JPS58182555A - Oxygen detecting composite - Google Patents
Oxygen detecting compositeInfo
- Publication number
- JPS58182555A JPS58182555A JP6516382A JP6516382A JPS58182555A JP S58182555 A JPS58182555 A JP S58182555A JP 6516382 A JP6516382 A JP 6516382A JP 6516382 A JP6516382 A JP 6516382A JP S58182555 A JPS58182555 A JP S58182555A
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
- G01N31/225—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for oxygen, e.g. including dissolved oxygen
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Biophysics (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、酸素感知組成物（＝係り、さら（二詳しくは
、保存安定性に優れた酸素感知組成物（＝関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxygen sensing composition, and more particularly, to an oxygen sensing composition with excellent storage stability.
酸素感知組成物は、従来、酸素の不存在トで行われる嫌
気性醗酵等の単位操作において、系内の酸素の存在の有
無を感知する目的（＝溶液状組成物を１紙等（−含浸さ
せた検知紙が使用されてきたが、近年では、食品添加剤
の使用規制等（二より、パックされた食品の酸化、腐敗
を防止するためにバンク内（二酸素吸収剤を同封する方
法が提案され、該酸素吸収剤の酸素吸収能を感知するた
めに錠剤形式の酸素感知組成物が要望されている。酸素
感知組成物は、酸化、還元（二より可逆的じ色−蛮化す
る酸化還元色素を呈色成分とし、該色素を還元型（二保
持しておく還元性物質と、還元助剤およびその他賦形剤
等の添加物とからなり、該色素が酸素の存在により還元
型から酸化型へ変化すること（二より呈色する反応を利
用するものであるが、古くから色素としてメチレンダブ
ル−９還元性物質と組成物または該水溶液状組成物を紙
等に含浸された検知紙等が知られているが、該組成物は
水溶液状であるため、呈色反応の応答速度は速い反面、
取扱い上下都合が多く、特に液状物の存在を嫌う物とは
共存させることができない欠点がある。また、還元助剤
として水酸化ナトリウムに替えてアルカリ土類金属水酸
化物を用いる実宵的に固体状の組成物が前記錠剤形式と
なし得る組成物として特公昭５６−２４９０６号公報（
＝提案されている。Ｉ２かしながら、該組成物（二おい
ても、アルカリ土類金属水酸化物として水酸化カルシウ
ムを使用すると、保存安定性が極めて悪く、この傾向は
６１１記水酸化ナトリウムを用いる場合（二も誌められ
る欠陥である。Conventionally, oxygen-sensing compositions have been used for the purpose of sensing the presence or absence of oxygen in a system in unit operations such as anaerobic fermentation, which are carried out in the absence of oxygen (= solution-like composition is mixed with a sheet of paper, etc. (-impregnated)). However, in recent years, regulations on the use of food additives, etc. (2) In order to prevent the oxidation and spoilage of packed foods, a method of enclosing a dioxygen absorbent inside the food bank has been introduced. There is a need for an oxygen sensing composition in the form of a tablet to sense the oxygen absorption capacity of the oxygen absorbent. The coloring component is a reduced dye, which is composed of a reducing substance that is kept in a reduced form (2), and additives such as a reduction aid and other excipients, and the dye is changed from a reduced form due to the presence of oxygen. Change to an oxidized form (it utilizes a reaction that produces color from two factors, but it has long been used as a pigment with a methylene double-9 reducing substance and a composition or with a detection paper etc. impregnated with the aqueous composition). etc. are known, but since the composition is in the form of an aqueous solution, the response speed of the coloring reaction is fast, but on the other hand,
It is difficult to handle and has the disadvantage that it cannot coexist with substances that do not particularly like the presence of liquid substances. Furthermore, Japanese Patent Publication No. 56-24906 (1986-24906) describes a practically solid composition that uses an alkaline earth metal hydroxide instead of sodium hydroxide as a reducing aid and can be made into the tablet form.
= proposed. However, when calcium hydroxide is used as the alkaline earth metal hydroxide in the composition (also in 2), the storage stability is extremely poor, and this tendency is observed when sodium hydroxide is used in 611 (2). This is a flaw that can be criticized.
本発明は呈色性に優れ、かつ長期保存安定性（＝優れた
酸素感知組成物を提供することを目的とする。An object of the present invention is to provide an oxygen-sensing composition that has excellent color development and long-term storage stability.
本発明者等は、前記目的を達成すべく鋭意研究の結果、
酸素感知組成物の呈色性および保存安定性は、該組成物
の水素イオン＃度（二大きく影響することを見出し本発
明を完成した２、
本発明は、メチレンブルー、還元性糖Ｑ、および塩基性
物質とからなる酸素感知組成物において、該組成物の水
素イオン濃度がＰＨ９ないしＰ）（１３ｉ二緩衝保持さ
れていることを特徴とする酸素感知組成物である。As a result of intensive research to achieve the above objective, the present inventors have found that
The present invention has been completed by discovering that the color development and storage stability of oxygen sensing compositions are greatly influenced by the hydrogen ion degree (2) of the composition. The oxygen sensing composition is characterized in that the hydrogen ion concentration of the composition is maintained at PH9 to P) (13i di-buffer).
本発明（二おいて、酸素感知組・酸物の水素イオンａ度
は、該組成物の５％（Ｉ（量）水溶液または、該組成物
を水に分散させた５％（重ｉｔ）スラリーの水素イオン
濃度であり、Ｐ）（緩倒能を有するアルカリ物質を用い
ることによりＰＩ−１９〜１３、好ましくは、ＰＨ、１
０〜１２に緩衝保持される。ＰＨＩＯ以下では、呈色反
応速度が遅くなり、また、ＰＨ１２以上ではメチレンダ
ブルーがアルカリ（二より分解され、保存安定性が慈く
なり好まし≦ない。 、本発明において、水素イオン
濃度の緩衛保持は、還元助剤として用いる塩基性物質と
して、ＰＨ緩慟能を有する＃ＩＡ基性塩性塩類わち、！
５ｉ酸性物質と強塩基との塩類たとえば、リン酸、炭酸
、ケイ酸。In the present invention (2), the hydrogen ion a degree of the oxygen sensing group/acid is a 5% (weight) aqueous solution of the composition or a 5% (weight) slurry in which the composition is dispersed in water. The hydrogen ion concentration is P) (PI-19 to 13 by using an alkaline substance having slow tonicity, preferably PH, 1
It is buffered and held between 0 and 12. If the pH is below PHIO, the coloring reaction rate will be slow, and if the pH is above PH12, methylene da blue will be decomposed by alkaline (2), resulting in poor storage stability, which is not preferable. As a basic substance used as a reducing aid, #IA basic salts with PH slowing ability are used to maintain health!
5i Salts of acidic substances and strong bases, such as phosphoric acid, carbonic acid, and silicic acid.
ホウ酸、または有機酸類のアルカリ金属塩類もしくは、
アルカリ土類金属塩類、具体的には、リン酸ｔトリウム
、リン酸カルシウム、ビロリン酸ナトリウム、メタリン
酸ナトリウム、ポリリン酸ナトリウム、リン酸カルシウ
ム、メタリン酸カルシウム、リン酸水素バリウム、等の
リン酸塩類。Boric acid, or alkali metal salts of organic acids, or
Alkaline earth metal salts, specifically phosphates such as thorium phosphate, calcium phosphate, sodium birophosphate, sodium metaphosphate, sodium polyphosphate, calcium phosphate, calcium metaphosphate, and barium hydrogen phosphate.
炭酸ナトリウム、重炭酸ナトリウム、塩基性炭酸マグネ
シウム等の炭酸塩類、ケイ酸ナトリウノ・。Carbonates such as sodium carbonate, sodium bicarbonate, basic magnesium carbonate, and sodium silicate.
メタケイ酸ナトリウム、セスキケイ酸ナトリウム。Sodium metasilicate, sodium sesquisilicate.
ケイ酸カルシウム、ケイ酸マグネシウム等のケイ酸塩類
、ホウ酸ナトリウム、ホウ酸カルシウム等のホウ酸塩類
、酢酸ナトリウム、シュウ酸ナトリウム、シュ、つ酸カ
ルシウム等の有機酸塩類の１種または２種以上を用いる
か、もしくは、前記塩基性塩類−のｌｌｉまたは２１１
以上と、アルカリ金属。One or more types of silicates such as calcium silicate and magnesium silicate, borates such as sodium borate and calcium borate, and organic acid salts such as sodium acetate, sodium oxalate, oxalate, and calcium oxalate. or lli or 211 of the basic salts.
Above, and alkali metals.
アルカリ土類金属の酸化物または水酸化物の１種とを用
いることにより行われる。This is carried out by using one of the oxides or hydroxides of alkaline earth metals.
本発明く二おいて、呈色成分としてメチレンブルーを使
用するが、メチレンブルーリ、外（二も一般式ｍ
で表わされる酸化還元色素、たとえばニューメデレンブ
ルー、ラウスバイオレット、メチレングリーン等および
、メチレンブルーの鍮塩類をも使用することができる。In the second aspect of the present invention, methylene blue is used as a coloring component. Salts can also be used.
還元性糖類としては、アルカリの存在下（−メチレンブ
ルーを無色の還元型（二還元し得る単糖類、たとえばＤ
−グルコース、Ｄ−キシロース、Ｄ−ラクトース、Ｄ−
ガラクトース等であればよく、還元力、入手の各編さを
考慮するとＤ−グルコース、Ｄ−キシロースを用いるの
が望ましい。As reducing sugars, in the presence of an alkali (-methylene blue can be converted into a colorless reduced form (monosaccharides that can be di-reduced, such as D
-glucose, D-xylose, D-lactose, D-
Any material such as galactose may be used, and it is preferable to use D-glucose or D-xylose in consideration of reducing power and availability.
本発明は、前記メチレンブルー、還元性糖類および、塩
基性物質とからなる水溶液状組成物、該水溶液状組成物
を紙、布、不繊布等に含浸担持させた組成物、およびさ
らに添加剤として保水性物質、たとえばケイ酸ゲル、ア
ルミナゲル、ポリエチレンクリコール、ポリプロピレン
グリコール。The present invention relates to an aqueous composition comprising the methylene blue, a reducing sugar, and a basic substance, a composition in which paper, cloth, nonwoven fabric, etc. are impregnated with the aqueous composition, and a water-retentive composition as an additive. substances such as silicic acid gel, alumina gel, polyethylene glycol, polypropylene glycol.
１紀グリコール類のエーテル類、カルボキシセルロース
、ヒドロキシエチルセルロース、ヒドロキシプロピルセ
ルロース、メチルセルロース等のセルロース誘導体等を
添加混合せしめた粉粒状、顆粒状、またはタブレット状
の組成物である。It is a powder, granule, or tablet-like composition in which ethers of primary glycols, cellulose derivatives such as carboxycellulose, hydroxyethylcellulose, hydroxypropylcellulose, and methylcellulose are added and mixed.
本発明（＝おいて、各組成物の組成比（二別（二制限は
ないが、メチレンブルーは、組成物全体を均一に着色し
得る量であればよい。塩基性物質の使用量は、使用する
塩基性物質の種類、単独使用か、複数使用か、また還元
性糖類の種類、添加剤の有無、種類、使用量等により異
るが、通常、還元性糖類１重量部当り００１重量部以上
、好ましくは、０．０５〜１重量部である。組成物が粉
粒状、顆粒状またはタブレット状等の固体組成物の場合
には、塩基性物質として離水溶性のカルシウム塩、バリ
ウム塩等を用いるのが好ましい。In the present invention (=, the composition ratio of each composition is divided into two (2) (there is no restriction, but methylene blue may be used in an amount that can uniformly color the entire composition. The amount of the basic substance used is Although it varies depending on the type of basic substance to be used, whether it is used alone or in combination, the type of reducing saccharide, the presence or absence of additives, the type, amount used, etc., it is usually 0.001 parts by weight or more per 1 part by weight of reducing saccharide. , preferably from 0.05 to 1 part by weight.When the composition is a solid composition in the form of powder, granules, or tablets, water-repellent calcium salts, barium salts, etc. are used as the basic substance. is preferable.
本発明は、呈色反応の応答速度が速く、かつ優れた長期
保存安定性を有する酸素感知組成物を提供するものであ
り、その産業的意義は極めて大きい。The present invention provides an oxygen sensing composition that has a fast response speed of color reaction and excellent long-term storage stability, and has extremely great industrial significance.
以下、実施例（二より本発明をさらに詳しく説明する。Hereinafter, the present invention will be explained in more detail from Example 2.
ただし、本発明は下記実施例Ｃ：限定されるものではな
い。However, the present invention is not limited to the following example C.
実施例Ｉ
Ｄ（＋）−ガラクトース２００部、炭酸ナトリウム１３
０部をよく混合し、これ（：メチレンブルー５部ボリエ
デレングリコール＃４００を１５０船 ヒドロキシプロ
ピルセルロース−Ｌの２０％０％ニブルアルコール１５
０部、水２０００部を加えて乳鉢でよく混合してスラリ
ーを作成した。Example I 200 parts of D(+)-galactose, 13 parts of sodium carbonate
0 parts of this (: 5 parts of methylene blue, 150 parts of polyethylene glycol #400, 20% of hydroxypropyl cellulose-L, 15% of nibble alcohol)
0 parts and 2000 parts of water were added and mixed well in a mortar to create a slurry.
このスラリーのＰＨは１１．０．９であった。The pH of this slurry was 11.0.9.
このスラリーを厚手のｒ紙片に含浸させ１日間室温乾燥
させた後、この青色１紙片を窒素雰囲気中（＝放置した
ところ白色に変色し、再び空気中に出すと青色（：呈色
した。A piece of thick R paper was impregnated with this slurry and dried at room temperature for one day. When this blue paper piece was left in a nitrogen atmosphere, it turned white, and when it was put out into the air again, it turned blue.
実施例２
Ｄ（＋）−ガラクトース２００部、リン酸三ナトリウム
１５０部をよく混合し、これ（：メチレンブルー１０部
、ポリエチレングリコール”１５００を２００部、カル
ボキレメチルセルロースナトリウム２００部、水２００
部を加えて乳鉢でよく混合してスラリーを作成した。Example 2 200 parts of D(+)-galactose and 150 parts of trisodium phosphate were mixed well, and mixed with the following: 10 parts of methylene blue, 200 parts of polyethylene glycol 1500, 200 parts of sodium carboxymethyl cellulose, and 200 parts of water.
and mixed well in a mortar to create a slurry.
このスラリーの田は１１．９０であった。The field of this slurry was 11.90.
このスラリーを乾燥して顆粒を作成し、この顆粒な打錠
機を用い直径１２簡のレンズ状の錠剤とした。この錠剤
を窒素雰囲気中に放置したところ白色に変色し、再び空
気中に出すと青色（二呈色した。This slurry was dried to form granules, which were made into lens-shaped tablets with a diameter of 12 pieces using this granular tableting machine. When this tablet was left in a nitrogen atmosphere, it turned white, and when it was put out into the air again, it turned blue (two colors).
実施例３
Ｄ（＋）−キＶロース７０部、リン酸三ナトリウム１２
水塩１５部、メチレンブルー０．２部、ポリエチレング
リコール ４００．６０部、水７，６５部を乳鉢でよく
混合してスラリーを作成した。Example 3 70 parts of D(+)-kiV loin, 12 parts of trisodium phosphate
A slurry was prepared by thoroughly mixing 15 parts of water salt, 0.2 parts of methylene blue, 400.60 parts of polyethylene glycol, and 7.65 parts of water in a mortar.
このスラリーのＰＨ）ｉｌｌ、０６であった、このスラ
リーを板目紙（二含浸させ１日間室温乾燥させた後、こ
の青色板目紙を窒素雰囲気中に放置したところ白色（二
変色し、再び空気中（二出すと青色（二呈色した。The slurry had a pH of 06 (PH)ill, 06. After impregnating this slurry with grained paper and drying it at room temperature for one day, the blue grained paper was left in a nitrogen atmosphere. When exposed to the air, it developed a blue color (two colors).
実施例４
Ｄ（＋）−キシロース顕部、リン酸三ナトリウム１２水
塩５部、メチレンブルー０．５部、ケイ酸カルシウム３
４０部、水ｎ部を混合しスラリーを作成した。Example 4 D(+)-xylose pigment, 5 parts of trisodium phosphate decahydrate, 0.5 part of methylene blue, 3 parts of calcium silicate
A slurry was prepared by mixing 40 parts and n parts of water.
このスラリーのＰＨは１１．８０であった。The pH of this slurry was 11.80.
このスラリーに、ヒドロキシプロピルセルロース−Ｌの
２０％エタノール溶液１００部を添加し、よく混合し、
乾燥して顆粒を作成した。To this slurry, 100 parts of a 20% ethanol solution of hydroxypropyl cellulose-L was added, mixed well,
It was dried to form granules.
この顆粒な打錠機を用い直径１２１１ｍのレンズ状の錠
剤とした。Using this granular tableting machine, lens-shaped tablets with a diameter of 1211 m were made.
この錠剤を窒素雰囲気中Ｃ二装置したところ白色（＝変
色し、再び空気中（二出すと青色に呈色した。When this tablet was exposed to carbon dioxide in a nitrogen atmosphere, it turned white (=discolored), and when it was exposed to air again, it turned blue.
出 願 人 日本曹達株式会社 代理人 伊 藤 晴 之 横 山 吉 美Applicant: Nippon Soda Co., Ltd. Agent Haruyuki Ito Horizontal Mountain Yoshi Beauty
Claims (1)
とからなる酸素感知組成物仁おいて、該組成物の水素イ
オン濃度が肺ないしＰＨ１３４：緩衛保持されているこ
とを特徴とする酸素感知組成物 ２５％水溶液またはスラリーの水素イオン濃度がＰＨ９
〜１３、好ましくは、ＰＩ（１０〜１２である特許請求
の範囲第１項記載の組成物 工 塩基性物質が、ＰＨ緩衝能を有する弱酸性物質と強
塩基との塩基性塩類の１種または２種以上である特許請
求の範囲第１項記載の組成物４ 塩基性物質がアルカリ
金属、アルカリ土類金属の酸化物または水酸化物の１種
と、ＰＨＩＩＩＩｉ能を賽する弱酸性物質と強塩基との
塩基性塩類の１種または２ＩｒＩ以上との温金物である
特許請求の範囲第１項記載の繊成物 ５、 弱酸性物質と強塩基との塩基性塩類が、リン酸、
炭酸、ケイ酸、ホウ酸または有機酸類のアルカリ金属塩
類もしくはアルカリ土類金＠塩類である特許請求の範囲
第３項および第４項記載の組成物 ４ 溶液状である特許請求の範囲第１項記転の組成物 ７ 溶液状組成物を固体に担持させた特許請求の範囲第
１項記載の組成物 ａ 粉粒状、ｌＩ粒状、またはタブレット状である特許
請求の範囲’ＪＪＩ項および第７項記載の組成物[Scope of Claims] 1. An oxygen-sensing composition comprising medelene blue, a reducing sugar, and a basic substance, characterized in that the hydrogen ion concentration of the composition is maintained at a moderate pH of 134 from the lung level. The hydrogen ion concentration of the 25% aqueous solution or slurry of the oxygen sensing composition is PH9.
-13, preferably PI (10-12) The composition according to claim 1, wherein the basic substance is one of basic salts of a weak acidic substance having pH buffering ability and a strong base, or Composition 4 according to claim 1, wherein the basic substance is one of the oxides or hydroxides of an alkali metal or alkaline earth metal, a weakly acidic substance that enhances PHIIIi ability, and a strong Fiber composition 5 according to claim 1, which is a hot metal material with one kind of basic salts with a base or 2IrI or more, wherein the basic salts with a weak acidic substance and a strong base are phosphoric acid,
Composition 4 according to claims 3 and 4, which is an alkali metal salt or alkaline earth gold@salt of carbonic acid, silicic acid, boric acid, or an organic acid.Claim 1, which is in the form of a solution. Composition 7 of the Notes Composition a according to claim 1, in which a solution composition is supported on a solid; Claims 'JJI and 7, which are in the form of powder, granules, or tablets; Composition as described
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6516382A JPS58182555A (en) | 1982-04-19 | 1982-04-19 | Oxygen detecting composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6516382A JPS58182555A (en) | 1982-04-19 | 1982-04-19 | Oxygen detecting composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58182555A true JPS58182555A (en) | 1983-10-25 |
Family
ID=13278936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6516382A Pending JPS58182555A (en) | 1982-04-19 | 1982-04-19 | Oxygen detecting composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58182555A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036542A1 (en) * | 1999-11-16 | 2001-05-25 | Betzdearborn Inc. | Method of stabilizing dye solutions and stabilized dye compositions |
| WO2007017555A1 (en) * | 2005-08-09 | 2007-02-15 | Valtion Teknillinen Tutkimuskeskus | INK COMPOSITION, OXYGEN AND/OR pH INDICATOR AND PACKAGE |
| JP2008110483A (en) * | 2006-10-27 | 2008-05-15 | Brother Ind Ltd | Printer |
| US20110097811A1 (en) * | 2009-10-28 | 2011-04-28 | Powdertech Co., Ltd. | Oxygen detector and method for manufacturing oxygen detector |
| US20110136238A1 (en) * | 2008-06-18 | 2011-06-09 | Teknologian Tutkimuskeskus Vtt | Oxygen indicator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568547A (en) * | 1979-07-03 | 1981-01-28 | Mitsubishi Gas Chem Co Inc | Printable detecting agent |
| JPS5684772A (en) * | 1979-12-13 | 1981-07-10 | Dainippon Printing Co Ltd | Oxygen indicator ink composition |
-
1982
- 1982-04-19 JP JP6516382A patent/JPS58182555A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568547A (en) * | 1979-07-03 | 1981-01-28 | Mitsubishi Gas Chem Co Inc | Printable detecting agent |
| JPS5684772A (en) * | 1979-12-13 | 1981-07-10 | Dainippon Printing Co Ltd | Oxygen indicator ink composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036542A1 (en) * | 1999-11-16 | 2001-05-25 | Betzdearborn Inc. | Method of stabilizing dye solutions and stabilized dye compositions |
| WO2007017555A1 (en) * | 2005-08-09 | 2007-02-15 | Valtion Teknillinen Tutkimuskeskus | INK COMPOSITION, OXYGEN AND/OR pH INDICATOR AND PACKAGE |
| JP2009504828A (en) * | 2005-08-09 | 2009-02-05 | ヴァルション テクニッリネン トゥトキムスケスクス | Ink composition, oxygen and / or pH indicator, and package |
| JP2008110483A (en) * | 2006-10-27 | 2008-05-15 | Brother Ind Ltd | Printer |
| US20110136238A1 (en) * | 2008-06-18 | 2011-06-09 | Teknologian Tutkimuskeskus Vtt | Oxygen indicator |
| US20110097811A1 (en) * | 2009-10-28 | 2011-04-28 | Powdertech Co., Ltd. | Oxygen detector and method for manufacturing oxygen detector |
| US8415167B2 (en) * | 2009-10-28 | 2013-04-09 | Powdertech Co., Ltd. | Oxygen detector and method for manufacturing oxygen detector |
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