the opening facing upward, and a disk for dissolution walls 12, 17, 19 is placed on the disk so that the center substantially matches the center of the pipe, and another container is placed on top of it. A pipe for the main body 9 is placed so that the outer circumferences thereof coincide with each other, and ultrasonic vibration is applied from above to weld. The injection of the detection liquid and the ultrasonic welding are repeated in the same manner, and finally, the dissolution liquid chamber is ultrasonically welded to obtain the container body 9.
【0023】変色パターンの他の例として、図2におい
て、1)検知試薬を溶解試薬とともに溶解液室5に入れ
る。溶解室2、変色室3に無色の希釈液を入れる。2)
検知試薬を溶解室2に入れる。溶解液室5には溶解液
を、変色室3には希釈液を入れる。3)着色剤(塩基性
から酸性に変わると変色するpH指示薬)を溶解試薬、
および溶解試薬の溶解能を妨げない塩基成分(溶解試薬
が塩基性の場合は不要)を溶解液室5に入れる。溶解室
2には中性の希釈液を、変色室3には溶解壁4の溶解能
がなく溶解液室内の塩基と等量以上の酸性液をいれる等
の例がある。As another example of the discoloration pattern, in FIG. 2, 1) a detection reagent is put into a lysis solution chamber 5 together with a lysis reagent. The colorless diluent is put into the dissolution chamber 2 and the discoloration chamber 3. 2)
The detection reagent is put into the dissolution chamber 2. The lysis solution chamber 5 contains a lysis solution, and the discoloration chamber 3 contains a diluent solution. 3) a dissolving reagent for a coloring agent (a pH indicator that changes color when changing from basic to acidic);
In addition, a base component that does not hinder the dissolving ability of the dissolving reagent (not necessary when the dissolving reagent is basic) is placed in the dissolving solution chamber 5. There is an example in which a neutral diluting solution is placed in the dissolving chamber 2 and an acidic solution having a capacity equal to or greater than that of the base in the dissolving chamber is used in the discoloring chamber 3 because the dissolving wall 4 has no dissolving ability.
【0024】1)の例においては計時開始前には溶解液
室5は着色、溶解室2および変色室3は無色。計時中は
溶解液室5および溶解室2は変色、変色室は無色。計時
終了後は溶解液室5、溶解室2、変色室3ともに変色と
なる。2)の例においては計時開始前はすべて非変色、
計時中は溶解室5および溶解室2は変色、変色室は非変
色。計時終了後は溶解液室5、溶解室2、変色室3とも
に変色となる。1)、2)ともに図4の多段階計時にお
いても同様で次の計時段階ごとの次の変色室が変色され
てゆく。3)の例では、計時開始前の溶解液室5はpH
指示薬の塩基性における色を呈し、溶解室2と変色室3
は非変色、計時中は、溶解液室5と溶解室2がpH指示
薬の塩基性における色に変色し、変色室3は非変色、計
時終了後は、溶解液室5、溶解室2、変色室3ともにp
H指示薬の酸性における色に変色する。In the example of 1), the lysis chamber 5 is colored and the lysis chamber 2 and the discoloration chamber 3 are colorless before the start of timing. During the timing, the dissolution chamber 5 and the dissolution chamber 2 are discolored, and the discoloration chamber is colorless. After the end of the timing, the dissolution chamber 5, the dissolution chamber 2, and the discoloration chamber 3 are all discolored. In the example of 2), before the start of the timing, all the colors are non-discolored,
During the timing, the dissolution chamber 5 and the dissolution chamber 2 are discolored, and the discoloration chamber is not discolored. After the end of the timing, the dissolution chamber 5, the dissolution chamber 2, and the discoloration chamber 3 are all discolored. 1) and 2) are the same in the multi-stage timing shown in FIG. 4, and the color of the next color changing chamber is changed in each next timing stage. In the example of 3), the solution chamber 5 before the start of the timing
Shows color in basicity of indicator, dissolution chamber 2 and discoloration chamber 3
Is non-discolored. During the timing, the dissolution solution chamber 5 and the dissolution chamber 2 change color to the basic color of the pH indicator, and the discoloration chamber 3 is non-discolored. Room 3 is p
The color of the H indicator changes to the acidic color.
【0025】図4の多段階計時においては、最後に変色
する第3変色室20に酸性液を入れれば同様に各段階に
各変色室が塩基側の色に変色してゆき、全計時終了時に
全体がpH指示薬の酸性における色に変色される。前項
までの例では、計時開始時点では変色しないため計時中
であることが分かりにくいが、ここであげた例において
は計時開始時点で変色がおこるので計時中であることが
判別しやすい。これまでの例では容器本体全体が透明で
あったが、片面を透明窓、その裏面を着色した不透明な
材質とすれば、中の液が透明の場合は裏面の色に、変色
した液はその液の色または裏面の色と液の色を混合した
色とし透明面から観察されることとなる。In the multi-stage timing shown in FIG. 4, if the acidic liquid is introduced into the third discoloration chamber 20 which changes color last, each discoloration chamber similarly changes color to the color of the base at each stage. The whole is discolored to the acidic color of the pH indicator. In the examples up to the preceding paragraph, it is difficult to know that the time is being measured because the color does not change at the start of timekeeping, but in the example given here, it is easy to determine that the time is being measured because the color changes at the time of start of timekeeping. In the previous examples, the entire container body was transparent.However, if one side is made of a transparent window and the back side is made of an opaque material that is colored, if the liquid inside is transparent, the color of the back side will be the color, and the discolored liquid will be The color of the liquid or the color of the back and the color of the liquid is mixed and observed from the transparent surface.
【0026】図6は、袋状のケミカルタイムインジケー
ターの正面図および中央部の断面図を示す。図6の21
は袋状の容器本体を、22は溶解室を、23は変色室を
表す。24は膜状の溶解壁を、25は溶解液室を、26
は溶解液室25を構成し溶解室22との隔壁となる薄膜
を表す。27は容器本体の表側膜を、28は容器本体の
裏側膜を、29は溶解液室の薄膜26の反対面の薄膜裏
面を、30は容器本体の表側膜27と裏側膜28の両側
辺を溶着した本体側面溶着部を表し、31は袋状容器本
体21の表裏の側面の溶着面30に挟み込んで溶着され
た溶解壁24の溶着部(溶解壁側面溶着部)を示す。3
2は袋状容器本体21の上辺における表側膜27と裏側
膜28の溶着部(本体上辺溶着部)を、33は溶着部3
2において挟み込まれて溶着している溶解壁24の溶着
面(溶解壁上辺溶着面)を、34は袋状容器本体21の
下辺における表側膜27と裏側膜28の溶着部(本体下
辺溶着部)を表す。さらに35は溶解液室25を構成す
る薄膜26と薄膜29の溶着面(溶解液室溶着面)を、
36は溶解液室25を構成する薄膜26と薄膜29との
仮溶着面(溶解液室仮溶着面)、37は袋状容器本体2
1上辺の溶着部34にはさみこんで溶着した溶解液室の
溶着面(溶解液室上辺溶着面)を表す。FIG. 6 shows a front view of a bag-shaped chemical time indicator and a sectional view of a central portion thereof. 6 in FIG.
Denotes a bag-shaped container main body, 22 denotes a melting chamber, and 23 denotes a discoloration chamber. 24 is a membrane-like dissolution wall, 25 is a solution chamber, 26
Denotes a thin film that constitutes the solution chamber 25 and serves as a partition wall from the solution chamber 22. 27 is the front side film of the container body, 28 is the back side film of the container body, 29 is the thin film back surface opposite to the thin film 26 of the solution chamber, and 30 is the both sides of the front film 27 and the back side film 28 of the container body. Reference numeral 31 denotes a welded portion of the welded main body side surface, and reference numeral 31 denotes a welded portion (dissolved wall side welded portion) of the melting wall 24 sandwiched and welded to the welding surfaces 30 on the front and back side surfaces of the bag-shaped container body 21. 3
Reference numeral 2 denotes a welded portion of the front side film 27 and the backside film 28 on the upper side of the bag-shaped container main body 21 (upper side welded portion of the main body);
Reference numeral 34 denotes a welded surface of the melting wall 24 sandwiched and welded (welded surface on the upper side of the melting wall). Represents Reference numeral 35 denotes a welding surface of the thin film 26 and the thin film 29 constituting the solution chamber 25 (solution solution welding surface).
36 is a temporary welding surface of the thin film 26 and the thin film 29 constituting the solution chamber 25 (solution solution chamber temporary welding surface), and 37 is a bag-like container main body 2.
A welding surface (an upper surface welding surface of the solution chamber) of the solution chamber which is inserted and welded to the welding portion 34 on the upper side is shown.
【0027】袋状容器本体21は長方形状のフィルム2
枚(表側膜27、裏側膜28)で構成され本体側面溶着
部30、本体上辺溶着部34、溶解液室溶着部35によ
り溶着されている。溶解壁24は、長方形状のフィルム
であり、折り曲げた状態でその両側面を溶解壁側面溶着
部31で、上面を溶解壁上辺溶着面33で袋状容器本体
21の表側膜27と裏側膜28に挟み込まれて溶着され
ている。溶解液室25は薄膜26と薄膜裏面29の2枚
の長方形のフィルムからなり、3辺を溶解液室溶着面3
5で溶着され1辺を溶解液室仮溶着部36で仮溶着(強
い圧力を受けると一部が剥がれるように溶着する)、溶
解液室仮溶着部36の対辺において溶解液室上辺溶着面
37で本体上辺溶着部32に挟み込まれるように溶着し
ている。溶解液室25には、溶解壁24を溶解しうる溶
解液が、溶解壁24によって囲まれた溶解室22には変
色成分を含んだ希釈液が、溶解壁24によって隔てられ
た下部の変色室23には希釈液が、それぞれ入れられて
いる。必要に応じて裏側膜28の表面に剥離性の粘着剤
をが塗布する。The bag-like container body 21 is made of a rectangular film 2.
It is composed of sheets (front side film 27, back side film 28) and is welded by the main body side welding part 30, the main body upper side welding part 34, and the solution chamber welding part 35. The dissolving wall 24 is a rectangular film, and in a bent state, both sides are dissolving wall side welding portions 31, and the upper surface is dissolving wall upper side welding surface 33, and the front side film 27 and the back side film 28 of the bag-shaped container body 21. It is sandwiched and welded. The solution chamber 25 is composed of two rectangular films, a thin film 26 and a thin film back surface 29, and has three sides on which the solution chamber welding surface 3 is formed.
5 and one side is temporarily welded (welded so as to be partially peeled off when subjected to a strong pressure) by the solution chamber temporary welding portion 36, and the solution solution upper side welding surface 37 on the opposite side of the solution solution chamber temporary welding portion 36. And is welded so as to be sandwiched by the welding portion 32 on the upper side of the main body. A dissolving solution capable of dissolving the dissolving wall 24 is contained in the dissolving solution chamber 25, and a diluent containing a discoloring component is contained in the dissolving chamber 22 surrounded by the dissolving wall 24, and a lower discoloration chamber separated by the dissolving wall 24. 23 contains a diluent. If necessary, a peelable adhesive is applied to the surface of the backside film 28.
【0028】この溶解液室25を一体化した形態の具体
的な1例と作成手順を示す。容器本体21の表側膜27
および裏側膜28をポリエチレンの長方形状のフィルム
(厚さ0.1mm、長さ100mm、巾20mm)、溶解液室
25の薄膜26、薄膜裏面29をポリエチレンの長方形
状のフィルム(厚さ0.1mm、長さ15mm、巾10m
m)、溶解壁24をポリ乳酸の長方形状のフィルム(厚
さ0.1mm、長さ40mm、巾17mm)とする。溶解液室
25を構成する2枚のフィルム(26、29)を重ね合
わせ、外周の3辺において巾2mmでヒートシールし、未
溶着の1辺より溶解液として2N−NaOH水溶液0.
5mlを注入した後、未溶着の辺を巾3mmで仮溶着す
る。仮溶着とは溶着時間を完全に溶着される最低時間よ
り短くして溶着することである。溶解壁24用のポリ乳
酸のフィルムを二つ折りにして、容器本体21の表側膜
27と裏側膜28の間に、溶解壁24の折り目の反対側
の辺を、表側膜27と裏側膜28の上辺(短辺に)と平
行に1.5mm程度内側に入った位置で、また両側面にお
いても平行で1.5mm程度内側に入った位置に挟み込ん
で両側面を巾3mmでヒートシールする。A specific example of a form in which the solution chamber 25 is integrated and a preparation procedure will be described. Front membrane 27 of container body 21
The back side film 28 is made of polyethylene rectangular film (thickness 0.1 mm, length 100 mm, width 20 mm), and the thin film 26 of the solution chamber 25 and the thin film back surface 29 are made of polyethylene rectangular film (thickness 0.1 mm). , Length 15mm, width 10m
m) The dissolving wall 24 is a rectangular film of polylactic acid (thickness 0.1 mm, length 40 mm, width 17 mm). The two films (26, 29) constituting the dissolving solution chamber 25 are overlapped, heat-sealed on the three sides of the outer periphery with a width of 2 mm, and a 2N-NaOH aqueous solution is used as a dissolving solution from one unwelded side.
After injecting 5 ml, the unwelded side is temporarily welded with a width of 3 mm. Temporary welding means welding with the welding time shorter than the minimum time for complete welding. The polylactic acid film for the dissolving wall 24 is folded in two, and the opposite side of the fold of the dissolving wall 24 between the front film 27 and the back film 28 of the container body 21 is formed by the front film 27 and the back film 28. Heat seal both sides with a width of 3 mm by sandwiching it at a position inward of about 1.5 mm parallel to the upper side (to the short side), and also at a position of about 1.5 mm parallel to both sides.
【0029】溶解壁24が溶着されている側の反対の開
口部から希釈液として水5mlを注入した後、本体上辺
溶着部34をヒートシールする。溶解壁24が溶着され
ている側の開口部を上にし、溶解壁24の間にフェノー
ルフタレイン液を2ml注入した後、溶解液室25の溶
解液室仮溶着部36の反対側の辺を溶解壁24の溶着さ
れていない辺に一致させ溶解液室25を内部に入れる様
にして重ねわせた状態で本体上辺溶着部32、溶解壁上
辺溶着面33、溶解液室上辺溶着面37のヒートシール
を行う。溶解壁24が溶着されている反対側を上にし、
開口部から希釈液として水5mlを注入した後、本体下
辺溶着部34をヒートシールする。幅20mmの両面粘
着テープまたは剥離性の粘着テープを裏側膜28に貼
る。After injecting 5 ml of water as a diluent from the opening opposite to the side where the melting wall 24 is welded, the upper side welded portion 34 is heat-sealed. With the opening on the side where the dissolution wall 24 is welded up, 2 ml of phenolphthalein solution is injected between the dissolution walls 24, and the side of the dissolution solution chamber 25 opposite to the dissolution solution chamber temporary welding portion 36 is removed. Heat is applied to the main body upper side welding portion 32, the melting wall upper side welding surface 33, and the melting solution chamber upper side welding surface 37 in a state where they are overlapped with each other so as to be aligned with the non-welded side of the melting wall 24 so as to put the solution chamber 25 inside. Perform sealing. With the opposite side where the melting wall 24 is welded up,
After injecting 5 ml of water as a diluent from the opening, the welded portion 34 on the lower side of the main body is heat-sealed. A double-sided adhesive tape or a peelable adhesive tape having a width of 20 mm is attached to the back film 28.
【0030】この例における使用方法は、まず、対象物
の有効期限にあった設定時間(溶解壁の厚さ)のものを
選択する。対象物の製造時または、出荷時、購入時等に
袋状容器本体21の外側から溶解液室25を指等でつぶ
す。薄膜26と薄膜裏面29の仮溶着部(溶解液室仮溶
着面36)の一部が剥がれ溶解室22に溶解液が流れ込
み、検知試薬により溶解室22内が変色する。溶解室の
変色を確認した後、時間計測対象物に袋状容器本体21
を裏側膜28上の粘着テープによって付着させる。変色
室23に変化がなければ、計時対象物は有効期限内であ
り使用可能と判断できる。変色室23に変化が認められ
る場合は、たとえ有効期限内といえども使用を控えた方
がよい。同じ形状で溶解液室25を省略し、容器本体2
1の裏側膜28を保管対象物の包装と一体化させ、対象
物の包装時点で溶解室に溶解液を注入した後溶着密封す
る形態とすることも出来る。In the method of use in this example, first, the one having a set time (thickness of the dissolving wall) that matches the expiration date of the object is selected. The lysing solution chamber 25 is crushed from the outside of the bag-shaped container body 21 with a finger or the like at the time of manufacturing, shipping, or purchasing the object. A part of the temporary welding portion (dissolving solution chamber temporary welding surface 36) of the thin film 26 and the thin film back surface 29 is peeled off, and the dissolving solution flows into the dissolving chamber 22, and the inside of the dissolving chamber 22 changes color by the detection reagent. After confirming the discoloration of the melting chamber, the bag-shaped container body 21
Is attached by an adhesive tape on the back film 28. If there is no change in the color changing room 23, it can be determined that the timed object is within the expiration date and can be used. If a change is found in the discoloration room 23, it is better to refrain from using it even within the expiration date. The solution chamber 25 is omitted in the same shape,
One backside film 28 may be integrated with the packaging of the storage object, and a solution may be injected into the melting chamber at the time of packaging the object and then sealed by welding.
【0031】[0031]
【発明の効果】本発明のケミカルタイムインジケーター
は、あらかじめ設定した時間−温度積算値を超過する
と、ほぼ瞬間的な色調変化を呈するため、極めて容易に
時間-温度積算値にもとづく品質管理が行える。設置場
所の自由度が高く、安価に提供できるため多様な用途に
適用できる。When the chemical time indicator of the present invention exceeds a preset time-temperature integrated value, it exhibits an almost instantaneous color tone change, so that quality control based on the time-temperature integrated value can be performed very easily. Since it can be provided at a low cost with a high degree of freedom in installation location, it can be applied to various uses.
【図1】本発明の基本形態の1例FIG. 1 shows an example of a basic embodiment of the present invention.
【図2】基本形態に溶解液室を付加した例FIG. 2 shows an example in which a solution chamber is added to the basic configuration.
【図3】図2の例による経時的色調変化例FIG. 3 shows an example of color change over time according to the example of FIG. 2;
【図4】段階的タイムインジケーターFIG. 4 Stepwise time indicator
【図5】段階的タイムインジケーターによる色調変化例FIG. 5 is an example of a color tone change by a stepwise time indicator.
【図6】袋状タイムインジケーターの1例の正面図と断
面図FIG. 6 is a front view and a sectional view of an example of a bag-shaped time indicator.
1.容器本体 2.溶解室
3.変色室 4.溶解壁 5.溶解液室
6.薄膜 7.突起部 8.可動部
9.容器本体 10.溶解室 11.第1変色室
12.第1溶解壁 13.溶解液室 14.薄膜
15.突起部 16.可動部 17.第2溶解壁
18.第2変色室 19.第3溶解壁 20.第3変色室
21.袋状容器本体 22.溶解室 23.変色室
24.膜状溶解壁 25.溶解液室 26.薄膜
27.表側膜 28.裏側膜 29.薄膜裏面
30.本体側面溶着部 31.溶解壁側面溶着部 32.本体上辺溶着部
33.溶解壁上辺溶着面 34.本体下辺溶着部 35.溶解液室溶着面
36.溶解液室仮溶着面 37.溶解液室上辺溶着面1. 1. Container body Melting chamber
3. Discoloration room 4. Melting wall 5. Lysis chamber
6. 6. Thin film Protrusion 8. movable part
9. Container body 10. Dissolution chamber 11. 1st discoloration room
12. First melting wall 13. Lysis chamber 14. Thin film
15. Projection part 16. Movable part 17. Second melting wall
18. Second color changing room 19. Third melting wall 20. Third color changing room
21. Bag-shaped container body 22. Dissolution chamber 23. Discoloration room
24. 25. Membranous dissolution wall Dissolution chamber 26. Thin film
27. Front membrane 28. Backside membrane 29. Thin film back
30. Body side welded portion 31. Fusion wall side welded portion 32. Welded part on the top
33. Deposition wall upper surface welding surface 34. Welding part on bottom side of main body 35. Dissolution liquid chamber welding surface
36. Dissolution liquid chamber temporary welding surface 37. Welding surface on the upper side of the solution chamber
Claims (15)
質で一部又は全部が構成される隔壁によって少なくとも
2室に仕切られた容器であって、該容器の少なくとも1
室に特定の溶解能を有する試薬が収容され、他の室は特
定の溶解能を有する試薬を検出する検知試薬が収容され
ている時間−温度積算値管理用ケミカルタイムインジケ
ーター。Claims: 1. A container divided into at least two chambers by a partition wall partially or wholly made of a material dissolvable in a reagent having a specific solubility, wherein at least one of the containers is provided.
A chemical time indicator for managing a time-temperature integrated value in which a chamber contains a reagent having a specific solubility and another chamber contains a detection reagent for detecting a reagent having a specific solubility.
質で一部又は全部が構成される隔壁によって少なくとも
2室に仕切られた容器であって、該容器の少なくとも1
室に特定の溶解能を有する試薬および色素が収容され、
該隔壁の溶解による色素の拡散によって経過時間を検知
する時間−温度積算値管理用ケミカルタイムインジケー
ター。2. A container partitioned into at least two chambers by a partition wall partially or wholly made of a material dissolvable in a reagent having a specific solubility, wherein at least one of said containers is provided.
A chamber containing reagents and dyes having a specific solubility,
A chemical time indicator for managing a time-temperature integrated value for detecting elapsed time by diffusion of a dye due to dissolution of the partition.
有する試薬と検知試薬の混合物が接触する次の隔壁を溶
解する段階的な隔壁溶解に伴う検知試薬の段階的変化に
よって、段階的に経過時間を認識する請求項1および2
に記載のケミカルタイムインジケーター。3. The method according to claim 1, wherein after one partition is dissolved, a mixture of a reagent having a specific solubilizing ability and a detection reagent comes into contact, and the next partition is dissolved. 3. The method according to claim 1, further comprising the steps of:
Chemical time indicator described in.
が透明である請求項1および2に記載のケミカルタイム
インジケーター。4. The chemical time indicator according to claim 1, wherein a part or all of the chamber containing the detection reagent is transparent.
の注入口を備えた請求項1および2に記載のケミカルタ
イムインジケーター。5. The chemical time indicator according to claim 1, further comprising an inlet for injecting a reagent having a specific solubility.
に、外部から物理的に破壊可能な隔壁を別途設け、計時
開始まで特定の溶解能を有する試薬を特定の試薬に溶解
可能な隔壁に接触させないことを特徴とする請求項1お
よび2に記載のケミカルタイムインジケーター。6. A partition which can be physically broken from the outside in a chamber for accommodating a reagent having a specific dissolving ability, and is capable of dissolving a reagent having a specific dissolving ability in a specific reagent until the start of timing. The chemical time indicator according to claim 1, wherein the chemical time indicator is not brought into contact with the chemical time indicator.
液であり、検知試薬がpH指示薬であって、隔壁の材質
の一部がポリ乳酸である請求項1に記載のケミカルタイ
ムインジケーター。7. The chemical time indicator according to claim 1, wherein the reagent having a specific solubility is an alkaline solution, the detection reagent is a pH indicator, and a part of the material of the partition is polylactic acid.
は水酸化カリウムであり、pH指示薬が、フェノールフ
タレインである請求項7に記載のケミカルタイムインジ
ケーター。8. The chemical time indicator according to claim 7, wherein the alkaline solution is sodium hydroxide or potassium hydroxide, and the pH indicator is phenolphthalein.
媒であり、隔壁の材質の一部が該有機溶媒に可溶なプラ
スチックである請求項1および2にに記載のケミカルタ
イムインジケーター。9. The chemical time indicator according to claim 1, wherein the reagent having a specific solubility is a water-soluble organic solvent, and a part of the material of the partition is a plastic soluble in the organic solvent.
容器の一部に塗布してある請求項1〜9に記載のケミカ
ルタイムインジケーター。10. The chemical time indicator according to claim 1, wherein an adhesive capable of adhering to an object to be time-controlled is applied to a part of the container.
0に記載のケミカルタイムインジケーター。11. The adhesive according to claim 1, wherein the adhesive is a peelable adhesive.
Chemical time indicator according to 0.
差を設け、隔壁の溶解後の2液の混合速度を高めること
を特徴とする請求項1〜11に記載のケミカルタイムイ
ンジケーター。12. The chemical time indicator according to claim 1, wherein a difference is provided in the internal pressure between the chambers partitioned by the partition walls to increase the mixing speed of the two liquids after the partition walls are dissolved.
材質からなる隔壁で仕切られた容器の1室に検知試薬を
収容しておき、他室に特定の溶解能を有する試薬を注入
して隔壁を溶解して2室を連通させ特定の溶解能を有す
る試薬と検知試薬と混合による変色反応から経過時間を
測定する方法。13. A detection reagent is accommodated in one chamber of a container partitioned by a partition made of a material dissolvable in a reagent having a specific solubility, and a reagent having a specific solubility is injected into another chamber. A method for measuring the elapsed time from a color change reaction caused by mixing a reagent having a specific dissolving ability with a detection reagent by dissolving the partition wall to allow the two chambers to communicate with each other.
材質からなる隔壁で仕切られた容器の1室に、特定の溶
解能を有する試薬および色素試薬を注入し、隔壁の溶解
によって他室へ拡散する色素を認識することから経過時
間を測定する方法。14. A reagent and a dye reagent having a specific solubility are injected into one chamber of a container partitioned by a partition made of a material dissolvable in a reagent having a specific solubility, and the other chamber is dissolved by dissolution of the partition. A method of measuring the elapsed time by recognizing the dye that diffuses to the surface.
質からなる小容器に特定の溶解能を有する試薬を検知す
る試薬または色素試薬を封入した容器を、特定の溶解能
を有する試薬を収容した容器に投入して時間計測を開始
する経過時間計測方法。15. A container in which a reagent or a dye reagent for detecting a reagent having a specific solubility is sealed in a small container made of a material soluble in a reagent having a specific solubility, and a reagent having a specific solubility is accommodated. Elapsed time measurement method to start time measurement by putting it in a filled container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13292897A JPH10307192A (en) | 1997-05-07 | 1997-05-07 | Chemical time indicator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13292897A JPH10307192A (en) | 1997-05-07 | 1997-05-07 | Chemical time indicator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10307192A true JPH10307192A (en) | 1998-11-17 |
Family
ID=15092783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13292897A Pending JPH10307192A (en) | 1997-05-07 | 1997-05-07 | Chemical time indicator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10307192A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017033489A1 (en) * | 2015-08-27 | 2017-03-02 | 株式会社日立製作所 | Temperature history display object |
| JP2019503498A (en) * | 2016-01-29 | 2019-02-07 | ティーティーアイ カンパニー,リミテッド | Time temperature display module and manufacturing method thereof |
| JP2019162869A (en) * | 2018-03-19 | 2019-09-26 | ゼロックス コーポレイションXerox Corporation | Color changing expiration indicator |
| JP2020526760A (en) * | 2017-07-11 | 2020-08-31 | イントレイ リミテッド | Time temperature indicator label |
-
1997
- 1997-05-07 JP JP13292897A patent/JPH10307192A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017033489A1 (en) * | 2015-08-27 | 2017-03-02 | 株式会社日立製作所 | Temperature history display object |
| JP2019503498A (en) * | 2016-01-29 | 2019-02-07 | ティーティーアイ カンパニー,リミテッド | Time temperature display module and manufacturing method thereof |
| JP2020526760A (en) * | 2017-07-11 | 2020-08-31 | イントレイ リミテッド | Time temperature indicator label |
| JP2019162869A (en) * | 2018-03-19 | 2019-09-26 | ゼロックス コーポレイションXerox Corporation | Color changing expiration indicator |
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