JPS5950905B2 - chemical warmer - Google Patents

Description

【発明の詳細な説明】 本発明は、被酸化剤として含イオウ化合物で加熱処理さ
れた鉄粉を用いることを特徴とする被酸化剤の空気酸化
によつて生ずる熱を利用する化学カイロに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chemical body warmer that utilizes heat generated by air oxidation of an oxidized agent, which is characterized by using iron powder heat-treated with a sulfur-containing compound as the oxidized agent.

鉄の空気酸化によつて生ずる熱を利用する化学カイロは
、火を使わず安全で手軽に使用できることから、近年、
たとえば使い捨てカイロとして広く販売されている。Chemical body warmers, which utilize the heat generated by air oxidation of iron, have become popular in recent years because they are safe and easy to use without using fire.
For example, they are widely sold as disposable body warmers.

そのような化学カイロは、鉄のほかに水、金属中性塩、
炭素質物質、保水剤などが配合された混合物を袋体に封
入することにより製造されている。鉄としては反応面積
を大きくするなどして酸化反応をスムーズに行なうため
に粒状または粉状のものが用いられ、さらに還元法によ
つてえられた還元鉄粉が一般に用いられている。In addition to iron, such chemical body warmers contain water, metal neutral salts,
It is manufactured by enclosing a mixture containing carbonaceous material, water retention agent, etc. into a bag. Granular or powdered iron is used in order to increase the reaction area and perform the oxidation reaction smoothly, and reduced iron powder obtained by a reduction method is generally used.

しかし、鉄の空気酸化という反応自体が本来激しいもの
ではないため、平衡温度（一般に５０〜６０℃）に達す
るまで約３〜４時間を必要としている。However, since the reaction itself of air oxidation of iron is not inherently violent, it takes about 3 to 4 hours to reach the equilibrium temperature (generally 50 to 60°C).

また寒冷地においてはさらに発熱開始時の温度の立上り
がわるく、役に立たないこともある。本発明の目的は発
熱開始時の温度の立上りが改善された化学カイロを提供
することを目的とするものであり、本発明者らは被酸化
剤である鉄粉に着目し、その改質につて種々研究を重ね
た結果、含イオウ化合物で加熱処理した鉄粉を被酸化剤
として用いるときは、発熱開始時の立上りがきわめて速
く、平衡温度に達するまでの時間が従来の未処理の鉄粉
に比して１／２〜１／１０に短縮される化学カイロがえ
られることを見出し、本発明を完成した。本発明に用い
る含イオウ化合物としては広範囲のものが使用できるが
、価格、入手のしやすさ、取り扱いの安全性などの点か
ら、たとえば硫酸、チオ硫酸、亜硫酸、スルファミン酸
などのナトリ、ウム塩、アンモニウム塩などや硫化アン
モニウム、水硫化アンモニウム、ポリ硫化アンモニウム
などの硫化物などの無機含イオウ化合物、チオグリコー
ル酸、チオ尿素、ジエチルジチオカルバミン酸ナトリウ
ムなどの有機含イオウ化合物の１種′または２種以上が
好ましい。In addition, in cold regions, the rise in temperature at the start of heat generation is slow and may be useless. The purpose of the present invention is to provide a chemical body warmer with improved temperature rise at the start of heat generation. As a result of various studies, we found that when iron powder heat-treated with a sulfur-containing compound is used as an oxidizing agent, the rise at the start of heat generation is extremely fast, and it takes longer than conventional untreated iron powder to reach equilibrium temperature. The present invention was completed based on the discovery that it is possible to obtain a chemical body warmer that is shortened to 1/2 to 1/10 compared to the conventional method. A wide range of sulfur-containing compounds can be used as the sulfur-containing compound used in the present invention, but from the viewpoint of price, ease of availability, safety in handling, etc. , one or two types of inorganic sulfur-containing compounds such as ammonium salts, sulfides such as ammonium sulfide, ammonium hydrosulfide, and ammonium polysulfide, and organic sulfur-containing compounds such as thioglycolic acid, thiourea, and sodium diethyldithiocarbamate. The above is preferable.

それらのうち、とくに硫酸アンモニウムおよびチオ硫酸
アンモニウムが安全性の点から好ましい。イオウの単体
で処理された鉄粉を用いた化学カイロも同様に温度の立
上りを改善するが、取り扱５い性の点で本発明に用いる
含イオウ化合物の方が数段すぐれている。Among them, ammonium sulfate and ammonium thiosulfate are particularly preferred from the viewpoint of safety. A chemical warmer using iron powder treated with sulfur alone also improves temperature rise, but the sulfur-containing compound used in the present invention is much superior in terms of ease of handling.

本発明における鉄粉の含イオウ化合物による加熱処理方
法は、たとえば含イオウ化合物が常温で固体であるばあ
い、鉄粉と含イオウ化合物の粉末とを均一に混合し、つ
いでそれらを加熱する方法、含イオウ化合物をその溶剤
に溶かし、その溶液を鉄粉に塗布するかまたは鉄粉を溶
液中に浸漬したのち乾燥して鉄粉表面を均一にコーテイ
ングし、ついで加熱する方法、含イオウ化合物をその溶
剤に溶かし、えられた溶液中で加熱する方法などが採用
される。The method of heat treating iron powder with a sulfur-containing compound in the present invention includes, for example, when the sulfur-containing compound is solid at room temperature, a method of uniformly mixing the iron powder and the powder of the sulfur-containing compound, and then heating them; A method in which a sulfur-containing compound is dissolved in the solvent and the solution is applied to the iron powder, or the iron powder is immersed in the solution and then dried to uniformly coat the surface of the iron powder, and then heated. The method used is to dissolve it in a solvent and heat it in the resulting solution.

含イオウ化合物が常温で液体のばあいは、鉄粉に含イオ
ウ化合物の液または溶液を付着させて加熱すればよい。
含イオウ化合物の使用量は、含イオウ化合物の種類、鉄
粉の種類や粒度、処理温度、処理方法などによつて異な
るが、一般に少量でよい。If the sulfur-containing compound is liquid at room temperature, the liquid or solution of the sulfur-containing compound may be applied to iron powder and then heated.
The amount of the sulfur-containing compound to be used varies depending on the type of sulfur-containing compound, the type and particle size of the iron powder, the treatment temperature, the treatment method, etc., but generally a small amount is sufficient.

たとえば鉄粉２００ｇに対して硫酸アンモニウムのばあ
い０．０１〜９０ｇ用いればよく、チオ硫酸アンモニウ
ムのばあい０．００５〜５０ｇ、スルフアミン酸アンモ
ニウムのばあい０．０７〜８０ｇで充分である。処理温
度も含イオウ化合物の種類、処理方法、処理時間などに
より異なるが、通常１００〜４５０℃で１０分間〜３時
間処理を行なえばよい。本発明に用いる含イオウ化合物
で加熱処理された鉄粉は、その表面の少なくとも一部が
硫化鉄に変化しているものと考えられるが、いまだ明ら
かではない。For example, it is sufficient to use 0.01 to 90 g of ammonium sulfate per 200 g of iron powder, 0.005 to 50 g of ammonium thiosulfate, and 0.07 to 80 g of ammonium sulfamate. Although the treatment temperature also varies depending on the type of sulfur-containing compound, treatment method, treatment time, etc., the treatment may normally be carried out at 100 to 450° C. for 10 minutes to 3 hours. It is thought that at least a portion of the surface of the iron powder heat-treated with the sulfur-containing compound used in the present invention has been changed to iron sulfide, but this is not clear yet.

処理する鉄粉としては、たとえば還元鉄粉やアトマイズ
法によりえられる鉄粉などがあげられる。Examples of the iron powder to be treated include reduced iron powder and iron powder obtained by an atomization method.

そられのうち還元鉄粉がとくに好ましい。また粒度が小
さくなる程立上りの時間が短縮される。粒度の適当な範
囲は３２メツシユパス、好まし５くは８０〜１４５メツ
シユであつて、それ以上に粒度が小さいものでは作業性
がわるくなるので好ましくない。鉄の空気酸化によつて
生ずる熱を利用する化学カイロには、前記のごとく鉄の
ほかに水、金属中５性塩、炭素質物質、保水剤などの成
分が配合されているが、本発明においても同様の成分が
配合される。Among them, reduced iron powder is particularly preferred. Also, the smaller the particle size, the shorter the rise time. A suitable range of particle size is 32 mesh passes, preferably 5 to 145 meshes, and smaller particle sizes are not preferred because workability deteriorates. Chemical body warmers that utilize the heat generated by air oxidation of iron contain ingredients such as water, pentametal salts, carbonaceous substances, and water retention agents in addition to iron as described above. Similar ingredients are also blended in.

金属中性塩としては塩化ナトリウム、塩化カリウム、塩
化カルシウムなどがあげられるが、価格４その他の点か
ら塩化ナトリウムが好ましい。Examples of neutral metal salts include sodium chloride, potassium chloride, calcium chloride, etc., but sodium chloride is preferred from the viewpoint of cost and other factors.

炭素質物質は酸化触媒として用いるものであり、たとえ
ば活性炭粉が好ましいが、適宜アン殻炭粉などに置き換
えてもよい。保水剤としては、木屑、バーミキユライト
、繊維粉、高吸水性樹脂またはそれらの混合物があげら
れる。また未処理鉄粉のみを用いるばあいガスが発生す
るが、従来その発生を抑えるためにガス発生抑制剤とし
て水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリ
ウム、炭酸ナトリウム、水酸化力ルシウム、炭酸カルシ
ウム、プロピオン酸ナトリウムなどの無機または有機の
アルカリまたはアルカリ弱酸塩などを配合していた。The carbonaceous material is used as an oxidation catalyst, and, for example, activated carbon powder is preferred, but it may be replaced with unshelled carbon powder or the like as appropriate. Examples of water retention agents include wood chips, vermiculite, fiber powder, superabsorbent resins, or mixtures thereof. In addition, gas is generated when using only untreated iron powder, but in order to suppress the generation, conventional gas generation suppressants are used such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, lucium hydroxide, and calcium carbonate. , inorganic or organic alkali or weak alkali salts such as sodium propionate.

しかし、そのようなガス発生抑制剤を添加すると発熱反
応が若干損なわれることがある。ところが、本発明で用
いる含イオウ化合物で処理された鉄粉を用いるときには
ガスの発生が少なくなるので、とくにガス発生抑制剤を
用いる必要はない。しかし、ガス抑制剤を用いることを
制限するものではない。本発明において含イオウ化合物
で処理されていない通常の鉄粉を含イオウ化合物で処理
された鉄粉と併用してもよい。However, the addition of such gassing inhibitors may slightly impair the exothermic reaction. However, when iron powder treated with a sulfur-containing compound used in the present invention is used, less gas is generated, so there is no need to use a gas generation inhibitor. However, this does not limit the use of gas suppressants. In the present invention, ordinary iron powder that has not been treated with a sulfur-containing compound may be used in combination with iron powder that has been treated with a sulfur-containing compound.

配合は通常の鉄粉／含イオウ化合物で処理された鉄粉が
９９／１〜０〜１００（重量比）の範囲で行うことがで
きるが、含イオウ化合物で処理された鉄粉の量が少なく
なれば発熱開始時の立上りがしだいに遅くなり、また水
素ガスなどのガスが発生する傾向にあるのであらかじめ
ガス発生抑制剤を加えておく。本発明の化学カイロにお
ける好ましい配合割合は含イオウ化合物で処理された鉄
粉１００部（重量部、以下同様）に対して水２０〜７０
部、炭素質物質０．１〜８０部金属中性塩１〜２０部、
保水剤１〜５００部である。The ratio of ordinary iron powder to iron powder treated with a sulfur-containing compound can be in the range of 99/1 to 0 to 100 (weight ratio), but if the amount of iron powder treated with a sulfur-containing compound is small. If this happens, the start of heat generation will gradually slow down, and gases such as hydrogen gas will tend to be generated, so add a gas generation inhibitor in advance. The preferred blending ratio in the chemical body warmer of the present invention is 20 to 70 parts water to 100 parts (parts by weight, same hereinafter) of iron powder treated with a sulfur-containing compound.
parts, carbonaceous material 0.1-80 parts metal neutral salt 1-20 parts,
The water retention agent is 1 to 500 parts.

また要すれば、前記ガス発生抑制剤を含イオウ化合物で
処理された鉄粉１００部に対して０．１〜４部配合して
もよい。なお、前記のごとく通常の鉄粉を前記の範囲で
併用してもよい。また要すれば酸化剤を適当量配合して
もよい。If necessary, 0.1 to 4 parts of the gas generation inhibitor may be added to 100 parts of iron powder treated with a sulfur-containing compound. In addition, as mentioned above, ordinary iron powder may be used in combination within the above range. Further, if necessary, an appropriate amount of an oxidizing agent may be added.

以上の混合物を封入する袋体としては、通常通気性を有
する内袋と非通気性の外袋からなるものが用いられる。
本発明の化学カイロに用いる外袋としては、非通気性の
ものであればそのほかの制限はなく、ラミネートされて
いるものでもよい。The bag for enclosing the above-mentioned mixture is usually one consisting of a breathable inner bag and a non-breathable outer bag.
The outer bag used in the chemical body warmer of the present invention is not subject to any other restrictions as long as it is non-breathable, and may be laminated.

好ましいものとしては、たとえば０ＰＰ．ＣＰＰ、ポリ
塩化ビニリデンなどにより防湿処理されたナイロン、ポ
リエステル、ポリプロピレンフイルム、さらにはアルミ
箔またはアルミ蒸着されたプラスチツクフイルムなどが
あげられる。この種の化学カイロの内袋は通常不織布が
用いられているが、通気性を有するものであればよく、
たとえば布、紙なども用いられうる。Preferably, for example, 0PP. Examples include nylon, polyester, and polypropylene films that have been moisture-proofed with CPP, polyvinylidene chloride, and the like, as well as aluminum foil or plastic films coated with aluminum. The inner bag of this type of chemical warmer is usually made of non-woven fabric, but any material that is breathable may be used.
For example, cloth, paper, etc. can also be used.

つぎに製造例、実施例および比較例をあげて本発明の化
学カイロを説明するが、本発明はかかる実施例のみに限
定されるものではない。Next, the chemical body warmer of the present invention will be explained with reference to production examples, working examples, and comparative examples, but the present invention is not limited only to these examples.

製造例 １〜４ 還元鉄粉（粒度６０メツシユパス）２００ｇに硫酸アン
モニウム粉（粒度工００メツシユパス）を第１表に示す
量加え、硫酸アンモニウム粉が均一に分散するように充
分混合した。Production Examples 1 to 4 Ammonium sulfate powder (particle size 00 mesh pass) was added in the amount shown in Table 1 to 200 g of reduced iron powder (particle size 60 mesh pass), and the mixture was thoroughly mixed so that the ammonium sulfate powder was uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分間かけ
て第１表に示す温度に加熱し、その温度に３０分間保持
して硫酸アンモニウムで処理された鉄粉をえた。実施例
１〜４ 製造例１〜４でそれぞれえられた硫酸アンモニウム処理
された鉄粉２５ｇ、水１０．５ｇ、塩化ナトリウム１．
５ｇおよび木屑１０．５ｇを充分混合したのち、通気性
の袋体に封入し、それらの発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated for 30 minutes to the temperature shown in Table 1, and held at that temperature for 30 minutes to obtain iron powder treated with ammonium sulfate. Examples 1 to 4 25 g of ammonium sulfate-treated iron powder obtained in Production Examples 1 to 4, 10.5 g of water, and 1.5 g of sodium chloride.
After thoroughly mixing 5 g and 10.5 g of wood chips, the mixture was sealed in a breathable bag and the state of heat generation was examined.

袋体としてはナイロン不織布の内面にポリエチレンをラ
ミネートしたものの中央部に４．３ｍｍ幅、６ｍｍ間隔
で片面３１５個穿孔（０．３ｍｍ径の針使用）したもの
を用いた。The bag used was a nylon nonwoven fabric laminated with polyethylene on the inner surface, with 315 perforations on each side (using needles of 0.3 mm diameter) having a width of 4.3 mm and an interval of 6 mm in the center.

測定は封入後、ただちに数十回振り、毛布４枚を重ねた
上におき、熱電対を挾んだ上に毛布２枚を重ね、室内温
度（以下、室温という）が約８℃に保たれた室内で行な
つた。For measurements, immediately after sealing the tube, shake it several dozen times, place it on top of 4 blankets, and stack 2 blankets on top of the thermocouple to keep the room temperature (hereinafter referred to as room temperature) at approximately 8℃. It was held indoors.

それらの結果を第１表に示す。The results are shown in Table 1.

比較例 １ 硫酸アンモニウムで処理された鉄粉に代えて還元鉄を用
いたほかは実施例１と同様に配合、混合し、袋体に封入
してその発熱の立上り状態を実施例１と同様にして測定
した。Comparative Example 1 The mixture was blended and mixed in the same manner as in Example 1, except that reduced iron was used in place of the iron powder treated with ammonium sulfate, and the mixture was sealed in a bag and the heat generation state was controlled in the same manner as in Example 1. It was measured.

比較例 ２〜３ 硫酸アンモニウムで処理された鉄粉に代えて硫化第一鉄
（一級試薬、和光純薬工業（株）製）または黄鉄鉱を用
いたほかは実施例１と同様に配合、混合し、不織布の袋
体に封入してその発熱の立上り状態を実施例１と同様に
して測定した。Comparative Examples 2 to 3 Compounding and mixing in the same manner as in Example 1 except that ferrous sulfide (first class reagent, manufactured by Wako Pure Chemical Industries, Ltd.) or pyrite was used instead of iron powder treated with ammonium sulfate, It was sealed in a nonwoven fabric bag and the rise of heat generation was measured in the same manner as in Example 1.

比較例 ４ 硫酸アンモニウムで処理された鉄粉および塩化ナトリウ
ムに代えてそれぞれ未処理の還元鉄粉および硫酸第１鉄
を用いたほかは実施例１と同様に配合、混合し、不織布
製の袋体に封入してその発熱の立上り状態を実施例１と
同様にして測定した。Comparative Example 4 Compounding and mixing were carried out in the same manner as in Example 1, except that untreated reduced iron powder and ferrous sulfate were used in place of iron powder treated with ammonium sulfate and sodium chloride, respectively, and the mixture was molded into a nonwoven fabric bag. The sample was sealed and the rise of heat generation was measured in the same manner as in Example 1.

その結果、３０℃までは１０５分間、４０℃までは２０
０分間と、いずれも未処理の鉄粉を使用したもの（比較
例１）よりも遅くなつた。As a result, the temperature up to 30℃ was 105 minutes, and the temperature up to 40℃ was 20 minutes.
0 minutes, which was slower than that using untreated iron powder (Comparative Example 1).

製造例 ５〜９ 還元鉄粉（粒度６０メツシユパス）２００ｇにチオ硫酸
アンモニウム粉（チオ硫酸ナトリウムを約３０′重量％
含有、粒度２０メツシユパス）を第２表に示す量加え、
チオ硫酸アンモニウム粉が均一に分散するように充分混
合した。Production Examples 5 to 9 Add ammonium thiosulfate powder (approximately 30% by weight of sodium thiosulfate to 200g of reduced iron powder (particle size: 60 mesh).
Add the amount shown in Table 2,
The ammonium thiosulfate powder was thoroughly mixed so that it was evenly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
第２表に示す温度に加熱し、その温度に３０分間保持し
てチオ硫酸アンモニウムで処理された鉄粉をえた。実施
例 ５〜９ 製造例５〜９でそれぞれえられたチオ硫酸アンモニウム
で処理された鉄粉２５ｇ、水１０．５ｇ、塩化１ナトリ
ウム１．５ｇおよび木屑１０．５ｇを充分混合したのち
実施例１と同様の袋体に封入し、実施例１と同様にして
それらの発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated for 30 minutes to the temperature shown in Table 2, and held at that temperature for 30 minutes to obtain iron powder treated with ammonium thiosulfate. Examples 5 to 9 After thoroughly mixing 25 g of iron powder treated with ammonium thiosulfate obtained in Production Examples 5 to 9, 10.5 g of water, 1.5 g of monosodium chloride, and 10.5 g of wood chips, Example 1 and They were sealed in a similar bag and the rise of heat generation was examined in the same manner as in Example 1.

結果を第２表に示す。製造例 １０〜１４ 還元鉄粉（粒度６０メツシユパス）２００ｇにスルフア
ミン酸アンモニウム粉（粒度２０メツシユパス）を第３
表に示す量加え、スルフアミン酸アンモニウム粉が均一
に分散するように充分混合した。The results are shown in Table 2. Production Examples 10 to 14 Add ammonium sulfamate powder (particle size 20 mesh pass) to 200 g of reduced iron powder (particle size 60 mesh pass) in the third
The amount shown in the table was added and mixed thoroughly so that the ammonium sulfamate powder was uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
第３表に示す温度に加熱し、その温度に３０分間保持し
てスルフアミン酸アンモニウムで処理された鉄粉をえた
。朱 ３実施例 １０〜１４ 製造例１０〜１４でそれぞれえられたスルフアミン酸ア
ンモニウムで処理された鉄粉２５ｇ、水１０．５ｇ、塩
化ナトリウム１．５ｇおよび木屑１０．５ｇを充分混合
したのち実施例１と同様の袋体に封入し、実施例１と同
様にしてそれらの発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated for 30 minutes to the temperature shown in Table 3, and held at that temperature for 30 minutes to obtain iron powder treated with ammonium sulfamate. Vermilion 3 Examples 10 to 14 After thoroughly mixing 25 g of iron powder treated with ammonium sulfamate obtained in Production Examples 10 to 14, 10.5 g of water, 1.5 g of sodium chloride, and 10.5 g of wood chips, Examples were prepared. They were sealed in a bag similar to Example 1, and the rise of heat generation was examined in the same manner as in Example 1.

結果を第３表に示す。The results are shown in Table 3.

製造例 １５ 還元鉄粉（粒度６０メツシユパス）２００ｇに硫化アン
モニウム水溶液（和光純薬工業（株）製）を０．５ｇ加
え、硫化アンモニウム溶液が均一に付着するように充分
混合した。Production Example 15 0.5 g of ammonium sulfide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 200 g of reduced iron powder (particle size: 60 mesh pass), and the mixture was thoroughly mixed so that the ammonium sulfide solution was uniformly adhered.

えられた混合物をガラス製の容器に入れ、３０分かけて
２００℃に加熱し、その温度に３０分間保持して硫化ア
ンモニウムで処理された鉄粉をえた。実施例 １５ 製造例１５においてえられた硫化アンモニウムで処理さ
れた鉄粉２５ｇ、水１０．５ｇ、塩化ナトリウム１．５
ｇおよび木屑１０．５ｇを充分混合したのち実施例１と
同様の袋体に封入し、実施例１と同様にしてそのものの
発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated to 200° C. over 30 minutes, and held at that temperature for 30 minutes to obtain iron powder treated with ammonium sulfide. Example 15 25 g of iron powder treated with ammonium sulfide obtained in Production Example 15, 10.5 g of water, 1.5 g of sodium chloride
After fully mixing 10.5 g of wood chips and 10.5 g of wood chips, the mixture was sealed in the same bag as in Example 1, and the state of heat generation was examined in the same manner as in Example 1.

その結果、室温８℃のときの３０℃および４０℃までの
立上り時間はそれぞれ４５分および９５分であつた。As a result, when the room temperature was 8°C, the rise times to 30°C and 40°C were 45 minutes and 95 minutes, respectively.

製造例 １６〜１８ 還元鉄粉（粒度６０メツシユパス）２００ｇにチオグリ
コール酸液（和光純薬工業（株）製、試薬特級）を０．
６ｇ加え、チオグリコール酸液が均一に付着するように
充分混合した。Production Examples 16 to 18 0.0 g of thioglycolic acid solution (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added to 200 g of reduced iron powder (particle size 60 mesh pass).
6 g was added and mixed thoroughly so that the thioglycolic acid solution was uniformly adhered.

えられた混合物をガラス製の容器に入れ、３０分かけて
第４表に示す温度に加熱し、その温度に３０分間保持し
てチオグリコ噛専 ール酸で処理された鉄粉をえた。The resulting mixture was placed in a glass container, heated for 30 minutes to the temperature shown in Table 4, and held at that temperature for 30 minutes to obtain iron powder treated with thioglycolic acid.

実施例 １６〜１８ 製造例１６〜１８でそれぞれえられたチオグリコール酸
液で処理された鉄粉２５ｇ、水１０．５ｇ、塩化ナトリ
ウム１．５ｇおよび木屑１０．５ｇを充分混合したのち
実施例１と同様の袋体に封入し、実施例１と同様にして
それらの発熱の立上り状態を調べた。Examples 16 to 18 After thoroughly mixing 25 g of iron powder treated with the thioglycolic acid solution obtained in Production Examples 16 to 18, 10.5 g of water, 1.5 g of sodium chloride, and 10.5 g of wood chips, Example 1 was prepared. The samples were sealed in a bag similar to that of Example 1, and the rise of heat generation was examined in the same manner as in Example 1.

結果を第４表に示す。製造例 １９〜２１ 還元鉄粉（粒度６０メツシユパス）２００ｇにチオ尿素
粉（粒度２０メツシユパス）を０．４ｇ加え、チオ尿素
粉が均一に分散するように充分混合した。The results are shown in Table 4. Production Examples 19-21 0.4 g of thiourea powder (particle size 20 mesh pass) was added to 200 g of reduced iron powder (particle size 60 mesh pass), and the mixture was thoroughly mixed so that the thiourea powder was uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
第５表に示す温度に加熱し、その温度に３０分間保持し
てチオ尿素で処理された鉄粉をえた。→６実施例 １９
〜２１ 製造例１９〜２１でそれぞれえられたチオ尿素処理され
た鉄粉２５ｇ、水１０．５ｇ、塩化ナトリウム１．５ｇ
および木屑１０．５ｇを充分混合したのち実施例１と同
様にしてそれらの発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated for 30 minutes to the temperature shown in Table 5, and held at that temperature for 30 minutes to obtain iron powder treated with thiourea. →6 Example 19
~21 25 g of thiourea-treated iron powder, 10.5 g of water, and 1.5 g of sodium chloride obtained in Production Examples 19 to 21, respectively.
After sufficiently mixing 10.5 g of wood chips, the rise of heat generation was examined in the same manner as in Example 1.

結果を第５表に示す。製造例 ２２〜２４ 還元鉄粉（粒度６０メツシユパス）２００ｇにジエチル
ジチオカルバミン酸ナトリウム粉（粒度２０メツシユパ
ス）を０．７ｇ加え、ジエチルジチオカルバミン酸ナト
リウム粉が均一に分散するように充分混合した。The results are shown in Table 5. Production Examples 22 to 24 0.7 g of sodium diethyldithiocarbamate powder (particle size 20 mesh) was added to 200 g of reduced iron powder (particle size 60 mesh) and thoroughly mixed so that the sodium diethyldithiocarbamate powder was uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
第６表に示す温度に加熱し、その温度に３０分間保持し
てジエチルジチオカルバミン酸ナトリウムで処理された
鉄粉をえた。実施例 ２２〜２４ 製造例２２〜２４でそれぞれえられたジエチルジオカル
バミン酸ナトリウム処理された鉄粉２５ｇ、水１０．５
ｇ、塩化ナトリウム１．５ｇおよび本屑１０．５ｇを充
分混合したのち実施例１と同様の袋体に封入し、実施例
１と同様にしてそれらの発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated for 30 minutes to the temperature shown in Table 6, and held at that temperature for 30 minutes to obtain iron powder treated with sodium diethyldithiocarbamate. Examples 22-24 25 g of sodium diethyldiocarbamate-treated iron powder obtained in Production Examples 22-24, respectively, and 10.5 g of water.
After thoroughly mixing 1.5 g of sodium chloride and 10.5 g of book waste, the mixture was sealed in the same bag as in Example 1, and the rise of heat generation was examined in the same manner as in Example 1.

結果を第６表に示す。The results are shown in Table 6.

製造例 ２５ 還元鉄粉（粒度６０メツシユパス）２００ｇに硫酸ナト
リウム粉（粒度２０メツシユパス）を０．９ｇ加えく硫
酸ナトリウム粉が均一に分散するように充分混合した。Production Example 25 0.9 g of sodium sulfate powder (particle size 20 mesh pass) was added to 200 g of reduced iron powder (particle size 60 mesh pass) and thoroughly mixed so that the sodium sulfate powder was uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
２００℃に加熱し、その温度に３０分間保持して硫酸ナ
トリウムで処理された鉄粉をえた。実施例 ２５ 製造例２５においてえられた硫酸ナトリウムで処理され
た２５ｇ、水１０．５ｇ、塩化ナトリウム１．５ｇおよ
び木屑１０．５ｇを充分混合したのち実施例１と同様の
袋体に封入し、実施例１と同様にしてそのものの発熱の
立上り状態を調べた。The resulting mixture was placed in a glass container, heated to 200° C. over 30 minutes, and held at that temperature for 30 minutes to obtain iron powder treated with sodium sulfate. Example 25 25 g treated with sodium sulfate obtained in Production Example 25, 10.5 g of water, 1.5 g of sodium chloride and 10.5 g of wood chips were thoroughly mixed and then sealed in the same bag as in Example 1, In the same manner as in Example 1, the rise of heat generation was investigated.

その結果、室温８℃のときの３０℃および４０℃ま；で
の立上り時間は、それぞれ５７分および１０５分であつ
た。As a result, the rise times at 30°C and 40°C when the room temperature was 8°C were 57 minutes and 105 minutes, respectively.

製造例 ２６ 還元鉄粉（粒度６０メツシユパス）２００ｇに硫酸ナト
リウム粉０．９ｇと塩化アンモニウム粉０．７ｇを加え
、それらが均一に分散するように充分混合した。Production Example 26 0.9 g of sodium sulfate powder and 0.7 g of ammonium chloride powder were added to 200 g of reduced iron powder (particle size: 60 mesh pass) and thoroughly mixed so that they were uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
２００℃に加熱し、その温度に３０分間保持して含イオ
ウ化合物の混合物で処理された鉄粉をえた。実施例 ２
６ 製造例２６においてえられた含イオウ化合物の混合物で
処理された鉄粉２５ｇ、水１０．５ｇ、塩化ナトリウム
１．５ｇおよび木屑１０．５ｇを充分混合したのち実施
例１と同様の袋体に封入し、実施例１と同様にしてその
ものの発熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated to 200° C. over 30 minutes, and held at that temperature for 30 minutes to obtain iron powder treated with the mixture of sulfur-containing compounds. Example 2
6 After thoroughly mixing 25 g of iron powder treated with the mixture of sulfur-containing compounds obtained in Production Example 26, 10.5 g of water, 1.5 g of sodium chloride, and 10.5 g of wood chips, the same bag as in Example 1 was prepared. The sample was sealed, and the rise of heat generation was examined in the same manner as in Example 1.

その結果、室温８℃のときの３０℃および４０℃までの
立上り時間は、それぞれ２０分および４４分であつた。
製造例 ２７ 還元鉄粉（粒度６０メツシユパス）２００ｇにチオ硫酸
ナトリウム粉０．７ｇと塩化アンモニウム粉０．３ｇを
加え、それらが均一に分散するように充分混合した。As a result, when the room temperature was 8°C, the rise times to 30°C and 40°C were 20 minutes and 44 minutes, respectively.
Production Example 27 0.7 g of sodium thiosulfate powder and 0.3 g of ammonium chloride powder were added to 200 g of reduced iron powder (particle size: 60 mesh pass) and thoroughly mixed so that they were uniformly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
２００℃に加熱し、その温度に３０分間保持して含イオ
ウ化合物の混合物で処理された鉄粉をえた。実施例 ２
７ 製造例２７でえられた含イオウ化合物の混合物で処理さ
れた鉄粉２５ｇ、水１０．５ｇ、塩化ナトリウム１．５
ｇおよび木屑１０．５ｇを充分混合したのち実施例１と
同様の袋体に封入し、実施例１と同様にしてそれらの発
熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated to 200° C. over 30 minutes, and held at that temperature for 30 minutes to obtain iron powder treated with the mixture of sulfur-containing compounds. Example 2
7 25 g of iron powder treated with the mixture of sulfur-containing compounds obtained in Production Example 27, 10.5 g of water, 1.5 g of sodium chloride
g and 10.5 g of wood chips were thoroughly mixed and then sealed in the same bag as in Example 1, and the rise of heat generation was examined in the same manner as in Example 1.

その結果、室温８℃のときの３０℃および４０℃までの
立上り時間は、それぞれ２７分および５４分であつた。As a result, when the room temperature was 8°C, the rise times to 30°C and 40°C were 27 minutes and 54 minutes, respectively.

製造例 ２８ 還元鉄粉（粒度６０メツシユパス）２００ｇに硫化ナト
リウ粉０．５ｇと塩化アンモニウム粉０．７ｇを加え、
それらが均一に分散するように充分混合した。Production example 28 Add 0.5 g of sodium sulfide powder and 0.7 g of ammonium chloride powder to 200 g of reduced iron powder (particle size 60 mesh pass),
Mix thoroughly so that they are evenly dispersed.

えられた混合物をガラス製の容器に入れ、３０分かけて
２００℃に加熱し、その温度に３０分間保持して含イオ
ウ化合物の混合物で処理された鉄粉をえた。実施例 ２
８ 製造例２８でえられた含イオウ化合物の混合物で処理さ
れた鉄粉２５ｇ、水１０．５ｇ、塩化ナトリウム１．５
ｇおよび木屑１０．５ｇを充分混合したのち実施例１と
同様の袋体に封入し、実施例１と同様にしてそれらの発
熱の立上り状態を調べた。The resulting mixture was placed in a glass container, heated to 200° C. over 30 minutes, and held at that temperature for 30 minutes to obtain iron powder treated with the mixture of sulfur-containing compounds. Example 2
8 25 g of iron powder treated with the mixture of sulfur-containing compounds obtained in Production Example 28, 10.5 g of water, 1.5 g of sodium chloride
g and 10.5 g of wood chips were thoroughly mixed and then sealed in the same bag as in Example 1, and the rise of heat generation was examined in the same manner as in Example 1.

その結果、室温８℃のときの３０℃および４０℃までの
立上り時間は、それぞれ５５分および１１５分であつた
。As a result, when the room temperature was 8°C, the rise times to 30°C and 40°C were 55 minutes and 115 minutes, respectively.

実施例 ２９〜３９ 第７表に示す含イオウ化合物で処理された鉄粉２５ｇ、
水１２．５ｇ、塩化ナトリウム１．７ｇ、バーミキュラ
イト３ｇ、活性炭（Ｅ−３０、武田薬品工業（株）製）
２．５ｇ、アン殻炭粉５．５ｇおよび高吸水性樹脂．・
（サンウエツトＩＭ−３００、二洋化成工業（株）製）
０．８３ｇを充分混合したのち、実施例１と同様の袋体
に封入し、数十回振つたのちそれらの温度変化を実施例
１と同様の測定方法によつて調べた。Examples 29-39 25 g of iron powder treated with the sulfur-containing compound shown in Table 7,
12.5 g of water, 1.7 g of sodium chloride, 3 g of vermiculite, activated carbon (E-30, manufactured by Takeda Pharmaceutical Co., Ltd.)
2.5g, unshelled coal powder 5.5g and super absorbent resin.・
(Sunwet IM-300, manufactured by Niyo Kasei Kogyo Co., Ltd.)
After thoroughly mixing 0.83 g, the mixture was sealed in the same bag as in Example 1, shaken several dozen times, and the temperature change was examined using the same measuring method as in Example 1.

なお、室温は８℃に維持した。結果を第７表に示す。Note that the room temperature was maintained at 8°C. The results are shown in Table 7.

比較例 ５〜７ 含イオウ化合物で処理された鉄粉に代えて未処理の還元
鉄粉、ＦｅＳまたはＦｅＳ２を用いたほかは実施例２９
と同様に袋体に封入してそれらの発熱時の温度変化を調
べた。Comparative Examples 5 to 7 Example 29 except that untreated reduced iron powder, FeS or FeS2 was used instead of iron powder treated with a sulfur-containing compound.
Similarly, they were sealed in bags and the temperature changes during heat generation were investigated.

結果を第７表に示す。The results are shown in Table 7.

比較例 ８ 含イオウ化合物で加熱処理された鉄粉および塩化ナトリ
ウムに代えて、それぞれ未処理の還元鉄粉２５ｇおよび
硫酸第１鉄１．７ｇを用いたほかは実施例２９と同様に
して各成分を充分混合したのち袋体に封入し、その発熱
時の温度変化を調べた。Comparative Example 8 Each component was prepared in the same manner as in Example 29, except that 25 g of untreated reduced iron powder and 1.7 g of ferrous sulfate were used in place of the iron powder heat-treated with a sulfur-containing compound and sodium chloride. After mixing thoroughly, the mixture was sealed in a bag and the temperature change during heat generation was examined.

その結果平衡温度および最高温度はそれぞれ５３℃およ
び５５℃であり、立上り時間は４０℃までが３０分間、
平衡温度までが１４０分間であり、立上り時間の短縮は
認められなかつた。なお、平衡温度以上および４０℃以
上における保持時間はそれぞれ６．５時間および１２．
０時間であつた。実施例４０〜４３および比較例９ 〜
１０製造例５、１７、２０および２３でそれぞれえられ
た含イオウ化合物で処理された鉄粉および未処理の還元
鉄粉を用いてガスの発生状態を調べた。As a result, the equilibrium temperature and maximum temperature were 53°C and 55°C, respectively, and the rise time was 30 minutes to 40°C.
It took 140 minutes to reach equilibrium temperature, and no shortening of the rise time was observed. The holding times at temperatures above the equilibrium temperature and above 40°C were 6.5 hours and 12.5 hours, respectively.
It was 0 hours. Examples 40 to 43 and Comparative Example 9 to
10 The state of gas generation was investigated using iron powder treated with a sulfur-containing compound and untreated reduced iron powder obtained in Production Examples 5, 17, 20 and 23, respectively.

鉄粉３０ｇ、水１２ｇ、塩化ナトリウム１．５ｇ、バー
ミキユライト２．５ｇ、活性炭（Ｅ−３０）２．５ｇ、
アン殻炭７ｇおよび高吸水性樹脂（サンウエツトＩＭ−
３００）０．８３ｇを、全成分を均一に混合したのち非
通気性のアルミ箔製の袋体に充填し真空密封してガスの
発生を調べた。えられた密封体を乾燥炉で８８℃で８時
間加熱してガスの発生度合を調べた。30g of iron powder, 12g of water, 1.5g of sodium chloride, 2.5g of vermiculite, 2.5g of activated carbon (E-30),
7g of unshelled charcoal and super absorbent resin (Sunwet IM-
After uniformly mixing all the components, 0.83 g of 300) was filled into a non-porous aluminum foil bag, vacuum-sealed, and gas generation was examined. The obtained sealed body was heated in a drying oven at 88° C. for 8 hours, and the degree of gas generation was examined.

それらの結果を第８表に示す。なお、比較のため含イオ
ウ化合物で処理された鉄粉に代えて未処理の還元鉄粉を
用いたもの（比較例９）と含イオウ化合物で処理された
鉄粉および塩化ナトリウムに代えてそれぞれ未処理の還
元鉄粉および硫酸第１鉄を用いたもの（比較例１０）に
ついても同様にしてガスの発生度合を調べた。The results are shown in Table 8. For comparison, the iron powder treated with a sulfur-containing compound was replaced with untreated reduced iron powder (Comparative Example 9), and the iron powder treated with a sulfur-containing compound and sodium chloride were replaced with untreated iron powder. The degree of gas generation was similarly investigated for the treatment using reduced iron powder and ferrous sulfate (Comparative Example 10).

結果を第８表に示す。The results are shown in Table 8.

ガス発生の度合は、つぎの基準で肉眼により観察評価し
た。The degree of gas generation was visually evaluated using the following criteria.

◎：まつたく変化なし ○：殆ど変化なし ×：袋体がふくれ、破裂したものもある。◎: No change at all ○: Almost no change ×: Some bags were swollen and burst.

Claims (1)

【特許請求の範囲】[Claims] １ 被酸化剤として含イオウ化合物で加熱処理された鉄
粉を用いることを特徴とする被酸化剤の空気酸化によつ
て生ずる熱を利用する化学カイロ。1. A chemical body warmer that utilizes the heat generated by air oxidation of the oxidizing agent, characterized in that iron powder heat-treated with a sulfur-containing compound is used as the oxidizing agent.