JPS6248714B2 - - Google Patents
Info
- Publication number
- JPS6248714B2 JPS6248714B2 JP10373679A JP10373679A JPS6248714B2 JP S6248714 B2 JPS6248714 B2 JP S6248714B2 JP 10373679 A JP10373679 A JP 10373679A JP 10373679 A JP10373679 A JP 10373679A JP S6248714 B2 JPS6248714 B2 JP S6248714B2
- Authority
- JP
- Japan
- Prior art keywords
- iron
- added
- water
- metal
- reaction
- 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.)
- Expired
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- -1 hydroxylamine inorganic acid salt Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- 230000020169 heat generation Effects 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 229910001006 Constantan Inorganic materials 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Thermotherapy And Cooling Therapy Devices (AREA)
Description
【発明の詳細な説明】
最近、鉄の酸化反応時の生成熱を利用した使い
捨てタイプの懐炉が旅行、レジヤー用として市場
で人気を得ている。これらに利用されている発熱
組成物は、主成分である鉄粉に金属の塩化物ある
いは硫酸塩を反応助成物として添加し、水および
酸素と反応させて発熱させるものである。しか
し、これらの発熱組成物は反応初期の温度特性を
得るために、主成分である鉄と、反応助成物とし
て使用する金属の塩化物あるいは硫酸塩の金属イ
オンのイオン化傾向による交換反応を利用するた
め、(例えばFe゜+Cu++→Fe+++Cu゜)反応助
成物として利用できる金属塩は著しく制限を受
け、かつこれらの金属塩は一般に貴な金属である
ことからコストが高いという問題点を有してい
る。また塩化物あるいは硫酸塩を構成する金属に
おいて鉄よりもイオン化傾向が大なる金属では初
期の交換反応は行なわれず、温度特性が著しく悪
く、発熱剤としての効能を発揮し得ない。DETAILED DESCRIPTION OF THE INVENTION Recently, disposable type hand warmers that utilize the heat generated during the oxidation reaction of iron have become popular in the market for travel and leisure use. The exothermic compositions used in these applications are those in which a metal chloride or sulfate is added as a reaction aid to iron powder, which is the main component, and the mixture reacts with water and oxygen to generate heat. However, in order to obtain the temperature characteristics at the initial stage of the reaction, these exothermic compositions utilize an exchange reaction between the main component iron and the ionization tendency of the metal ion of the metal chloride or sulfate used as a reaction aid. Therefore, the metal salts that can be used as reaction aids (for example, Fe゜ + Cu ++ → Fe ++ + Cu゜) are severely limited, and these metal salts are generally noble metals, so they are expensive. have. Furthermore, among the metals constituting the chloride or sulfate, if the metal has a greater ionization tendency than iron, the initial exchange reaction will not take place, the temperature characteristics will be extremely poor, and the metal will not be effective as a heat generating agent.
本発明は上記の点に鑑み、水溶性ヒドロキシル
アミン無機酸塩を反応開始剤として添加し、かつ
金属の酸化物を補助の反応助成物として添加する
ことにより、発熱温度が高く、かつ発熱時間も長
い発熱組成物を提供するものである。 In view of the above points, the present invention provides a high exothermic temperature and short exothermic time by adding a water-soluble hydroxylamine inorganic acid salt as a reaction initiator and a metal oxide as an auxiliary reaction aid. It provides a long exothermic composition.
以下、本発明の詳細について説明する。本発明
の発熱組成物の主成分である鉄については発熱が
可能な鉄材であればよく、形状としては粉体、粒
体などが使用される。また反応助成物としての金
属の塩化物あるいは硫酸塩は高純度のものを使用
する必要はなく、その添加量は鉄100重量部に対
して0.5〜20重量部程度である。この場合、コス
トの安いアルカリ金属やアルカリ土類金属の塩を
用いればよく、また海水等を加えることも可能で
ある。 The details of the present invention will be explained below. Iron, which is the main component of the heat generating composition of the present invention, may be any iron material that can generate heat, and may be in the form of powder, granules, etc. Furthermore, it is not necessary to use a highly pure metal chloride or sulfate as a reaction aid, and the amount added is approximately 0.5 to 20 parts by weight per 100 parts by weight of iron. In this case, inexpensive alkali metal or alkaline earth metal salts may be used, and seawater or the like may also be added.
また反応開始剤としての水溶性ヒドロキシルア
ミン無機酸塩および補助の反応助成物としての金
属の酸化物は、特に高純度のものを使用する必要
はなく、その添加量は鉄100重量部に対して水溶
性ヒドロキシル無機酸塩は0.5重量部以上で、か
つ金属の酸化物は1〜20重量部で充分である。 Furthermore, it is not necessary to use particularly high-purity water-soluble hydroxylamine inorganic acid salts as a reaction initiator and metal oxides as auxiliary reaction aids, and the amount added is limited to 100 parts by weight of iron. It is sufficient to use 0.5 parts by weight or more of the water-soluble hydroxyl inorganic acid salt and 1 to 20 parts by weight of the metal oxide.
また水としては一般に用いられているものであ
ればよく、その添加量は鉄100重量部に対して10
〜100重量部であり、この場合、海水も可能であ
る。また水を含浸し得る保水材としての素灰、活
性炭などの炭素、シリカゲル、木粉などの添加量
は鉄100重量部に対して10〜100重量部が最適であ
る。 In addition, any commonly used water may be used, and the amount added is 10 parts by weight per 100 parts by weight of iron.
~100 parts by weight, in which case seawater is also possible. The optimal amount of water-retaining materials that can be impregnated with water, such as raw ash, carbon such as activated carbon, silica gel, and wood powder, is 10 to 100 parts by weight per 100 parts by weight of iron.
さらに酸素としては一般的に空気を用いる。 Furthermore, air is generally used as oxygen.
次に本発明の発熱組成物を懐炉として応用した
場合の実施例について説明する。まず発熱組成物
を入れる袋は、不織布の内面を厚さ30μのポリエ
チレンシートでラミネートした大きさが120×85
mmのものを用いた。また発熱組成物の混合比は鉄
粉30g、保水材として素灰10g、反応開始剤とな
る水溶性ヒドロキシルアミン無機酸塩として塩酸
ヒドロキシルアミン0.5g、水15c.c.、金属の酸化
物として酸化銅1.5g、鉄よりもイオン化傾向が
大なる金属の塩化物としてNac12gである。これ
らの混合物を上記袋に入れ、そして袋の開口部を
ヒートシールにより密封し、懷炉としての発熱特
性(発熱温度−発熱時間特性)を測定した。この
場合、発熱温度の測定は銅コンスタンタン熱電対
を用い、気温25℃、湿度45%RHの恒温恒湿室で
行なつた。 Next, an example in which the exothermic composition of the present invention is applied as a hand warmer will be described. First, the bag to contain the exothermic composition is made of a non-woven fabric laminated with a 30μ thick polyethylene sheet and has a size of 120 x 85 mm.
mm was used. The mixing ratio of the exothermic composition is 30 g of iron powder, 10 g of raw ash as a water-retaining material, 0.5 g of hydroxylamine hydrochloride as a water-soluble hydroxylamine inorganic acid salt serving as a reaction initiator, 15 c.c. of water, and oxidation as a metal oxide. 1.5g of copper, 12g of Nac as a chloride of a metal with a greater tendency to ionize than iron. These mixtures were placed in the bag, and the opening of the bag was sealed by heat sealing, and the heat generation characteristics (heat generation temperature - heat generation time characteristics) as a sulfur furnace were measured. In this case, the heat generation temperature was measured using a copper constantan thermocouple in a constant temperature and humidity room with an air temperature of 25°C and a humidity of 45% RH.
なお、第1図は反応開始剤を添加しない場合A
と、反応開始剤は添加しているが、酸化銅は添加
していない場合Bと、反応開始剤、酸化銅とも添
加した場合Cの発熱特性の比較を示したもので、
この第1図からも明らかなように、反応開始剤を
添加しない場合Aは、発熱が始まるのが遅く、か
つ発熱温度も低く、発熱剤としての効果はほとん
どない。また酸化銅を添加していない場合Bは、
酸化銅を添加している場合Cに比べ、若干発熱温
度が低く、かつ初期の温度特性も悪い。 In addition, Figure 1 shows A when no reaction initiator is added.
This shows a comparison of the exothermic properties of B, where a reaction initiator is added but no copper oxide, and C, where both a reaction initiator and copper oxide are added.
As is clear from FIG. 1, in the case where no reaction initiator is added, the heat generation starts slowly and the heat generation temperature is low, so that it has almost no effect as an exothermic agent. In addition, in case B does not contain copper oxide,
When copper oxide is added, the exothermic temperature is slightly lower than that of C, and the initial temperature characteristics are also poor.
第2図は従来使用されている塩化銅を反応助成
物として用いている従来品Dと、上記本発明の実
施例品Eとの低温時における発熱特性の比較を示
したもので、この第2図からも明らかなように、
従来品Dは懐炉として使用した場合の適温範囲X
(45℃〜65℃)が得られる時間は約5時間程度で
あるのに対し、本発明の実施例品Eは約10時間以
上である。このことからも本発明の実施例品Eは
低温においても性能が優れており、特に寒冷地や
冬期の屋外での使用に有効である。またこの低温
の発熱温度の測定は銅コンスタンタン熱電対を用
い、気温5℃、湿度60%RHの恒温恒湿室で行な
つた。 Figure 2 shows a comparison of the exothermic properties at low temperatures between conventional product D, which uses conventionally used copper chloride as a reaction aid, and the above-mentioned example product E of the present invention. As is clear from the figure,
Conventional product D has an appropriate temperature range X when used as a pocket warmer.
(45°C to 65°C) is about 5 hours, whereas Example Product E of the present invention takes about 10 hours or more. From this fact, Example Product E of the present invention has excellent performance even at low temperatures, and is particularly effective for use in cold regions or outdoors in winter. The low-temperature heat generation temperature was measured using a copper constantan thermocouple in a constant temperature and humidity room with an air temperature of 5°C and a humidity of 60% RH.
なお、上記実施例においては、金属の酸化物と
して酸化銅を用いたものについて説明したが、こ
れ以外としてはマンガン、クロム、カルシウム、
コバルト、ニツケル、マグネシウムの酸化物が有
効であり、これらを単独あるいは複数の混合物と
して添加しても上記実施例と同様の作用効果を奏
するものである。 In the above example, copper oxide was used as the metal oxide, but other metal oxides include manganese, chromium, calcium,
Oxides of cobalt, nickel, and magnesium are effective, and even if they are added alone or as a mixture of a plurality of them, the same effects as in the above embodiments can be obtained.
以上のように本発明の発熱組成物は、水溶性ヒ
ドロキシルアミン無機酸塩を反応開始剤として添
加し、かつ金属の酸化物を補助の反応助成物とし
て添加しているため、発熱の立ち上がりが速く、
かつ発熱温度も高く、しかも懐炉として使用した
場合の適温範囲の得られる発熱時間も長い等種々
の優れた特長を有する。 As described above, in the exothermic composition of the present invention, the water-soluble hydroxylamine inorganic acid salt is added as a reaction initiator, and the metal oxide is added as an auxiliary reaction aid, so that the exothermic composition quickly generates heat. ,
It also has various excellent features, such as a high heat generation temperature and a long heat generation time that provides an appropriate temperature range when used as a hand warmer.
第1図は本発明の実施例品と、酸化銅を添加し
ていないものあるいは反応開始剤を添加していな
いものとの発熱特性の比較を示すグラフ、第2図
は従来品と本発明の実施例品との低温時における
発熱特性の比較を示すグラフである。
Figure 1 is a graph showing a comparison of exothermic characteristics between the example product of the present invention and the product without copper oxide or reaction initiator added, and Figure 2 is a graph showing the comparison between the conventional product and the product of the present invention. It is a graph showing a comparison of heat generation characteristics at low temperatures with Example products.
Claims (1)
塩化物または硫酸塩を有効成分とし、かつこの有
効成分に金属の酸化物を補助の反応助成物として
添加するとともに、水溶性ヒドロキシルアミン無
機酸塩を反応開始剤として添加し、水および酸素
と反応して発熱することを特徴とする発熱組成
物。 2 前記金属の酸化物は銅、マンガン、クロム、
カルシウム、コバルト、ニツケル、マグネシウム
からなる群の酸化物であつて、これらを単独ある
いは複数の混合物として添加してなる特許請求の
範囲第1項記載の発熱組成物。[Scope of Claims] 1 Iron and a chloride or sulfate of a metal with a greater ionization tendency than iron are used as active ingredients, and a metal oxide is added to this active ingredient as an auxiliary reaction aid, and a water-soluble 1. A heat-generating composition containing a hydroxylamine inorganic acid salt as a reaction initiator, which reacts with water and oxygen to generate heat. 2 The oxides of the metals include copper, manganese, chromium,
2. The exothermic composition according to claim 1, which is an oxide of the group consisting of calcium, cobalt, nickel, and magnesium, and is added singly or as a mixture of a plurality of these.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10373679A JPS5628272A (en) | 1979-08-15 | 1979-08-15 | Pyrogenic composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10373679A JPS5628272A (en) | 1979-08-15 | 1979-08-15 | Pyrogenic composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5628272A JPS5628272A (en) | 1981-03-19 |
JPS6248714B2 true JPS6248714B2 (en) | 1987-10-15 |
Family
ID=14361907
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10373679A Granted JPS5628272A (en) | 1979-08-15 | 1979-08-15 | Pyrogenic composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5628272A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024014022A1 (en) * | 2022-07-11 | 2024-01-18 | Jfeスチール株式会社 | Iron-based powder for oxygen reaction agent, and oxygen reaction agent |
-
1979
- 1979-08-15 JP JP10373679A patent/JPS5628272A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5628272A (en) | 1981-03-19 |
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