JP4420914B2 - Heating equipment - Google Patents

Description

  The present invention relates to a heating device using heat generated by an oxidation reaction between oxygen in air and an oxidizable metal.

  For example, a heating tool described in Patent Document 1 is known as a conventional technique related to a heating tool that uses heat generated by an oxidation reaction between oxygen in the air and an oxidizable metal powder.

  In this heating device, a plurality of heating elements each containing heating powder in a flat bag body having air permeability are attached to a cap-shaped base sheet arranged along the head.

  By the way, this heating tool has become rugged when the flexibility of the heating element is lost as the heating powder is solidified. For this reason, the heating tool which was excellent in the touch and the mounting | wearing property to a body and can be applied to various uses was desired.

JP 2003-332 A

  Therefore, the present invention has been made in view of the above-described problems, and has an object to provide a novel heating device that has good touch and wearability to the body and can be applied to various uses. To do.

  The present invention relates to a heating device including a heat generating body composed of a heat generating element having a water vapor generating capacity and a breathable container that stores the heat generating element, wherein the heat generating main body generates heat from the heat generating element. The above-mentioned object is achieved by providing a heating tool provided so as to be expanded by water vapor generated along with the above.

The present invention relates to a heating device including a heat generating body composed of a heat generating element having water vapor generating ability and a breathable container for accommodating the heat generating element , wherein the heat generating element is an oxidizable metal, a water retaining material. A paper sheet containing an agent, a fibrous material, and water, and the amount of water vapor generated with the heat generation of the heating element in the heat generating body is 1.0 to 100 mg / (cm ² · 10 min) The object is achieved by providing a warming tool.

  ADVANTAGE OF THE INVENTION According to this invention, the novel warming tool which is favorable to the touch and the mounting | wearing property to a body, and can be applied to various uses is provided.

  The present invention will be described below based on preferred embodiments with reference to the drawings.

  1 to 4 show an embodiment of the heating device of the present invention. In these drawings, reference numeral 1 denotes a heating tool.

  As shown in FIG. 1, the heating device 1 includes a heat generating body 4 including a heat generating element 2 having a water vapor generating ability and a breathable container 3 that stores the heat generating element 2. The exothermic main body 4 can be provided so as to expand due to water vapor generated as the heating element 2 generates heat, as will be described later.

  The heating tool 1 of the present embodiment has an insertion portion 5 for inserting a part of the body. Further, in the warming tool 1, the insertion portion forming material 6 is joined to the upper surface of the exothermic main body 4, and the insertion portion 5 having the insertion port 50 is formed outside the exothermic main body 4.

  The heating tool of the present invention preferably has an exothermic temperature of 30 to 100 ° C, and more preferably 35 to 60 ° C. Here, the heat generation attainable temperature is, for example, a testing machine capable of supplying 5.0 liter / min of dry air into the sealed system in an environment with a volume of 4.2 liters and a relative humidity of 1% or less. It is the value which measured the temperature under a heating tool with the thermocouple when it prepares and leaves a heating tool in the inside, and it was made to heat | fever-generate. The temperature at which the heating device generates heat can be arbitrarily designed by combining the composition and sheet configuration described below, depending on the product application, such as when rapid heat generation is required or when it is necessary to maintain a relatively low temperature for a long time. it can.

In the heating device of the present invention, the amount of water vapor generated per unit area of the heating element is preferably 1 to 100 mg / (cm ² · 10 min), and is preferably 5.0 to 50.0 mg / (cm ² -10 min) is more preferable. The amount of water vapor generated is determined by measuring the humidity changed by the generated water vapor. The amount of water vapor generated is a combination of the composition and sheet configuration described below depending on the application of the product, such as when rapid heat generation is required depending on the product application, as well as the heat generation arrival time, or when it is necessary to maintain for a long time at a relatively low temperature. Can be designed arbitrarily.

  The heating tool 1 preferably has an overall thickness of 0.1 to 10 mm, particularly 0.3 to 5.0 mm. By setting the thickness of the heating tool 1 in such a range, in addition to being excellent in portability, it is very soft and flexible, so that the usability and feeling of use are very excellent. When the heating device is provided with expansibility by water vapor generated by the heat generation of the heating element 2, a comfortable feeling of pressure can be given to the inside of the insertion portion due to the heat expansion during use.

  When imparting expandability to the heating device of the present invention by water vapor generated with the heat generation of the heating element, the volume expansion ratio of the heating device (the exothermic main body in this embodiment) is that of the heating device. Although a preferable range varies depending on the application, it is preferably about 1.5 to 10,000 times, more preferably about 3 to 7000 times, from the viewpoint that the touch is good and the skin has an appropriate feeling of pressure (adhesion). Here, the volume expansion ratio can be measured, for example, as follows. That is, ultrafine particle expanded beads (hereinafter simply referred to as expanded beads) are filled into a container of a certain capacity (for example, a cube whose upper side is 30 cm open). Thereafter, a sample of a heating tool before and after heat generation (in this embodiment, a heat generating main body) is put in the container, and the foamed beads are filled without a gap. Then, the weight of the expanded beads that cannot be contained in the container is measured by adding the sample, and the volume of the sample before and after the heat generation is calculated by dividing by the density. After calculating the volume of the sample before and after heat generation in this way, the volume expansion ratio is calculated by dividing the volume of the sample after heat generation by the volume of the sample before heat generation. Here, the density is obtained by dividing the weight of the foam beads filled in the container by the volume of the container. As a simple method, a sample of a heating tool before and after heat generation (in this embodiment, a heat generating main body) is placed in a container filled with a predetermined amount of water, and the volume change can be obtained.

In the heating device of the present invention, in order to expand the exothermic body, the moisture permeability is preferably 1.5 to 10 kg / (m ² · 24 h), more preferably ^{2 to} 8 kg / (m ² · 24 h). And the air permeability is preferably 10 to 5000 seconds / 100 ml, more preferably 30 to 1000 seconds / 100 ml. Here, the moisture permeability of the exothermic main body is a value measured according to JIS Z208. The air permeability refers to the Oken type air permeability unless otherwise specified, and is a value measured by the time required for 100 ml of air to pass through an area of 645 mm ² .

  In the heating device 1 of the present embodiment, the heating element 2 is a paper sheet containing an oxidizable metal, a water retention agent, a fibrous material, and water (hereinafter referred to as an exothermic intermediate and a case where no electrolyte component and moisture are contained). The case of containing a sheet, an electrolyte component, and moisture is referred to as a heat generating sheet). In the heating device 1 of the present embodiment, the heating element 2 is formed by laminating two heating sheets 20 (see FIG. 2).

  The exothermic intermediate sheet 20 preferably contains 50% by weight or more of components other than the fibrous material, more preferably 70% by weight or more, and further preferably 80% by weight or more. When the component other than the fibrous material is 50% by weight or more, the heat generation temperature rises to a level that makes it feel hot when touched with a human fingertip or the like. The more components other than the fibrous material, the better. However, the upper limit is 98% by weight from the viewpoint of obtaining the strength necessary to maintain the workability of the exothermic intermediate sheet 20. Here, components other than the fibrous material are measured as follows.

Components other than the fibrous material in the exothermic intermediate sheet 20 can be obtained from the following formula from the solid content weight and composition in the raw material composition and the dry weight of the exothermic intermediate sheet 20.
Weight of raw material composition: Ms
Content of fibrous material in solid content of raw material composition: a (%)
Dry weight of exothermic intermediate sheet: Mh
Content of components other than the fibrous material in the exothermic intermediate sheet: b
b = (Mh / Ms) × (100−a)

  As the oxidizable metal, an oxidizable metal conventionally used in this type of exothermic molded body can be used without particular limitation. As the form of the oxidizable metal, it is preferable to use a form having a powdery or fibrous form from the viewpoint of handleability and moldability.

  Examples of the oxidizable metal having a powder form include iron powder, aluminum powder, zinc powder, manganese powder, magnesium powder, and calcium powder. Among these, handling property, safety, and manufacturing cost are included. Iron powder is preferably used. The oxidizable metal has a particle size (hereinafter referred to as the particle size, the maximum length in the form of powder, or dynamic light scattering because the fixability to a fibrous material and control of the reaction are good. Means an average particle diameter measured by a laser diffraction method, etc.) is preferably 0.1 to 300 μm, and contains 50% by weight or more of 0.1 to 150 μm in particle diameter. More preferably, it is used.

  Examples of the oxidizable metal having a fibrous form include steel fibers, aluminum fibers, and magnesium fibers. Among these, steel fibers, aluminum fibers, and the like are preferably used from the viewpoints of handleability, safety, and manufacturing cost. As the oxidizable metal having a fibrous form, a fiber having a fiber length of 0.1 to 50 mm and a thickness of 1 to 1000 μm is used in terms of formability, mechanical strength of the obtained sheet, surface smoothness, and heat generation performance. It is preferable.

  The blending amount of the oxidizable metal in the exothermic intermediate sheet 20 is preferably 10 to 95% by weight, and more preferably 30 to 80% by weight. When the blending amount is 10% by weight or more, the heat generation temperature of the heat generating sheet 20 rises to a level that a person feels hot by touching with a fingertip or the like. Moreover, since the fibrous material and the adhesive component to be described later for molding the heat generating sheet do not increase, it is excellent in feeling of use without becoming hard. When the blending amount is 95% by weight or less, formation of an oxide film such as an oxidizable metal on the surface of the heat generating sheet 20 is suppressed, and air permeability is not impaired. As a result, the reaction easily occurs up to the inside of the sheet, and the heat generation temperature rises. Further, it does not become too hard due to expansion and condensation of the oxidizable metal due to the oxidation reaction, and the heat generation time is maintained. Moreover, the water supply by the water retaining agent is sufficient, and the oxidizable metal can be prevented from falling off. In addition, the fibrous material and adhesive components (flocculating agent, etc.) that form the heat generating sheet 20 are not reduced, and mechanical strength such as bending strength and tensile strength is also maintained. Here, the blending amount of the oxidizable metal in the heat generating sheet 20 can be obtained by an ash test or a thermogravimetric instrument according to JIS P8128. For example, in the case of iron, 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.

  As the water retentive agent, a water retentive agent that has been conventionally used for exothermic molded bodies can be used without particular limitation. In addition to functioning as a water retention agent, the water retention agent also has a function as an oxygen retention / supply agent for the oxidizable metal. Examples of the water retention agent include activated carbon (coconut husk charcoal, charcoal powder, calendar bituminous coal, peat, lignite), carbon black, acetylene black, graphite, zeolite, perlite, vermiculite, silica, cancrinite, fluorite and the like. Among these, activated carbon is preferably used because it has water retention ability, oxygen supply ability, and catalytic ability. As the water retention agent, it is preferable to use a powdery one having a particle size of 0.1 to 500 μm, and 50 to 0.1 to 200 μm from the viewpoint that an effective contact state with an oxidizable metal can be formed. It is more preferable to use those containing at least wt%. As the water retention agent, a form other than the powder form as described above can be used. For example, a form of a fiber form such as activated carbon fiber can be used.

  The blending amount of the water retention agent in the exothermic intermediate sheet 20 is preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight. When the blending amount is 0.5% by weight or more, moisture necessary for maintaining the reaction to such an extent that the oxidizable metal rises to a temperature higher than the human body temperature due to the oxidation reaction can be accumulated in the heating sheet 20. Further, since the air permeability of the heat generating sheet 20 is not impaired, the oxygen supply is good and the heat generation efficiency is excellent. When the blending amount is 60% by weight or less, the heat capacity of the heat generation sheet 20 with respect to the heat generation amount obtained is not increased, and an increase in heat generation temperature that can be experienced when a person is warm is obtained. In addition, the occurrence of falling off of components such as water retention agents can be suppressed. Further, a fibrous material and an adhesive component described later for forming the heat generating sheet 20 are not decreased, and mechanical strength such as bending strength and tensile strength is also maintained.

  Examples of the fibrous material include, for example, plant fibers (cotton, kabok, wood pulp, non-wood pulp, peanut protein fiber, corn protein fiber, soybean protein fiber, mannan fiber, rubber fiber, hemp, Manila hemp Sisal, New Zealand hemp, Rafu hemp, eggplant, rush, straw, etc.), animal fibers (wool, goat hair, mohair, cashmere, alkapa, Angola, camel, vicuña, silk, feathers, down, feather, algin fiber, chitin Fiber, casein fiber, etc.) and mineral fiber (asbestos, etc.). Examples of synthetic fibers include semi-synthetic fibers (acetate, triacetate, oxide acetate, promix, chlorinated rubber, hydrochloric acid rubber, etc.), metal fibers , Carbon fiber, glass fiber and the like. Also, polyolefins such as high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, etc., polyester, polyvinylidene chloride, starch, polyvinyl alcohol or polyvinyl acetate, single fibers such as copolymers or modified products thereof, or these A core-sheath composite fiber having a resin component in the sheath can be used. Among these, polyolefins and modified polyesters are preferably used because they have high adhesive strength between fibers, are easy to form a three-dimensional network structure by fusion of fibers, and have a melting point lower than the ignition point of pulp fibers. Synthetic fibers such as branched polyolefins are also preferably used because of their good fixability with materials such as oxidizable metals and water retention agents. These fibers can be used alone or in combination of two or more. In addition, these fibers can be used in the form of collected and reused. Among these, wood pulp, cotton from the viewpoints of fixability of components such as the oxidizable metal and the water retention agent, flexibility of the resulting molded sheet, oxygen permeability resulting from the presence of voids, production cost, etc. Is preferably used.

  The fibrous material preferably has a CSF (Canadian Standard Freeness) of 600 ml or less, and more preferably 450 ml or less. When the amount is 600 ml or less, the fixing ratio between the fibrous material and the components such as the oxidizable metal and the water retention agent is good, and the heating device obtained by maintaining a predetermined blending amount has excellent heat generation performance. . In addition, the formability is good, for example, a sheet having a uniform thickness can be obtained. In addition, since the fixing between the fibrous material and the component is good, it is possible to obtain a bond strength derived from the dropping of the component, the entanglement between the component and the fibrous material, and hydrogen bonding. For this reason, mechanical strength, such as bending strength and tensile strength, is obtained, and workability is also improved.

The lower the CSF of the fibrous material, the better. However, in the normal papermaking only of pulp fiber, when the component ratio other than the fibrous material is low, the drainage is very poor and the dehydration is difficult when the CSF is less than 100 ml. As a result, a heat-generating sheet with a uniform thickness cannot be obtained, or a molding failure such as blister breakage during drying occurs. In the present invention, since the ratio of components other than the fibrous material is high, it is possible to obtain a heat generating sheet with good drainage and uniform thickness. Further, since the CSF is lower as the CSF is lower, the fixability between the fibrous material and components other than the fibrous material is improved, and a high sheet strength can be obtained.
Adjustment of the CSF of the fibrous material can be performed by a beating process or the like. CSF may be adjusted by mixing low and high CSF fibers.

  The fibrous material preferably has a negative (negative) surface charge. As the surface charge is strongly negatively charged, the fixability of powder components such as oxidizable metals and water retention agents to the fibrous material is good, and the powder holding property is improved. The heat generation characteristics are further improved. Further, it is possible to prevent a large amount of powder components such as an oxidizable metal and a water retaining agent from being mixed in the waste water in the wet papermaking process, and this does not adversely affect productivity and environmental conservation. Here, the charge amount of the fibrous material is measured by colloid titration. The same applies to the zeta potential, which is the apparent potential at the shear plane between the charged particle interface and the solution. The zeta potential is measured by streaming potential method, electrophoresis method or the like.

  The fibrous material preferably has an average fiber length of 0.1 to 50 mm, and more preferably 0.2 to 20 mm. When the average fiber length is within such a range, sufficient mechanical strength such as bending strength and tensile strength of the resulting heat generating sheet 20 can be obtained. Further, since the fiber layer is not formed too densely and the air permeability of the heat generating sheet 20 is not impaired, the oxygen supply is good and the heat generation is excellent. Further, the fibrous material is uniformly dispersed in the heat generating sheet 20, and uniform mechanical strength is obtained. Further, the heat generating sheet 20 having a uniform thickness is obtained, the fiber spacing is not too wide, and the ability to hold components such as the oxidizable metal and the water retention agent by the fibers can be obtained, so that dropping of the components can be suppressed. .

  The amount of the fibrous material in the exothermic intermediate sheet 20 is preferably 2 to 50% by weight, and more preferably 5 to 40% by weight. When the blending amount is 2% by weight or more, an effect of preventing the components such as the oxidizable metal and the water retention agent from falling off can be obtained. Further, the heat generating sheet 20 is also flexible. When the blending amount is 50% by weight or less, the heat capacity with respect to the calorific value of the exothermic molded body is not increased, and a sufficient temperature rise can be obtained. Moreover, the ratio of the component in the heat generating sheet 20 to be obtained is not lowered, and a desired heat generation performance can be obtained.

  Here, the composition ratio of each component can determine the content of the fibrous material and the content of the oxidizable substance by, for example, a thermogravimetric measuring device, and the content of the water retention agent by subtraction from the total amount.

A flocculant may be added to the heat generating sheet 20 as described later.
In addition, the heat generating sheet 20 includes additives usually used for paper making such as a sizing agent, a colorant, a paper strength enhancer, a yield improver, a filler, a thickener, a pH control agent, and a bulking agent. The product can be added without any particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.

The exothermic sheet 20 preferably contains an electrolyte.
As the electrolyte, there can be used any electrolyte that has been conventionally used in this type of exothermic molded body without particular limitation. Examples of the electrolyte include alkali metal, alkaline earth metal or heavy metal sulfates, carbonates, chlorides or hydroxides. Among these, various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and iron chloride (first and second) are preferably used from the viewpoint of excellent conductivity, chemical stability, and production cost. These electrolytes can be used alone or in combination of two or more.

  The amount of the electrolyte in the heat generating sheet 20 is preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight in terms of the weight ratio of water in the heat generating sheet 20. When the blending amount is 0.5% by weight or more, the oxidation reaction of the resulting heat generating sheet 20 proceeds sufficiently. Further, the moisture ratio in the heat generating sheet 20 for securing the electrolyte necessary for the heat generating function does not increase. As a result, the heat capacity of the heat generating sheet 20 does not increase, and a sufficient heat generation temperature rise can be obtained. When the blending amount is 30% by weight or less, excess electrolyte does not precipitate, and the air permeability of the heat generating sheet 20 is not impaired. In addition, the water ratio in the heat generating sheet 20 for securing the electrolyte necessary for the heat generating function is not lowered, and sufficient water can be supplied to the oxidizable metal or the like, and the electrolyte can be uniformly supplied to the heat generating sheet 20. Therefore, the heat generation performance is excellent.

  The heat generating sheet 20 preferably has a moisture content (weight moisture content, the same applies hereinafter) of 10 to 80%, and more preferably 20 to 60%. When the water content is 10% or more, water necessary for maintaining the oxidation reaction can be secured, and the oxidation reaction proceeds sufficiently. Moreover, since moisture can be uniformly supplied to the heat generating sheet 20, uniform heat generation performance can be obtained. When the moisture content is 80% or less, the heat capacity with respect to the heat generation amount of the heat generating sheet 20 does not increase, and the heat generation temperature rises sufficiently. Further, since the air permeability of the heat generating sheet 20 is not impaired, the heat generating performance is excellent, and sufficient shape retention and mechanical strength can be obtained.

  The thickness of the heat generating intermediate sheet 20 is preferably 0.08 to 1.2 mm, and more preferably 0.1 to 0.6 mm. When the thickness is 0.08 mm or more, the heat generation performance and mechanical strength are excellent, the fixing ratio of components such as the oxidizable metal and the water retention agent is good, and a stable and uniform thickness and composition distribution are obtained. be able to. Sheet breakage due to the occurrence of pinholes, etc. is difficult to occur, and there is no hindrance to productivity and workability. When the thickness is within 1.2 mm, a decrease in the bending strength of the sheet can be suppressed. In addition, it is difficult to cause brittle fracture, is soft, and can be worn on the body without a sense of incongruity. In terms of productivity, the paper layer formation time and drying time can be shortened, and the operability is excellent. Also, the heat generation performance is good. In addition, it is excellent in workability because it is difficult to break and break. Here, the thickness of the exothermic intermediate sheet can be measured by measuring the thickness of five or more points using a Digimagic indicator (Mitutoyo Corporation, IDF-112, pressurizing force 1.28 N) and obtaining an average value. it can.

Heating the intermediate sheet 20 is preferably a basis weight of one that is 10~1500g / m ^2, and more preferably 50~900g / m ^2. When the basis weight is 10 g / m ² or more, a particularly stable sheet can be formed when an oxidizable metal having a large specific gravity is used. When the basis weight is 1500 g / m ^{2 or} less, there is no feeling of weight and the feeling of use is good. In addition, productivity and operability are also improved.

The exothermic intermediate sheet 20 preferably has a breaking length of 100 to 4000 m, and more preferably 200 to 3000 m. When the breaking length is 100 m or more, the sheet can be stably formed without breaking or cutting the sheet during operation. In addition, the product can be processed well for the same reason during processing. In addition, even when in use, there is a moderate waist and excellent usability. When the breaking length is 4000 m or less, the fibrous material and adhesive component forming the exothermic intermediate sheet 20 do not increase excessively, and it is flexible and has excellent exothermic performance. Here, the tearing length is determined by cutting a test piece of length 150 mm × width 15 mm from the heat generating intermediate sheet 20 and then mounting the test piece on a tensile tester with a chuck interval of 100 mm according to JIS P8113. It is a value calculated by the following calculation formula after performing a tensile test at / min.
Breaking length [m] = (1 / 9.8) × (Tensile strength [N / m]) × 10 ⁶ / (Test piece basis weight [g / m ² ])

The exothermic sheet 20 preferably has an exothermic temperature of 30 to 100 ° C, and more preferably 35 to 90 ° C. Here, the heat generation reached temperature is determined by cutting a 50 mm × 50 mm test piece from the heat generating sheet and then impermeable to the moisture permeable sheet having a moisture permeability of 5 kg / (m ² · 24 h) measured by JIS Z208. A tester capable of supplying 5.0 liters / min of dry air into a sealed system in an environment with a volume of 4.2 liters and a relative humidity of 1% or less after packaging with a wet sheet attached to both sides in a bag shape. Is a value obtained by measuring the temperature of the lower side of the heat generating sheet with a thermocouple when the moisture permeable sheet side is left as an upper surface to generate heat. The heat generation temperature of the heat generating sheet 20 can be arbitrarily designed by combining the above-described blending composition according to the application of the heating device, such as when rapid heat generation is required or when it is necessary to maintain a relatively low temperature for a long time. .

In the heat generating sheet 20, the amount of water vapor generated per unit area for 10 minutes is preferably 1 to 100 mg / (cm ² · 10 min), more preferably 1.0 to 50 mg / (cm ² · 10 min). preferable. Here, the water vapor amount is measured as follows.

Prepare a tester with a volume of 4.2 liters and a humidity of 1 RH% or less and capable of supplying 5.0 liters / min of dry air in a closed system, and place the sheet in such a way that water vapor can evaporate. Heat. And the humidity of the air discharged | emitted in the said closed system was assumed with the hygrometer, the amount of water vapor | steam generated after the start of heat_generation | fever was calculated | required using following formula (1), and it was set as the amount of water vapor | steam per unit time. And the cumulative value for 10 minutes was calculated | required as a steam generation amount, and converted per unit area. Here, e is a water vapor pressure (Pa), es is a saturated water vapor pressure (Pa: quoted from JIS Z8806), T is a temperature (° C .: dry bulb temperature), and s is a sampling period (seconds).
Relative humidity U (% RH) = (e / es) × 100
Absolute humidity D (g / m ³ ) = (0.794 × 10 ⁻² × e) / (1 + 0.00366T)
= (0.794 × 10 ^-2 × U × es) / [100 × (1 + 0.00366T)]
Unit air volume P (liter) = (2.1 x s) / 60
Amount of water vapor per unit time A (g) = (P × D) / 1000 (1)

  The amount of water vapor can be arbitrarily designed depending on the combination of the above-mentioned blending compositions, such as when a rapid heat generation is required depending on the product application, as well as the heat generation arrival time, or a product that needs to be maintained at a relatively low temperature for a long time.

  As shown in FIG. 1, the peripheral part of the container 3 is joined by a joining part 30 having a predetermined width so as to seal the heating element 2. In the present embodiment, the joint portion 30 is formed by heat sealing.

The container 3 preferably has a moisture permeability of 0.4 to 10 kg / (m ² · 24h). By combining the moisture permeability in such a range and the water vapor generation amount of the heat generating sheet 20, it is possible to obtain a heating device that is excellent in touch and wearability to the body and has various characteristics.
For example, when the packaging is opened and the exothermic reaction of the heating element 2 starts, heat and water vapor are gradually generated, and the thermal effect is maintained over a long period of time without substantially expanding, so that it is excellent in wearability to the body. In the case of making it, the moisture permeability of the container 3 is preferably 0.4 to 1.5 kg / (m ² · 24 h).
In addition, when the package is opened, heat and water vapor are generated immediately, expansion starts without delay, and the touch and adhesion to the skin is good. The moisture permeability of No. 3 is preferably 1.5 to 10 kg / (m ² · 24 h), particularly preferably 2.0 to 8.0 kg / (m ² · 24 h).
Furthermore, although heat and water vapor are immediately generated when the package is opened, the moisture permeability is 1. when it is possible to realize a sense of warmth and moisture with little swelling and excellent wearability to the body. At 5 to 10 g / (m ² · 24 h), the air permeability of the sheet is preferably 30 seconds / 100 ml or less, particularly preferably 10 seconds / 100 ml or less.
The entire surface of the container 3 may be air permeable or partially air permeable.

  As shown in FIG. 2, in the heating device 1 of the present embodiment, the container 3 has a breathable sheet 31 disposed on the upper side of the heating element 2 and a non-breathable sheet 32 on the lower side of the heating element 2. Is arranged. In the heating device 1 of the present embodiment, the air-permeable sheet 31 is disposed on the insertion portion 5 side of the heating element 2, and is provided so that water vapor is evaporated in the insertion portion 5. In this way, by providing the insertion portion 5 so that water vapor is evaporated, a humidification function in the insertion portion 5 is obtained in addition to heating, and the function when combined with various functional agents as described later. A high penetration effect of the agent can be obtained.

  In the heating device 1 of the present embodiment, the container 3 has a three-layer structure on the upper side of the heating element 2 and a four-layer structure on the lower side. That is, as will be described later, it has a three-layer structure in which a two-layer breathable sheet 31 is disposed and a surface material 33 is disposed on the breathable sheet 31, and below the two-layer non-breathable sheet 32. It has a four-layer structure in which a decorating material 34 and a surface material 35 are arranged.

  The breathable sheet 31 can set the moisture permeability and the air permeability according to the moisture permeability and the air permeability required for the container 3.

The breathable sheet 31 preferably has a basis weight of 10 to 200 g / m ² , particularly 20 to 100 g / m ² . When the basis weight of the air-permeable sheet 31 is within such a range, the sheet is thin, flexible, and very comfortable to touch, and the softness of the heating element is not impaired.

  The breathable sheet 31 is a sheet made of a synthetic resin such as polyolefin, such as polyethylene or polypropylene, polyester, polyamide, polyurethane, polyurethane, polystyrene, polyethylene-vinyl acetate copolymer, or the like. Examples thereof include those in which a mixed sheet of a resin and an inorganic filler such as titanium oxide is subjected to interfacial peeling by stretching to provide micropores, and those in which micropores are communicated using continuous foaming by foam molding. Further, synthetic pulp such as polyolefin, wood pulp, non-wood pulp, semi-synthetic fiber such as rayon and acetate, non-woven fabric, woven fabric, synthetic paper, paper and the like formed from vinylon fiber, polyester fiber, and the like are also included. The breathable sheet 31 may be only one layer, but by using a plurality of sheets, it is possible to provide effects such as imparting the concealability of the color of the heat generating sheet and preventing surface precipitation of the fallen powder.

The non-breathable sheet 32 is not particularly limited as long as it is a non-breathable sheet, but the moisture permeability is 10 g / (m ² · 24 h) or less, particularly 1.0 g / (m ² · 24 h) or less. Is preferred. When the moisture permeability is in such a range, steam can be selectively released from the breathable sheet 31 side, and only the heat can be preferentially supplied to the non-ventilated sheet 32 side.

The non-breathable sheet 32 preferably has a basis weight of 10 to 200 g / m ² , particularly 20 to 100 g / m ² . When the basis weight of the non-breathable sheet 32 is within such a range, the sheet is thin, flexible, very comfortable to touch, and does not impair the softness of the heating element.

  Examples of the non-breathable sheet 32 include sheets made of a synthetic resin such as polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrenes, nylons, polyvinylidene chloride, and polyethylene-vinyl acetate copolymers. When a concealing property is required, a sheet in which an inorganic filler such as titanium oxide is blended in the resin is used. In the heating device 1 of the present embodiment, two non-breathable sheets 32 are stacked, but only one sheet or three or more sheets can be stacked.

  In the heating device 1, a surface material 33 is disposed on the surface (upper surface) of the air-permeable sheet 31, and a surface material 35 is disposed on the surface (lower surface) of the non-air-permeable sheet 32. By disposing such a surface material 34, the touch when the hand is inserted into the insertion portion 5 can be improved, the heat conduction is relaxed and a soft warm feeling is given, and the surface material is added. Various chemicals such as skin cleansers, furniture and house cleansers, medicinal components such as moisturizers and wrinkle removers, heat-soluble gel components, sol components, heat volatile aroma components, etc. It can give a special effect.

  The surface materials 33 and 35 are not particularly limited as long as they have good texture and flexibility, but the surface material thickness is preferably 0.1 to 2.0 mm, particularly preferably 0.2 to 1.0 mm. When the thickness of the surface material is in such a range, the heat of the heating element is relaxed by the surface material, and a soft warm feeling can be given.

The surface materials 33 and 35 preferably have a basis weight of 5.0 to 200.0 g / m ² , particularly 10.0 to 100.0 g / m ² . When the basis weight of the surface material is smaller than 5.0 g / m ² , the strength may be weak and easily broken. On the other hand, if the basis weight exceeds 200.0 g / m ² , the touch such as the touch may be deteriorated, or the surface material may act as a heat insulating material and heat may not be transmitted.

  As the surface materials 33 and 35, polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrenes, polyethylene-vinyl acetate copolymers, synthetic fibers such as polyethylene terephthalate, plant fibers such as cotton and hemp, wool, silk, etc. Non-woven fabrics and woven fabrics using regenerated fibers such as animal fibers, rayon and cupra, semi-synthetic fibers such as acetate, woven materials such as Japanese paper / Western paper / synthetic paper, cloth, woolen fabric, leather materials, and the like. A plurality of surface materials 33 and 35 may be used.

The heating tool 1 is provided with a decorating material 34 on the surface (lower surface) of the non-breathable sheet 32. The decorative material 34 is not particularly limited as long as it has a decorative property and is non-ventilated, but the moisture permeability is 10 g / (m ² · 24 h) or less, particularly 1.0 g / (m ² · 24 h) or less. It is preferable. When the moisture permeability is in such a range, the direction of water vapor generation accompanying heat generation can be regulated. Thereby, for example, as in the heating device 1, oxygen is supplied from the breathable sheet 31 side, generation of water vapor can be suppressed from the non-breathable sheet 32 side, and water vapor is generated only from the breathable sheet side. To be able to.

The decorating material 34 preferably has a basis weight of 10 to 200 g / m ² , particularly 20 to 200 g / m ² . When the basis weight of the decorating material 34 is in such a range, the softness and flexibility of the heating tool can be maintained and the concealability of the heating element can be improved.

  Examples of the decorating material 34 include sheets made of synthetic resins such as polyolefins such as polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrenes, nylons, polyvinylidene chloride, and polyethylene-vinyl acetate copolymers. When concealability is required, a sheet in which an inorganic filler such as titanium oxide is blended in the resin is used. A plurality of decorating materials 34 can be used in a stacked manner.

  In the container 3, the members having the above-described layer configuration are heat-sealed at the peripheral portion, and the heating element 2 (the heating sheet 20) is sealed therein.

The thickness of the exothermic main body 4 is preferably 0.1 to 3.0 mm, particularly preferably 0.3 to 2.0 mm. Moreover, it is preferable that the basic weight of the exothermic main body 4 is 100-9000 g / m < ² >, especially 200-4500 g / m < ² >. By setting the thickness and basis weight of the exothermic body 4 in such a range, a heating device that is thin, excellent in flexibility, and more wearable can be obtained.

  The insertion portion forming material 6 is continuously joined to the heat generating main body 4 by heat sealing so that the insertion port 50 is formed. The insertion portion forming member 6 may be discontinuously joined to the exothermic main body 4 at an arbitrary interval in order to smoothly supply oxygen.

  In the heating device 1 of the present embodiment, the insertion portion forming material 6 is formed of the same surface material as the surface material 34. By using the same surface material as the surface material 34 for the insertion portion forming material 6 that forms the insertion portion 5 in this way, when the molded body is heated and expanded, a soft feeling is given to the inside of the insertion portion. be able to. The insertion portion forming material 6 can be formed of another material, for example, the breathable sheet, the non-breathable sheet or the decorating material, depending on the use of the heating tool, and these sheet and the surface material. It is also possible to form a composite sheet in which is laminated.

  The heating tool 1 is, for example, arranged with a heat generating sheet 20 manufactured as described below at a predetermined position between layers constituting the container 3 as shown in FIG. 2 so that the heat generating sheet 20 does not shift. The peripheral portion and the sheet itself are fixed by heat sealing or a binder, and the layers are joined so as to seal the heat generating sheet 20, and then cut into a predetermined shape to form the heat generating body 4, and the insertion portion forming material 6 It is manufactured by joining. The insertion portion forming material 6 can be joined at the same time when the exothermic main body 4 is formed.

  In manufacturing the heat generating sheet 20, first, a raw material composition (slurry) containing the oxidizable metal, the water retention agent, the fibrous material, and water is prepared.

The flocculant is preferably added to the raw material composition.
Examples of the flocculant include inorganic flocculants composed of metal salts such as sulfate band, polyaluminum chloride, ferric chloride, polyferric sulfate, and ferrous sulfate; polyacrylamide, sodium polyacrylate, polyacrylamide Mannich modified products, poly (meth) acrylic acid aminoalkyl ester-based, carboxymethylcellulose sodium-based, chitosan-based, starch-based, polyamide epichlorohydrin-based polymer flocculants; dimethyldiallylammonium chloride-based or ethyleneimine-based Organic coagulants such as condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide / formalin condensates; clay minerals such as montmorillonite and bentonite; silicon dioxide such as colloidal silica or hydrates thereof; hydrous magnesium silicate such as talc And the like. Among these flocculants, anionic colloidal silica, bentonite, etc. and cations are used from the viewpoint of improving sheet surface properties, texture formation, moldability, fixing rate of materials such as oxidizable metals and water retention agents, and paper strength. Particularly preferred are the combined use of anionic starch and polyacrylamide, and the combined use of an anionic carboxymethylcellulose sodium salt and a cationic polyamide epichlorohydrin cationic and anionic agent. Besides these combinations, these flocculants can be used alone or in combination of two or more.

  The amount of the flocculant added is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the solid content of the raw material composition. When the added amount is within such a range, an aggregating effect can be obtained, and dropping of components such as the oxidizable metal and water retention agent during papermaking can be suppressed. Moreover, the raw material composition becomes uniform, and a molded sheet having a uniform thickness and composition can be obtained. Further, it does not cause sticking to the drying roll, tearing, burning or scorching during drying, and it does not adversely affect productivity. Further, the potential balance of the raw material composition is maintained, and the amount of the component dropped into the white water during papermaking can be suppressed. Further, the oxidation reaction of the molded sheet does not proceed, and storage stability such as deoxygenation characteristics and strength can be obtained.

  The concentration of the raw material composition is preferably 0.05 to 10% by weight, and more preferably 0.1 to 2% by weight. With such a concentration, a large amount of water is not required, and time is not required for molding the molded body. Moreover, since the raw material composition is uniformly dispersed, the surface properties of the obtained molded body are good, and a molded body having a uniform thickness can be obtained.

Next, the raw material composition is paper-made to form the molded sheet (exothermic intermediate sheet).
Examples of the paper making method of the molded sheet include a continuous paper making type circular paper machine, a long paper machine, a short paper machine, a twin wire paper machine, and a batch type paper making method. For example, there is an acupuncture method. Furthermore, a molded sheet can also be formed by multilayer lamination using the raw material composition and a composition having a composition different from the raw material composition. In addition, by bonding the formed sheets obtained by papermaking the raw material composition in multiple layers, or by bonding a sheet-like material obtained from a composition having a composition different from the raw material composition to the molded sheet A molded sheet can also be formed.

  The molded sheet can be dehydrated until the moisture content (weight moisture content, the same shall apply hereinafter) is 70% or less from the viewpoint of maintaining the form after papermaking (shape retention) and maintaining mechanical strength. Preferably, it is more preferable to dehydrate to 60% or less. Examples of the method for dewatering the molded sheet after papermaking include dewatering by suction, a method of dehydrating by blowing pressurized air, a method of dehydrating by pressing with a pressure roll or a pressure plate, and the like.

  The molded sheet containing the oxidizable metal (having heat reactivity in a normal atmosphere) is actively dried to separate the moisture, thereby suppressing the oxidation of the oxidizable metal during the manufacturing process. A molded sheet having excellent storage stability can be obtained. Furthermore, in addition to the point of increasing the supporting force of the oxidizable metal to the fibrous material after drying and suppressing its falling off, from the point of expectation of improvement in mechanical strength due to the addition of a hot melt component and a thermal crosslinking component, It is preferable that the molded sheet is dried after the molded sheet is formed and before the electrolytic solution of the electrolyte is contained.

  The molded sheet is preferably dried by heat drying. In this case, the heat drying temperature is preferably 60 to 300 ° C, more preferably 80 to 250 ° C. When the heating and drying temperature of the molded sheet is within such a range, the drying time is not prolonged, the oxidation reaction of the oxidizable metal that proceeds with moisture drying is suppressed, and the exothermic property of the heat generating sheet is kept good. Further, the oxidation reaction of the oxidizable metal is promoted only in the front and back layers of the heat generating sheet, and the color does not change to light brown. In addition, the heat generation effect of the heat generating sheet is kept good without causing performance deterioration of the water retention agent or the like. There is no sudden vaporization of moisture inside the molded sheet, and the structure of the molded sheet is not destroyed.

  The moisture content of the molded sheet (exothermic intermediate sheet) after drying is preferably 20% or less, and more preferably 10% or less. When the moisture content is 20% or less, excellent long-term storage stability, for example, when temporarily stored in a wound roll state, moisture does not move in the thickness direction of the roll, and the heat generation performance and mechanical strength change. Never come.

  The drying method of the molded sheet can be appropriately selected according to the thickness of the molded sheet, the processing method of the molded sheet before drying, the moisture content before drying, the moisture content after drying, and the like. Examples of the drying method include drying methods such as contact with a heating structure (heating element), spraying of heated air or steam (superheated steam), vacuum drying, electromagnetic wave heating, and electric heating. Moreover, it can also implement simultaneously with the above-mentioned dehydration method.

  The molding (dehydration and drying) of the molded sheet is preferably performed in an inert gas atmosphere. However, as described above, the molded sheet does not contain an electrolyte that serves as an oxidizing aid. Molding can also be performed in an air atmosphere. For this reason, manufacturing equipment can be simplified. Further, if necessary, it is possible to perform creping, slitting, trimming, and processing such as changing the form by processing. Since the obtained molded sheet is thin and difficult to break, it can be rolled up as necessary. In addition, by forming the molded sheet alone or in layers or with other sheets such as paper, cloth (woven fabric or non-woven fabric), film, and pressurizing, further pressurizing and embossing or needle punching, A plurality of sheets can be laminated and integrated, and uneven forming and punching can also be performed. Moreover, by including a thermoplastic resin component or a hot water-dissolving component in the raw material composition, heat sealing can be performed to facilitate bonding and the like.

Next, the molded sheet contains the electrolyte. The step of containing the electrolyte is preferably performed in an inert gas atmosphere such as nitrogen or argon. However, when the electrolyte is added by impregnation with the electrolytic solution, the oxidation reaction immediately after the addition is gentle, The electrolyte may be contained in an air atmosphere.
As the electrolyte contained in the molded sheet, the electrolyte used in the heat generating sheet can be used.

  The method of incorporating the electrolyte into the molded sheet can be appropriately set according to the processing method, moisture content, form, etc. of the molded sheet after papermaking. Examples of the method for containing the electrolyte include a method in which the molded sheet is impregnated with an electrolyte solution having a predetermined concentration of the electrolyte, and a method in which the electrolyte having a predetermined particle size is added as a solid and contained in the molded sheet. Etc. From the viewpoint that the electrolyte can be uniformly contained in the molded sheet and that the moisture content can be adjusted at the same time, a method of impregnating an electrolytic solution of a predetermined concentration is preferable.

  As described above, when the molded sheet is impregnated with the electrolyte, the impregnation method can be appropriately selected according to the form such as the thickness of the molded sheet and the water content. In the impregnation method, the electrolytic solution is spray-coated on the molded sheet, the electrolytic solution is injected into a part of the molded sheet with a syringe or the like, and the molded sheet is utilized using the capillary phenomenon of the fibrous material. Examples include a method of penetrating the whole, a method of coating with a brush, a method of immersing in the electrolytic solution, a gravure coating method, a reverse coating method, a doctor blade method, etc. Among these, the electrolyte can be uniformly distributed, and simple Thus, the spray coating method is preferable because the equipment cost is relatively low. In addition, in the case of a product having a complicated shape and layer structure, the syringe, etc. are used from the viewpoint of improving productivity, improving the flexibility of production by making the final finishing as a separate process, and simplifying the equipment. The method of injecting is preferable. This method of injecting the electrolytic solution can also be performed after the molded sheet is accommodated in the container.

  After the electrolyte is contained in the molded sheet as described above, the moisture content can be adjusted and stabilized as necessary to obtain a heat generating sheet. Then, if necessary, it can be processed into a predetermined size by performing processing such as trimming, lamination of two or more sheets, and the like.

  The warming tool 1 of this embodiment is provided sealed in a non-breathable packaging material when not in use. When the heating device 1 is taken out from the packaging material, as shown in FIG. 3, the exothermic main body 4 expands due to water vapor generated by the exothermic reaction of the heating element 2. Then, as shown in FIG. 4, the insertion portion 5 is put into a hand from the insertion port 50, and the inside of the insertion portion 5 is heated by the heat generated by the oxidation of the oxidizable metal and is humidified by the generated steam. In the heating tool 1, a good wearing feeling can be obtained by appropriate pressure bonding in the insertion portion 5. The heating tool 1 can also perform only heating by bringing the side of the exothermic main body 4 on which the water vapor does not evaporate into contact with the object.

  When the heating device 1 of the present embodiment is provided so that the exothermic main body 4 expands due to water vapor generated by the heat generation of the heating element 2, there is an appropriate feeling of touch when the touch or hand is inserted into the insertion portion. Good wearability is obtained. Further, in addition to heating due to heat generated by the oxidation of the oxidizable metal, water vapor generated along with the heat generation evaporates into the insertion portion 5, so that the inserted hand can be humidified. Furthermore, since the heat generating body 2 is composed of the heat generating sheet 20, it is thin and convenient for carrying. In addition, it is excellent in flexibility even after the exothermic reaction is completed before use, and in this respect, the wearability is also good.

  The heating tool 1 of the present embodiment can be applied to various uses by combining the heating, the humidifying function and the adhesiveness in the insertion portion 5 with various functional agents. For example, after applying various functional materials to each part of the body, inserting the heating tool into an arbitrary part, or impregnating the inner layer material of the insertion part with the functional agent, the functional agent is highly applied to the skin. Permeability can be obtained. In addition, as a heat pack combined with a pack agent, for skin care applications such as moisturizing and wrinkle removal, as a hot pap combined with a distribution agent (heat distribution), for health care applications such as hand pain relief, in particular this embodiment This warming tool can be moisturized in addition to warming in a state where moderate adhesion is obtained in the insertion part, so when combined with such a functional agent, high penetration of the functional agent into the skin Sex is obtained. In addition, in applications where heating or humidification is applied directly to the body or by contact, it may be preferable to contact the object uniformly without expanding, and the expansion function of the heating device is an effect of the product, Arbitrarily designed to maximize efficacy.

  The present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit of the present invention.

  For example, the heating device 1 of the above embodiment is provided so as to have air permeability only on the side where the insertion portion 5 is formed in the container 3, but only when the insertion portion is not formed. It can also be provided. In this case, the effect of humidification can be obtained in addition to heating by directing or contacting the air-permeable side to the object. Such a heating device is used as a heating device in combination with various functions such as washing / disinfecting, wax sustained release, aroma, deodorization, etc., for house care applications such as flooring, folding, range, ventilation fan, etc. It can be applied to air care applications that make space comfortable, car care applications such as car washing, waxing, and other skin care applications such as facial and body washing, disinfection, moisturizing, and makeup removal. In addition, as a hot pack device combined with a pack agent, skin care applications such as moisturizing, darkening, wrinkle removal, dullness, slimming, eye care applications such as eye relief, eyesight improvement, hot combination with a wrapping agent As a wrapping tool, use for health care such as relief of pain and menstrual pains such as neck, shoulders, feet, and lower back, hair care use such as palmer, coloring and hair growth promotion, and pharmaceutical agents such as athlete's foot Combined medical use, disposable bedding such as futon, blanket or their cover, cushion, rug, leisure sheet, disposable rug such as pet sheet, disposable horticultural sheet such as anti-frost sheet such as bonsai and plants, food etc. It can be applied to other packaging materials.

  Moreover, the heating tool of this invention WHEREIN: The layer structure of a heat generating body, a container, and an insertion part formation material can be suitably changed according to the use of a heating tool. For example, in the above-described embodiment, only one of the exothermic main bodies is provided with air permeability so that water vapor is evaporated to only one side, but water vapor is evaporated from both the inside of the insertion portion and the side where the insertion portion is not formed. It can also be made.

  Moreover, in the said embodiment, although the container 3 was made into the multilayer structure, the container has the function which prevents the fall of the air permeability required for the oxidation reaction and the expansion | swelling function of a heat generating main body, and the component of a heat generating body. If so, a single-layer structure may be used.

  Moreover, in the heating tool 1 of the said embodiment, although sealing of the container and joining of a container and an insertion part formation material were performed by heat sealing, these sealing and joining methods are other methods, for example, Other methods such as a method using an adhesive and a method using suturing can also be employed.

  The heating device of the present invention can form an exothermic main body and an insertion portion according to a portion into which a part of the body is inserted, in addition to the hand as in the above-described embodiment. It can be applied for use. For example, when an insertion portion for inserting the head is provided, it can be applied to hair care applications such as palmer, coloring, and hair growth promotion. Further, in the case of a face mask type heating device, it is possible to improve the adhesion to the skin by forming an ear hook and to apply uniform heating and humidification to the entire face.

  In addition to providing the insertion portion forming material 6 to the exothermic main body 4 as in the heating device 1 of the embodiment, the insertion portion may be provided by partially joining the exothermic main bodies. it can. In this case, the water vapor can be provided so as to be vaporized only in the insertion portion, can be provided so as to be vaporized only outside, or can be provided so as to be vaporized both inside and outside the insertion portion. .

  The heating tool of the present invention preferably has an insertion part, but the insertion part can be omitted depending on the application of the heating tool.

Hereinafter, the present invention will be described more specifically with reference to examples.
As shown in Examples 1 to 4 and Comparative Example 1 below, the heating device was prepared, and the heating sheet obtained had a duration of 40 ° C. or higher, the maximum temperature reached, the amount of water vapor generated, and the expansibility of the heating device as described above. And measured and evaluated. The results are shown in Table 1.

[Example 1]
Oxidizable metal: Iron powder, manufactured by Dowa Iron Mining Co., Ltd., trade name “RKH”, 75% by weight
Fibrous: Pulp fiber (NBKP, manufacturer: Fletcher Challenge Canada, trade name “Mackenzi”, CSF 200 ml), 10% by weight
Water retention agent: activated carbon (average particle size 10 μm, manufactured by Nimura Chemical Industry Co., Ltd., trade name “Dazai SA1000”), 15% by weight
Flocculant: 0.2 parts by weight of sodium carboxymethylcellulose (Daiichi Kogyo Kagaku Co., Ltd., trade name “Serogen WS-C”) and polyamide epichlorohydrin resin (Japan) with respect to 100 parts by weight of the raw material composition PMC Co., Ltd., trade name “WS552”) 0.3 parts by weight Water: industrial water, added until solids concentration is 0.3%

<Paper making conditions>
Using the raw material composition, a paper sheet was made by a slanted short net paper machine to prepare a wet molded sheet.

<Drying conditions>
It was sandwiched with felt and dehydrated under pressure, passed through a heating roll at 120 ° C. as it was, and dried until the water content became 5% by weight or less. And the papermaking sheet | seat (heat_generation | fever intermediate sheet) with a basic weight of 180 g / m < ² > and thickness 0.25mm was obtained. As a result of measuring the composition of the obtained exothermic intermediate sheet using a thermogravimetric measuring device (TG / DTA6200, manufactured by Seiko Instruments Inc.), it was 69% by weight of iron, 19% by weight of pulp, and 12% by weight of activated carbon.

<Electrolytic solution addition conditions>
By applying the following electrolytic solution to the dried papermaking sheet (exothermic intermediate sheet), 60 parts by weight of the electrolyte was added to 100 parts by weight of the exothermic intermediate sheet to obtain a desired papermaking sheet (exothermic sheet).

<Electrolyte>
Electrolyte: Purified salt (NaCl)
Water: Industrial water Electrolyte concentration: 5% by mass
The composition of the obtained exothermic sheet was 43.1% by weight of iron, 11.9% by weight of pulp, 7.5% by weight of activated carbon, 1.9% by weight of NaCl, and 35.6% by weight of water.

<Preparation of heating equipment>
Three heating sheets (size 50mm x 50mm) obtained are stacked, the following breathable sheet and non-breathable sheet are laminated on the top and bottom, and the surroundings of the heating sheet are joined by heat-sealing (heating unit) Was made.
[Example 1]
Breathable sheet: Synthetic polyethylene sheet, moisture permeability 4.482 kg / (m ² · 24 h), air permeability 53 seconds / 100 ml, basis weight 40 g / m ²
Non-breathable sheet: PE sheet (basis weight 20 g / m ² )

[Example 2]
A heating tool was produced in the same manner as in Example 1 except that the breathable sheet was replaced with the following sheet.
Breathable sheet: porous polyethylene, moisture permeability 5.114 kg / (m ² · 24 h), air permeability 484 seconds / 100 ml, basis weight 36 g / m ²

Example 3
A heating tool was produced in the same manner as in Example 1 except that the breathable sheet was replaced with the following sheet.
Breathable sheet: Polypropylene melt blown nonwoven fabric, moisture permeability 4.357 kg / (m ² · 24 h), air permeability 0 sec / 100 ml, basis weight 30 g / m ²

Example 4
A heating tool was produced in the same manner as in Example 1 except that the breathable sheet was replaced with the following sheet.
Breathable sheet: porous polyethylene, moisture permeability 1.124 kg / (m ² · 24 h), air permeability 5043 sec / 100 ml, basis weight 50 g / m ²

[Comparative Example 1]
A heating device was produced in the same manner as in Example 1 except that the breathable sheet was replaced with the following sheet.
Breathable sheet: porous polyethylene, moisture permeability 0.359 kg / (m ² · 24h), air permeability 28840 sec / 100 ml, basis weight 90 g / m ²

GIF" \* MERGEFORMAT \d

GIF "\ * MERGEFORMAT \ d

  As shown in Table 1, in the examples, the type that generates heat quickly and expands while generating a lot of water vapor, the type that further increases the expansion ratio, and the type that generates heat quickly and generates a lot of water vapor. It was possible to produce warming devices with various heat and water vapor generation characteristics, such as a type that does not expand, a type that is sustained at a relatively low temperature, and that gradually generates water vapor. On the other hand, in the comparative example, both the heat generation temperature and the water vapor generation amount were low.

It is a perspective view which shows typically one Embodiment of the heating tool of this invention. It is a disassembled perspective view which shows the heating tool of the said embodiment typically. It is a perspective view which shows typically the state which the exothermic main body expanded in the heating tool of the said embodiment. It is a perspective view which shows typically the use condition of the heating tool of the said embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heating tool 2 Heat generating body 20 Heat generating sheet (papermaking sheet)
DESCRIPTION OF SYMBOLS 3 Container 30 Junction part 4 Exothermic main body 5 Insertion part 50 Insertion port 6 Insertion part formation material

Claims (4)

A heating device comprising a heat generating body composed of a heat generating element having water vapor generating capacity and a breathable container for accommodating the heat generating element,
The heating element comprises a papermaking sheet containing an oxidizable metal, a water retention agent, a fibrous material, and water,
Two or more of the heating elements are stacked,
The thickness of each heating element is 0.08 to 1.2 mm,
The total thickness of the heating tool is 0.3 to 5.0 mm,
The amount of water vapor generated with the heat generation of the heating element in each of the exothermic main bodies is a heating tool in which the amount of water vapor generated by the following proviso is 1.0 to 100 mg / (cm ² · 10 min).
However, the heat generating sheet is prepared so that the volume is 4.2 liters and the humidity is 1 RH% or less, and a test machine capable of supplying 5.0 liters / min of dry air in the closed system is provided, and water vapor can be evaporated therein. Assuming the humidity of the air discharged into the closed system with a hygrometer, the amount of water vapor generated after the start of heat generation is obtained using the following formula (1), and the amount of water vapor per unit time Then, a cumulative value for 10 minutes is obtained as a steam generation amount, and converted per unit area. Here, e is a water vapor pressure (Pa), es is a saturated water vapor pressure (Pa: quoted from JIS Z8806), T is a temperature (° C .: dry bulb temperature), and s is a sampling period (seconds).
Relative humidity U (% RH) = (e / es) × 100
Absolute humidity D (g / m ³ ) = (0.794 × 10 ⁻² × e) / (1 + 0.00366T)
= (0.794 × 10 ^-2 × U × es) / [100 × (1 + 0.00366T)]
Unit air volume P (liter) = (2.1 x s) / 60
Amount of water vapor per unit time A (g) = (P × D) / 1000 (1) 2. The heating device according to claim 1, wherein a component other than the fibrous material contained in the papermaking sheet is 50 wt% or more and 98 wt% or less , and a CSF defined in JIS P8121 of the fibrous material is 600 ml or less. . The heating tool according to claim 1 or 2 , further comprising an insertion part for inserting a part of the body. The heating device according to any one of claims 1 to 3, wherein the heating element on which two or more sheets are stacked is laminated and integrated by embossing.

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