JPH01284582A - Safe heat generating agent composition - Google Patents
Safe heat generating agent compositionInfo
- Publication number
- JPH01284582A JPH01284582A JP63112571A JP11257188A JPH01284582A JP H01284582 A JPH01284582 A JP H01284582A JP 63112571 A JP63112571 A JP 63112571A JP 11257188 A JP11257188 A JP 11257188A JP H01284582 A JPH01284582 A JP H01284582A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- powder
- composition
- iron powder
- red phosphorus
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 3
- 239000004254 Ammonium phosphate Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract description 2
- 235000019289 ammonium phosphates Nutrition 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004576 sand Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 abstract 2
- -1 (thio)urea Chemical class 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- SSGGNFYQMRDXFH-UHFFFAOYSA-N sulfanylurea Chemical compound NC(=O)NS SSGGNFYQMRDXFH-UHFFFAOYSA-N 0.000 abstract 1
- 235000013305 food Nutrition 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004343 Calcium peroxide Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、自己燃焼の反応熱によって飲食品等を加熱す
るための発熱剤組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a heat-generating agent composition for heating food, drink, etc. using reaction heat of self-combustion.
［従来の技術］
従来より金属粉末と酸化性物質を主成分とする発熱剤を
、飲食品などの加熱用途に用いることはよく知られてい
る。例えば、特公昭２７−５８２号公報、実公昭５８−
２４１１．９号公報、米国特許２，３８４，２７８号、
同３，５２７，２０１号、同４．６６４．［ｉ７４号な
どに記載されているように、金属粉末としては鉄、ケイ
素鉄、アルミニウム、マグネシウム、銅なと、また酸化
性物質としては、鉛丹、過マンガン酸カリウム、二酸化
マンガン、過酸化カルシウムなとが挙げられているる。[Prior Art] It has been well known that exothermic agents containing metal powder and oxidizing substances as main components are used for heating foods and drinks. For example, Japanese Patent Publication No. 27-582, Utility Model Publication No. 58-
No. 2411.9, U.S. Patent No. 2,384,278,
No. 3,527,201, No. 4.664. [As described in No. i74, etc., metal powders include iron, silicon iron, aluminum, magnesium, and copper, and oxidizing substances include red lead, potassium permanganate, manganese dioxide, and calcium peroxide. Nato is mentioned.
［発明が解決しようとする課題］
これらの発熱剤組成物は、特に飲食品の加熱などに用い
ようとすると、中位重量当たりの発熱量を確保するため
と着火装置による着火性を良くするために酸化性物質の
量を多めにする必要があった。その結果、発熱剤組成物
の取扱い上発火しやすくなったり、燃焼中に発熱剤組成
物が溶融して吹き出したりするので、酸化性物質が少な
い領域でも安全性の高い発熱剤組成物が要求されていた
。[Problems to be Solved by the Invention] These exothermic agent compositions, especially when used for heating food and drink products, are used in order to ensure a calorific value per medium weight and to improve ignitability with an ignition device. It was necessary to increase the amount of oxidizing substances. As a result, the exothermic composition may easily catch fire when handled, or it may melt and blow out during combustion, so a highly safe exothermic composition is required even in areas with few oxidizing substances. was.
［課題を解決するための手段］
本発明者らは、上記の問題点を解決するために研究を重
ねた結果、飲食品などの加熱に適した発熱剤組成物を発
明することができた。[Means for Solving the Problems] As a result of repeated research to solve the above-mentioned problems, the present inventors were able to invent a heat generating composition suitable for heating foods and drinks.
すなわち、本発明は金属粉末と酸化性物質を主成分とす
る発熱剤組成物であって、鉄粉末か５５〜８５重皿％、
ケイ素鉄粉末が０〜２０重量％、過マンガン酸カリウム
が１０〜２５重量％、赤リン０．１〜３．０重量％の混
合物からなることを特徴とする発熱剤組成物、そしても
う１つは、金属粉末と酸化性物質を主成分とする発熱剤
組成物であって、鉄粉末が５５〜８５重量％、ケイ素鉄
粉末が０〜２０重量％、過マンガン酸カリウムか１０〜
２５重量％、赤リン０．１〜３．０重量％、燃焼調整剤
が０．１〜２，０重量２６の混合物からなることを特徴
とする発熱剤組成物である。That is, the present invention is a heat generating composition mainly composed of metal powder and an oxidizing substance, which contains iron powder in an amount of 55 to 85%,
A heating agent composition comprising a mixture of 0 to 20% by weight of silicon iron powder, 10 to 25% by weight of potassium permanganate, and 0.1 to 3.0% by weight of red phosphorus; is a heat generating composition mainly composed of metal powder and oxidizing substance, which contains 55 to 85% by weight of iron powder, 0 to 20% by weight of silicon iron powder, and 10 to 10% by weight of potassium permanganate.
25% by weight of red phosphorus, 0.1 to 3.0% by weight of red phosphorus, and 0.1 to 2.0% by weight of a combustion modifier.
本発明の鉄粉末、ケイ素鉄粉末、過マンガン酸カリウム
、赤リン、燃焼調整剤は、酸化還元反応及びそれぞれの
成分の分離を防止するために、１００〜４００メツシユ
程ｊ女のものか用いられる。The iron powder, silicon iron powder, potassium permanganate, red phosphorus, and combustion modifier of the present invention are used in amounts of about 100 to 400 mesh in order to prevent redox reactions and separation of the respective components. .
本発明において、過マンガン酸カリウムは燃焼反応を決
定するもので、１０〜２５重量％が望ましく、２５重量
％を超えると燃焼反応が激しくなり取扱い」−の安全性
が低下する場合がある。また、１０重量％未満になると
発熱量が小さくなり、飲食物の加熱に適さない。In the present invention, potassium permanganate determines the combustion reaction, and is preferably in the range of 10 to 25% by weight; if it exceeds 25% by weight, the combustion reaction becomes intense and safety in handling may decrease. Moreover, if it is less than 10% by weight, the calorific value will be small, making it unsuitable for heating food and drinks.
また、ケイ素鉄粉末も発熱量のコントロールに寄与して
おり、必要に応して２０重量％まで添加される。ケイ素
鉄粉末は添加量の増加につれて発熱量が大きくなるが、
２０重量％を超えると燃焼時に溶融して、発熱剤組成物
を収納した容器から流れ出すこととがあり、取扱い上危
険である。Silicon iron powder also contributes to controlling the calorific value, and is added up to 20% by weight if necessary. The calorific value of silicon iron powder increases as the amount added increases, but
If it exceeds 20% by weight, it may melt during combustion and flow out of the container containing the exothermic composition, making it dangerous to handle.
次に、赤リンは発熱量をコントロールするたけでなく石
火性を良好にするので、小さな台火エネルギーを有する
石火装置でも着火かｉ＋Ｊ能となる。Next, since red phosphorus not only controls the calorific value but also improves the fireability, even a rockfire device with a small torch energy can be ignited with i+J ability.
本発明に用いられる燃焼調整剤は、リン酸アンモニウム
、シュウ酸アンモニウムなどのアンモニウム塩、尿素、
チオ尿素などのアミン類、炭酸カルシウムなどの炭酸塩
等、一般に難燃剤、防炎剤として用いられるものであれ
ば良い。The combustion modifier used in the present invention includes ammonium salts such as ammonium phosphate and ammonium oxalate, urea,
Any material generally used as a flame retardant or flame retardant may be used, such as amines such as thiourea or carbonates such as calcium carbonate.
本発明の発熱剤組成物は、上記組成物のほかに無機不活
性物を加えることができる。無機不活性物としては、ケ
イ砂、ガラス粉、アルミナなど高温でガスや蒸気を発生
しないものが好ましい。In addition to the above composition, an inorganic inert substance can be added to the exothermic composition of the present invention. The inorganic inert material is preferably one that does not generate gas or steam at high temperatures, such as silica sand, glass powder, and alumina.
本発明の発熱剤組成物の製造方法は、特に限定されるも
のではないが、例えば鉄粉末とケイ素鉄粉末と赤リンと
燃焼調整剤をあらかじめ混合し、次いで過マンガン酸カ
リウムとを均一に混合することによって得られる。The method for producing the exothermic composition of the present invention is not particularly limited, but for example, iron powder, silicon iron powder, red phosphorus, and a combustion modifier are mixed in advance, and then potassium permanganate is mixed uniformly. obtained by doing.
実施例１〜８
鉄粉末またはケイ素鉄粉末と赤リン、または燃焼調整剤
をあらかじめ均一に混合しておき、次いで過マンガン酸
カリウムを均一に混合する。Examples 1 to 8 Iron powder or silicon iron powder and red phosphorus or a combustion modifier are uniformly mixed in advance, and then potassium permanganate is uniformly mixed.
−５＝
次に、混合した試料１０ｇをスレート板の上に円錐状に
のせ、石火性と溶融状態を評価する。-5= Next, 10 g of the mixed sample was placed in a conical shape on a slate plate, and the pyrotechnic properties and melting state were evaluated.
石火性は、チャツカマン（■東海）の炎を５秒間あて、
それ以内に石火するものを良好と判定した。また溶融状
態は、着火する前の形状を保っているものを良好とした
。For stone fire, apply the flame of Chutkaman (■Tokai) for 5 seconds,
Those that erupted within this time were judged to be good. The melted state was evaluated as good if it maintained its shape before ignition.
木粉燃焼試験は、発熱剤組成物と木粉（桐木粉、１０〜
２０メツンユ）を４＝１の重量比で混合し、円錐状にス
レート板上に積んだ後、すその円周に配置したニクロム
線を赤熱させて着火させる。１０秒間赤熱したニクロム
線を接触させたあと除去し、その後炎を上げずにくすぶ
るものは、取扱い上の安全性が高く良好な発熱剤と判定
した。一方、連続的または途中で炎を上げて燃えるもの
は、取扱い上の安全性が低いと判定した。The wood powder combustion test was conducted using a heat generating agent composition and wood powder (paulownia wood powder, 10~
20 Metsuyu) were mixed at a weight ratio of 4=1, stacked in a conical shape on a slate board, and then ignited by making a nichrome wire placed around the circumference of the base red hot. If a red-hot nichrome wire is brought into contact with the wire for 10 seconds and then removed, and if it smolders without emitting a flame, it is judged to be a good exothermic agent with high safety in handling. On the other hand, items that burn continuously or with flames during the process were judged to have low handling safety.
また、発熱量は深さ８０ｍｍ、径２０ｍｍのアルミ製容
器に発熱剤組成物３０ｇを入れ、２００ｃｃの水（２０
℃）の入ったガラスビーカーに入れて発熱剤組成物に導
火線で石火して加熱し、５５℃を越−６＝
えたものを良好とした。In addition, the calorific value was determined by placing 30 g of the exothermic composition in an aluminum container with a depth of 80 mm and a diameter of 20 mm, and adding 200 cc of water (20
The exothermic composition was placed in a glass beaker containing a temperature of 55°C and heated with a fuse, and those that exceeded -6 = 55°C were considered good.
比較例１〜３ 実施例１〜８と同様の評価を行った。Comparative examples 1 to 3 Evaluations similar to Examples 1 to 8 were performed.
以上の結果を表に示す。The above results are shown in the table.
＝ ７−
［効 果コ
本発明の発熱剤組成物は、酸化性物質か少ない領域にお
いても、希火性が優れているたけでなく、燃焼中に溶融
することもない。また、燃焼調整剤を含むものは、他の
１−ＩＪ燃物との接触において、急激に燃え上がるのを
防止するため、異常時に有効である。= 7- [Effects] The exothermic composition of the present invention not only has excellent rarefiring properties even in areas with a small amount of oxidizing substances, but also does not melt during combustion. Furthermore, those containing a combustion modifier are effective in times of abnormality because they prevent sudden flare-ups upon contact with other 1-IJ fuels.
更に、赤リンの量の加減により、燃焼速度とｉｒｊ火性
をコントロールすることもできるので、飲食品用の容器
と組合せて、加熱用途に用いれば最適である。Furthermore, the combustion rate and IRJ flammability can be controlled by adjusting the amount of red phosphorus, so it is optimal if used for heating purposes in combination with food and drink containers.
特許出願人 旭化成工業株式会社 代理人 弁理士 小 松 秀 岳Patent applicant: Asahi Kasei Industries, Ltd. Agent Patent Attorney Hidetake Komatsu
Claims (2)
物であって、鉄粉末が５５〜８５重量％、ケイ素鉄粉末
が０〜２０重量％、過マンガン酸カリウムが１０〜２５
重量％、赤リン０．１〜３．０重量％の混合物からなる
ことを特徴とする発熱剤組成物。(1) A heat generating composition mainly composed of metal powder and an oxidizing substance, in which iron powder is 55 to 85% by weight, silicon iron powder is 0 to 20% by weight, and potassium permanganate is 10 to 25% by weight.
% by weight, and red phosphorus in a mixture of 0.1 to 3.0% by weight.
物であって、鉄粉末が５５〜８５重量％、ケイ素鉄粉末
が０〜２０重量％、過マンガン酸カリウムが１０〜２５
重量％、赤リン０．１〜３．０重量％、燃焼調整剤が０
．１〜２．０重量％の混合物からなることを特徴とする
発熱剤組成物。(2) A heat generating composition mainly composed of metal powder and an oxidizing substance, including 55 to 85% by weight of iron powder, 0 to 20% by weight of silicon iron powder, and 10 to 25% by weight of potassium permanganate.
wt%, red phosphorus 0.1-3.0 wt%, combustion modifier 0
．． A heating agent composition comprising a mixture of 1 to 2.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63112571A JPH01284582A (en) | 1988-05-11 | 1988-05-11 | Safe heat generating agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63112571A JPH01284582A (en) | 1988-05-11 | 1988-05-11 | Safe heat generating agent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01284582A true JPH01284582A (en) | 1989-11-15 |
Family
ID=14590043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63112571A Pending JPH01284582A (en) | 1988-05-11 | 1988-05-11 | Safe heat generating agent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01284582A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005529216A (en) * | 2002-06-05 | 2005-09-29 | ジ アディショナル ディレクター（アイピーアール）、ディフェンス リサーチ アンド デベロップメント オーガニゼイション | Electrochemically reacting composition and process for producing the same |
| JP2007511644A (en) * | 2003-11-13 | 2007-05-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Composition and method for reducing the fire hazard of flammable refrigerants |
| CN101925309A (en) * | 2008-01-22 | 2010-12-22 | 斯泰格莫德有限公司 | Smoking article |
| CN103205245A (en) * | 2013-04-25 | 2013-07-17 | 青岛大学 | Preparation method of Fe-KMnO4-MnO2 spontaneous heating material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6318579U (en) * | 1986-07-17 | 1988-02-06 |
-
1988
- 1988-05-11 JP JP63112571A patent/JPH01284582A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6318579U (en) * | 1986-07-17 | 1988-02-06 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005529216A (en) * | 2002-06-05 | 2005-09-29 | ジ アディショナル ディレクター（アイピーアール）、ディフェンス リサーチ アンド デベロップメント オーガニゼイション | Electrochemically reacting composition and process for producing the same |
| JP4731905B2 (en) * | 2002-06-05 | 2011-07-27 | ジ アディショナル ディレクター（アイピーアール）、ディフェンス リサーチ アンド デベロップメント オーガニゼイション | Electrochemically reacting composition and process for producing the same |
| JP2007511644A (en) * | 2003-11-13 | 2007-05-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Composition and method for reducing the fire hazard of flammable refrigerants |
| CN101925309A (en) * | 2008-01-22 | 2010-12-22 | 斯泰格莫德有限公司 | Smoking article |
| JP2011509667A (en) * | 2008-01-22 | 2011-03-31 | ステージモード オイ | Smoking |
| JP2015051015A (en) * | 2008-01-22 | 2015-03-19 | ステージモード オイＳｔａｇｅｍｏｄｅ Ｏｙ | Smoking material |
| CN103205245A (en) * | 2013-04-25 | 2013-07-17 | 青岛大学 | Preparation method of Fe-KMnO4-MnO2 spontaneous heating material |
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