WO2017014271A1

WO2017014271A1 - Heating tool

Info

Publication number: WO2017014271A1
Application number: PCT/JP2016/071420
Authority: WO
Inventors: 翔平相川; 陽一遠藤
Original assignee: 花王株式会社
Priority date: 2015-07-21
Filing date: 2016-07-21
Publication date: 2017-01-26

Abstract

This heating tool (100) is provided with the following: a steam generator (10) which is obtained by laminating a water-absorbing sheet (102) that holds water and an exothermic layer (11) that contains an oxidizable metal, a carbon component, a water-absorbing polymer and water; and a bag (20) which houses the steam generator (10) and is at least partially air-permeable. The mass ratio of the water-absorbing sheet (102) relative to the water-absorbing polymer contained in the exothermic layer (11) is 0.9-15.

Description

Heating equipment

The present invention relates to a heating tool.

Conventionally, there is a heating element that generates heat due to an oxidation reaction of an oxidizable metal, and it is configured to include an oxidizable metal such as iron powder, a carbon component, and water. For example, those disclosed in Patent Documents 1 and 2 are known as the heating elements.

Patent Document 1 describes a heating element using an ink-like or cream-like heating composition. According to this heating element, the generation of dust during production of the heating element is prevented, and the exothermic reaction of the exothermic composition is suppressed to prevent loss due to the exothermic reaction during production, deterioration of the quality of the exothermic composition, and solidification. It is supposed to be possible.

Patent Document 2 describes a heating element in which the composition of the heating layer and the water retaining layer is appropriately controlled. According to this heating element, when the heating element is manufactured, even if the heating composition is filled in a large amount for some reason or is unevenly distributed in a specific location, abnormal heating is prevented and good heating characteristics are obtained. It is described that it can be stably obtained, and that it may be accompanied by generation of water vapor.

JP-A-9-75388 JP 2013-146555 A

That is, the present invention
A heat generating layer containing an oxidizable metal, a carbon component, a water-absorbing polymer, and water;
A water absorbent sheet carrying water;
A water vapor generator formed by laminating
A heating device comprising at least a part of air permeability and a bag body containing the water vapor generating body,
The present invention relates to a heating tool, wherein a mass ratio of the water absorbent sheet to the water absorbent polymer contained in the heat generating layer is 0.9 or more and 15 or less.

The present invention also provides:
A heat generating layer containing an oxidizable metal, a carbon component, a water-absorbing polymer, and water;
A water absorbent sheet carrying water;
A water vapor generator formed by laminating
A heating device comprising at least a part of air permeability and a bag body containing the water vapor generating body,
The basis weight of the water-absorbing polymer contained in the heat generating layer is 20 g / m ² or more and 100 g / m ² or less in a dry state, and the basis weight of the water-absorbing sheet is 50 g / m ² in a dry state. The present invention relates to a heating tool that is 500 g / m ² or more.

The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.

It is sectional drawing which showed typically the water vapor generating body used for embodiment. It is a figure explaining the method to manufacture the water vapor generating body used for embodiment. It is sectional drawing which showed typically an example of the heating tool which concerns on embodiment. It is a schematic diagram which shows the apparatus which measures water vapor generation amount.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.
In the present specification, “to” represents the following unless otherwise specified.

As a result of investigations by the present inventors, it has been found that there is room for improvement in the following points when the heating element as in the above-mentioned prior art document is to be of a type that stably generates water vapor.

That is, in the heating tool described in Patent Document 2, a wood sheet made of wood pulp, a water-absorbing polymer and wood pulp paper are laminated and integrated on the heat generation layer with a first polymer sheet. Used as a water absorbing sheet. This configuration is excellent in that it does not generate abnormal heat even if there are fluctuations in manufacturing conditions and raw material components, but it has been found that there is a limit in terms of generating water vapor without increasing the temperature. did.
As a result of the examination by the present inventors about this point, it is difficult to convert the heat generated by the heat generation layer into steam because the water-absorbing polymer and the heat generation layer are arranged via wood pulp paper. It turned out that there is room for improvement. In addition, since wood pulp paper exists between the water-absorbing polymer and the heat generating layer as described above, it is difficult to supply moisture to the heat generating layer, and as a result, a large amount of water vapor is generated. In this case, it has been found that there is room for improvement in that the temperature of the heating element may be higher than necessary.

On the other hand, Patent Document 1 discloses a technique for producing a heating element by spraying a water-absorbing agent on a heating composition to form a water-absorbing layer. However, if a large amount of water is contained in order to generate water vapor, simply spraying a water-absorbing agent on the heat-generating composition will increase the amount of water in the heat-generating layer, making it difficult to generate heat. It has been found that there is a problem that the rise of temperature is slow and the amount of water vapor generated is also reduced.

The present invention has been made in view of the background art as described above, and provides a heating device that quickly rises in temperature, stably generates water vapor, and can be easily controlled at an appropriate temperature.

The present inventors constituted a water vapor generating body in which a heat generating layer containing an oxidizable metal, a carbon component, a water absorbing polymer and water and a water absorbing sheet having a specific maximum water absorbing capacity were laminated from a ventilation sheet. It has been found that by storing in a bag body, it is possible to provide a heating device that quickly rises in temperature, stably generates water vapor, and can be easily controlled to an appropriate temperature.

According to the heating tool of the present embodiment, a heating tool that stably generates water vapor and easily controls the skin temperature to an appropriate temperature is provided.

FIG. 1 is a cross-sectional view schematically showing a water vapor generator 10 used in the embodiment. The water vapor generator 10 is formed by laminating a heat generating layer 11 and a water absorbent sheet 102. In FIG. 1, a base material layer 13 (base material 103) is additionally provided. The heat generating layer 11 contains an oxidizable metal 21, a carbon component 22, a water-absorbing polymer 23, and water.

The water vapor generator 10 generates heat by the oxidation reaction of the oxidizable metal 21 and gives a sufficient thermal effect, and has a performance of, for example, an exothermic temperature of 38 to 70 ° C. in the measurement according to JIS standard S4100. Can do.

The oxidizable metal 21 is a metal that generates heat of oxidation reaction, and examples thereof include one or more powders and fibers selected from the group consisting of iron, aluminum, zinc, manganese, magnesium, and calcium. Among these, iron powder is preferable from the viewpoints of handleability, safety, manufacturing cost, storage stability, and stability. Examples of the iron powder include one or more selected from the group consisting of reduced iron powder and atomized iron powder.

When the oxidizable metal 21 is a powder, the average particle diameter is preferably 10 μm or more and 200 μm or less, and the average particle diameter is 20 μm or more and 150 μm or less from the viewpoint that the oxidation reaction is efficiently performed. More preferred. The particle size of the oxidizable metal 21 refers to the maximum length in the form of powder, and is measured by classification using a sieve, a dynamic light scattering method, a laser diffraction method, or the like. Among these, in this embodiment, it is preferable that the particle size of the oxidizable metal 21 is measured by a laser diffraction method.
From the same viewpoint, the average particle diameter of the oxidizable metal 21 is preferably 10 μm or more, and more preferably 20 μm or more. Moreover, the average particle diameter of the oxidizable metal 21 is preferably 200 μm or less, and more preferably 150 μm or less.

The content of the oxidizable metal 21 in the heat generating layer 11 is preferably 100 g / m ² or more and 3000 g / m ² or less, and 200 g / m ² or more and 1500 g / m ² or less, expressed as basis weight. Is more preferable. Thereby, the heat_generation | fever temperature of the steam generator 10 can be raised to desired temperature. Here, the content of the oxidizable metal 21 in the water vapor generator 10 can be determined by an ash test according to JIS P8128 or a thermogravimetric measuring instrument. In addition, it can be quantified by a vibration sample type magnetization measurement test or the like using the property that magnetization occurs when an external magnetic field is applied. Among these, in the present embodiment, it is preferable to obtain the content of the oxidizable metal 21 by a thermogravimetric instrument.
From the same point of view, the content of the oxidizable metal 21 in the heat generating layer 11 is preferably 100 g / m ² or more, more preferably 200 g / m ² or more, expressed as basis weight. Further, it is preferably 3000 g / ^{m 2} or less, and more preferably 1500 g / ^{m 2} or less.

The carbon component 22 has water retention ability, oxygen supply ability, and catalytic ability. For example, one or more kinds selected from the group consisting of activated carbon, acetylene black, and graphite can be used. From the viewpoint of easily adsorbing oxygen when wet, the ability to keep moisture in the heat generating layer 11 constant, and the viewpoint that the amount of water carried on the water absorbent sheet 102 can be easily controlled within a specific range, activated carbon is preferable. Used. More preferably, 1 type, or 2 or more types of fine powder or small granular materials selected from the group consisting of coconut shell charcoal, wood powder charcoal, and peat charcoal are used. Among these, charcoal charcoal is preferable in order to easily maintain the amount of water carried on the water absorbent sheet 102 within a specific range.

The carbon component 22 has an average particle diameter of 10 μm or more from the viewpoint of being uniformly mixed with the oxidizable metal 21 and maintaining the amount of water carried on the water absorbent sheet 102 within a specific range. It is preferable to use those having a particle size of 200 μm or less, and it is more preferable to use those having an average particle size of 12 μm to 100 μm. In addition, the average particle diameter of the carbon component 22 means the maximum length in the form of powder, and is measured by a dynamic light scattering method, a laser diffraction method, or the like. Among these, in this embodiment, it is preferable that the average particle diameter of the carbon component 22 is measured by a laser diffraction method.
The carbon component 22 is preferably in the form of powder, but may be in a form other than powder, for example, in the form of fiber.
From the same viewpoint, the carbon component 22 preferably has an average particle size of 10 μm or more, and more preferably 12 μm or more. The carbon component 22 preferably has an average particle size of 200 μm or less, and more preferably 100 μm or less.

The content of the carbon component 22 in the heat generating layer 11 is preferably 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal 21, and 1 part by mass or more and 15 parts by mass. Part or less is more preferable, and 3 parts by mass or more and 13 parts by mass or less is more preferable. By doing so, moisture necessary for maintaining the oxidation reaction can be accumulated in the steam generator 10 obtained. Moreover, the oxygen supply to the water vapor | steam generator 10 is fully obtained, and the heating tool with high heat_generation | fever efficiency is obtained. Moreover, since the heat capacity of the water vapor generator 10 with respect to the heat generation amount obtained can be kept small, the heat generation temperature rises and a desired temperature rise can be obtained.
Further, the content of the carbon component 22 in the heat generating layer 11 is preferably 0.3 parts by mass or more, and preferably 1 part by mass or more with respect to 100 parts by mass of the oxidizable metal 21 content. More preferably, it is 3 parts by mass or more. Further, the content of the carbon component 22 in the heat generating layer 11 is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, with respect to 100 parts by mass of the oxidizable metal 21. More preferably, it is 13 parts by mass or less.
In addition, the content of the carbon component 22 in the heat generating layer 11 is preferably 4 g / m ² or more and 290 g / m ² or less, more preferably 7 g / m ² or more and 160 g / m ² or less, expressed as basis weight. It is preferable.
The content of the carbon component 22 in the heat generating layer 11 is expressed as basis weight, and is preferably 4 g / m ² or more, and more preferably 7 g / m ² or more. Further, the content of the carbon component 22 is preferably 290 g / m ² or less, more preferably 160 g / m ² or less, expressed as basis weight.

Examples of the water-absorbing polymer 23 include a hydrophilic polymer having a crosslinked structure capable of absorbing and retaining a liquid having a weight 20 times or more of its own weight. Examples of the shape of the water-absorbing polymer 23 include one or more selected from the group consisting of a spherical shape, a lump shape, a grape bunch shape, and a fiber shape. The mass average particle size of the water-absorbing polymer 23 is preferably 1 μm or more and 1000 μm or less, and more preferably 10 μm or more and 500 μm or less. The particle size of the water-absorbing polymer 23 is measured by a dynamic light scattering method, a laser diffraction method, or the like.
The mass average particle diameter of the water-absorbing polymer 23 is preferably 1 μm or more, and more preferably 10 μm or more. The average particle diameter of the water-absorbing polymer 23 is preferably 1000 μm or less, and more preferably 500 μm or less.

Specific examples of the water-absorbing polymer 23 include, for example, starch, crosslinked carboxylmethylated cellulose, a polymer or copolymer of acrylic acid or an alkali metal acrylate, polyacrylic acid and a salt thereof, and a polyacrylate graft weight. 1 type (s) or 2 or more types selected from the group which consists of coalescence are mentioned. Among them, use of polyacrylic acid and a salt thereof and a polyacrylate graft polymer such as a polymer or a copolymer of acrylic acid or an alkali metal acrylate can reduce the amount of water carried on the water absorbent sheet 102. , Because it is easy to maintain in a specific range.

The content of the water-absorbing polymer 23 in the heat generating layer 11 is 5 parts by mass or more with respect to 100 parts by mass of the oxidizable metal 21 from the viewpoint of the rapid rise of the temperature of the water vapor generator 10. It is preferably 7 parts by mass or more, and more preferably 9 parts by mass or more. The content of the water-absorbing polymer 23 in the heat generating layer 11 is preferably 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal 21 from the viewpoint of stably generating water vapor. 18 parts by mass or less, more preferably 16 parts by mass or less.

The basis weight of the water-absorbing polymer 23 contained in the heat generating layer 11 is 20 g / m ² or more, and 25 g / m ² or more in the dry state, from the viewpoint of the rapid rise of the temperature of the water vapor generator 10. It is preferable that it is 30 g / m ² or more. In addition, the basis weight of the water-absorbing polymer 23 contained in the heat generating layer 11 is 100 g / m ² or less, preferably 80 g / m ² or less, and 60 g / m ² or less in a dry state from the same viewpoint. More preferably, it is m ² or less. Moreover, the basic weight in the dry state of the water absorbing polymer 23 contained in the heat generating layer 11 is 20 g / m ² or more and 100 g / m ² or less from the viewpoint of making the thickness of the heat generating layer 11 appropriate and improving the production efficiency. Yes, it is preferably 25 g / m ² or more and 80 g / m ² or less, and more preferably 30 g / m ² or more and 60 g / m ² or less.

The water-absorbing polymer 23 may be present uniformly in the heat generating layer 11, but as shown in FIG. 1 from the viewpoint of the rapid rise of the temperature of the water vapor generator 10 and stable generation of water vapor. The water absorbent polymer 23 is preferably disposed so as to be in contact with the water absorbent sheet 102. In order to arrange in this way, the water-absorbing polymer 23 is laminated on, for example, one surface of the heat generating layer 11 and has a substantially sheet shape on the surface of the heat generating layer 11 on the side in contact with the water absorbing sheet 102. Be placed. The laminating method may be appropriately selected from known methods. For example, the water-absorbing polymer 23 is sprayed on a layer containing a material other than the water-absorbing polymer 23 by a spraying method, and then the water-absorbing sheet 102. The method of laminating can be employed.
As shown in FIG. 1, it is not necessary for all of the water-absorbing polymer 23 to be in contact with the water-absorbent sheet 102, and it is sufficient that at least a part of it is in contact. Further, the oxidizable metal 21 and the carbon component 22 may be partially in contact with the water absorbent sheet 102.

Further, in the heat generating layer 11, a powder having water absorption can be used in combination for the purpose of improving water absorption. Examples of the water-absorbing powder include one or more selected from vermiculite, sawdust, silica gel, and pulp powder.

The content of water in the heat generating layer 11 is preferably 12% by mass or more, more preferably 13% by mass or more, and further preferably 15% by mass or more from the viewpoint of stably generating water vapor. preferable. In addition, the content of water in the heat generating layer 11 is preferably 28% by mass or less, more preferably 27% by mass or less, from the viewpoint of the rapid rise of the temperature of the water vapor generator, more preferably 25% by mass. More preferably, it is% or less.
The water content in the heat generating layer 11 is, for example, collected about 1 g of the heat generating layer, accurately weighed mass, then measured the mass after drying the collected heat generating layer, and collected the mass difference. It can be calculated by dividing by the mass of the heat generating layer. Numerical values can be expressed as percentages as described above. Drying conditions can be 10 minutes at 150 ° C., for example.

In the heat generation layer 11, the mass ratio of the water content to the carbon component 22 content (water / carbon component) is the speed at which the temperature of the water vapor generator rises, the amount of steam generated, and the temperature control. From the viewpoint of ease, it is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 1 or more. In addition, the mass ratio of the water content to the carbon component 22 content (water / carbon component) is preferably 8.3 or less, more preferably 7.7 or less, and 6.4 or less. More preferably it is.
Furthermore, since the air permeability of the water vapor generator 10 is sufficiently ensured, a water vapor generator with sufficient oxygen supply and high heat generation efficiency can be obtained. Moreover, since the heat capacity of the water vapor generator relative to the amount of heat generated can be kept small, the heat generation temperature rises and a desired temperature rise can be obtained.

In the heat generating layer 11, the mass ratio of the water-absorbing polymer 23 to the content of the carbon component 22 (water-absorbing polymer / carbon component) is 0.4 or more from the viewpoint of the rapid rise of the temperature of the water vapor generator. Is more preferable, 0.8 or more is more preferable, and 1.1 or more is further preferable. Further, the mass ratio of the water-absorbing polymer 23 to the content of the carbon component 22 (water-absorbing polymer / carbon component) is preferably 5 or less, and preferably 3.5 or less, from the viewpoint of ease of temperature control. More preferably, it is more preferably 2.5 or less.

The exothermic layer 11 can further contain a reaction accelerator. By including the reaction accelerator, the oxidation reaction of the oxidizable metal 21 can be easily maintained. In addition, by using a reaction accelerator, the oxide film formed on the oxidizable metal 21 with the oxidation reaction can be destroyed to promote the oxidation reaction. Examples of the reaction accelerator include one or more selected from the group consisting of alkali metals, alkaline earth metal sulfates, and chlorides. Among them, a group consisting of various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride and ferric chloride, and sodium sulfate from the viewpoint of excellent conductivity, chemical stability and production cost. It is preferable to use 1 type, or 2 or more types selected from.

The content of the reaction accelerator in the heat generating layer 11 is 2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the oxidizable metal 21 from the viewpoint that a sufficient calorific value is maintained for a long time. Preferably, it is 3 parts by mass or more and 13 parts by mass or less.
From the same viewpoint, the content of the reaction accelerator in the heat generating layer 11 is preferably 2 parts by mass or more and preferably 3 parts by mass or more with respect to 100 parts by mass of the oxidizable metal 21. More preferred. Further, the content of the reaction accelerator in the heat generating layer 11 is preferably 15 parts by mass or less, and more preferably 13 parts by mass or less with respect to 100 parts by mass of the oxidizable metal 21.

The heat generating layer 11 can further contain a thickener. As a thickener, a substance that absorbs moisture and increases consistency or imparts thixotropic properties can be used. Alginate such as sodium alginate, gum arabic, tragacanth gum, locust bean gum, guar gum, gum arabic Polysaccharide thickeners such as carrageenan, agar and xanthan gum; starch thickeners such as dextrin, pregelatinized starch and starch for processing; cellulose such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose or hydroxypropylcellulose One or a mixture of two or more selected from a derivative thickener; a metal soap thickener such as stearate; and a mineral thickener such as bentonite can be used.
Among these, polysaccharide thickeners are preferable from the viewpoint that good coating performance and the amount of water carried on the water-absorbent sheet 102 can be maintained at a specific value, and a polysaccharide having a molecular weight of 1 million to 50 million. Saccharide-based thickeners are preferable, and polysaccharide-based thickeners having a molecular weight of 1.5 million to 40 million are particularly preferable. In addition, xanthan gum is preferable from the viewpoint of having good coating performance and salt resistance.

The content of the thickener in the heat generating layer 11 is preferably 0.05 parts by mass or more and 5 parts by mass or less, and 0.1 parts by mass or more with respect to 100 parts by mass of the oxidizable metal 21. More preferably, it is 4 parts by mass or less. By setting it as this range, solid content, such as the oxidizable metal 21 and the carbon component 22, can be disperse | distributed stably. Moreover, thixotropy can be imparted and the coating performance can be further improved. Furthermore, the amount of water carried on the water absorbent sheet 102 is preferable because it can be easily maintained within a specific range.
From the same viewpoint, the content of the thickener in the heat generating layer 11 is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the oxidizable metal 21, and 0.1 parts by mass. More preferably. Moreover, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of content of the oxidizable metal 21, and, as for content of the thickener in the heat generating layer 11, it is more preferable that it is 4 mass parts or less.

The heat generating layer 11 may contain a surfactant, a drug, a flocculant, a colorant, a paper strength enhancer, a pH control agent, a bulking agent, and the like as necessary.

Next, the water absorbent sheet 102 provided in the water vapor generator 10 of this embodiment will be described.
The water-absorbent sheet 102 preferably has a maximum water absorption capacity of 0.1 g / cm ² or more in terms of the rapid rise in temperature of the water vapor generator, the stability of water vapor generation, and the ease of temperature control. It is more preferably 0.15 g / cm ² or more, further preferably 0.2 g / cm ² or more, further preferably 0.5 g / cm ² or more, and 0.7 g / cm ² or more. It is even more preferred that it be. Further, from the same viewpoint, it is preferably 5 g / cm ² or less, more preferably 4 g / cm ² or less, and further preferably 3 g / cm ² or less. In the present invention, the maximum water absorption capacity of the water absorbent sheet 102 is measured by the following method.
[Measurement method of maximum water absorption capacity (Z _max ) of water absorbent sheet]
Only the water absorbent sheet is peeled off from the water vapor generator, washed with ion-exchanged water, and then heated and dried at 80 ° C. for 10 minutes. The dried water-absorbent sheet is cut into a size of about 5 cm square, and after measuring the area (S) [cm ² ] and mass (W ₀ ) [g], it is immersed in a 5 mass% sodium chloride aqueous solution for 5 minutes. Thereafter, the water absorbent sheet is taken out with tweezers and suspended in the air for 5 minutes to drip or drop water that cannot be held by the water absorbent sheet. Then, the mass (W ₁ ) [g] is measured, and the following formula (1 ) To calculate the maximum water absorption capacity (Z _max ) [g / cm ² ] of the water absorbent sheet.
Z _max = (W ₁ −W ₀ ) / S (Expression 1)

Here, the amount of water carried on the water-absorbent sheet 102 is 28 g / m ² or more in terms of basis weight from the viewpoint of the rapid rise of the temperature of the water vapor generator and the stability of the generation of the water vapor. Is more preferable, 30 g / m ² or more is more preferable, and 35 g / m ² or more is more preferable. The amount of water carried on the water-absorbent sheet 102 is preferably 150 g / m ² or less, and 140 g / m ² or less in terms of basis weight, from the viewpoint of ease of temperature control. More preferably, it is more preferably 130 g / m ² or less.
The amount of water carried on the water absorbent sheet 102 is measured, for example, by removing only the water absorbent sheet from the water vapor generator and measuring the area and mass, and then measuring the mass after drying the peeled water absorbent sheet. The mass difference can be calculated by dividing the mass difference by the area of the water absorbent sheet. Numerical values can be expressed in basis weight as described above. Drying conditions can be 10 minutes at 80 ° C., for example. The “area of the water-absorbent sheet” here refers to the area of the water-absorbent sheet in the portion laminated to the heat-generating layer. For example, when the area of the heat-generating layer is smaller than the area of the water-absorbent sheet, the heat-generating layer It calculates with the area of the water-absorbent sheet of the part which overlaps.

The mass ratio of the water absorbent sheet 102 to the water absorbent polymer 23 contained in the heat generating layer 11 is 0.9 or more and 15 or less, but is 1.5 or more from the viewpoint of the rapid rise of the temperature of the water vapor generator. It is preferable that it is 2 or more. Moreover, from a viewpoint of generating water vapor | steam stably, it is preferable that it is 13 or less, and it is more preferable that it is 10 or less.

As described above, Patent Document 1 discloses a technique for forming a water absorbing layer by spraying a water absorbing agent on a heat generating composition. However, if a large amount of water is contained in order to generate a large amount of water vapor, simply spraying a water-absorbing agent on the heat-generating composition will increase the amount of water in the heat-generating layer, making it difficult to generate heat. As a result, there was a problem that the rise of temperature was slow and the amount of water vapor generated was also reduced. On the other hand, in order to improve the temperature rise as a heating element, it is conceivable to coat the upper surface of the water-absorbing agent with another material, but this covering material prevents the passage of oxygen, resulting in water vapor. There is also a concern that the occurrence of this will be suppressed.
That is, by appropriately setting the mass ratio of the water absorbent sheet 102 to the water absorbent polymer 23 as described above, the temperature rise as the water vapor generator is effectively improved, and in addition to this, The amount of generation can be improved.
Moreover, by combining the basis weight in the dry state of the water-absorbent polymer 23 contained in the heat generating layer 11 and the basis weight in the dry state of the water-absorbent sheet 102 described later, the temperature of the heating device 100 can be appropriately controlled. Appropriate thickness makes it easy to handle and makes it possible to efficiently impart a thermal effect, and to improve manufacturing efficiency.

The water absorbent sheet 102 may be composed of, for example, a single fiber sheet, or two or more layers may be laminated.

Specific examples of the water-absorbent sheet 102 include paper, non-woven fabric, or a laminate of paper and non-woven fabric manufactured from a fiber material to be described later. Further, it may be a sheet material such as papermaking or non-woven fabric in which another fiber material is laminated or mixed with a fiber material such as pulp fiber or rayon fiber.
By using such a water-absorbent sheet 102, the amount of water carried in the sheet can be easily set within a specific range, and the temperature rise of the water vapor generator can be accelerated to generate water vapor generated. Can be effectively released.

As the fiber material, any of hydrophilic fibers and hydrophobic fibers can be used. However, it is preferable to use hydrophilic fibers, and among them, the amount of water carried on the water-absorbent sheet 102 is preferably cellulose fibers. Is more preferable because it can be easily in a specific range and the generated water vapor can be effectively released. As the cellulose fiber, chemical fiber (synthetic fiber) or natural fiber can be used.

Among chemical fibers, for example, rayon or acetate can be used as chemical fibers. On the other hand, natural fibers among cellulose fibers include, for example, various plant fibers, wood pulp fibers, non-wood pulp fibers, cotton fibers, hemp fibers, wheat straw fibers, hemp fibers, jute fibers, kapok fibers, palm fibers, and igusa. One type or two or more types selected from fibers can be used. Among these cellulose fibers, the use of crepe paper using wood pulp fibers can easily make the amount of water carried on the water absorbent sheet 102 within a specific range, and the generated water vapor can be reduced. It is preferable because it can be effectively released.

The various fiber materials preferably have a fiber length of 0.5 mm or more and 6 mm or less, and more preferably 0.8 mm or more and 4 mm or less. The fiber material preferably has a fiber length of 0.5 mm or more, and more preferably 0.8 mm or more. The fiber material preferably has a fiber length of 6 mm or less, and more preferably 4 mm or less.

In addition to the hydrophilic fiber, the water-absorbent sheet 102 may contain a hydrophobic fiber, particularly a heat-fusible fiber, if necessary. The blending amount in the case of blending the heat-fusible fiber is preferably 0.1% by mass or more and 10% by mass or less, and 0.5% by mass or more and 5% by mass or less with respect to the total amount of fibers in the water absorbent sheet 102. The following is more preferable.
From the same viewpoint, the blending amount of the heat-fusible fiber is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more with respect to the total amount of fibers in the water absorbent sheet 102. Further, the blending amount of the heat-fusible fiber is preferably 10% by mass or less, and more preferably 5% by mass or less with respect to the total amount of fibers in the water-absorbent sheet 102.

Further, the water-absorbent sheet 102 preferably has air permeability, but is normally set to a value sufficiently smaller than the air permeability value of the first bag sheet 20a described later.

The water absorbent sheet 102 has a basis weight of 50 g / m ² or more and 100 g / m ² or more in a dry state because the amount of water carried on the sheet can be easily adjusted to a specific range. Is preferable, and it is more preferable that it is 150 g / m ² or more. Further, the water-absorbent sheet 102, a basis weight in the dry state is at 500 g / ^{m 2} or less, preferably 400 g / ^{m 2} or less, more preferably 300 g / ^{m 2} or less. Further, from the viewpoint of making the thickness of the water absorbent sheet 102 appropriate and improving the production efficiency, the basis weight in the dry state of the water absorbent sheet 102 is 50 g / m ² or more and 500 g / m ² or less, and 100 g / m. preferably ² or more 400 g / ^{m 2} or less, more preferably 150 g / ^{m 2} or more 300 g / ^{m 2} or less.

As a specific aspect of the water vapor generator 10 of the present embodiment, another base material layer 13 is provided separately from the water absorbent sheet 102 described above, and in these water absorbent sheet 102 and the base material layer 13, A so-called sandwich structure is formed by sandwiching the heat generating layer 11.
Here, the base material layer 13 can be appropriately set according to the application of the heating tool to be manufactured, but is usually made of a material having poor water absorption, and is made of, for example, a synthetic resin film. can do. More specifically, a polyethylene film, a polyethylene terephthalate film, a Teflon (registered trademark) film, or the like can be used.

Here, the effect of the steam generator 10 of this embodiment is demonstrated.
The water vapor generator 10 of the present embodiment has a structure in which a heat generating layer 11 and a water absorbent sheet 102 are laminated.
By adopting this structure, moisture is present in the vicinity of the heat generating layer 11, so that the heat energy generated by the heat generating layer 11 can be effectively changed to steam. In addition, there is an effect that the temperature does not become excessively high by supplying moderate water from the water absorbent sheet 102.
Further, since the water absorbent sheet 102 exhibits specific physical properties, it is easy to supply external oxygen to the heat generating layer 11 and heat energy generated by the heat generating layer 11 can not be released to the outside.
From the above, the water vapor generator 10 of the present embodiment can realize the characteristics that the temperature rises quickly, the water vapor is stably generated, and is easily controlled to an appropriate temperature.
In addition, the water vapor generator 10 of the present embodiment has a structure in which the heat generating layer 11 and the water absorbent sheet 102 are laminated, but the water absorbent sheet 102 is located on the skin side of the user of the heating tool 100, It is preferable that the heat generating layer 11 is disposed so as to be located on the side opposite to the user's skin side. Thereby, the above characteristics can be effectively given to the user.

It continues and demonstrates an example of the manufacturing method of the water vapor generation body 10. FIG. For example, the water vapor generator 10 applies a heat-generating powder water dispersion containing an oxidizable metal 21, a carbon component 22, water, and the like to the base material layer 13, and then the applied heat-generating powder water dispersion layer. The water-absorbing polymer 23 is sprayed on the surface, and the water-absorbing sheet 102 is disposed on the water-absorbing polymer 23 sprayed last.
The exothermic powder water dispersion may be prepared by mixing all of the above-mentioned components at once, but prepare an aqueous solution by dissolving the reaction accelerator in advance in a thickener dissolved in water. Alternatively, a premixed oxidizable metal 21 and carbon component 22 may be mixed with an aqueous solution.

The reaction accelerator may be mixed with other components in the exothermic powder water dispersion at the same time. However, after coating the exothermic powder water dispersion, a reaction accelerator separately dissolved in water or the like is infiltrated and sprayed. Or you may add by dripping etc. and you may sprinkle the powder of a reaction accelerator.

In the stage of spraying the water-absorbing polymer 23 to the layer of the exothermic powder water dispersion and further disposing the water-absorbing sheet 102, water is partially absorbed in the water-absorbing polymer 23 and the water-absorbing sheet 102, The heat generating layer 11 is formed.
That is, the heat generating layer 11 is composed of the remaining components that are not absorbed by the water absorbent sheet 102.

FIG. 2 is a diagram for explaining this manufacturing method more specifically. First, an exothermic powder water dispersion 302 containing an oxidizable metal 21, a carbon component 22, water and the like is prepared in a coating tank 301. The exothermic powder water dispersion 302 may be stirred by the stirrer 303 to more uniformly disperse components insoluble in water such as the oxidizable metal 21 and the carbon component 22. The exothermic powder water dispersion 302 may be prepared by mixing all of the above-mentioned components at once. However, an aqueous solution is prepared by dissolving the reaction accelerator in advance in a thickener dissolved in water. Next, a premixed oxidizable metal 21 and carbon component 22 may be mixed with an aqueous solution.

Next, the exothermic powder water dispersion 302 is pumped up to the die head 305 by the pump 304. The heated exothermic powder water dispersion 302 is applied to the base material 103 using the die head 305 while pressing and extruding. At this time, the coating basis weight of the exothermic powder aqueous dispersion 302 is preferably 160 g / ^{m 2} or more 4,800g / ^{m 2} or less, and more preferably to 320 g / ^{m 2} or more 2,200g / ^{m 2} or less .

In addition, in FIG. 2, although the coating by die coating was illustrated, the coating method is not limited to this, For example, roll coating, screen printing, roll gravure, knife coding, a curtain coater etc. can also be used. .

By the above procedure, a continuous long product including the heat generating layer 11 and the base material 103 is obtained. On the other hand, the water-absorbing polymer 23 is sprayed and finally the water-absorbing sheet 102 is laminated to form the laminate. obtain. Finally, the water vapor generator 10 is formed by cutting this into an arbitrary size.

In the above-described method, means for keeping a non-oxidizing atmosphere may be used as necessary in order to suppress oxidation of the oxidizable metal 21 during the manufacturing process.

FIG. 3 is a schematic cross-sectional view showing an example of a heating tool provided with the steam generator 10 shown in FIG. As shown in the figure, the heating device 100 has a water vapor generator 10 having a sandwich structure in which a heat generating layer 11 is sandwiched between a water absorbent sheet 102 and a base material layer 13, and at least partly has air permeability. And a bag body 20 that houses the water vapor generator 10.

More specifically, in the heating device 100, a water vapor generator 10 having a heat generating layer 11 and a water absorbent sheet 102 is placed in a bag body 20 composed of a breathable sheet having air permeability at least partially. The periphery of the bag 20 is joined and sealed. In the heating device 100, since the heat generating layer 11 is sandwiched between the water absorbent sheet 102 and the base material layer 13, it is possible to prevent the heat generating layer 11 from adhering to the bag body 20.

The bag body 20 is preferably composed of a first bag body sheet 20a and a second bag body sheet 20b.

The first bag body sheet 20a and the second bag sheet 20b each have an extending area extending outward from the periphery of the water vapor generating body 10, and are joined in each extending area. preferable. This joining is preferably a continuous airtight joining at the periphery. The bag body 20 formed by joining the first bag body sheet 20a and the second bag body sheet 20b has a space for accommodating the water vapor generator 10 therein. The steam generator 10 is accommodated in this space. The steam generator 10 may be in a fixed state with respect to the bag body 20 or may be in a non-fixed state.

Part or all of the first bag body sheet 20a has air permeability. The air permeability of the first bag body sheet 20a (JIS P8117, revised version 2009, all the same in this specification) is preferably more than 500 seconds / 100 mL from the viewpoint of ease of temperature control. More than 1,000 seconds / 100 mL, more preferably more than 1,200 seconds / 100 mL, even more preferably 1,500 seconds / 100 mL or more.
As the first bag sheet 20a having such air permeability, for example, a porous sheet made of a synthetic resin having moisture permeability but not water permeability is preferably used. Specifically, a stretched film containing calcium carbonate or the like in polyethylene can be used. When such a porous sheet is used, various fiber sheets including one or more nonwoven fabrics selected from needle punched nonwoven fabric, air-through nonwoven fabric, and spunbonded nonwoven fabric are laminated on the outer surface of the porous sheet. Then, the texture of the first bag sheet 20a may be enhanced. The first bag body sheet 20a may be a breathable sheet that is partially or entirely breathable, or may be a non-breathable sheet that does not have breathability. A sheet having higher air permeability than the sheet 20b (that is, a sheet having low air permeability) is preferable.
The air permeability of the first bag sheet 20a is preferably 10,000 seconds / 100 mL or less from the viewpoint of the rapid rise of the temperature of the water vapor generator and the amount of generated steam. More preferably, it is 5,000 seconds / 100 mL or less, more preferably 5,000 seconds / 100 mL or less, and particularly preferably 4,000 seconds / 100 mL or less.

The second bag sheet 20b may be a part or all of a breathable sheet that is breathable or may be a non-breathable sheet that is not breathable. A sheet having a lower air permeability than the sheet 20a (that is, a sheet having a high air permeability) is preferable. By setting it as such a structure, as a heating tool which generate | occur | produces water vapor | steam, more water vapor | steam will generate | occur | produce from the 1st bag sheet | seat 20a which contact | connects the water absorbing sheet | seat 102 which is the water vapor | steam generation surface of a heat generating body, When applied to the body, the application site can be heated more efficiently.

When the second bag sheet 20b is a non-breathable sheet, a single layer or multilayer synthetic resin film, a needle punched nonwoven fabric, an air-through nonwoven fabric, and a spunbond on the outer surface of the single layer or multilayer synthetic resin film Various kinds of fiber sheets including one type or two or more types of non-woven fabric selected from non-woven fabrics may be laminated to enhance the texture of the second bag sheet 20b. Specifically, a two-layer film composed of a polyethylene film and a polyethylene terephthalate film, a laminate film composed of a polyethylene film and a nonwoven fabric, a laminate film composed of a polyethylene film and a pulp sheet, etc. are used. A film is even more preferred.

When the second bag sheet 20b is a breathable sheet, the same one as the first bag sheet 20a or a different one may be used. A sheet having a lower air permeability than the bag sheet 20a (that is, a sheet having a high air permeability) is preferable. In the case of using a different one, the second bag sheet 20b has a lower air permeability than that of the first bag sheet 20a, from the viewpoint of ease of temperature control. The air permeability of the body sheet 20b is preferably 5,000 seconds / 100 mL or more, and more preferably 8,000 seconds / 100 mL or more.

In addition, the air permeability of the second bag sheet 20b is 150,000 seconds / in terms of the rapid rise in temperature of the water vapor generator and the amount of steam generated from the first bag sheet 20a side. It is preferably 100 mL or less, and more preferably 100,000 seconds / 100 mL or less.
When the water vapor generating body 10 is accommodated in the bag body 20, the water absorbent sheet 102 is put on the first bag body sheet 20a side, and the base material layer 13 is put on the second bag body sheet 20b side, respectively, Is hermetically sealed, because the oxidation reaction of the oxidizable metal 21 is improved and a large amount of water vapor can be generated from the first bag sheet 20a side. Moreover, it is preferable that the heating tool which accommodated the water vapor generation body 10 in the bag body 20 is what the 1st bag body sheet 20a side, ie, the water absorbing sheet 102 side, applies to skin.

The water vapor generator 10 accommodated in the bag body 20 may be one sheet or may be accommodated in a multilayer state in which a plurality of sheets are laminated.

As described above, the bag body 20 may be laminated with various fiber sheets in order to enhance the texture. However, the bag body 20 is further accommodated in an exterior body (not shown) having air permeability, so that the texture and usability are increased. May be increased. The exterior body is preferably composed of a first exterior sheet and a second exterior sheet, the first exterior sheet covers one surface of the bag body 20, and the second exterior sheet covers the other side of the bag body 20. The first exterior sheet and the second exterior sheet are joined and preferably hermetically joined in an extended region that extends outward from the periphery of the bag body 20. Preferably it is. Thereby, the space for accommodating the bag body 20 is formed inside the exterior body, and the water vapor generator 10 surrounded by the bag body 20 can be accommodated in this space. The bag body 20 may be fixed to the exterior body, or may be in an unfixed state.

The air permeability of the exterior body sheet, that is, the first exterior sheet and the second exterior sheet is set to 3,000 seconds / 100 mL or less on condition that the air permeability of the first bag body sheet 20a is higher. It is preferable to set it to 1 second / 100 mL or more and 100 seconds / 100 mL or less. By setting such an air permeability, the oxidation reaction of the oxidizable metal 21 can be improved and a large amount of water vapor can be generated.

As long as the first and second exterior sheets constituting the exterior body have air permeability, for example, various fiber sheets including nonwoven fabrics, the type is not particularly limited. 1 type, or 2 or more types selected from an air through nonwoven fabric and a spun bond nonwoven fabric can be used.

The heating tool 100 can be a steam heating tool capable of generating water vapor along with the oxidation reaction of the oxidizable metal 21 because the bag body 20 has air permeability and the exterior body also has air permeability.

The heating tool 100 has an adhesive layer (not shown) formed by applying an adhesive to the outer surface of the exterior body, for example, the surface of the first exterior sheet or the second exterior sheet constituting the exterior body. You may have. The adhesive layer is used to attach the heating tool 100 to human skin or clothing. As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, the same materials as used so far in the technical field including hot melt pressure-sensitive adhesive can be used.

The heating device 100 is preferably hermetically housed in a packaging bag (not shown) having oxygen barrier properties until just before use.

The heating tool 100 is applied directly to the human body or attached to clothing and is suitably used for warming the human body. Examples of the application site in the human body include shoulders, neck, eyes, eye circumference, waist, elbows, knees, thighs, lower legs, abdomen, lower abdomen, hands, and soles. Further, in addition to the human body, the present invention is applied to various articles and suitably used for heating and keeping warm.

In addition, said water vapor | steam generator 10 can also be used for the heating tool of the structure other than shown in FIG. 3, and another use.

As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

Regarding the embodiment described above, the present invention further discloses the following composition, production method, or use.

<1> a heat generating layer containing an oxidizable metal, a carbon component, a water-absorbing polymer, and water;
A water absorbent sheet carrying water;
A water vapor generator formed by laminating
A heating device comprising at least a part of air permeability and a bag body containing the water vapor generating body,
The heating tool whose mass ratio of the said water absorbing sheet with respect to the said water absorbing polymer contained in the said heat generating layer is 0.9-15.
<2> The amount of water in the water-absorbent sheet is preferably 28 g / m ² or more, more preferably 30 g / m ² or more, and even more preferably 35 g / m ² or more, expressed as basis weight. The heating tool according to <1>, which is preferably 150 g / m ² or less, more preferably 140 g / m ² or less, and still more preferably 130 g / m ² or less.
<3> The water content in the heat generating layer is preferably 12% by mass or more, more preferably 13% by mass or more, still more preferably 15% by mass or more, and preferably 28% by mass. It is below, More preferably, it is 27 mass% or less, More preferably, it is 25 mass% or less, The heating tool as described in <1> or <2>.
<4> The content of the water-absorbing polymer in the heat generating layer is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and further preferably 9 with respect to 100 parts by mass of the oxidizable metal. The heating tool according to any one of <1> to <3>, which is not less than 20 parts by mass, preferably not more than 20 parts by mass, more preferably not more than 18 parts by mass, and still more preferably not more than 16 parts by mass.
<5> The mass ratio of the water-absorbing polymer content to the carbon component content (water-absorbing polymer / carbon component) in the heat generation layer is preferably 0.4 or more, more preferably 0.8 or more. More preferably, it is 1.1 or more, preferably 5 or less, more preferably 3.5 or less, further preferably 2.5 or less, from <1> to <4> The heating tool according to any one of the above.
<6> The basis weight in the dry state of the water-absorbent sheet is preferably 20 g / m ² or more, more preferably 35 g / m ² or more, and further preferably 50 g / m ² or more. The heating tool according to any one of <1> to <5>, in which is 500 g / m ² or less, more preferably 450 g / m ² or less, and still more preferably 400 g / m ² or less.
<7> The heating device according to any one of <1> to <6>, wherein at least a part of the water-absorbing polymer is preferably disposed in contact with the water-absorbent sheet.
<8> The content of the carbon component is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, further preferably 100 parts by mass of the oxidizable metal content. It is 3 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 13 parts by mass or less. Any one of <1> to <7> The heating device described.
<9> The heating device according to any one of <1> to <8>, wherein the heat generating layer preferably further includes a thickener.
<10> The thickener is preferably a polysaccharide thickener such as alginates such as sodium alginate, gum arabic, tragacanth gum, locust bean gum, guar gum, gum arabic, carrageenan, agar, xanthan gum; dextrin, gelatinization Starch-based thickeners such as starch and starch for processing; cellulose derivative-based thickeners such as carboxymethylcellulose, ethyl acetate, hydroxyethylcellulose, hydroxymethylcellulose or hydroxypropylcellulose; metal soap-based thickeners such as stearate; bentonite 1 type or 2 or more types selected from mineral type thickeners such as, more preferably polysaccharide type thickeners, more preferably polysaccharide type thickeners having a molecular weight of 1 million to 50 million. And more preferably molecular weight 1 0 10,000 or more 40 million or less polysaccharide thickener, warming device according to <9>.
<11> The content of the thickener is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 5 parts per 100 parts by mass of the oxidizable metal. The heating tool according to <9> or <10>, which is not more than part by mass, more preferably not more than 4 parts by mass.
<12> The air permeability of the bag body containing the water vapor generator is more than 500 seconds / 100 mL, more preferably more than 1,000 seconds / 100 mL, and still more preferably more than 1,200 seconds / 100 mL. More preferably 1,500 seconds / 100 mL or more, preferably 10,000 seconds / 100 mL or less, more preferably 8,000 seconds / 100 mL or less, and further preferably 5,000 seconds. The heating device according to any one of <1> to <11>, comprising a ventilation sheet that is not more than / 100 mL, and more preferably not more than 4,000 seconds / 100 mL.

<13> The average particle diameter of the carbon component is preferably 10 μm or more, more preferably 12 μm or more, and preferably 200 μm or less, more preferably 100 μm or less, any one of <1> to <12> The heating tool according to 1.
<14> The maximum water absorption capacity of the water absorbent sheet is preferably 0.1 g / cm ² or more, more preferably 0.15 g / cm ² or more, and further preferably 0.2 g / cm ² or more. More preferably, it is 0.5 g / cm ² or more, particularly preferably 0.7 g / cm ² or more, preferably 5 g / cm ² or less, more preferably 4 g / cm ² or less. More preferably, the heating tool according to any one of <1> to <13>, which is 3 g / cm ² or less.
<15> The content of the oxidizable metal in the heat generating layer, expressed as basis weight, is preferably 100 g / m ² or more, more preferably 200 g / m ² or more, and preferably 3, 000 g / ^{m 2} or less, and more preferably not more than 1,500 g / ^{m 2,} <1> ~ warming device according to any one of <14>.
<16> The mass ratio (water / carbon component) of the water content to the carbon component content in the heat generating layer is preferably 0.5 or more, more preferably 0.6 or more, Preferably it is 1 or more, preferably 8.3 or less, more preferably 7.7 or less, and even more preferably 6.4 or less. Any one of <1> to <15> The heating device described.
<17> The mass ratio of the water absorbent sheet to the water absorbent polymer contained in the heat generating layer is preferably 1.5 or more, more preferably 2 or more, and preferably 13 or less, The heating tool according to any one of <1> to <16>, more preferably 10 or less.

<18> The bag body containing the water vapor generator is preferably composed of a first bag sheet and a second bag sheet, and is joined in an extending region extending outward from the periphery of the water vapor generator. The heating device according to any one of <1> to <17>.
<19> The heating tool according to <18>, wherein the air permeability of the first bag sheet is preferably lower than the air permeability of the second bag sheet.
<20> The air permeability of the first bag sheet is preferably more than 500 seconds / 100 mL, more preferably more than 1,000 seconds / 100 mL, and still more preferably more than 1,200 seconds / 100 mL. More preferably, it is 1,500 seconds / 100 mL or more, preferably 10,000 seconds / 100 mL or less, more preferably 8,000 seconds / 100 mL or less, and further preferably 5,000 seconds / 100 mL. The heating tool according to <18> or <19>, which is 100 mL or less, and more preferably 4,000 seconds / 100 mL or less.
<21> The air permeability of the second bag sheet is preferably 5,000 seconds / 100 mL or more, more preferably on the assumption that the air permeability of the first bag sheet is higher than that of the first bag sheet, more preferably 8,000 sec / 100 mL or more, preferably 150,000 sec / 100 mL or less, more preferably 100,000 sec / 100 mL or less, <18> to <20> Heating equipment.
<22> The heating tool according to any one of <18> to <21>, wherein the water vapor generator is preferably housed such that the water absorbent sheet is on the first bag sheet side.
<23> The heating tool according to any one of <1> to <22>, wherein the bag body is preferably housed in a breathable exterior body.

Example 1
A heating tool having the structure shown in FIG. 3 was produced as follows.
[Preparation of exothermic powder water dispersion]
Prepare the oxidizable metal, carbon component, water, reaction accelerator, pH control agent, thickener, etc. at the blending ratio (mass ratio) shown in Table 1. (Exothermic composition) was prepared. The thickener was dissolved in water, and then the reaction accelerator and pH control agent were dissolved to prepare an aqueous solution. On the other hand, a powder in which an oxidizable metal and a carbon component are pre-mixed is prepared, and the pre-mixed powder is put into an aqueous solution. Got.
The types, product names, and manufacturers of oxidizable metals, carbon components, water, reaction accelerators, and thickeners are as follows.
Oxidizable metal: Iron powder (Iron powder RKH, DOWA IP CREATION Co., Ltd.) average particle size 45 μm
Carbon component: activated carbon (Calboraphin, manufactured by Nippon Enviro Chemicals Co., Ltd.) average particle size 40 μm
Thickener: Xanthan gum (Echo Gum BT, manufactured by DSP Gokyo Food & Chemical Co., Ltd.) Molecular weight 2,000,000
Water: tap water pH control agent 1: tripotassium phosphate (manufactured by Yoneyama Chemical Co., Ltd.)
pH control agent 2: 48% potassium hydroxide solution (manufactured by Kanto Chemical Co., Inc.)
Reaction accelerator: Sodium chloride (Japanese Pharmacopoeia sodium chloride, manufactured by Tomita Pharmaceutical Co., Ltd.)

(Preparation of steam generator)
As the base material layer, PE laminated paper (manufactured by Knit Co., Ltd.) was used, and the exothermic powder water dispersion was applied to the surface of the base material layer of 24.01 cm ² (4.9 cm × 4.9 cm) with a thickness of about 3 mm. Coated. The exothermic powder water dispersion used at this time was 1.4 g.
Subsequently, 0.12 g of a water-absorbing polymer (spherical, average particle size 300 μm, Aquaric CAW-151, manufactured by Nippon Shokubai Co., Ltd.) was added to the coated surface of the above exothermic powder water dispersion by about 0.5 mm. (Basis weight 50 g / m ² ).
Subsequently, a 4.9 cm × 4.9 cm crepe paper (basis weight 63 g / m ² , manufactured by Daishowa Paper Industry Co., Ltd.) was used as a water absorbent sheet and laminated on the sprayed part of the water absorbent polymer. The water vapor generating body was produced by integrating them.
In addition, the maximum water absorption capacity of the water absorbent sheet used here was 0.24 g / cm ² as a result of measurement by the method described later (hereinafter the same).

[Preparation of heating tool]
The water vapor generator obtained above in a bag having air permeability (6.5 cm × 6.5 cm: the air permeability of the first bag sheet is 1500 seconds / 100 mL, the second bag sheet is air-impermeable). The peripheral part was hermetically sealed so that the water-absorbent sheet was on the first bag sheet side and the base material layer was on the second bag sheet side.
Furthermore, in an outer bag (7.5 cm × 7.5 cm) made of an air-through non-woven fabric (air permeability 1 second / 100 mL, 30 g / m ² ), a pressure sensitive adhesive is placed 1 cm wide × 4 cm long, 100 g / m ^{2 on} one side periphery. The one coated with a release paper and covered with a release paper was prepared, and the one in which the water vapor generator was contained in the bag body was put in the outer bag, and the peripheral portion was hermetically sealed as a heating tool. The heating tool was put in an oxygen-blocking bag until the evaluation described later was carried out. The series of operations was performed under a nitrogen stream.

(Examples 2 to 6)
A heating tool was prepared in the same manner as in Example 1 except that the maximum water absorption capacity of the water absorbent sheet used and the content of the water absorbent polymer were those shown in Table 2 or Table 3.

(Comparative Examples 1 to 3)
A heating tool was prepared in the same manner as in Example 1 except that the maximum water absorption capacity of the water absorbent sheet used and the content of the water absorbent polymer were those shown in Table 2 or Table 3.

[Evaluation]
The steam generators of the examples and comparative examples, and the heating tools provided with the steam generators were analyzed and evaluated in the following points. The results are shown in Table 2 or Table 3.

1. Moisture content measurement The maximum water absorption capacity and moisture content of the water-absorbent sheet and the moisture content of the heat generation layer for the water vapor generators of the examples and comparative examples were measured as follows.

<1> Method for measuring maximum water absorption capacity (Z _max ) of water-absorbent sheet Only the water-absorbent sheet was peeled from the water vapor generator, washed with ion-exchanged water, and then heated and dried at 80 ° C. for 10 minutes. The dried water-absorbent sheet was cut into a size of about 5 cm square, and after measuring the area (S) [cm ² ] and mass (W ₀ ) [g], it was immersed in a 5 mass% sodium chloride aqueous solution for 5 minutes. Take out with tweezers and hang it in the air for 5 minutes to drain or drop the water that the water absorbent sheet cannot hold, measure the mass (W ₁ ) [g], and use the following formula (1) to determine the water absorbent sheet The maximum water absorption capacity (Z _max ) [g / cm ² ] was calculated.
Z _max = (W ₁ −W ₀ ) / S (Expression 1)

<2> Water content of water-absorbent sheet (W ₁₁ )
Only the water-absorbent sheet was peeled off from the water vapor generator, and the area (S) [cm ² ] and the mass (W ₂ ) were measured. The mass after drying the water absorbent sheet at 80 ° C. for 10 minutes was measured (W ₃ ), and the water content (W ₁₁ ) of the water absorbent sheet was calculated based on the following (Equation 2) (g / m ² ). It calculated in.
W ₁₁ = (W ₂ −W ₃ ) / (S × 10 ⁻⁴ ) (Expression 2)

<3> Moisture content of heat generation layer (W ₁₂ )
About 1 g of the heat generation layer formed on the substrate was collected and weighed precisely (W ₄ ). The mass after drying the heat generating layer after drying at 150 ° C. for 10 minutes was measured (W ₅ ), and the water content of the heat generating layer was calculated by the following (Formula 3).
W ₁₂ = (W ₄ −W ₅ ) / W ₄ × 100 (Equation 3)

2. Exothermic measurement Using the measuring machine based on JIS S4100, the 1st bag body sheet side of a heating tool was affixed on the measurement surface, and the exothermic measurement was performed. In this exothermic measurement, the time axis is plotted on the horizontal axis and the temperature is plotted on the vertical axis.
In addition, [maximum temperature (° C.)], [temperature rise time (min)], and [duration (min)] are obtained from the plot results. Specifically, for [maximum temperature (° C.)], the highest temperature (° C.) from the start of measurement to the end of measurement, and for [temperature rise time (min)], 35 ° C. The time (minutes) and [duration (min)] required to reach 45 ° C. from 45 ° C. were set to 45 ° C. or more (minutes) from the start of measurement to the end of measurement.

3. Water vapor generation amount The water vapor generation amount was measured as follows using a water vapor generation amount measuring device 30 shown in FIG. The water vapor generation amount measuring device 30 shown in FIG. 4 allows dehumidified air (humidity less than 2%, flow rate 2.1 L / min) to flow into an aluminum measurement chamber (volume 2.1 L) and a lower portion of the measurement chamber 31. An inflow path 32 and an outflow path 33 through which air flows out from the upper part of the measurement chamber 31 are provided. An inlet temperature / humidity meter 34 and an inlet flow meter 35 are attached to the inflow path 32. On the other hand, an outlet temperature / humidity meter 36 and an outlet flow meter 37 are attached to the outflow passage 33. A thermometer (thermistor) 38 is attached in the measurement chamber 31. A thermometer having a temperature resolution of about 0.01 ° C. was used.
The heating tool was taken out of the packaging material at a measurement environment temperature of 30 ° C. (30 ± 1 ° C.) and placed in the measurement chamber 31 with its water vapor generating surface facing up. A thermometer 38 with a metal ball (4.5 g) was placed on it. In this state, dehumidified air was flowed from the lower part of the measurement chamber 31. The difference in absolute humidity before and after the air flowed into the measurement chamber 31 was determined from the temperature and humidity measured by the inlet temperature and humidity meter 34 and the outlet temperature and humidity meter 36. Further, the amount of water vapor released by the heating tool was calculated from the flow rates measured by the inlet flow meter 35 and the outlet flow meter 37. Table 2 or Table 3 shows the amount of water vapor generated for 10 minutes from the start of measurement.

4). Maximum skin temperature The heating tool obtained as described above was applied to the eye, and the skin temperature of the upper eyelid was measured using a temperature logger LT8A (manufactured by Gram Corporation). The highest temperature in 15 minutes after wearing was defined as the maximum skin temperature.
Table 2 or Table 3 shows the maximum temperature among the skin temperatures thus measured as [skin maximum temperature [° C.]].

As shown in Table 2 and Table 3, the heating tools obtained in the examples had a faster temperature rise than the heating tools obtained in the respective comparative examples, and the amount of generated steam was also good. It was. Further, the temperature of the heat generation was also appropriate, and when applied to the skin, a comfortable degree of warmth could be given.

This application claims priority based on Japanese Patent Application No. 2015-144450 filed on July 21, 2015, and Japanese Patent Application No. 2016-128749 filed on June 29, 2016. The entire disclosure of which is incorporated herein.

Claims

A heat generating layer containing an oxidizable metal, a carbon component, a water-absorbing polymer, and water;
A water absorbent sheet carrying water;
A water vapor generator formed by laminating
A heating device comprising at least a part of air permeability and a bag body containing the water vapor generating body,
The heating tool whose mass ratio of the said water absorbing sheet with respect to the said water absorbing polymer contained in the said heat generating layer is 0.9-15.
A heat generating layer containing an oxidizable metal, a carbon component, a water-absorbing polymer, and water;
A water absorbent sheet carrying water;
A water vapor generator formed by laminating
A heating device comprising at least a part of air permeability and a bag body containing the water vapor generating body,
The basis weight of the water-absorbing polymer contained in the heat generating layer is 20 g / m 2 or more and 100 g / m 2 or less in a dry state, and the basis weight of the water-absorbing sheet is 50 g / m 2 in a dry state. A heating tool that is 500 g / m 2 or more.
The heating tool according to claim 1 or 2, wherein the amount of water in the water-absorbent sheet is 28 g / m 2 or more and 150 g / m 2 or less in terms of basis weight.
The heating tool according to any one of claims 1 to 3, wherein a content of the water in the heat generating layer is 12 mass% or more and 28 mass% or less.
The content of the water-absorbing polymer in the heat generating layer is 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. Heating tool as described in.
The mass ratio of the water-absorbing polymer content to the carbon component content in the heat-generating layer (water-absorbing polymer / carbon component) is 0.4 or more and 5 or less. The heating tool according to Item 1.
The heating tool according to any one of claims 1, 3 to 6, wherein the water-absorbent sheet has a dry basis weight of 50 g / m 2 or more and 500 g / m 2 or less.
The heating tool according to any one of claims 1 to 7, wherein at least a part of the water-absorbing polymer is disposed in contact with the water-absorbing sheet.
9. The apparatus according to claim 1, wherein the water absorbent sheet is disposed on a skin side of a user of the heating tool, and the heat generation layer is disposed on a side opposite to the skin side of the user. The heating tool described in the item.
The basis weight of the water-absorbing polymer contained in the heat generating layer is 25 g / m 2 or more and 80 g / m 2 or less in a dry state, and the basis weight of the water-absorbing sheet is 100 g / m 2 in a dry state. The heating tool according to any one of claims 1 to 9, wherein the heating tool is 400 g / m 2 or less.
The warm heat according to any one of claims 1 to 10, wherein a content of the carbon component is 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. Ingredients.
The heating tool according to any one of claims 1 to 11, wherein the heat generating layer further contains a thickener.
The heating tool according to claim 12, wherein the content of the thickener is 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the oxidizable metal.
The thickener is one or two selected from polysaccharide thickeners, starch thickeners, cellulose derivative thickeners, metal soap thickeners, and mineral thickeners. It is the above, The heating tool of Claim 12 or 13.
The heating tool according to any one of claims 12 to 14, wherein the thickener includes a polysaccharide thickener having a molecular weight of 1 million to 50 million.
The heating tool according to any one of claims 1 to 15, wherein the bag body containing the water vapor generating body includes a ventilation sheet having an air permeability of more than 500 seconds / 100 mL and 10,000 seconds / 100 mL or less.
The heat according to any one of claims 12 to 16, wherein the content of the thickener is 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. Ingredients.
The heating tool according to any one of claims 1 to 17, wherein an average particle size of the carbon component is 10 µm or more and 200 µm or less.
The heating tool according to any one of claims 1 to 18, wherein a maximum water absorption capacity of the water absorbent sheet is 0.1 g / cm 2 or more and 5 g / cm 2 or less.
The warm heat according to any one of claims 1 to 19, wherein a content of the oxidizable metal in the heat generating layer is 100 g / m 2 or more and 3,000 g / m 2 or less in terms of basis weight. Ingredients.
21. The mass ratio (water / carbon component) of the water content to the carbon component content in the heat generation layer is 0.5 or more and 8.3 or less. Heating tool as described in.
The heating tool according to any one of claims 1 to 21, wherein a mass ratio of the water absorbent sheet to the water absorbent polymer contained in the heat generating layer is 1.5 or more and 13 or less.
The bag body containing the water vapor generator is composed of a first bag sheet and a second bag sheet, and the first bag is extended in an extending area extending outward from the periphery of the water vapor generator. The heating tool according to any one of claims 1 to 22, wherein the bag sheet and the second bag sheet are joined.
The heating tool according to claim 23, wherein the air permeability of the first bag body sheet is lower than the air permeability of the second bag body sheet.
The heating tool according to claim 23 or 24, wherein the first bag sheet has an air permeability of more than 500 seconds / 100 mL and 10,000 seconds / 100 mL or less.
The air permeability of the second bag sheet is higher than the air permeability of the first bag sheet, and is 5,000 seconds / 100 mL or more and 150,000 seconds / 100 mL or less. The heating tool according to claim 1.
The heating device according to any one of claims 23 to 26, wherein the water vapor generator is accommodated such that the water absorbent sheet is on the first bag sheet side.
The heating tool according to any one of claims 1 to 27, wherein the bag body is accommodated in an exterior body having air permeability.