JPS6318105B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heating mat that can be heated without using thermal power. More specifically, the present invention relates to a heating mat that utilizes the amount of heat generated when an oxidizing agent and a reducing agent react and does not require oxygen gas. You want to heat so-called instant foods such as canned, bottled, and retort pouch foods that you carry with you on outdoor recreation activities such as mountain climbing, hiking, and fishing, or when you go to the theater, or canned or bottled beverages sold in vending machines. Sometimes I long for it. However, in such places, there is generally no convenient heating source, and the only options are to either give up on heating and eat the food cold, or to start a fire and heat it up. Naturally, when heating with firepower, a container is required, which results in larger tools. Also,
In so-called chemical body warmers that utilize air (oxygen gas) oxidation of iron, the temperature reached at which heat is generated is low (at most about
65℃), and the onset of heat generation is slow, making it unusable for heating foods. The inventor of the present invention has conducted extensive research to provide a portable heating element that can easily heat objects anywhere. By enclosing an oxidizing agent in one side of the pouch and a reducing agent in the other, making at least one of the oxidizing agent or the reducing agent into a solvent system such as a solution or suspension, and breaking the pouch, the oxidizing agent can be removed. The present invention was completed based on the discovery that an object to be heated can be heated by reacting a reducing agent with a reducing agent and utilizing the heat generated by the reaction. The amount of heat generated by the reaction between the oxidizing agent and the reducing agent utilized in the present invention is sufficient to boil water. The present invention relates to a portable heating mat consisting of the bag body and the small bag body, in which an oxidizing agent is sealed in one of the bag body or the small bag body, and a reducing agent is sealed in the other, and the oxidizing agent used and The reducing agent is as follows. That is, the oxidizing agent is
The reducing agent is at least one selected from the group consisting of NaClO ₃ , Na ₂ Cr ₂ O ₇ , MnO ₂ , H ₂ O ₂ and salad powder, and the reducing agent is CaSO ₃ , Na ₂ SO ₃ , NaHSO ₃ , ethyl alcohol, At least one member selected from the group consisting of Zn and formaldehyde. Preferred combinations include NaClO ₃ and CaSO ₃ ,
Na ₂ SO ₃ and NaHSO ₃ ; Na ₂ Cr ₂ O ₇ and ethyl alcohol; MnO ₂ and Zn; H ₂ O ₂ and formaldehyde or Na ₂ SO ₃ ; Depending on the combination, a reaction initiator such as a catalyst, acid, or alkali may be required. The type and amount of the reaction initiator and whether it is added to the oxidizing agent or reducing agent depend on the combination of the oxidizing agent and reducing agent and the intended use of the heating mat of the present invention, but usually each combination is Catalysts, alkalis, acids, etc. that can be used as oxidizing agents can be used.
When using Na ₂ Cr ₂ O ₇・2H ₂ O and ethanol as a reducing agent, add sulfuric acid to the ethanol, and when combining MnO ₂ and Zn powder, add sulfuric acid to the ethanol.
Aluminum chloride and carbon powder may be blended with MnO ₂ , and in the case of a combination of H ₂ O ₂ and formaldehyde, an appropriate amount of iron sulfate may be blended with formaldehyde. The reaction between the oxidizing agent and the reducing agent in the present invention proceeds quantitatively, and heat is generated thermodynamically. When using an oxidizing agent and a reducing agent, at least one of them is used in the form of a solution or suspension.
In such a form, the reaction progresses well, the amount of heat generated can be stored, and the temperature rise stops at the boiling point of the solvent used, making it possible to heat quickly and for a relatively long time. It can sustain heating and prevent dangerously high temperatures.
Therefore, the solvent to be used should be one that does not react with the oxidizing agent and reducing agent and does not participate in their reactions;
Water is used that satisfies the following conditions: it does not deteriorate, it has a relatively large specific heat, its boiling point is slightly higher than the desired heating temperature, and it is inexpensive. Water has a large specific heat of 1, and a boiling point of 100°C, which is suitable for heating the object mentioned above, and also satisfies all of the above conditions. It is most suitable as a solvent for use in the invention. The reaction may be initiated by bursting the pouch by applying an appropriate force such as compression from the outside of the pouch. The time from the bursting of the pouch to the time it generates heat usually takes some time to rise, although it varies depending on the combination of oxidizing agent and reducing agent, and this time is used as the time for wrapping the bag around the object to be heated. The winding time may be about 1 to 5 minutes, preferably 2 to 3 minutes. However, there are some combinations of oxidizing agents and reducing agents that do not start the reaction unless the temperature exceeds a certain temperature. For example, in the case of a combination of NaClO ₃ and aldehydes, the reaction will not start unless the temperature reaches about 20 to 30°C, and therefore there is a risk that the reaction will not start in winter or at the top of a mountain. In such cases, the system must be raised to the reaction initiation temperature. As a method for this, heat may be applied from the outside, or a reactant that can react and generate heat even at low temperatures may be separately sealed in the bag and the pouch. Examples of reactions that can be used for such preheating include neutralization reactions between acids and alkalis. In other words, either an acid or an alkali is sealed in a bag and the other in a pouch, and when the pouch is ruptured, the acid and alkali first react to generate heat of neutralization, which increases the temperature of the system and causes oxidation. It induces a reaction between the agent and the reducing agent, and the heat generated thereby heats the object to be heated. Examples of acids used include hydrochloric acid, sulfuric acid, and acetic acid, and examples of alkalis include sodium hydroxide, calcium hydroxide, and calcium oxide. The temperature increase due to the heat of neutralization may be local, and once the oxidizing agent and reducing agent begin to react, the reaction proceeds in a chain manner. Therefore, the amount of acid and alkali used is sufficient to raise a part of the system to the temperature at which the reaction between the oxidizing agent and the reducing agent starts. The amount of heat generated by the reaction between the oxidizing agent and the reducing agent used in the present invention is sufficient to boil water. However, because of this, there is a risk that the water as a solvent may also be boiled and the bag may burst. Generally, the reaction between an oxidizing agent and a reducing agent proceeds all at once in a short period of time, so the reaction cannot be controlled by quantitative adjustment. Therefore, boiling can be suppressed by controlling the reaction system pH, using a catalyst, and adjusting the particle size of the solid oxidizing agent (reducing agent). For example, when using NaClO ₃ as the oxidizing agent, NaHSO ₃ , Na ₂ SO ₃ and CaSO ₃ 2H ₂ O as the reducing agent, and CaCl ₂ as the reaction initiator, the reaction proceeds as follows and generates heat. . Oxidizing agents exhibit strong oxidizing power in the presence of acids, but when the temperature rises,
H ₂ SO ₃ decomposes into H ₂ O and SO ₂ and vaporizes, reducing the amount of oxidized SO ₂ in the reaction system, increasing the PH and thus reducing the oxidizing power of the oxidizing agent. reaction can be suppressed. In this way, the reaction rate (that is, the exothermic rate) can be adjusted by adjusting the pH dependence of the oxidizing power of the oxidizing agent, the use of a catalyst, and the difference in reactivity depending on the particle size of the reducing agent (oxidizing agent). H ₂ O and SO ₂ generated by the reaction, and water vapor evaporated by heating, easily dissolve in water, which is present in large quantities as a solvent, and do not generate enough pressure to burst the bag. The heating mat of the invention is safe. Another method is to increase the heat capacity of the entire system. For example, the rise time may be adjusted by blending an appropriate amount of a compound having a melting point lower than the boiling point of the solvent, which does not participate in the reaction and which does not deteriorate as a heat storage agent. Examples of heat storage agents used include naphthalene (melting point 80°C), stearic acid (melting point 71.5-72°C),
Examples include palmitic acid (melting point 63-64°C) and liquid paraffin (melting point 60-80°C). The compounding amount is
The winding time may be appropriately selected so as to be approximately 1 minute or more as described above. Next, the bags and pouches for enclosing the oxidizing agent, reducing agent, solvent, and heat storage agent will be explained. The bag may be of any shape or material as long as it does not react with the contents, the contents do not leak to the outside, and it does not melt or deteriorate when heated. In a preferred embodiment of the present invention, either an oxidizing agent or a reducing agent is enclosed in the bag together with a solvent. The shape and material of the pouch are not particularly limited as long as it exists inside the pouch and can be torn by applying force from outside the pouch. In a preferred embodiment of the present invention, a small volume or liquid substance is enclosed in the pouch. For example, the material of the bag is preferably polypropylene, nylon, Tetron, etc., and the bag may be made of a single film or a laminate film of these materials. The outer layer of the laminate film is preferably made of nylon or Tetron due to the problem of pinhole formation. Examples of the material for the pouch body include polyolefins such as polyethylene and polypropylene. When using the heating mat of the present invention constructed as described above, first pressurize the bag from the outside to break the inner small bag, and then attach it to the object to be heated within the wrapping time, or Pour into the object to be heated. When placed in the object to be heated, the heat conduction from the heating mat becomes even better, resulting in the effect that the heating time can be shortened. Once the object to be heated reaches a desired temperature, the heating mat can be removed as appropriate. Therefore, the heating temperature of the object to be heated can be adjusted by adjusting the time period during which the heating mat and the object to be heated are in contact with each other. Although the above description has mainly been given to the case of heating food, the heating mat of the present invention is not limited thereto, and the heating mat of the present invention can be used, for example, to prevent batteries from freezing or as a heat storage type anchor. It can be applied to various heating purposes within a range not departing from the above. That is, suitable objects to which the present invention can be applied include, for example, canned or bottled beverages and foods, retort pouch foods, heating appliances such as heat storage anchors, and antifreeze devices for batteries. Next, the heating mat of the present invention will be explained with reference to Examples. Example 1 12.6 g of NaClO ₃ , 5.8 g of CaCl ₂ , and 50 ml of water were sealed in a polyethylene pouch, and the pouch was sealed in a bag made of a laminate film made of polypropylene and nylon. to CaSO ₃・2H ₂ O 50g, Na ₂ SO ₃ 3.25g,
1.44 g of NaHSO ₃ and 100 ml of water were sealed and sealed. The object to be heated is 0 placed in a glass cup.
250 ml of water at ℃ was used. First, when we applied strong pressure to the heating pine pouch from the outside with our fingers, only the pouch broke. Immediately, this heating mat was wrapped around a glass tip, and in order to prevent the heating mat from coming off the tip, it was wrapped in cardboard paper and secured with cellophane tape from above. 15 minutes after tearing the pouch and 10 minutes after wrapping it around the glass tip, the water inside the glass tip reaches 80℃.
It became. Approximately 40 minutes after the pouch was ruptured, the temperature of the heating mat began to drop, but no abnormality was observed in the pouch up to that time or thereafter. Example 2 Put 300ml of water at 25℃ into a Duwa bottle with a capacity of 500ml,
22.2 ml of concentrated sulfuric acid was added as a reaction initiator, and 16 ml of ethyl alcohol was added as a reducing agent. 30 g of Na ₂ Cr ₂ O ₇ was added as an oxidizing agent to this aqueous solution, and the temperature of the mixture was measured. Exotherm started after 2 minutes, rose to 63°C after 5 minutes, and then reached a steady state. The calorific value was calculated from this temperature difference and was 12.5 Kcal. Examples 3 to 6 The calorific value was determined in the same manner as in Example 2, except that the types and amounts of the oxidizing agent, reducing agent, and reaction initiator and the amount of water as shown in Table 1 were used. The results are shown in Table 1.

[Table] Comparative Example 1 A total of 150 g of 15% cupric chloride aqueous solution and 15% calcium chloride aqueous solution as oxidizing agents were sealed in a polyethylene pouch, and this pouch was replaced with a polypropylene polyethylene laminate film pouch. (130mm x 250mm), and an aluminum plate (30mm x 10mm x 2
40g of the sample (cut into strips of mm) was placed in the bag and the bag was sealed. Next, the inner bag was strongly pressed from the outside of the bag to break the small bag, and the oxidizing agent solution was brought into contact with the aluminum plate to initiate a reaction. An attempt was made to wrap this bag around the same object to be heated as used in Example 1 (a glass pot containing 250 ml of water at 0°C), but during the process, the bag expanded greatly and burst. The time required for rupture was approximately 30 seconds. The cause of the expansion and bursting of the bag was hydrogen gas generated by the reaction between cupric chloride and aluminum. Comparative Example 2 After putting 40 g of the same aluminum plate as in Comparative Example 1 into a polypropylene polyethylene laminate film bag (130 mm x 250 mm) and sealing it, cut one corner of the bag (length 10 mm) and insert it from this opening. 150 g of an oxidizing agent solution prepared in the same manner as in Comparative Example 1 was injected. The reaction started immediately, and hydrogen gas was generated violently and escaped through the cut opening. This product was wrapped and fixed around an object to be heated (a glass cup containing 250 ml of water at 0° C.) in the same manner as in Example 1 to prevent the oxidizing agent solution from coming out, and the change in water temperature inside the glass pot over time was examined. As a result, the water temperature inside the glass pot gradually rose, but at a slow rate, reaching 14°C after 1 hour and reaching its maximum temperature after 6 hours, but that temperature was still as low as 39°C.

Claims (1)

[Scope of Claims] 1 Consists of a watertight bag and a small bag inside the bag, and either the bag or the small bag has a
At least one oxidizing agent selected from the group consisting of NaClO ₃ , Na ₂ Cr ₂ O ₇ , MnO ₂ , H ₂ O ₂ and salad powder, and CaSO ₃ , Na ₂ SO ₃ , NaHSO ₃ , ethyl alcohol on the other hand. , Zn, and formaldehyde, and at least one of the oxidizing agent and the reducing agent is in the form of an aqueous solution or suspension, and does not require oxygen gas. Taingmatsuto. 2. The heating mat according to claim 1, wherein the bag body is made of one material selected from the group consisting of polypropylene film, nylon film, Tetron film, and laminate films thereof. 3. The heating mat according to claim 1 or 2, wherein the pouch body is made of polyethylene film.