JP2012020119A - Heating appliance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heating appliance which can uniformly generate heat and hardly causes falling off of a heat generation composition layer even when a user moves.SOLUTION: The heating appliance 100 is provided: with a heating element formed by disposing the heat-generating composition layer containing oxidizable metal particles on one surface of a substrate sheet comprising high-absorbency polymer particles and hydrophilic fibers; and a packaging material that surrounds the entire heating element. The packaging material is formed by joining a first covering sheet 4 and a second covering sheet 5 at the peripheral edges of the sheets, and the inside of the packaging material serves as a housing space for the heating element 10. The heating element 10 is housed in the housing space in an unfixed state with respect to the packaging material. A portion of the first covering sheet 4 has air permeability and the first covering material 4 is positioned at the side of the heat-generating composition layer. When used, the heating appliance 100 has ability of generating steam from the side where the first covering sheet 4 is positioned.

Description

  The present invention relates to a heating tool using heat generated by oxidation of an oxidizable metal.

  A heating element technology is known in which a heat generating composition containing an oxidizable metal is laminated with a sheet having water absorption. For example, in a heating element in which an ink-like or cream-like exothermic composition is laminated and enclosed in a sheet-like packaging material, a part of the packaging material having air permeability and water absorption is used, and A heating element has been proposed in which a part of the moisture of the creamy exothermic composition is absorbed by the packaging material (see Patent Document 1). In this exothermic composition, excess water, free water and / or hydrous gel express a function as a barrier layer against air, and the exothermic reaction is suppressed by the barrier layer. The barrier layer disappears when excess water or the like is absorbed by the packaging material having water absorption, and heat generation proceeds accordingly.

  Separately from this technology, a viscous heat-generating composition having fluidity is laminated and enclosed in a sheet-like packaging material, and a breathable water-absorbing sheet covers one or both surfaces of the heat-generating composition, and a seal portion. A heating element is also proposed which is laminated so as not to intervene (see Patent Document 2). In this heating element, a part of the sheet-like packaging material has air permeability. The breathable water absorbing sheet is positioned and fixed on the exothermic composition by the adhesive force of the exothermic composition.

Japanese Unexamined Patent Publication No. 09-075388 JP 2002-253593 A

  However, in the techniques described in the above-mentioned documents, the exothermic composition that is in a water-containing state and has a viscosity is directly laminated with a breathable sheet, Therefore, the air permeability of the sheet is easily impaired by the viscosity of the exothermic composition, and as a result, a uniform exothermic reaction is unlikely to occur. In addition, since the sheet on which the exothermic composition layer is formed is made of a packaging material, the user's action is directly transmitted to the exothermic composition layer, whereby the exothermic composition layer is likely to fall off. Further, in the technique described in Patent Document 2, a heat-generating composition having viscosity is laminated on an absorbent sheet separate from the packaging material, and another absorbent sheet is disposed from above using this viscosity. A form in which a laminated body sandwiching a heat generating composition is formed and enclosed in a packaging material is also disclosed, but sufficient air permeability cannot be ensured. When the exothermic composition is capable of generating water vapor with heat, the generation of water vapor is also inhibited.

  Therefore, the subject of this invention is providing the heating tool which can eliminate the fault which the prior art mentioned above has.

  As a result of intensive investigations by the present inventors to solve the above-mentioned problems, by using a heating element in which a layer of a heating composition is formed on a fiber sheet having water absorption, the water absorption of the fiber sheet is utilized. By adjusting the moisture content of the layer of the exothermic composition and surrounding the heating element in a non-fixed state by a breathable packaging material separate from this, sufficient air permeability can be secured, and It has been found that even when the user operates, the exothermic composition layer is less likely to fall off.

The present invention has been made on the basis of the above findings, and a layer of a heat generating composition containing particles of an oxidizable metal on one surface of a base sheet made of a fiber sheet containing superabsorbent polymer particles and hydrophilic fibers. A heating element provided with a packaging material surrounding the entire heating element,
The packaging material is formed by joining the first covering sheet and the second covering sheet at their peripheral portions, and the inside thereof is a housing space for the heating element,
The heating element is housed in the housing space in a non-fixed state with respect to the packaging material,
The first covering sheet has air permeability in a part thereof and is disposed on the side of the layer,
The present invention solves the above-mentioned problem by providing a heating tool in which steam can be generated from the side on which the first covering sheet is disposed during use.

  ADVANTAGE OF THE INVENTION According to this invention, the heat-generating tool which can generate | occur | produce uniformly heat | fever from the heat_generation | fever start to the heat | fever end, and is hard to drop | omit of the layer of exothermic composition even if a user operate | moves is provided. In addition, since the heating tool of the present invention has flexibility even after the end of heat generation, it can fit the shape of the user's body from the start of heat generation to the end of heat generation. It is possible to reduce a sense of discomfort. In particular, even non-planar parts such as joints and curved parts of the body are easy to fit. As a result, a uniform warm feeling can be given to the user.

Fig.1 (a) is a side view which shows the measuring method of the three-point bending load of a heating tool, and FIG.1 (b) is a top view which shows the measuring method of the three-point bending load of a heating tool. FIG. 2 is a schematic view showing an example of an apparatus suitably used for manufacturing the heating tool of the present invention. FIG. 3 is a schematic view showing the structure of a longitudinal section in one embodiment of the heating tool of the present invention. FIG. 4 is a schematic view showing another apparatus suitably used for manufacturing the heating tool of the present invention. FIG. 5 is a schematic diagram showing a longitudinal cross-sectional structure of the base material sheet used in Example 1. 6A is a microscopic image of a longitudinal section of the heating element in the heating tool obtained in Example 1, and FIG. 6B is a longitudinal section of the heating element in the heating tool obtained in Comparative Example 2. It is a microscopic image.

  Hereinafter, the present invention will be described based on preferred embodiments thereof. The heating tool of the present invention includes a heating element and a packaging material as its constituent members. The heating element is a member that generates heat in the heating tool of the present invention. The packaging material is a member that surrounds the entire heating element and forms the outer surface of the heating tool of the present invention, and part or all of the packaging material has air permeability.

  The heating element includes a base sheet and a layer of a heat generating composition (hereinafter also referred to as “heat generation layer”) provided on one surface of the base sheet. The base sheet is composed of a fiber sheet containing superabsorbent polymer particles and hydrophilic fibers. The heat generating layer includes particles of an oxidizable metal.

  The base sheet made of a fiber sheet may be (a) one sheet in a state where the particles of the superabsorbent polymer and the hydrophilic fiber are uniformly mixed. In the base sheet, (b) the superabsorbent polymer particles are mainly present in a substantially central region in the thickness direction of the base sheet, and the particles are substantially present on the surface of the base sheet. It can also be one-ply with a structure that is not. Further, the base sheet may be (c) a laminate of two fiber sheets in which particles of superabsorbent polymer are arranged between the same or different fiber sheets containing hydrophilic fibers. Of these base sheets that can take various forms, it is preferable to use the base sheet having the form (b) from the viewpoint of easily controlling the moisture content of the heat generating layer.

  As the hydrophilic fiber contained in the base sheet made of the fiber sheet, any of natural fiber and synthetic fiber can be used. By using hydrophilic fibers as the constituent fibers of the base sheet, there is an advantage that hydrogen bonds are easily formed with the oxidizable metal contained in the heat generating layer, and the shape retention of the heat generating layer is improved. . In addition, the use of hydrophilic fibers also has the advantage that the water absorption or water retention of the base sheet is improved and the water content of the heat generating layer can be easily controlled. From these viewpoints, cellulose fibers are preferably used as the hydrophilic fibers. Chemical fibers (synthetic fibers) and natural fibers can be used as the cellulose fibers.

  As chemical fibers of cellulose, for example, rayon and acetate can be used. On the other hand, various vegetable fibers such as wood pulp, non-wood pulp, cotton, hemp, wheat straw, hemp, jute, kapok, palm, rush and the like can be used as the natural cellulose fiber. Of these cellulose fibers, it is preferable to use wood pulp from the viewpoint that a thick fiber can be easily obtained. The use of thick fibers as the cellulose fibers is advantageous from the viewpoints of water absorption or water retention of the base sheet, retention of the heat generating layer, and the like.

  In particular, it is preferable to use bulky cellulose fibers as the natural cellulose fibers. By using the bulky cellulose fiber, it becomes easy to make the inter-fiber distance of the constituent fibers in the base sheet suitable. As specific examples of the bulky cellulose fiber, (a) the fiber shape has a three-dimensional structure of a twisted structure, a crimped structure, a bent and / or branched structure, or (b) the fiber roughness is 0.2 mg / m or more. Or (c) those in which the intramolecular and intermolecular molecules of the cellulose fiber are crosslinked.

  Specific examples of the fiber having a three-dimensional structure such as a twisted structure, a crimped structure, a bent structure and / or a branched structure of (a) above include chemical pulp obtained by decomposing wood pulp by a chemical reaction, and mechanical treatment ( Pulp decomposed by beating) or pulp obtained by combining chemical reaction and mechanical treatment can be used.

  The fiber (b) is a bulky state in which cellulose fibers are accumulated, thereby reducing the movement resistance of the liquid and increasing the permeation speed of the liquid. When the coating of the heat generating composition is applied to the base sheet in the production process, the moisture in the heat generating composition is easily transferred into the base sheet, so that the moisture content of the heat generating layer can be controlled. It becomes easy. In addition, a bulky network structure that can maintain the solid content of the paint constituting the heat generating layer is easily formed. From these viewpoints, the fiber roughness of the fiber (b) is preferably 0.2 to 2 mg / m, particularly preferably 0.3 to 1 mg / m.

  The fiber roughness is used as a scale representing the fiber thickness in fibers having non-uniform fiber thickness, such as wood pulp. For example, a fiber roughness meter (FS-200, KAJANNIELECTRONICSLTD. ). Examples of cellulose fibers with a fiber roughness of 0.2 mg / m or more include softwood kraft pulp (“ALBACEL” (trade name) from Federal Paper Board Co. and “INDORAYON” (trade name) from PT Inti Indorayon Utama. )] And the like.

The fiber (b) preferably has a roundness of the fiber cross section of 0.5 to 1, particularly 0.55 to 1. By using the cellulose fiber having such roundness, the movement resistance of the liquid in the base sheet is further reduced, and the passing speed of the liquid is further increased. The method of measuring roundness is as follows. The fiber is sliced perpendicular to the cross-sectional direction so that the area does not change, and a cross-sectional photograph is taken with an electron microscope. The cross-sectional photograph is analyzed by an image diffractometer [“Avio EXCEL” (trade name) manufactured by Nippon Avionics Co., Ltd.], and the cross-sectional area and circumference of the measurement fiber are measured. Using these values, the roundness is calculated using the following formula. The roundness is an average value obtained by measuring 100 arbitrary fiber cross sections.
Roundness = 4π (cross-sectional area of measurement fiber) / (peripheral length of cross-section of measurement fiber) ²

  When wood pulp is used as the bulky cellulose fiber, the cross section of the wood pulp is generally flattened by delignification treatment, and most of the roundness is less than 0.5. In order to make it 0.5 or more, for example, the wood pulp may be mercerized to swell the cross section of the wood pulp. Examples of commercially available mercerized pulp include “FILTRANIER” (trade name) manufactured by ITT Rayonier Inc. and “POROSANIER” (trade name) manufactured by the same company.

  The crosslinked cellulose fiber as the fiber (c) is preferable because it can maintain a bulky structure even in a wet state. Examples of the method for crosslinking the cellulose fiber include a crosslinking method using a crosslinking agent. Examples of such crosslinking agents include N-methylol compounds such as dimethylolethyleneurea and dimethyloldihydroxyethyleneurea; polycarboxylic acids such as citric acid, tricarballylic acid and butanetetracarboxylic acid; polyols such as dimethylhydroxyethyleneurea A cross-linking agent for polyglycidyl ether compounds. It is preferable that the usage-amount of a crosslinking agent shall be 0.2-20 mass parts with respect to 100 mass parts of cellulose fibers. The crosslinked cellulose fiber has a fiber roughness of preferably 0.1 to 2 mg / m, particularly preferably 0.2 to 1 mg / m. The cross-linked cellulose fiber preferably has a roundness of the fiber cross section of 0.5 to 1, particularly 0.55 to 1. Examples of commercially available crosslinked cellulose fibers include “High Bulk Additive” manufactured by Weyerhaeuser Paper Co.

  Among the fibers (a) to (c) described above, particularly when the fiber (c) is used, the integrity of the base sheet and the heat generating layer is enhanced, and the advantageous effect that the heat generating layer is less likely to fall off. Is played. Further, the heating element becomes flexible, and there is an advantageous effect that the fitting property is improved when the heating tool of the present invention is attached to an object to be attached, for example, the skin or clothing of a human body. Surprisingly, it is worth noting that the flexibility of the heating element is maintained even after the end of heat generation.

  The above-mentioned various hydrophilic fibers preferably have a fiber length of 0.5 to 6 mm, particularly 0.8 to 4 mm, from the viewpoint of easy production of a substrate sheet by a wet method or a dry method.

  In addition to the above-described hydrophilic fibers, heat-fusible fibers may be blended in the base sheet as necessary. By blending this fiber, the strength of the substrate sheet in a wet state can be increased. The compounding amount of the heat-fusible fiber is preferably 0.1 to 10% by mass, particularly 0.5 to 5% by mass, based on the total amount of fibers in the base sheet.

  As described above, the base sheet made of the fiber sheet contains particles of the superabsorbent polymer. The location of the superabsorbent polymer particles in the base sheet is as described above. As the superabsorbent polymer, it is preferable to use a hydrogel material that can absorb and hold a liquid having a weight 20 times or more of its own weight and can be gelled. The shape of the particles can be spherical, massive, grape bunches, fibers and the like. The particle size of the particles is preferably 1 to 1000 μm, particularly preferably 10 to 500 μm. Specific examples of superabsorbent polymers include starch, crosslinked carboxylmethylated cellulose, polymers or copolymers of acrylic acid or alkali metal acrylates, polyacrylic acid and salts thereof, and polyacrylate graft polymers. Is mentioned. The superabsorbent polymer particles are preferably bonded to the fiber material contained in the base sheet. For the joining, for example, viscosity generated by wetting the particles of the superabsorbent polymer can be used. Alternatively, a superabsorbent polymer particle formed by attaching and polymerizing a liquid material containing a polymerizable monomer and / or a polymerized product of the monomer to a web made of a fiber material may be used. The particles of the superabsorbent polymer are bonded to the fiber material.

  The ratio of the superabsorbent polymer in the base sheet is 10 to 70% by weight, particularly 20 to 55% by weight, and the viewpoint of making the water absorption or water retention of the base sheet suitable and the heat generating layer This is preferable from the viewpoint of controlling the water content. This ratio is a value measured for the base sheet in a dry state before the heat generation layer is formed on the base sheet.

The base sheet preferably has a basis weight of 10 to 200 g / m ² , particularly 35 to 150 g / m ² . By setting the basis weight of the base sheet within this range, sufficient strength of the base sheet in a wet state can be secured, and water absorption or water retention of the base sheet should be suitable. Can do. On the other hand, the basis weight of the superabsorbent polymer contained in the base sheet is preferably 5 to 150 g / m ² , particularly 10 to 100 g / m ² . By setting the basis weight of the superabsorbent polymer within this range, the water absorption or water retention of the base sheet can be further improved. Moreover, it becomes easier to control the moisture content of the heat generating layer. These basis weights are values measured for the base sheet in a dry state before the heat generation layer is formed on the base sheet.

  The substrate sheet can be produced by, for example, the airlaid method when it is in the form of (a). In the case of (b), it can be produced, for example, by the wet papermaking method described in JP-A-8-246395 related to the previous application of the present applicant. In the case of (c), it can be produced by the airlaid method or the wet papermaking method.

  The base sheet is provided with a heat generating layer on at least one surface thereof. The heat generating layer may be provided only on one side of the base sheet, or may be provided on both sides. As another embodiment, a heat generating layer may be provided between two identical or different substrate sheets. When the heat generating layer is provided between the two base material sheets, the heat generating layer is effectively prevented from sticking to the packaging material. When the heat generating layer is provided between the two substrate sheets, one of the substrate sheets may not include the superabsorbent polymer particles. The heat generating layer is a water-containing layer containing particles of an oxidizable metal, an electrolyte, and water. The heat generating layer may further contain a reaction accelerator. The heat generating layer may be present on the base sheet, or the lower part of the heat generating layer may be embedded in the base sheet. Among these, it is preferable that the lower part of the heat generating layer is buried in the base material sheet. That is, it is preferable that a part of solid content constituting the heat generating layer is carried in a three-dimensional network formed on the fiber sheet constituting the base sheet. Since part of the heat generation layer is embedded in the base sheet, the unity of the heat generation layer and the base sheet is increased, and the heat generation layer is removed from the base sheet (before, during, and after use). Effectively prevented.

  Examples of the oxidizable metal contained in the heat generating layer include iron, aluminum, zinc, manganese, magnesium, calcium and the like. The particle size of the oxidizable metal particles can be, for example, about 0.1 to 300 μm. As the reaction accelerator, it is preferable to use a reaction accelerator that has a function as an oxygen retention / supply agent for an oxidizable metal in addition to acting as a moisture retention agent. Examples of the reaction accelerator include activated carbon (coconut shell charcoal, charcoal powder, calendar bituminous coal, peat, lignite), carbon black, acetylene black, graphite, zeolite, perlite, vermiculite, silica and the like. As the electrolyte, an electrolyte capable of dissolving an oxide formed on the surface of the oxidizable metal particles is used. Examples thereof include alkali metal, alkaline earth metal or transition metal sulfates, carbonates, chlorides or hydroxides. Among these, chlorides of alkali metals, alkaline earth metals or transition metals are preferably used from the viewpoint of excellent conductivity, chemical stability and production cost, and particularly sodium chloride, potassium chloride, calcium chloride, magnesium chloride, chloride. Ferrous and ferric chloride are preferably used.

On the condition that the basis weight of the base sheet is in the above-mentioned range, the amount of the oxidizable metal in the heating element is 100 to 3,000 g / m ² , particularly 200 to 1,500 g, expressed in basis weight. / M ² is preferable from the viewpoint of securing a sufficient calorific value. The amount of the reaction accelerator in the heating element is preferably 4 to 300 g / m ² , particularly 4 to 80 g / m ² , especially 8 to 50 g / m ² , from the viewpoint of maintaining stable heat generation for a long time. For the same reason, the amount of the electrolyte in the heating element is preferably 4 to 80 g / m ² , particularly 4 to 40 g / m ² , particularly 5 to 30 g / m ² . These basis weights are values in the case where one layer of heat generation layer is formed on one side of the base sheet. Therefore, when the heat generating layers are formed on both sides of the base sheet, these basis weights are double the above-mentioned values. Further, the basis weight is appropriately adjusted according to the specific application of the heating element.

  As described above, the heat generating layer is in a water-containing state. The moisture content of the heat generating layer is preferably 5 to 50% by mass, particularly 6 to 40% by mass. By setting the moisture content of the heat generating layer within this range, the fluidity of the heat generating layer decreases, and consequently the viscosity decreases. As a result, as described later, even if a sheet having air permeability is arranged on the upper side of the heat generating layer, the inconvenience that the air permeability of the sheet is impaired by sticking of the heat generating layer is less likely to occur. The moisture content of the heat generating layer is measured with respect to a portion located above the surface of the base sheet. Therefore, the site | part embedded in the base material sheet among heat_generation | fever layers is excluded from the measuring object of a moisture content. A specific method for measuring the moisture content of the heat generating layer is as follows. That is, the exothermic layer at a position located above the surface of the base sheet is taken out in a nitrogen environment, and its mass is measured. Thereafter, moisture is removed for 2 hours in a drying furnace at a temperature of 105 ° C. in a vacuum state, the mass is measured again, and the water content is measured. The moisture content of the heat generating layer is a value per heat generating layer.

  By setting the moisture content of the heat generating layer within the above range, the heat generating layer is effectively prevented from sticking to the breathable sheet disposed thereon. There may be a concern that the heat generation characteristics are reduced due to the decrease in the amount of the above. However, in the present invention, since the base sheet contains water and water is supplied from the base sheet to the heat generating layer during heat generation, the heat generation characteristics are not deteriorated. In particular, since the base sheet contains a superabsorbent polymer, and the release of water from the superabsorbent polymer proceeds gradually, the heat generation characteristics are stable over a long period of time. From these viewpoints, the proportion of water in the heating element, that is, the moisture content of the heating element is preferably 10 to 60% by mass, particularly 12 to 50% by mass. The specific method for measuring the moisture content of the heating element is as follows. That is, the mass of the heating element is measured under a nitrogen environment, and then placed in a drying oven at a temperature of 105 ° C. in a vacuum state for 2 hours, moisture is removed, the mass is measured again, and the difference mass is determined as the moisture content. To do. The moisture content is calculated by dividing the moisture content by the mass of the heating element before removing moisture and multiplying by 100. The moisture content of the heating element described above is a value when one heating layer is formed on one side of the base sheet, but the above range is maintained even when a heating layer is formed on each side of the base sheet. It is preferable to satisfy.

  In the heating element, it is preferable from the viewpoint of achieving uniform heat generation that water is uniformly present throughout the entire surface (the entire area in the plane direction and the entire area in the thickness direction). The rate part and the low water content part may be mixed. For example, stripe-shaped high water content portions and low water content portions extending in one direction can be alternately formed in the in-plane direction of the heating element. By adopting such a configuration, the rigidity of the heating element can be made different between the high moisture content part and the low moisture content part, and thereby the heating tool is attached to an object to be attached, for example, human skin or clothing. There is an advantageous effect that the fit at the time becomes even better. The reason for this is that the hardness of the heating element is increased with the progress of the oxidation reaction of the heating element, and since the oxidation reaction stops midway at the part where the moisture content is low, the part does not become so hard. This is because the oxidation reaction continues at a site where the rate is high, and the site becomes harder to that extent. From this viewpoint, the moisture content at the high moisture content portion in the heating element is preferably 20 to 60% by mass, particularly preferably 25 to 50% by mass. On the other hand, the moisture content in the low moisture content region of the heating element is preferably 10 to 40% by mass, particularly preferably 10 to 30% by mass, provided that the moisture content in the high moisture content region is lower.

  In the heating element, when the heating layer is formed only on one side of the base sheet, the moisture content on the side of the base sheet where the heating layer is not provided is greater than the moisture content of the heating layer. Is also preferably low. In this way, on the side where the heat generating layer is formed, moisture supply for heat generation is performed on the heat generating layer, while on the side where the heat generating layer is not provided, the base sheet and Adhesiveness with the covering sheet is prevented, and an advantageous effect is obtained that the flow of air in the heating tool is hardly hindered. In order to achieve such a moisture content relationship, it is advantageous to use, for example, a substrate sheet having the above-described structure (b) or (c). In the base sheet having the structure of (b) or (c), since the superabsorbent polymer particles are unevenly distributed in the central region in the thickness direction, a heat generating layer is formed only on one surface of the base sheet. This is because water permeation is prevented at the site where the superabsorbent polymer particles are unevenly distributed, so that the water content on the opposite side of the base sheet can be kept low.

  The moisture content of the heating element on the side where the heating layer is not provided is determined by cutting out the layer on the side where the heating layer is not provided in a nitrogen environment, measuring its mass, and then measuring the temperature at 105 ° C. under vacuum. Put in a drying oven for 2 hours, remove the moisture, measure the mass again, and use the difference mass as the moisture content. The moisture content is calculated by dividing the moisture content by the mass of the heating element before removing moisture and multiplying by 100.

  In the heating tool of the present invention, as described above, the heating element is surrounded by the packaging material. This packaging material includes a first cover sheet and a second cover sheet. The first cover sheet is disposed on the heat generating layer side of the heat generating element. The second cover sheet is disposed on the side of the heat generating element where the heat generating layer is not formed (when the heat generating layer is formed only on one side of one base sheet) or disposed on the side of the heat generating layer. (For example, when a heat generating layer is formed on both surfaces of one base sheet).

  The first cover sheet and the second cover sheet each have an extended area extending outward from the periphery of the heating element, and the extended areas are joined to each other. This joining is preferably an annular continuous airtight joining surrounding the heating element. The packaging material formed by joining both covering sheets has a space for accommodating a heating element therein. A heating element is accommodated in this space. In the case where the joints between the extension regions are annular and continuous airtight joints, it is ensured that solids (for example, oxidizable metal particles) are removed from the heating element contained in the packaging material. Since it is prevented, it is preferable.

  The heating element accommodated in the packaging material is not fixed to the packaging material. In other words, the movement of the heating element is not restricted by the packaging material, and can be moved independently of the packaging material. Therefore, for example, when an adhesive is applied to the second covering sheet of the packaging material to form an adhesive part, and the heating tool of the present invention is attached to the user's skin or the like via the adhesive part, Even if the second covering sheet is pulled due to the fact that the pulled state does not propagate to the heating element, the solid content (for example, oxidizable metal particles) is removed from the heating element. Effectively prevented. Further, since the heating element is not constrained, it can move independently from the packaging material, and since it is difficult to adhere to the covering sheet, the air permeability of the covering sheet is not hindered. Moreover, the flow of air around the base sheet is not inhibited in the packaging material, and a good exothermic reaction can be obtained. Thus, according to the present invention, the heat generation of the heating element proceeds uniformly, so that the curing of the heating element caused by the heat generation also progresses uniformly. As a result, the heating tool of the present invention is less likely to lose flexibility even after the end of heat generation, and can fit the shape of the user's body from the start of heat generation to the end of heat generation. In particular, even non-planar parts such as joints and curved parts of the body can be fitted successfully.

  The flexibility of the heating tool of the present invention can be evaluated by a three-point bending load. It can be determined that the smaller the value of the bending load, the higher the flexibility of the heating tool of the present invention. The three-point bending load is measured as follows. The measuring instrument is Tensilon Universal Tester RTA-500 manufactured by ORIENTEC. The heating tool as the measurement sample is a 65 mm square. As shown in FIG. 1, the heating tool 100 is spanned between a pair of plate-like supports 90 and 90 having a width of 6 mm. The interval between the supports 90 is 25 mm. Further, the length of the support 90 is made longer than the length of the heating tool 100. The plate-like pusher 91 is lowered at a rate of 100 mm / min from the top of the heating tool 100 spanned between the supports 90, and the heating tool 100 is pushed in. The plate-like pusher 91 has a width of 1.5 mm and a length longer than the length of the heating tool 100. The position where the plate-like pusher 91 is pushed in is an intermediate position between the pair of supports 90. The plate-like push-in body 91 is pushed into the support 90 by 15 mm, and the maximum value of the load generated during the movement amount is defined as a three-point bending load. In the present invention, the value of the three-point bending load is preferably 0 to 1.5 N / 65 mm, and more preferably 0 to 1.0 N / 65 mm before the start of heat generation. The value of the three-point bending load after the end of heat generation is preferably 0.01 to 1.8 N / 65 mm, particularly preferably 0.1 to 1.5 N / 65 mm. Furthermore, the rate of change of the three-point bending load after the end of heat generation relative to the three-point bending load before the start of heat generation is preferably 350% or less, particularly preferably 330% or less. This rate of change is defined as [(L2-L1) / L1] × 100, where L1 is the three-point bending load before the start of heat generation and L2 is the three-point bending load after the end of heat generation. The term “after heat generation” means a state where the temperature of the heating element is 42 ° C. or lower.

A part of the first covering sheet in the packaging material has air permeability, or the whole has air permeability. As described above, since the first cover sheet is disposed so as to face the heat generating layer in the heating element, the first cover sheet has air permeability, so that oxygen can be smoothly supplied to the heat generating layer. Performed and a stable exotherm is maintained for a long time. From this viewpoint, the air permeability of the first covering sheet (JIS P8117 B type, hereinafter referred to as the measured value of this method when referred to as air permeability) is 1 to 50,000 seconds / (100 ml · 6.42 cm ² ), In particular, it is preferably 10 to 40,000 seconds / (100 ml · 6.42 cm ² ). As the first covering sheet having such air permeability, for example, a porous sheet made of a synthetic resin having moisture permeability but not water permeability is preferably used. When using such a porous sheet, various fiber sheets such as needle punched nonwoven fabric and air-through nonwoven fabric are laminated on the outer surface of the porous sheet (the surface facing outward in the first covering sheet). Thus, the texture of the first cover sheet may be enhanced.

As the second covering sheet in the packaging material, an appropriate one is selected according to the structure of the heating element. The second cover sheet is preferably a sheet having a lower air permeability than the first cover sheet from the viewpoint of stably generating water vapor through the first cover sheet. In particular, when the heat generation layer of the base sheet is not located on the second covering sheet side, the second covering sheet is preferably a sheet having lower air permeability than the first covering sheet. The “sheet with low air permeability” as used herein refers to a non-breathable sheet that is partially breathable but has a lower degree of breathability than the first covering sheet and does not have breathability. Includes both cases. When the second cover sheet is a non-breathable sheet, examples of the non-breathable sheet include a synthetic resin film, a needle punched non-woven fabric on the outer surface of the film (the surface facing outward in the second cover sheet), A composite sheet obtained by laminating various fiber sheets including a nonwoven fabric such as an air-through nonwoven fabric can be used. When the second cover sheet is a breathable sheet, the same breathable sheet as that of the first cover sheet can be used. In this case, the air permeability of the second cover sheet is 200 to 150,000 seconds / (100 ml · 6.42 cm ² ), particularly 300 to 100, provided that the air permeability of the second cover sheet is lower than that of the first cover sheet. It is preferably 000 seconds / (100 ml · 6.42 cm ² ). When the second cover sheet is a breathable sheet, stable heat generation can be performed even in a use state in which the outer surface of the first cover sheet is in close contact with the user's skin or clothes, for example.

  In the heating element, the heating layer may be formed on only one side of one base sheet, or may be formed on both sides. In the case where the heat generating layer is formed on both sides, for example, a base sheet coated with a paint described later is turned upside down with a turn bar or the like, and a second sheet is formed on the other side of the base sheet. What is necessary is just to apply a paint. Further, the number of heating elements housed in the heating tool may be one, or a plurality of heating elements may be used and housed in a multilayer state in which they are laminated.

The heating tool of the present invention can generate water vapor from the side where the first covering sheet 4 is disposed. In order to enable the generation of water vapor, (b) on the premise that the heat generating layer contains a large amount of water, (b) a method of adjusting the proportion of each component constituting the heat generating layer, (c) Examples thereof include a method of adjusting the air permeability of the first and second cover sheets 4 and 5 surrounding the heating element, and a method of using (d) (b) and (c) in combination. In the heating tool of the present invention, a large amount of water can be retained when the base sheet contains hydrophilic fibers. Due to this, the heating tool of the present invention can generate a large amount of water vapor. Moreover, in the heating tool of the present invention, since the base sheet contains a hydrophilic polymer in addition to containing the hydrophilic fiber, the base sheet can retain a large amount of water also by this. As a result, a large amount of water vapor can be generated. The ratio of each component constituting the heat generation layer (b) is as described above. The air permeability of the first and second covering sheets 4 and 5 in (C) is also as described above. The amount of water vapor that is released through the first cover sheet ^{4, 0.01~0.8mg / (cm 2 · min} ) in accordance with the measuring method described later, especially 0.03~0.4mg / (cm ² · min) It is preferable that

  When both the first covering sheet 4 and the second covering sheet 5 have air permeability, the air permeability value of the first covering sheet 4 is smaller than the air permeability value of the second covering sheet 5. Therefore, the amount of water vapor released through the first cover sheet 4 is set to be larger than the amount of water vapor released through the second cover sheet 5. Is preferred. As long as the amount of water vapor released through the first cover sheet 4 is larger than the amount of water vapor released through the second cover sheet 5, water vapor is released through the second cover sheet 5. Is not disturbed at all.

In the heating tool of the present invention, the amount of water vapor released through the first cover sheet 4 is measured as follows. That is, heating is started by bringing the heating tool into contact with air at 20 ° C. and 65% RH. Immediately place the heating tool on a pan balance capable of measuring 1 mg, and then measure the mass for 15 minutes. Steam generated from the following equation when the mass at the start of measurement is Wt ₀ (g), the mass after 15 minutes is Wt ₁₅ (g), and the steam generation area of the heating tool is S (cm ² ) Calculate the amount of
Water vapor release [mg / (cm ² · min)] = {(Wt ₀ −Wt ₁₅ ) × 1000} / 15S

  The first covering sheet in the packaging material may have an adhesive layer formed by applying an adhesive on the outer surface thereof. The pressure-sensitive adhesive layer is used for attaching the heating tool of the present invention to human skin or clothing. As an adhesive which comprises an adhesion layer, the thing similar to what was used until now in the said technical field including a hot-melt adhesive can be used. From the viewpoint of not impairing the air permeability, it is preferable to provide an adhesive layer on the peripheral portion of the first cover sheet.

  Next, the suitable method for manufacturing the heating tool of this invention is demonstrated. This method includes (i) a first step of manufacturing a heating element by applying a paint of a heating composition to a base sheet, and (ii) a first step of manufacturing a heating tool by surrounding the heating element with a packaging material. 2 steps.

  The paint used in the first step contains oxidizable metal particles, a reaction accelerator, an electrolyte, and water. Moreover, you may mix | blend a thickener and surfactant from a viewpoint of improving the dispersibility of the solid content in a coating material. The coating material containing these components is continuously applied on one surface of a base sheet made of a continuous long material using, for example, various coating methods. As the coating method, various known coating methods can be used without particular limitation. For example, roll coating, die coating, screen printing, roll gravure, knife coating, curtain coater and the like are used. Die coating is preferable from the viewpoint of easy application, easy control of the application amount, and uniform coating of the paint. Details of the coating of the heat-generating composition using the die coater are described in, for example, Japanese Patent No. 415791 related to the earlier application of the present applicant.

  By applying the paint, a continuous heat generating layer is formed on one surface of the base sheet. In this case, since the base sheet contains particles of the superabsorbent polymer, water contained in the paint is appropriately absorbed and held in the superabsorbent polymer, and the moisture content of the heat generation layer is determined by the moisture content of the paint. Decrease than rate. As a result, the fluidity of the heat generating layer is reduced, and preferably no fluidity is provided. In addition, since the base sheet contains hydrophilic fibers, this also allows water contained in the paint to be appropriately absorbed and held in the base sheet, thereby reducing the moisture content of the heat generating layer.

  When manufacturing a heating element having a heat generating layer on each surface of the base sheet, the base sheet is formed after the heat generating layer is continuously formed on one surface of the base sheet or simultaneously with the formation of the heat generating layer. A heat generating layer may be continuously formed on the other surface using a die coater or the like.

In the coating of the exothermic composition used for forming the exothermic layer, 1 to 20 parts by mass, particularly 2 to 14 parts by mass of the reaction accelerator is contained with respect to 100 parts by mass of the oxidizable metal particles. Is preferred. The electrolyte is preferably contained in an amount of 0.5 to 15 parts by mass, particularly 1 to 10 parts by mass. It is preferable that water is contained in 30 to 90 parts by mass, particularly 40 to 80 parts by mass. The thickener is preferably contained in an amount of 0.05 to 10 parts by mass, particularly 0.1 to 5 parts by mass. The surfactant is preferably contained in an amount of 0.1 to 15 parts by mass, particularly 0.2 to 10 parts by mass. Further, water is preferably contained in an amount of 20 to 50% by mass, particularly 25 to 45% by mass, assuming that the total mass of the paint is 100%. The viscosity of the paint is preferably 500 to 30,000 Pa · s at 23 ° C. and 50 RH, more preferably 500 to 20,000 mPa · s, and still more preferably 1,000 to 15,000 mPa · s. Even more preferably, it is 1,000 to 10,000 mPa · s. For measurement of the viscosity, a No. 4 rotor of a B-type viscometer was used. The measurement was performed by rotating the rotor at 6 rpm. The coating basis weight of the paint is preferably 150 to 5,000 g / m ² , particularly preferably 300 to 2,500 g / m ² .

  If the heating element which consists of a continuous long thing is manufactured by the above operation, this heating element will be coat | covered with a packaging material in a 2nd process next. Prior to this operation, it is preferable to produce a heating element for each leaf by cutting a heating element made of a continuous long object in the width direction. Next, while running the heating element of each leaf in one direction at a predetermined interval, the first covering sheet made of a continuous long object is disposed on the side where the heating layer is formed, and on the other side, Similarly, a second covering sheet made of a continuous long object is disposed. Subsequently, the extension area | region from the heat generating body in a 1st coating sheet and a 2nd coating sheet is joined by a predetermined joining means. Joining is performed outside the left and right side edges and outside the front and rear edges of the heating element. Examples of the bonding means include heat fusion, ultrasonic bonding, and adhesion using an adhesive.

  In disposing the first covering sheet on the heat generating layer, the moisture content of the heat generating layer is reduced and the fluidity is lowered, and preferably the fluidity is lost. Even if the sheet is arranged, the inconvenience that the heat generating layer sticks to the first covering sheet is avoided. As a result, the air permeability of the first cover sheet is successfully maintained.

  In this manner, a continuous long object in which a plurality of heating tools are connected in one direction is obtained. By cutting this continuous long object across the width direction between adjacent heating elements, the intended heating tool is obtained. In the next step, the heating tool is hermetically housed in a packaging bag having oxygen barrier properties.

  In the above-described method, a means for keeping the production line in a non-oxidizing atmosphere may be used as needed in order to suppress oxidation of the oxidizable metal during the production process, including the preparation of the paint. .

  In the above method, two kinds of paints can be used. As the two types of paints, the above-described high water content paint for forming a high water content region and the low water content paint for forming a low water content region can be used. These paints are stored in different tanks so that they do not mix with each other until applied to the substrate sheet. As an apparatus for applying these paints, for example, one coater head having two supply ports for high water content paint and low water content paint can be used. Alternatively, these coating materials may be sequentially applied to different portions in the width direction of the base sheet using a coating device for a high moisture content paint and a coating device for a low moisture content paint. By carrying out like this, the stripe-shaped multi-row high moisture content site | part extended in one direction and the low moisture content site | part can be alternately formed in the in-plane direction of the heat generating body obtained.

  As an alternative to this method, after applying the paint to one side of the substrate sheet using one type of paint, water is partially added on the coated surface, and the water content of the part where the water is applied is determined. It can also be increased. Also by doing so, stripe-shaped multi-stripe high water content portions and low water content portions extending in one direction can be alternately formed in the in-plane direction of the heat generating element to be obtained.

  In the above manufacturing method, the paint of the exothermic composition was applied to the base sheet, but instead, a paint containing oxidizable metal particles and no electrolyte was applied to the base sheet, Next, an aqueous electrolyte solution may be added to the coating surface of the paint. Specifically, a paint containing oxidizable metal particles, a reaction accelerator, water, a thickener and a surfactant is prepared, and this paint is applied to a base sheet to form a coating film. An electrolyte aqueous solution containing an electrolyte and water can be added to the coating film. What is necessary is just to adjust the density | concentration of each component in this coating material and electrolyte aqueous solution, and the usage-amount of a coating material and electrolyte aqueous solution so that the quantity of each component in the target heat generating body may become said range.

  When this method is adopted, a heating element is obtained by coating paints having different basis weights or moisture contents in a multi-stripe pattern, or by adding electrolyte aqueous solutions having different concentrations or amounts in a multi-stripe pattern. In the in-plane direction, stripe-shaped high water content portions and low water content portions extending in one direction can be alternately formed.

  Further, in this method, the paint containing the particles of the oxidizable metal and not containing the electrolyte was first applied, and then the aqueous electrolyte solution was added. Alternatively, the aqueous electrolyte solution was added first, A paint containing particles of an oxidizable metal and not containing an electrolyte may be applied. Even in the case of adopting this alternative method, by adding the aqueous electrolyte solution and / or applying the paint in a multi-striped shape, a stripe-shaped high extending in one direction in the in-plane direction of the heating element to be obtained. Water content sites and low water content sites can be formed alternately.

  The heating tool of the present invention produced in this way is applied directly to the human body or applied to clothing and is suitably used for warming the human body. Examples of the application site in the human body include the shoulder, neck, face, eyes, waist, elbow, knee, thigh, lower leg, 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. When used for heating the human body, the first covering sheet that generates water vapor is applied toward the skin side (human body side).

  FIG. 2 shows an example of a preferable apparatus used for manufacturing the heating tool of the present invention. This apparatus includes a coating part 20 of a heat generating composition paint, a first cutting part 40, a re-pitch part 50, a covering part 60, a sealing part 70, and a second cutting part 80.

  The coating unit 20 includes a die coater 21. Moreover, the endless belt 22 of the wire mesh which opposes the die lip of the die coater 21 and circulates in the arrow direction is also provided. Further, a suction box 23 is also provided opposite to the die lip of the die coater 21 with the endless belt 22 interposed therebetween. The base sheet 1 made of a continuous long material fed from the base roll 1A of the base sheet is conveyed by the endless belt 22, and a coating of the heat generating composition is applied to one surface thereof by the die coater 21, A heat generating layer is formed. When the base sheet 1 is transported by the endless belt 22, the suction box 23 is operated to stabilize the transport, and the paint is sucked and stably held on the base sheet 1. Since the water in the paint is absorbed by the base sheet 1 by applying the paint, the moisture content of the heat generating layer is lower than the moisture content in the paint. As a result, the fluidity of the heat generating layer decreases.

  When the heating element 10A made of a continuous long object is formed in this way, the heating element 10A is cut in the first cutting part 40 in the width direction. The first cutting unit 40 includes a rotary die cutter 42 and an anvil roll 43. Cutting is performed by the heating element 10A passing between both members, whereby the heating element 10 of each leaf is obtained.

  The heating element 10A made of a continuous long object may be cut so as to extend in the width direction of the heating element 10A. For example, the heating element 10A can be linearly formed in the width direction of the heating element 10A.

  In the re-pitch portion 50, the heating element 10 that has become a leaf is changed in pitch in the front-rear direction in the transport direction, and the heating elements 10 that are adjacent to each other in the front-rear direction are rearranged at a predetermined distance. As such a re-pitch mechanism, a conventionally known one can be used without particular limitation.

  The re-pitched heating element 10 is conveyed to the covering section 60 and is entirely covered by the first covering sheet 4 made of a continuous long object and the second covering sheet 5 also made of a continuous long object. The first cover sheet 4 covers the side of the heat generating element 10 where the heat generating layer is formed, and the second cover sheet 5 covers the side of the heat generating element 10 where the heat generating layer is not formed. The heating element 10 is introduced into the sealing portion 70 while maintaining this covering state. The sealing portion includes a first roll 71 having a seal convex portion 72 and a second roll 73 having the seal convex portion 72. Both rolls 71 and 73 are arranged in such a positional relationship that the axial directions thereof are parallel to each other and the seal convex portions 72 of the rolls 71 and 73 are in contact with each other or a predetermined clearance is generated therebetween. ing. In the sealing part 70, the extended part of the 1st and 2nd coating sheets 4 and 5 extended from the front and rear, right and left of the heat generating body 10 is joined by heat sealing. This joint is a continuous airtight joint surrounding the heating element 10 or a discontinuous joint surrounding the heating element 10.

  In this manner, a continuous long object in which a plurality of heating tools are connected in one direction is obtained. The continuous long object is cut in the width direction in the second cutting portion 80. The second cutting unit 80 includes a rotary die cutter 82 and an anvil roll 83. Cutting is performed by passing the continuous long object between the two members, whereby the intended heating tool 100 is obtained. In the cutting, when the cutting line of the heating element 10A in the first cutting part 40 described above is, for example, a straight line, the cutting line in the main cutting part 80 is also preferably a straight line. As shown in FIG. 3, in the obtained heating tool 100, the entire heating element 10 is surrounded by the first cover sheet 4 and the second cover sheet 5. The heating tool 100 has a surface on which the first covering sheet 4 is disposed on the side of the heating element 10 on which the heating layer is formed and the heating layer on the other side is not formed. On the side, the second covering sheet 5 is arranged.

  Moreover, another example of the preferable apparatus used for manufacture of the heating tool of this invention is shown in FIG. The difference between the apparatus shown in FIG. 2 and the apparatus shown in FIG. 2 is that, in the apparatus shown in FIG. 4, a continuous long object is formed on the heat generating layer at a position between the coating unit 20 and the first cutting unit 40. The base sheet 1 ′ is supplied, and the base sheet 1 ′ is overlaid on the heat generating layer. According to this apparatus, it is possible to easily manufacture a heating element in which a heating layer is provided between two identical or different base material sheets 1 and 1 ′. Either the base material sheet 1 to which the paint is applied or the base material sheet 1 ′ to be superposed on the applied heat generation layer may not contain the superabsorbent polymer particles. It is preferable that particles of the superabsorbent polymer are included in both of the base sheet 1 ′.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.

[Example 1]
(1) Preparation of exothermic composition paint As exothermic composition paint, 100 parts of oxidizable metal (iron powder, average particle size 45 μm), reaction accelerator (activated carbon, average particle size 42 μm) 8 parts, electrolyte ( Sodium chloride) 3 parts, thickener (guam gum) 0.2 parts, surfactant (polycarboxylic acid type polymer surfactant) 0.25 parts, and water 60 parts were used. The viscosity of the obtained coating material was 4,500 mPa · s. The viscosity was measured using a B-type viscometer No. 4 rotor in an environment of 23 ° C. and 50% RH.

(2) Preparation of substrate sheet The substrate sheet shown in FIG. 5 was used. This base material sheet 1 was produced according to the method described in JP-A-8-246395. In the base sheet 1, the sodium polyacrylate-based superabsorbent polymer particles 12 are mainly present in a substantially central region in the thickness direction of the base sheet 1, and the particles are formed on the surface of the base sheet 1. 12 (one ply) having a structure in which 12 does not substantially exist. The base material sheet 1 has layers 11 and 13 of hydrophilic cross-linked bulky cellulose fibers 11a on the front and back sides of the site where the superabsorbent polymer particles 12 are present. The crosslinked bulky cellulose fiber 11a had a fiber roughness of 0.22 mg / m and an average fiber length of 2.5 mm. The layers 11 and 13 of the crosslinked bulky cellulose fiber 11a further contained softwood bleached kraft pulp and a paper strength enhancer (PVA). A superabsorbent polymer having an average particle size of 340 μm was used. The basis weight of the layer 11 was 30 g / m ² , and the basis weight of the layer 13 was 20 g / m ² . The basis weight of the superabsorbent polymer particles 12 was 30 g / m ² . Therefore, the basis weight of the base material sheet 1 was 80 g / m ² .

(3) Production of heating element and heating tool The coating material was applied to one surface of the base sheet. The coating basis weight of the paint was 1,300 g / m ² . In this way, after the heating element 10A made of a continuous long object was formed, the heating element 10A was cut in the width direction. Thereby, the heating element 10 of every leaf was obtained. The heating element was a 50 mm × 50 mm rectangle.

  The obtained heating element 10 of each leaf was covered entirely with the first cover sheet 4 and the second cover sheet 5. At this time, the side where the heat generating layer is formed in the heating element 10 is covered with the first covering sheet 4, and the side where the heating layer is not formed in the heating element 10 is covered with the second covering sheet 5. . Next, the extending portions of the first and second cover sheets 4 and 5 extending from the front, rear, left and right of the heating element 10 were joined by heat sealing. This joining was a continuous airtight joining surrounding the heating element 10. The seal width was 5 mm.

As the first covering sheet 4, a polyethylene porous sheet having a basis weight of 50 g / m ² and an air permeability of 2500 s / (100 ml · 6.42 cm ² ) was used. As the second cover sheet 5, a non-ventilated sheet made of a polyethylene film having a basis weight of 30 g / m ² was used. Moreover, each coating sheet 4 and 5 was a 65 mm x 65 mm rectangular thing.

  FIG. 6A shows a microscopic image of a longitudinal section of the heating element 10. In the obtained heating element 10, the moisture content of the heating layer measured in accordance with the method described above was 21%, the moisture content of the heating element was 35%, and the moisture content of the heating element on which the heating layer was not provided was 17%. Met.

Moreover, about the obtained heat generating body 10, temperature measurement was performed with the test method based on the thermal apparatus for JIS S4100 disposable warmer temperature characteristic measurement. The obtained heating tool 100 was inserted into a needle punched nonwoven fabric bag having a basis weight of 100 g / m ² and placed on a constant temperature bath at 40 ° C. to evaluate temperature characteristics. This bag is formed into a bag shape by sealing three sides of the needle punched nonwoven fabric. The thermometer was arrange | positioned between the heating tool 100 and the thermostat surface. The heating tool 100 was placed so that the side on which the heat generation layer was formed faced upward (the direction opposite to the thermometer). As a result, the maximum temperature reached 62 ° C. 15 minutes after the start of measurement.
Moreover, after putting it on the skin of a human body for 30 minutes and using it, the mass of the fallen material from the heat generating layer was measured, and the dropout amount ratio was calculated. For mounting on the human body, the heating tool 100 was fixed to the arm using a supporter. The mass of the fallen object was measured by collecting the fallen substance remaining in the accommodation space of the first and second covering sheets and adhering to the sheet. As a result, the mass ratio after falling off was 1.3%, and it was confirmed that the heating element was not easily dropped off. The dropout ratio (%) was calculated from (mass of fallout / mass of heating element after use) × 100.

Furthermore, when the amount of water vapor released from the first covering sheet 4 side in the obtained heating tool 100 was measured by the above-described method, it was 0.19 mg / (cm ² · min). Further, when the three-point bending load in the obtained heating tool 100 before the start of heat generation and after the end of heat generation was measured by the above method, it was 0.40 N / 65 mm before the start of heat generation, and 1.21 N after the end of heat generation. / 65 mm.

[Example 2]
In Example 1, after coating a coating on one surface of the base sheet 1, a base sheet 1 ′ of the same type as the base sheet 1 is superimposed on the coated surface as shown in FIG. 4 to obtain a heating element. It was. Thereafter, a heating tool was obtained in the same manner as in Example 1. The obtained heating tool was measured in the same manner as in Example 1. The results are shown in Table 1 below.

Example 3
In Example 1, the amount of paint applied to one surface of the base sheet 1 was reduced to 700 g / m ² . Thereafter, a heating tool was obtained in the same manner as in Example 1. The obtained heating tool was measured in the same manner as in Example 1. The results are shown in Table 1 below.

Example 4
In Example 1, after coating a coating material on one surface of the base sheet 1, a heating element was obtained on the coated surface using pulp paper having a basis weight of 50 g / m ² as the base sheet. This pulp paper had a smooth surface. The pulp paper contained no superabsorbent polymer particles. The heating layer in this heating element has a part of the surface facing the base sheet embedded in the base sheet, and the side facing the pulp paper is not embedded in the pulp paper Met. Thereafter, a heating tool was obtained in the same manner as in Example 1. The obtained heating tool was measured in the same manner as in Example 1. The results are shown in Table 1 below.

[Comparative Example 1]
In Example 1, the non-coating surface of the paint in the heating element 10 and the inner surface of the second cover sheet 5 were joined together with an adhesive. The basis weight of the adhesive was 30 g / m ^2, and the adhesive was uniformly applied to the entire area of the opposing surfaces. Thereafter, a heating tool was obtained in the same manner as in Example 1. The obtained heating tool was measured in the same manner as in Example 1. The results are shown in Table 1 below.

[Comparative Example 2]
In Example 1, pulp paper having a basis weight of 150 g / m ² was used as the base sheet. This pulp paper has a smooth surface. The pulp paper does not contain superabsorbent polymer particles. Thereafter, a heating tool was obtained in the same manner as in Example 1. The obtained heating tool was measured in the same manner as in Example 1. The results are shown in Table 1 below. FIG. 6B shows a microscopic image of a longitudinal section of the heating element.

[Comparative Example 3]
The same measurement as in Example 1 was performed using a “Megurisum (registered trademark) hot eye mask with steam” manufactured by Kao Corporation. The results are shown in Table 1 below.

  As is clear from the results shown in Table 1, it can be seen that the heating tools obtained in each example reach the maximum temperature in a short time. It can also be seen that the increase rate of the three-point bending load after the end of heat generation is small, and the decrease in flexibility is small even after the end of heat generation. Further, it can be seen that the amount of exothermic composition falling off the exothermic layer is small. On the other hand, although the heating tool obtained in Comparative Example 1 reaches the maximum temperature in a short time, the rate of increase in the three-point bending load after the end of heat generation is large, and the flexibility is lost after the end of heat generation. I know that. It can also be seen that the exothermic composition is largely removed from the exothermic layer. It can be seen that the heating tool obtained in Comparative Example 2 takes a long time to reach the maximum temperature, and the maximum temperature itself is low. Further, it can be seen that the increase rate of the three-point bending load after the end of heat generation is large, and the flexibility is lost after the end of heat generation. It can also be seen that the exothermic composition is largely removed from the exothermic layer.

  Further, as is clear from the comparison between FIG. 6A and FIG. 6B, in the heating tool obtained in Example 1, it was observed that the lower part of the heating layer was buried in the base sheet. Is done. On the other hand, in the heating tool obtained in Comparative Example 2, the heating layer is not embedded in the base sheet. In Example 1, it is considered that the fact that the lower part of the heat generation layer is buried in the base material sheet contributes to the prevention of a decrease in flexibility of the heating tool after the heat generation is completed.

DESCRIPTION OF SYMBOLS 1 Base sheet 10 Heat generating body 11 Layer of hydrophilic fiber 12 Particle of superabsorbent polymer 13 Layer of hydrophilic fiber 100 Heating tool

Claims (12)

A heating element in which a layer of a heat generating composition containing particles of an oxidizable metal is provided on one surface of a base sheet comprising a fiber sheet containing superabsorbent polymer particles and hydrophilic fibers, and the whole heating element And surrounding wrapping material,
The packaging material is formed by joining the first covering sheet and the second covering sheet at their peripheral portions, and the inside thereof is a housing space for the heating element,
The heating element is housed in the housing space in a non-fixed state with respect to the packaging material,
The first covering sheet has air permeability in a part thereof and is arranged on the layer side of the exothermic composition,
A heating tool capable of generating water vapor from the side on which the first covering sheet is disposed during use.   The heating tool according to claim 1, wherein the second covering sheet has a lower air permeability than that of the first covering sheet.   The heating tool according to claim 1 or 2, wherein a layer of the heat generating composition is provided only on one surface of the base sheet.   The heating tool according to claim 1 or 2, wherein a layer of the heat generating composition is provided between two identical or different base material sheets.   The heating tool according to claim 1, wherein the layer of the heating composition is in a water-containing state.   The heating tool according to any one of claims 1 to 5, wherein the hydrophilic fibers are made of cellulose fibers.   The heating tool according to claim 6, wherein the cellulose fibers are bulky cellulose fibers.   The bulky cellulose fiber (a) has a three-dimensional structure in which the fiber shape is a twisted structure, a crimped structure, a bent and / or branched structure, (b) the fiber roughness is 0.2 mg / m or more, or (C) The heating tool according to claim 7, wherein cellulose molecules are crosslinked in and between molecules.   In the base sheet, the superabsorbent polymer particles are mainly present in a substantially central region in the thickness direction of the base sheet, and the particles are substantially present on the surface of the base sheet. The heating tool according to any one of claims 1 to 8, comprising a single sheet having an unstructured structure.   10. The moisture content on the side of the base sheet on which the exothermic composition layer is not provided is lower than the moisture content of the exothermic composition layer. The heating tool according to Item.   The heating tool according to any one of claims 1 to 10, wherein a lower portion of the heating composition is embedded in the base sheet.   The heating tool according to any one of claims 1 to 11, wherein a change rate of the three-point bending load after the end of heat generation with respect to the three-point bending load before the start of heat generation is 350% or less.