JPS5843430B2 - Cairo - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a body warmer characterized by using sulfur-treated iron powder as an oxidizing agent.

Warmers, which utilize the heat generated by the air oxidation of iron, are safe and easy to use without the use of fire, so they have been widely sold as disposable body warmers in recent years.

Such body warmers are manufactured by filling a bag with a mixture containing water, neutral metal salts, carbonaceous substances, water retention agents, etc. in addition to iron.

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.

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).

In addition, in cold regions, the rise in temperature at the start of heat generation is slow and may be useless.

The inventors of the present invention have conducted various studies to improve the temperature rise at the start of heat generation, but have not been able to find anything satisfactory.

The present inventors (mainly as a result of further research) found that when using sulfur-treated iron powder as an oxidizing agent, the rise at the start of heat generation is extremely rapid, and the time it takes to reach equilibrium temperature is longer than that of conventional untreated iron powder. The present invention was completed by discovering that a warmer can be replaced that is 1/2 to 1/10 shorter than iron powder.

The method for treating iron powder with sulfur in the present invention includes, for example, (1
) A method in which iron powder and sulfur powder are mixed uniformly and then heated; (2) A method in which sulfur is dissolved in a solvent and the solution is applied to the iron powder, or the iron powder is immersed in the solution and then dried. (3) Dissolving sulfur in a solvent and heating it in the resulting solution.

As the sulfur solvent in the sulfur treatment method 2) of iron powder, for example, carbon disulfide, benzene, toluene, xylene, carbon tetrachloride, chloroform, benzine, kerosene, etc. can be used.

For methods 1) and (2), the heating temperature is usually about 50°C.
As mentioned above, it is appropriate to conduct the heating at a temperature of <100 to 450°C, and the heating time is from several seconds to 180°C (around 200'C).
minutes, preferably 30 to 60 minutes.

However, these processing conditions are dependent on the type and amount of iron powder used,
It depends on many factors such as grain size and sulfur grain size.

It is thought that at least a portion of the surface of the sulfur-treated iron powder used in the present invention has been changed to iron sulfide, but this is not yet clear.

Examples of the iron powder to be treated include reduced iron powder and iron powder obtained by an atomization method.

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 80 mesh passes.
-145 mesh, and particles with a smaller particle size are not preferred because workability deteriorates.

The amount of sulfur used is 15 parts or less, preferably 0.01 to 5 parts, based on 100 parts (by weight) of iron powder.

When using iron powder treated with more than 15 parts of sulfur, the rise speed at the start of heat generation gradually becomes slower, the maximum temperature decreases, and the holding time also decreases.

Furthermore, when the amount of sulfur used increases, the odor of sulfur during and after the treatment becomes strong, and the environment 1 deteriorates.

Warmers that utilize the heat generated by air oxidation of iron include
As mentioned above, in addition to iron, water, neutral metal salts, carbonaceous substances,
Although components such as water retention agents are blended, similar components are also blended in the present invention.

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.

The carbonaceous material is used as an oxidation catalyst, and, for example, activated return powder is preferable, but it may be replaced with coconut shell charcoal powder or the like as appropriate.

Examples of water retention agents include wood chips, vermiculite, fiber powder, superabsorbent resins, or mixtures thereof.

Also, if only untreated iron powder is used, gas will be generated.
Sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate,
Sodium carbonate, calcium hydroxide, calcium carbonate,
It contains inorganic or organic alkali or weak alkali salts such as sodium propionate.

However, the addition of such gassing inhibitors may slightly impair the exothermic reaction.

However, when using the sulfur-treated iron powder used in the present invention, 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 sulfur may be used in combination with iron powder that has been treated with sulfur.

The composition is regular iron powder/sulfur-treated iron powder from 99/1.
It can be carried out within the range of O/100 (weight ratio), but as the amount of sulfur-treated iron powder decreases, the rise of heat generation will gradually become slower, and gases such as hydrogen gas will tend to be generated. Add a gas generation inhibitor in advance.

The preferred mixing ratio in the warmer of the present invention is 20 to 70 parts of water, 0.1 to 80 parts of carbonaceous material, 1 to 20 parts of metal neutral salt, and 1 to 100 parts of water retention agent to 100 parts of sulfur-treated iron powder.
500 copies.

If necessary, 0.1 to 4 parts of the gas generation inhibitor may be added to 100 parts of sulfur-treated iron powder.

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.

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 body warmer of the present invention is not subject to any other restrictions as long as it is non-breathable, and may be laminated.

Preferred examples include nylon, polyester, and polypropylene films that have been moisture-proofed with OPP, CPP, polyvinylidene chloride, etc., as well as aluminum foil*t, and plastic films coated with aluminum.

The inner bag of this type of body warmer is usually made of non-woven fabric,
Any material may be used as long as it has air permeability; for example, cloth, paper, etc. may also be used.

Next, the present invention will be explained in detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples.

Production Examples 1 to 13 Sulfur powder (particle size 100 mesh pass) was added in the amount shown in Table 1 to 20Of reduced iron powder (particle size 60 mesh pass), and the mixture was thoroughly mixed so that the sulfur powder was uniformly dispersed.

The resulting mixture was placed in a glass container, heated to 200°C under heat for 30 minutes, and held at 200°C for 30 minutes to obtain sulfur-treated iron powder.

Examples 1 to 13 After thoroughly mixing 25 g of sulfur-treated iron powder obtained in Production Examples 1 to 13, 10.5 F of water, 1.5 f of sodium chloride, and 10.5 f of wood chips, a breathable bag was formed. They were sealed and their heat generation status was examined.

The bag used was a nylon nonwoven fabric laminated with polyethylene on the inner surface, with 150 perforations on each side (using needles with a diameter of 0.5 mm) having a width of 6 ms and an interval of 8 in the center of the bag.

Immediately after enclosing the sample, the sample was shaken several dozen times, placed on top of four blankets, and two blankets were placed on top of the thermocouple.

Room temperature was maintained at approximately 8°C. The results are shown in Table 1.

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 sulfur-treated iron powder, and the mixture was sealed in a bag and its heat generation state was measured in the same manner as in Example 1.

Comparative Examples 2-3 Ferrous sulfide (-grade reagent,
The mixture was blended and mixed in the same manner as in Example 1, except that Wako Tsumugi Kogyo Co., Ltd. (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) or pyrite was used, and the mixture was sealed in a bag made of nonwoven fabric, and the heat generation state was measured in the same manner as in Example 1.

The results are shown in Table 1.

In addition, the numerical value shown in parentheses in the column of holding time at 40°C or higher in Table 1 indicates the total holding time at 40°C or higher when shaking is added several times when the temperature drops below 40°C.

This display is the same for Tables 2 and 3.

Production Examples 14 to 24 0.02 S' of sulfur powder (100 mesh pass) was added to 200 f of reduced iron powder (particle size: 80 mesh pass), and the mixture was thoroughly mixed so that the sulfur powder was uniformly dispersed.

The resulting mixture was placed in a glass container, heated to the temperature shown in Table 2 for 30 minutes, and maintained at the temperature shown in Table 2 for 30 minutes to obtain sulfur-treated iron powder.

Examples 14-24 Sulfur-treated iron powder 2511 water obtained in Production Examples 14-24, respectively 10. ! l, Sodium chloride*Nimu 1.5
10. ! After sufficiently mixing 11, Example 1
They were sealed in a bag similar to that of Example 1, and their heat generation state was examined in the same manner as in Example 1.

The results are shown in Table 2.

Production Examples 25 to 34 200P of reduced iron powder (particle size 60 mesh pulse) and 0.02S' of sulfur powder (particle size 100 mesh pulse) were sufficiently mixed so that the sulfur powder was uniformly dispersed.

The resulting mixture was placed in a glass container and maintained at 200° C. for the time shown in Table 3 to obtain sulfur-treated iron powder.

*Examples 25 to 34 Sulfur-treated iron powder 2001 obtained in Production Examples 25 to 34, 10.5 f of water, 1.5 i of sodium chloride
and 10.5 f of wood chips were thoroughly mixed and then 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.

The results are shown in Table 3.

Examples 35 to 37 Reduced iron powder 20 (1) with the particle size shown in Table 4 was prepared using 0.2P of sulfur powder (particle size 100 mesh pass).
By heating at 0°C for 30 minutes, sulfur-treated iron powder with different particle sizes was obtained.

Each obtained sulfur-treated iron powder 30f, *water 1
0.5 g, sodium chloride 1.5 g, wood chips 10.51 g, and activated return powder (E-30, manufactured by Narita Pharmaceutical Co., Ltd., 14
Example 1
The samples were sealed in a bag similar to the above, and their heat generation state was measured in the same manner as in the example.

The results are shown in Table 4.

Furthermore, when the state of heat generation was investigated by changing the amount and particle size of activated carbon, it was found that the higher the blending amount and the smaller the particle size, the faster the start of heat generation.

Example 38 Reduced iron particles (particle size 1゛00 mesh pass) were mixed with 0.2 sulfur.
25 g of sulfur-treated iron powder obtained by processing at 200°C for 30 minutes using 1.1 g of sulfur-treated iron powder and 12 g of water. , sodium chloride 1.
51, vermiculite 2.5 liters, activated carbon (E-30)
After thoroughly mixing 2.5 f, 7 g of coconut shell charcoal (particle size 50 mesh pass) and 0.83 f of a super absorbent resin (Sunwet M-300, manufactured by Sanyo Chemical Industries, Ltd.), the same process as in Example 1 was carried out. It was sealed in a bag, and the state of heat generation was measured in the same manner as in Example 1.

The results are shown in Table 5.

Comparative Example 4 The bag was sealed in the same manner as in Example 38, except that untreated reduced iron powder (particle size: 100 mesh pass) was used in place of the sulfur-treated iron powder, and the state of heat generation was measured.

The results are shown in Table 5. Examples 39 to 42 and Comparative Example 5 The state of gas generation was investigated using the sulfur-treated iron powder and the untreated reduced iron powder obtained in Production Examples 1.3.5 and 6, respectively.

Iron powder 31, water 122, sodium chloride 1.5fI, vermiculite 2.55', activated carbon (E-30) 2.5v
, coconut shell charcoal 7v and super absorbent resin (Sanuyutsu) IM
-300) 0.83r, (Ai) When iron powder is placed in an air-impermeable aluminum foil bag, then other ingredients are filled and vacuum sealed (in this case, iron powder is placed at the interface with other ingredients). (hereinafter referred to as filling method (4)),
(B) When all ingredients are mixed uniformly and then filled into a non-porous aluminum foil bag and vacuum-sealed (hereinafter referred to as filling tooth B
We investigated the gas generation in two cases.

The obtained sealed body was heated in a drying oven at 88° C. for 8 hours, and the degree of gas generation was examined.

The results are shown in Table 6.

The degree of gas generation was visually evaluated using the following criteria.

◎: No change ○: The degree of vacuum is slightly decreased.

△: The bag body is slightly swollen.

×: Some bags were swollen and burst.

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Claims (1)

[Claims] 1. A hand warmer characterized by using sulfur-treated iron powder as an oxidizing agent.