JP5840554B2 - Heating equipment - Google Patents

Description

  The present invention relates to a heating tool.

2. Description of the Related Art Conventionally, various kinds of heating tools that generate heat due to an oxidation reaction of an oxidizable metal have been developed.
For example, in Patent Document 1, an exothermic substance, a water-absorbing polymer and / or a thickener, a carbon component and / or a metal chloride, and water are essential components, which are formed in an ink form or a cream form as a whole. An ink-like or cream-like exothermic composition is disclosed. In Patent Document 1, this exothermic composition is laminated and encapsulated in a sheet-like wrapping material, and at least a part of the wrapping material has air permeability, and a part of the moisture of the exothermic composition is described above. A heating element characterized by being absorbed by a sheet-like packaging material is also disclosed.

JP-A-9-75388

However, as in Patent Document 1, the exothermic composition in which the exothermic substance, the water-absorbing polymer and / or the thickener, the carbon component and / or the metal chloride are dispersed in a large excess of water to form a paint is produced. It was found that there was a tendency for water separation to occur from the ink-like or cream-like exothermic composition during the process, and there was room for examination in production stability.
In addition to this, in recent years, it is also required to improve the heat generation performance of the heat generator.

According to the present invention,
A heating tool in which a heat generating layer containing an oxidizable metal, a carbon component, a water-soluble polymer having a molecular weight of 1 million or more, and water, and a base material layer are laminated,
The carbon component has a water absorption rate of 160% or more and 400% or less of its own weight, and an average particle size of 10 to 400 μm.
A heating tool is provided in which the mass ratio (water / oxidizable metal) of the water content in the base material layer to the oxidizable metal content in the heating tool is 0.05 to 0.38. Is done.

  In the present invention, the heating tool contains a specific water-soluble polymer and a specific carbon component, and the mass of the water content in the base material layer and the oxidizable metal content in the heating tool. By prescribing the ratio (water / oxidizable metal), it is possible to improve the production stability because the oxidizable metal, carbon component, water-soluble polymer and water form a very good structure as the coating before lamination. The heating product is excellent and has a good exothermic performance after being laminated on the base material layer, that is, a heating tool having a short time to temperature rise and a moderately high maximum temperature.

  ADVANTAGE OF THE INVENTION According to this invention, the heating tool which is excellent in manufacture stability and has favorable heat_generation | fever performance is provided.

It is sectional drawing which shows the heat generating body concerning one Embodiment of this invention. It is a top view which shows a heating tool. It is a disassembled perspective view of a heating tool. It is sectional drawing of a heating tool. It is sectional drawing of a heat-emitting part. It is a schematic diagram which shows a manufacturing apparatus. It is a schematic diagram which shows the apparatus which measures water vapor generation amount.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and detailed description thereof is appropriately omitted so as not to overlap.
With reference to FIGS. 1-4, the heating tool 100 of this embodiment is demonstrated.
The heating tool 100 has a heating element 120 shown in FIG. The heating element 120 includes a heating part 121 and a first bag body 122 that encloses the heating part 121. The heat generating part 121 includes a heat generating layer 121A and a base material layer 121C.

This heat generating part 121 is
A heating layer 121A containing an oxidizable metal, a carbon component, a water-soluble polymer having a molecular weight of 1 million or more, and water, and a base material layer 121C are laminated. And
The carbon component has a water absorption rate of 160% or more and 400% or less of its own weight, and an average particle size of 10 to 400 μm.
The mass ratio (water / oxidizable metal) of the water content in the base material layer 121C and the oxidizable metal content in the heating tool is 0.05 to 0.38.

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

  When the oxidizable metal is a powder, the average particle size is preferably 10 to 200 μm and more preferably 20 to 150 μm from the viewpoint that the oxidation reaction is efficiently performed. The particle size of the oxidizable metal refers to the maximum length in the form of powder, and is measured by classification using a sieve, dynamic light scattering method, laser diffraction method or the like.

The content of the oxidizable metal, expressed as the basis weight is preferably from 100 to 3000 g / ^{m 2,} preferably further a 200~1600g / ^{m 2.} Thereby, the heat generation temperature of the heat generating body 120 can be raised to a desired temperature. Here, the content of the oxidizable metal can be determined by an ash content test according to JIS P8128 or a thermogravimetric instrument. In addition, it can be quantified by a vibration sample type magnetization measurement test or the like using the property that magnetization occurs when an external magnetic field is applied.

  As a result of intensive studies by the present inventors, a carbon component having a specific particle diameter and water absorption rate and a water-soluble polymer having a molecular weight as large as 1,000,000 or more have excellent production stability during production. In addition, it is understood that a heating tool with good heat generation performance of the product can be provided by making the water in the base material layer and the oxidizable metal in the heating tool have a specific mass ratio. It was.

The carbon component combines with an oxidizable metal, a water-soluble polymer, and water to form a very good structure, has excellent manufacturing stability as a coating before coating, and has a heat generation performance as a product obtained. In order to make it favorable, what can hold | maintain a fixed water | moisture content is preferable. That is, the water absorption rate of the carbon component is 160% or more and 400% or less of the weight of the carbon component, and in particular, from the viewpoint of improving the heat generation performance, a carbon component having a water absorption rate of 170% or more and 300% or less may be used. It is preferable to use those that are 180% or more and 250% or less.
By setting the water absorption rate to 160% or more of the weight of the carbon component, it becomes easy to sufficiently supply moisture necessary for heat generation to the heat generation layer, and the heat generation temperature can be improved.
On the other hand, by setting the water absorption rate to 400% or less, preferably 300% or less, of the weight of the carbon component, the amount of water necessary for satisfactorily dispersing the carbon component or the like can be suppressed, and the exothermic composition is moderate. Since it has a high viscosity, good coatability is exhibited, and the temperature raising time can be shortened while keeping the maximum temperature moderate.

  Further, in order to increase the heat generation efficiency, it is necessary to increase the efficiency of the oxidation reaction of the oxidizable metal, and the carbon component needs to have a particle size of a certain value or less. Therefore, the carbon component has an average particle diameter of 10 to 400 μm, and in particular, from the viewpoint of shortening the heating time and appropriately increasing the maximum temperature, the average particle diameter is preferably 12 to 280 μm. More preferably, the diameter is 14 to 110 μm.

  The average particle diameter of the carbon component refers to the maximum length in the form of powder, and can be measured by a dynamic light scattering method or a laser diffraction scattering method. For example, by dispersing the carbon component in water, creating a particle size distribution of the carbon component on a volume basis with a laser diffraction particle size distribution analyzer (manufactured by SHIMADZU, SALD-300), and setting the median diameter as the average particle size Can be measured.

The content of the carbon component is preferably 15 to 290 g / m ² and more preferably ²⁰ to 160 g / m ² in terms of basis weight. Moreover, 0.3-20 mass parts is preferable with respect to 100 mass parts of oxidizable metals, and, as for content of a carbon component, 1-15 mass parts is preferable, and 3-13 mass parts is more preferable. In this way, the carbon component, the oxidizable metal, the water-soluble polymer, and water form a very good structure, and the production stability is excellent during production, and the heat generation performance of the obtained product is good. It is more preferable because it can be made. Further, moisture necessary for sustaining the oxidation reaction can be retained in the heat generation layer, and sufficient heat generation can be obtained. Furthermore, the oxygen supply to the heat generating layer is sufficiently achieved, and a heat generating layer with high heat generation efficiency is obtained. In addition, since the heat capacity of the heating element with respect to the amount of heat generated can be kept small, the heat generation temperature rises and a desired temperature rise can be obtained.

  As the preferred carbon component for the present invention, for example, one or two or more types of activated carbon selected from coconut shell charcoal, charcoal powder, calendar bituminous coal, peat, and lignite can be used, but it is easy to adsorb oxygen when wet. In addition, the water component in the heat generating layer can be kept constant, the carbon component, the oxidizable metal, the water-soluble polymer, and water form a very good structure, and the manufacturing stability is excellent during manufacturing. From the viewpoint of improving the heat generation performance of the obtained product, activated carbon having a water absorption rate of 160% to 400% of the weight of the carbon component and an average particle diameter of 10 to 400 μm is used. More preferably, from the viewpoint of improving heat generation performance, the carbon component is coconut shell charcoal having a water absorption rate of 160% to 400% of its own weight and an average particle size of 10 to 400 μm. , And one or more selected from peat charcoal. Among them, coconut shell charcoal having an excellent water-absorbing rate of 160% or more and 400% or less of its own weight and an average particle diameter of 10 to 400 μm is preferable for excellent production stability and good heat generation performance.

In the heating tool 100 of the present invention, the mass ratio (water / carbon component) of the water content in the heating layer 121A to the carbon component content contained in the entire heating tool is preferably 0.8 to 4. . By so doing, the air permeability of the heat generating layer 121A is sufficiently ensured, so that the heating element 120 with sufficient oxygen supply and high heat generation efficiency can be obtained. In addition, since the heat capacity of the heating element with respect to the amount of heat generated can be kept small, the heat generation temperature rises and a desired temperature rise can be obtained.
Especially, mass ratio (water / carbon component) of the content of water in the heat generating layer 121A with respect to the content of the carbon component is 1.5 to 3 in that the temperature rise time is shortened while making the maximum temperature moderate. It is preferable.

  Water-soluble polymers with a molecular weight of 1 million or more can absorb moisture to increase consistency or use substances that impart thixotropy. Carbon components, oxidizable metals, water-soluble polymers, and water are extremely Is a water-soluble polymer having a molecular weight of 1 million or more, preferably 1 million or more and 50 million or less, from the viewpoint of forming a good structure, excellent production stability, and good heat generation performance. The water-soluble polymer is preferably 2 million or more and 40 million or less. Xanthan gum is particularly preferable from the viewpoint of good coating performance, salt resistance, and thickening even with a small amount.

  The heating tool 100 of the present invention has a mass ratio (water / polymer) of the water content in the heating tool and the content of water-soluble polymer having a molecular weight of 1 million or more in the heating tool (water / polymer). , Preferably 180 to 400. By doing so, the coating properties are improved while the solids such as the oxidizable metal and the carbon component can be stably dispersed. Moreover, thixotropy can be imparted and the coating performance can be further improved. Furthermore, the carbon component, the oxidizable metal, the water-soluble polymer, and water form a very good structure, so that the production stability is excellent and the heat generation performance is good.

Furthermore, in the heating tool 100 of the present invention, water-soluble polymers other than the water-soluble polymer having a molecular weight of 1 million or more in addition to the above-described water-soluble polymer having a molecular weight of 1 million or more in a range not affecting the effects of the present invention. It may contain a polymer.
Other water-soluble polymers include polysaccharides such as alginates such as sodium alginate, gum arabic, tragacanth, locust bean gum, gum arabic, carrageenan, agar, etc .; dextrin, pregelatinized starch, starch for processing Starch-based water-soluble polymers such as: cellulose acetate-based water-soluble polymers such as ethyl acetate, hydroxyethyl cellulose, hydroxymethyl cellulose or hydroxypropyl cellulose; water-soluble polymers such as polyvinyl alcohol; metal soap-based water-soluble such as stearates One kind or a mixture of two or more kinds selected from polymers can be used in combination.
However, from the viewpoint of heat generation performance, the water-soluble polymer other than the water-soluble polymer having a molecular weight of 1 million or more is preferably 0.5 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. 0.2 part by mass or less, and it is more preferable that no other water-soluble polymer other than the water-soluble polymer having a molecular weight of 1,000,000 or more is contained.

  The water content in the heating tool 100 is preferably 35 to 55 parts by mass with respect to 100 parts by mass of the oxidizable metal. Among them, the carbon component, the oxidizable metal, the water-soluble polymer, and water form a very good structure, have excellent manufacturing stability, and good heat generation performance. From the viewpoint of heat resistance and the heat generation of the heat generating layer 121A, it is more preferably 38 to 50 parts by mass.

The amount of moisture Z in the heat generating layer 121A is determined as follows. The mass of the composition constituting the heating layer 121A is measured (mass P), and then dried for 15 minutes at 120 ° C. using a Kett moisture meter (FD-240) under a nitrogen stream (mass Q). ).
The moisture content (R) of the heat generating layer is expressed by the following equation.
R (mass%) = (P−Q) / P × 100.
Moisture content in the heat-generating layer, where X is the solid content calculated from the ratio of the exothermic composition (the value obtained by dividing the total composition ratio excluding water by the total composition ratio) and the coating amount is Y Z is represented by the following formula.
Z (g) = (R × X × Y / 100) / (1-R / 100)

  The moisture content in the heat generating layer 121A is preferably 22% by mass or less. By doing in this way, the heat capacity of a heat generating body becomes small, and even if comparatively much water exists in base material layer 121C, the fall of the exothermic temperature rise rate of heating tool 100 can be prevented. Furthermore, the moisture content in the heat generating layer 121A is 18.5% by mass or less, preferably 15% by mass or less, and more preferably 14% by mass or less. However, the moisture content in the heat generating layer 121A is 10% by mass or more, preferably 12% by mass or more in consideration of heat generation characteristics.

Further, the heat generating layer 121A may contain a reaction accelerator in addition to the components described above.
The reaction accelerator is used for the purpose of maintaining the oxidation reaction of the oxidizable metal. In addition, by using a reaction accelerator, it is possible to accelerate the oxidation reaction by destroying the oxide film formed on the oxidizable metal with the oxidation reaction. Examples of the reaction accelerator include one or more selected from alkali metals, alkaline earth metal sulfates, and chlorides. Above all, it is selected from various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride and ferric chloride, and sodium sulfate because of its excellent conductivity, chemical stability and production cost. It is preferable to use 1 type (s) or 2 or more types.

  The content of the reaction accelerator in the heat generating layer 121A is preferably 2 to 15 parts by mass with respect to 100 parts by mass of the oxidizable metal from the viewpoint that a sufficient calorific value is maintained for a long time. More preferably, it is 3-13 mass parts.

The base material layer 121C is preferably laminated so as to be in direct contact with the heat generating layer 121A. The mass ratio of the content of water in the base material layer 121C and the content of the oxidizable metal in the heating tool 100 (water in the base material layer / oxidizable metal) is 0.05 to 0.38. It is. By setting it to 0.38 or less, the amount of water contained in the base material layer 121C becomes a relatively small amount, the time to temperature rise can be shortened, and the maximum temperature can be made a moderately high heating tool. On the other hand, the heat generation time can be further sustained by setting it to 0.05 or more. Especially, it is preferable that mass ratio of content of the water in the base material layer 121C and content of the oxidizable metal in a heating tool is 0.1-0.35.
By doing so, it is possible to optimize the balance between the heat generation in the heat generating layer 121A, the heat used to warm the water in the whole heating tool 100, and the amount of steam generated per unit time. By generating heat in the heat generating layer 121A, the moisture in the heat generating layer 121A and the moisture in the base material layer 121C become vapor and are released to the outside of the heating tool 100.
In addition, it is preferable that the distribution state of water in the heating device 100 (the amount of water in the heat generating layer / the amount of water in the base material layer) is preferably 40 to 120, more preferably 50 to 100. It is possible to make the heating tool 100 very high.

Here, as the base material layer 121 </ b> C, moisture-absorbing and holding is possible, and a flexible sheet material is used, but a material having air permeability is preferable. Examples of such a material include fiber sheets such as paper, non-woven fabric, woven fabric, and knitted fabric made from fibers. Examples of the fibers include those mainly composed of natural fibers such as plant fibers and animal fibers, and those mainly composed of chemical fibers. Examples of plant fibers include cotton, kabok, wood pulp, non-wood pulp, peanut protein fiber, corn protein fiber, soy protein fiber, mannan fiber, rubber fiber, hemp, Manila hemp, sisal hemp, New Zealand hemp, Rafu hemp, eggplant, One or two or more selected from igusa and straw are mentioned, and among these, paper is preferable in terms of moisture absorption retention, flexibility, and air permeability. Examples of animal fibers include one or more selected from wool, goat hair, mohair, cashmere, alkapa, angora, camel, vicuña, silk, feathers, down, feather, algin fiber, chitin fiber, and casein fiber. Can be mentioned. As the chemical fiber, for example, one or more selected from rayon, acetate, and cellulose can be used.
In particular, the base material layer 121C preferably includes a fiber material composed of the fibers described above and a water-absorbing polymer.
In FIG. 5, the example which made the base material layer 121C what contains the component (a) fiber material and the component (b) water-absorbing polymer is shown. When the base material layer 121C contains the component (b), the form of the base material layer 121C is (i) a single sheet in which the component (a) and the component (b) are uniformly mixed, (ii ) Examples in which the component (b) is disposed between the same or different sheets containing the component (a), and (iii) those in which the component (b) is dispersed to form a sheet. Especially, since the water content of the heat generating layer 121A can be easily controlled, the preferable one is in the form (ii). In addition, the base material layer 121C in the form of (ii) specifically, for example, uniformly spreads the component (b) water-absorbing polymer on the sheet containing the component (a), and 200 g / m ² from above. After spraying an amount of water, the same or different sheet containing the component (a) is further laminated thereon, and press-dried at 100 ± 0.5 ° C. and a pressure of 5 kg / cm ² to obtain a moisture content. It is possible to produce by drying until it is 5% by mass or less.

  As the water-absorbing polymer, it is preferable to use a hydrogel material that can absorb and retain a liquid having a weight 20 times or more of its own weight and can be gelled. Examples of the shape of the water-absorbing polymer particles include a spherical shape, a lump shape, a grape bunch shape, and a fiber shape. The particle size of the water-absorbing polymer particles in a dry state is preferably 1 to 1,000 μm, particularly preferably 10 to 500 μm. The particle size of the water-absorbing polymer particles in the dry state is measured by a dynamic light scattering method, a laser diffraction method, or the like.

  Specific examples of water-absorbing polymers include polymers or copolymers of acrylic acid or alkali metal acrylates, polyacrylic acid and its salts, and polyacrylate graft polymers, polysulfonates, maleic anhydrides, Examples thereof include one or more selected from polyacrylamide, polyvinyl alcohol, polyethylene oxide, polyasparagine salt, polyglutamate, starch, and cellulose. Among them, it is preferable to use polyacrylic acid and a salt thereof, and a polyacrylate graft polymer such as a polymer or copolymer of acrylic acid or an alkali metal acrylate.

  The amount of the component (b) water-absorbing polymer particles in the base material layer 121C is preferably 10 to 70% by mass, particularly 20 to 65% by mass in the dry state.

The heat generating part 121 as described above is accommodated in the first bag body 122, and the heat generating part 121 and the first bag body 122 constitute the heat generating body 120.
The first bag body 122 includes a first bag body first sheet 122A and a first bag body second sheet 122B, and these first bag body first sheet 122A and first bag body second. The first bag body 122 is configured by preferably sealingly joining the peripheral edge of the sheet 122B. The region other than the peripheral portion of the first bag body first sheet 122A and the first bag body second sheet 122B is a non-joining region, and the heat generating portion 121 is disposed in the non-joining region.

The first bag body first sheet 122A is positioned on the side close to the wearer's skin (skin-side surface), and the first bag body second sheet 122B is positioned on the side far from the wearer's skin. In this case, the air permeability of the first bag body first sheet 122A is preferably 1,000 to 7,000 seconds / 100 ml, more preferably 1,500 to 6,000 seconds / 100 ml, and still more preferably. 1,800 to 5,000 seconds / 100 ml. By setting the air permeability of the first bag body first sheet 122A to 7,000 seconds / 100 ml or less, the air permeability of the first bag body first sheet 122A is secured, and a large amount of steam is generated outside the first bag body 122. Easy to release. On the other hand, when the air permeability of the first bag body first sheet 122A is 1,000 seconds / 100 ml or more, abnormal heat generation can be prevented and the temperature can be controlled.
As the first bag body first sheet 122A having such air permeability, for example, a synthetic resin porous sheet having moisture permeability but not water permeability is preferably used. Specifically, a film obtained by stretching a film obtained by containing polyethylene in a fine powder such as calcium carbonate can be used. When such a porous sheet is used, various fiber sheets including one or more nonwoven fabrics selected from needle punched nonwoven fabric, air-through nonwoven fabric, and spunbonded nonwoven fabric are laminated on the outer surface of the porous sheet. Then, the texture of the first bag body first sheet 122A may be enhanced. The first bag body first sheet 122A may be a breathable sheet, part or all of which is breathable, but is a sheet that is more breathable than the second sheet 122B (ie, a sheet having a lower air permeability). It is preferable.

  The first bag body second sheet 122B may be a part or all of a breathable sheet having a breathability or a non-breathable sheet having no breathability. A sheet having a lower air permeability than the first sheet 122A (that is, a sheet having a high air permeability) is preferable.

  When the first bag body second sheet 122B is a non-breathable sheet, a needle punched nonwoven fabric, an air-through nonwoven fabric, and a span are formed on the outer surface of the single layer or multilayer synthetic resin film or the single layer or multilayer synthetic resin film. Various fiber sheets including one or two or more kinds of nonwoven fabrics selected from bond nonwoven fabrics may be laminated to enhance the texture of the first bag body second sheet 122B. Specifically, a two-layer film composed of a polyethylene film and a polyethylene terephthalate film, a laminate film composed of a polyethylene film and a nonwoven fabric, a laminate film composed of a polyethylene film and a pulp sheet, etc. are used. A film is even more preferred.

  When the first bag body second sheet 122B is a breathable sheet, the same one as the first bag body first sheet 122A can be used, or a different one can be used. When using a different one, the air permeability of the first bag body second sheet 122B is set on the condition that the air permeability of the first bag body second sheet 122B is lower than the air permeability of the first bag body first sheet 122A. 50,000 seconds / 100 ml or more, more preferably 80,000 seconds / 100 ml or more. By making the air permeability of the first bag body second sheet 122B lower than that of the first sheet 122A, the steam generated in the heat generating part 121 can be released from the first bag body first sheet 122A side. In particular, when the air permeability of the first bag body first sheet 122A is set to 2,000 to 4,000 seconds / 100 ml and the air permeability of the first bag body second sheet 122B is set to 100,000 seconds / 100 ml or more, particularly. Is preferable. By setting such an air permeability, it is possible to improve the oxidation reaction of the oxidizable metal and to generate a large amount of water vapor from the first bag body first sheet 122A side.

  In addition, the heat generating part 121 is arrange | positioned so that the base material layer 121C side may oppose a user's skin surface. That is, the base layer 121C side is disposed on the first bag body first sheet 122A side and is closer to the skin, and the heat generation layer 121A side is disposed on the first bag body second sheet 122B side and is the side far from the skin. The part 121 is disposed in the first bag body 122. In the present invention, since the water content in the base material layer 121C is specific, the steam from the heat generating portion 121 can be efficiently discharged from the first bag body first sheet 122A.

  When only the base material layer 121C is formed on the heat generating layer 121A and the base material layer 121C is not used, the surface of the heat generating layer 121A directly contacts the first bag second sheet 122B and the first bag second sheet. There is a possibility that the breathability of 122B may affect the breathability due to the adhesion of the heat generating layer. For this reason, it is preferable to make the 2nd sheet | seat 122B into a non-breathable sheet | seat.

  The heat generating part 121 accommodated in the first bag body 122 may be one or may be accommodated in a multilayer state in which a plurality of sheets are laminated.

  Next, an example of a method for manufacturing the heating element 120 will be described. The heating element 120 can be manufactured, for example, by applying and stacking a heating composition containing an oxidizable metal, a carbon component, and water on the base material layer 121C. The exothermic composition may be prepared by mixing all the above-mentioned components at once. However, an aqueous solution is prepared by dissolving a reaction accelerator in a solution obtained by dissolving a thickener in water, and A mixture obtained by premixing an oxidizing metal and a carbon component may be mixed with an aqueous solution.

  The reaction accelerator may be mixed at the same time as other components in the exothermic composition. However, after laminating the exothermic composition, a reaction accelerator separately dissolved in water or the like is added by infiltration, spraying, or dropping. Alternatively, a reaction accelerator powder may be sprayed.

  When the above-described exothermic composition is laminated on at least one surface of the base material layer 121C, at least a part of water in the exothermic composition is absorbed by the base material layer 121C, and the exothermic layer 121A is formed on the base material layer 121C. Is formed. The heat generating layer 121A is composed of the remaining components that are not absorbed by the base material layer 121C. The heat generation layer 121A may exist on the base material layer 121C, or the lower part of the heat generation layer 121A may be at least partially embedded in the base material layer 121C. In addition, the heat generating layer 121A may be provided on one surface of the base material layer 121C, or may be provided between the base material layer 121C and the base material layer 121B (not shown). FIG. 1 shows an example in which the heat generating layer 121A is provided on one surface of the base material layer 121C.

  FIG. 6 is a diagram for explaining this manufacturing method more specifically. First, a raw material constituting the exothermic composition 302 is prepared in the coating tank 301. The exothermic composition 302 may be stirred by the stirrer 303 to more uniformly disperse the oxidizable metal, the water retention agent, and the water-insoluble component.

Next, the heat generating composition 302 is pumped up to the die head 305 by the pump 304. The heated exothermic composition 302 is applied to the base material layer 121C using the die head 305 while pressing and extruding. At this time, the coating basis weight of the exothermic composition 302 is preferably 160~4,800g / ^{m 2,} and more preferably a 320~2,200g / ^{m 2.}

  In addition, in FIG. 6, although the coating by die coating was illustrated, the coating method is not limited to this, For example, roll coating, screen printing, roll gravure, knife coding, a curtain coater, etc. are used. You can also.

  By the above operation, a continuous long product of the heat generating material including the heat generating layer 121A and the base material layer 121C is obtained. By cutting this into an arbitrary size and storing it in the first bag body 122, heat generation A body 120 is formed.

  Here, the viscosity of the exothermic composition is preferably 8,000 mPa · s to 28,000 mPa · s with a B-type viscometer at 24 ° C., more preferably 9,000 mPa · s to 25,000 mPa · s, Further, it is preferably 10,000 mPa · s to 20,000 mPa · s. By doing in this way, the workability | operativity at the time of application | coating is improved and the uniform heat generating layer 121A can be formed.

Next, other configurations of the heating tool 100 will be described with reference to FIGS.
The heating tool 100 generates heat by an oxidation reaction of an oxidizable metal and imparts a sufficient heating effect, and can have a performance of an exothermic temperature of 40 to 70 ° C. in measurement based on JIS standard S4100. In the present embodiment, the heating tool 100 is a steam heating tool accompanied by the generation of water vapor. In the present embodiment, the heating device 100 is of a so-called eye mask type, and steam heated to a predetermined temperature in contact with the human eye and its surroundings (hereinafter also referred to as “steam temperature heat”). It is used to apply to the eyes and their surroundings.

The heating tool 100 includes a main body 101 and an ear hooking portion 102 in which a hole 104 into which an ear is inserted is formed.
The main body 101 has a horizontally long shape having a longitudinal direction X and a width direction Y orthogonal thereto. The main body 101 has a substantially oval shape. The ear hooks 102 are used as a pair, and each ear hook 102 is attached to each end of the main body 101 in the longitudinal direction (X direction). The heating tool 100 is mounted so that each ear hook 102 is hung on the wearer's ear and the main body 101 is covered with both eyes of the wearer. Under this wearing condition, steam heat generated from the heating device 100 is applied to the wearer's eyes, and eye fatigue, redness, and eye strain are alleviated, and a relaxed feeling is obtained. In addition, a feeling of falling asleep is also induced.

  FIG. 3 shows an exploded perspective view of the heating tool 100. In the figure, the ear hooking portion 102 is disposed on the main body portion 101. 4 shows a cross-sectional view of the heating device 100 along the X direction. The main body 101 of the heating tool 100 includes the above-described heating element 120 and the second bag body 110 that houses the heating element 120.

  The second bag body 110 has a second bag body first sheet 110A located on the side close to the wearer's skin and a second bag body second sheet 110B located on the side far from the wearer's skin. Yes.

The basis weight of the second bag body first sheet 110A is preferably ²⁰ to 200 g / m ² from the viewpoints of preventing the inside from being seen through and from the viewpoints of heat retention, flexibility, and thickness, and the basis weight is 40. It is preferably ˜110 g / m ² .

In addition, the basis weight of 20 to 200 g / m ² is preferable from the viewpoint of preventing the inside of the second bag body second sheet 110B from being seen through and the heat retention, flexibility, and thickness, and the basis weight is 40. It is preferably ˜110 g / m ² .
From the viewpoint of releasing steam and supplying oxygen to the heat generating layer 121A, the air permeability of the second bag first sheet 110A is 6,000 seconds / 100 ml or less, and 1,000 seconds / 100 ml or less. It is more preferable. The water vapor evaporated from the heat generating part 121 passes through the first sheet 122A of the first bag and the first sheet 110A of the second bag and reaches the skin.

  The second bag body first sheet 110A and the second bag body second sheet 110B have the same shape, and are substantially oval. The outer shapes of the second bag body first sheet 110 </ b> A and the second bag body second sheet 110 </ b> B form the outer shape of the main body 101. The first bag body first sheet 110A and the second bag body first sheet 110B are overlapped with each other, joined at the periphery thereof, and joined at the center in the X direction along the Y direction. The bag body 110 has two spaces. And the heat generating body 120 is accommodated in each space, respectively. In order to join the first bag body first sheet 110A and the second bag body second sheet 110B, for example, a hot melt adhesive can be used. In addition, although the heat generating body 120 is accommodated in the bag body 110, the heat generating body 120 may be fixed to the bag body 110 by an adhesive, heat sealing, or the like (not shown).

  As the second bag body first sheet 110A and the second bag body second sheet 110B, for example, a fiber sheet including a non-woven fabric can be used. For example, a needle punched nonwoven fabric, an air-through nonwoven fabric, a spunbonded nonwoven fabric, or the like can be used.

  The bag body 110 is formed with substantially V-shaped notches 113A and 113B cut inwardly along the Y direction from the long side at the position of the center of the two long sides extending in the X direction. . Notch portions 113A and 113B have different degrees of notches. The notch portion 113A is located between or near the wearer's eyebrows when the heating tool 100 is attached. The notch portion 113B is located on the wearer's nose bridge when the heating tool 100 is worn. Therefore, the notch portion 113B is more severely cut than the notch portion 113A. Note that at least one of the notch portions 113A and 113B shown in FIG. 2 may be a slit.

  As shown in FIGS. 3 and 4, the ear hooking portion 102 in the heating tool 100 is disposed on the second bag body first sheet 110 </ b> A in the main body portion 101 as shown in FIGS. 3 and 4. When the heating device 100 is used, as shown in FIG. 2, the ear hooking portion 102 is reversed outward in the X direction so as to be opened. In a state before use, that is, in a state where the left and right ear hooks 102 are located on the main body 101, the contour formed by the left and right ear hooks 102 is substantially the same as the contour of the main body 101. Yes. The ear hook 102 can be made of the same material as the bag 110.

  The heating tool 100 of the present embodiment is entirely packaged by a packaging material (not shown) having an oxygen barrier property before use, so that the heat generating part 121 does not come into contact with oxygen in the air. .

The present invention is not limited to the above-described embodiment, and modifications, configurations, arrangement changes, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in the said embodiment, although the eye mask type thing used making it contact | abut to a wearer's eyes was illustrated as a heating tool, it is not restricted to this.
For example, the heating tool may be used in contact with the shoulder, knee, elbow, etc. of the wearer. In this case, it is preferable to provide a fixing means such as an adhesive instead of the ear hook 102.

Next, examples of the present invention will be described.
(Example)
(Preparation of exothermic composition)
First, slurry-like exothermic compositions were prepared with the compositions of Examples 1 to 8 shown in Table 1 and Comparative Examples 1 to 4 shown in Table 2.
The types, product names, and manufacturers of oxidizable metals, carbon components, water, reaction accelerators, and water-soluble polymers are as follows.
Oxidizable metal: Iron powder (Iron powder RKH, average particle size 45 μm, DOWA IP Creation Co., Ltd.)
Carbon component:
・ DO-2 (Nippon Enviro Chemicals Co., Ltd.)
・ CB (Futamura Chemical Co., Ltd.)
・ KR (Futamura Chemical Co., Ltd.)
-Activated carbon crushed I (Wako Pure Chemical Industries, Ltd.) average particle size 60 μm
Active carbon crushed II (Wako Pure Chemical Industries, Ltd.) average particle size 175 μm
・ Granular white birch WH-2c (manufactured by Nippon Enviro Chemicals)
・ Carborafin (manufactured by Nippon Enviro Chemicals)
Water: Tap water reaction accelerator: Sodium chloride (Pharmacopoeia sodium chloride, manufactured by Otsuka Chemical Co., Ltd.)
Water-soluble polymer:
・ Xanthan gum (Echo Gum BT, DSP Gokyo Food & Chemical Co., Ltd.) average molecular weight 2 million ・ Guar gum: (manufactured by Taiyo Chemical) average molecular weight 200 to 300,000 ・ Hydroxymethylpropylcellulose: (Shin-Etsu Chemical) average molecular weight 1 In addition, the average molecular weight of water-soluble polymer is a weight average molecular weight, and is measured by gel permeation chromatography.

[Manufacture of heating part 121]
The exothermic compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were each applied on a 25 cm ² (5 cm × 5 cm) substrate layer 121C, and the exothermic composition was applied in an amount of 2.0 g per heating tool. (The amount of iron powder was applied at 1.09 to 1.33 g per 25 cm ² ) to obtain a heat generating part 121. The coating method used was a die coating method.
As the base material layer 121C, wood pulp paper (20 g / m ² , manufactured by Ino Paper Co., Ltd.) and water-absorbing polymer (sodium polyacrylate, spherical, average particle size 300 μm, 30 g / m ² 50 g / m) ² , Aquaric CA (manufactured by Nippon Shokubai Co., Ltd.) and wood pulp paper (30 g / m ² , manufactured by Ino Paper Co., Ltd.) were laminated and integrated into a polymer sheet.
[Manufacture of heating equipment]
The entire heat generating part thus obtained was covered with a first bag body to produce a heat generating element. Specifically, a 6.5 cm × 6.5 cm first bag body with air permeability [first bag body first sheet on the skin side (air permeability 2,500 seconds / ml, basis weight 50 g / m ² , TSF -EU, manufactured by Kojin Co., Ltd.) Examples 1 to 8, comparative example on first bag body second sheet (non-breathable, basis weight 40 g / m ² , 100% polyethylene) on the opposite side to the skin 1-4 exothermic parts were put, respectively, and the peripheral part was hermetically sealed. At this time, the heat generating portion was arranged in the first bag body so that the base material layer side was positioned on the first bag body first sheet side.
The obtained heating element was made into a second bag body 7.5 cm × 7.5 cm [second bag body first sheet (air-through nonwoven fabric, polypropylene 100%, fiber diameter 1 dtex, air permeability 1 second / 100 ml, basis weight 30 g / m ² ), second bag second sheet (made of needle punched nonwoven fabric PP, fiber diameter 2.2 dtex, air permeability 1 second / 100 ml, basis weight 80 g / m ² )] What was put and the peripheral part was hermetically sealed was used as a heating tool (see FIG. 1). The heating tool was put in an oxygen-blocking bag until the evaluation described later was carried out.

(Evaluation method)
About the heating tool of Examples 1-8 and Comparative Examples 1-4, it evaluated as follows. The evaluation results are shown in Tables 1 and 2.
Hereinafter, 1. Stability, 2. 2. Coating property, 3. viscosity, 4. Moisture content of heat generation layer 5. Moisture content of the heat generating layer 6. Moisture content of base material layer Water absorption of carbon components, 8. 8. average particle diameter of carbon component, 10. Average particle diameter of oxidizable metal The measurement method is described for the exothermic properties and the amount of steam for 11.10 minutes.
1. Stability Stability was confirmed by visually checking the exothermic composition in a 200 ml beaker manufactured by TOKI SANGYO (VISCOMETER B type viscometer) using a # 4 rotor at 200 rpm for 20 minutes and standing for 30 minutes. Judgment was made based on whether separation or sedimentation occurred. Those separated and settled were regarded as defective, and those not separated and settled were regarded as good. Examples 1 to 8 were excellent in stability.
2. Coating property The coating property was judged by whether or not the coating was evenly wet by die coating. As shown in Table 1, in Examples 1 to 8, the coatability was good.
3. Viscosity Viscosity was measured as follows.
A viscosity value was measured after 1 minute at a measurement temperature of 20 ° C. using a # 4 or # 3 rotor with a rotational speed of 6 rpm and a 100 ml tall beaker manufactured by TOKI SANGYO (VISCOMETER BH viscometer). As shown in Table 1, in Examples 1 to 8, the viscosity of the exothermic composition was 14,200 mPa · s to 25,000 mPa · s.
4). Moisture content R of heat generation layer (%)
The moisture content in the heat generating layer 121A is determined as follows. The entire exothermic layer 121A applied to the base material layer 121C is recovered by scraping 1 to 2 g with a spoon, and the mass is measured (mass P). Then, it is dried at 120 ° C. for 15 minutes using a Kett moisture meter (FD-240) under a nitrogen stream, and the mass is measured again (mass Q). The moisture content R of the heat generating layer is expressed by the following formula.
R (%) = (P−Q) / P × 100.
5. Moisture content of heat generation layer C (g)
When the solid content calculated from the ratio of the exothermic composition (the value obtained by dividing the total composition ratio excluding water by the total composition ratio) is X and the coating amount is Y (g), The water content Z is expressed by the following equation.
Z (g) = (R × X × Y / 100) / (1-R / 100)
6). Moisture content D (g) of base material layer
The moisture content D contained in the base material layer 121C is expressed by the following formula from the blending ratio of the heat generating composition, where the coating amount is Y (g).
D (g) = Y * (1-X) -Z
7). Carbon component water absorption (%)
The water absorption rate of the carbon component was measured as follows.
First, the tip of a 5.0 mL bellows pipette with filter paper is immersed in water for 2 minutes to allow the filter paper to absorb water completely. Weigh the carbon component on the filter paper (mass a) and immerse the tip of the dropper in water again. The mass (mass b) when the water absorption of the carbon component reaches saturation due to capillary action is measured. The maximum water absorption of the carbon component is expressed as {(mass b−mass a) / (mass a)} × 100. In addition, the time when the water absorption amount of the carbon component reaches saturation refers to a state when the mass b no longer fluctuates.
8). Average particle diameter of carbon component The average particle diameter of the carbon component was measured by a laser diffraction scattering method. The carbon component was dispersed in water, and the particle size distribution of the carbon component was created on a volume basis with a laser diffraction particle size distribution analyzer (manufactured by SHIMADZU, SALD-300), and the median diameter was measured as the average particle size. .
9. Average particle diameter of iron powder The average particle diameter of iron powder was measured by a laser diffraction scattering method. By dispersing the iron powder component in water, creating a particle size distribution of the iron powder component on a volume basis with a laser diffraction particle size distribution analyzer (manufactured by SHIMADZU, SALD-300), and making the median diameter the average particle diameter It was measured.
10. Evaluation of heat generation characteristics (temperature rise time, maximum temperature)
Using the measuring machine based on JIS S4100, the skin surface side of the heating tool 100 was made the outside, and the temperature sensor was installed and fixed on the surface opposite to the skin side surface. For fixing, a mesh material (polyester, double raschel fabric having a thickness of 8 mm) was used. After opening, the temperature was measured at intervals of 10 seconds and measured for 40 minutes, and the maximum temperatures were compared. Specifically, the temperature rise (starting from 35 ° C., time (minutes) when the exothermic temperature reached 45 ° C.) and the maximum temperature (° C.) after opening from the oxygen blocking bag were evaluated.
11. Steam amount for 15 minutes The duration of generation of water vapor was measured as follows using the apparatus 30 shown in FIG. The apparatus 30 shown in FIG. 7 includes an aluminum measurement chamber (volume 2.1 L) 31, and an inflow path 32 through which dehumidified air (humidity less than 2%, flow rate 2.1 L / min) flows into the lower portion of the measurement chamber 31. And an outflow passage 33 through which air flows out from the upper part of the measurement chamber 31. An inlet temperature / humidity meter 34 and an inlet flow meter 35 are attached to the inflow path 32. On the other hand, an outlet temperature / humidity meter 36 and an outlet flow meter 37 are attached to the outflow passage 33. A thermometer (thermistor) 38 is attached in the measurement chamber 31. A thermometer having a temperature resolution of about 0.01 ° C. was used. At a measurement environment temperature of 30 ° C. (30 ± 1 ° C.), the heating tool is taken out of the packaging material and placed in the measurement chamber 31 with its water vapor release surface facing up. A thermometer 38 with a metal ball (4.5 g) is placed on it. In this state, dehumidified air is flowed from the lower part of the measurement chamber 31. A difference in absolute humidity before and after the air flows into the measurement chamber 31 is obtained from the temperature and humidity measured by the inlet temperature and humidity meter 34 and the outlet temperature and humidity meter 36. Further, the amount of water vapor released by the heating tool is calculated from the flow rates measured by the inlet flow meter 35 and the outlet flow meter 37. Details of this apparatus are described in Japanese Patent Application Laid-Open No. 2004-73688, which is related to the earlier application of the present applicant.

In each of Examples 1 to 8, the exothermic composition was excellent in stability, the temperature rising time was relatively short, and the maximum temperature was appropriate. Furthermore, the amount of steam generated for 15 minutes was large, and the coatability was also good. Among them, in Examples 1 to 5 and Example 8 using a carbon component having an average particle diameter of 110 μm or less, the oxidizable metal, the carbon component, the water-soluble polymer, and water form a very good structure. The heating time was very short, the maximum temperature was moderately high, and the amount of steam generated for 15 minutes was very large.
Furthermore, in Examples 1 to 7 using a carbon component having a water absorption rate of 300% or less, the exothermic composition has a low viscosity, the coating property is very good, and the maximum temperature is moderate. I was able to. In view of the above points, among Examples 1 to 8, a water-soluble polymer having a molecular weight of 1 million or more is used, a water absorption is 300% or less, and an average particle diameter is 100 μm or less, particularly 30 μm or less. It can be seen that when the components are used, the balance between the heat generation characteristics and the viscosity of the heat generation composition is very good, and the stability of the heat generation composition is also good.
On the other hand, in Comparative Examples 1 to 3, the exothermic composition was separated and the coatability was not good. In Comparative Example 4, since a carbon component having a low water absorption rate was used, the exothermic composition separated and the coatability was poor.

30 Apparatus 31 Measurement chamber 32 Inflow path 33 Outflow path 34 Inlet temperature / humidity meter 35 Inlet flow meter 36 Outlet temperature / humidity meter 37 Outlet flow meter 38 Thermometer 100 Heating tool 101 Main body portion 102 Ear hook portion 104 Hole 110 Second bag body 110A 2nd bag body 1st sheet 110B 2nd bag body 2nd sheet 113A Notch part 113B Notch part 120 Heat generating body 121 Heat generating part 121A Heat generating layer 121C Base material layer 122 1st bag body 122A 1st bag body 1st sheet 122B 1st Bag second sheet 301 Coating tank 302 Exothermic composition 303 Stirrer 304 Pump 305 Die head

Claims (5)

A heating tool in which a heat generating layer containing an oxidizable metal, a carbon component, a water-soluble polymer having a molecular weight of 1 million or more, and water, and a base material layer are laminated,
The carbon component has a water absorption rate of 160% or more and 400% or less of its own weight, and an average particle size of 10 to 400 μm.
The heating tool whose mass ratio (water / metal) of content of the water in the said base material layer and content of the oxidizable metal in the said heating tool is 0.05-0.38.   The heating tool according to claim 1, wherein the mass ratio (water / carbon component) of the water content in the heat generating layer to the carbon component content is 0.8-4.   The heating tool according to claim 1 or 2, wherein the content of water in the heating tool is 35 to 55 parts by weight with respect to 100 parts by weight of the oxidizable metal, and the moisture content in the heating layer is 22% by weight or less. .   The mass ratio (water / polymer) between the content of water in the heating tool and the content of a water-soluble polymer having a molecular weight of 1,000,000 or more in the heating tool is 60 to 500. The heating tool according to claim 1.   The heating tool according to any one of claims 1 to 4, wherein the water-soluble polymer is xanthan gum.

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