JP2017170114A - Hyperthermia tool - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hyperthermia tool capable of giving a cold sense in a comfortable thermal sense.SOLUTION: A hyperthermia tool 50 includes an exothermic body 100 having an exothermic part 10 containing oxidizable metal, a carbon component and water, and a storage body 20 for storing the exothermic part 10, and holds menthol as a cold sensing agent. A volatilization amount of the menthol after the exothermic body 100 starts heat generation is 0.04-0.30 mg/30 min, and a steam generation amount after the exothermic body 100 starts heat generation is 40-3,000 mg/10 min.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a heating tool.

  2. Description of the Related Art Conventionally, a steam heating device that includes an oxidizable metal such as iron powder, an electrolyte such as sodium chloride, and water and that utilizes oxidation heat generated by an oxidation reaction of the oxidizable metal has been used. In addition, with the diversification of steam heaters, steam heaters including menthol as a cooling sensation agent have been developed.

  In Patent Document 1, menthol is included as a cooling sensation agent, including an oxidizable metal, a reaction accelerator, an electrolyte, and water, from the viewpoint of suppressing the heat sensation that is likely to occur when a steam heating device is used in a hot summer season. A heating tool is described. And it is disclosed by using the said heating tool to provide simultaneously the warm irritation | stimulation and cool feeling by skin temperature becoming high.

JP 2014-205072 A

  However, with the recent high level of user demand, it has become impossible to satisfy the user sufficiently only by providing warm stimulation and a refreshing feeling simultaneously as in the technique described in Patent Document 1. It was. As a result of intensive studies to meet the high demands of users, the present inventors have not only given warm stimuli and refreshing feelings, but new feelings such as giving cool feelings in pleasant warm feelings. I found a problem.

As a means for solving the problem, the present inventors have obtained the knowledge that it is effective to control by combining parameters such as menthol volatilization amount and water vapor generation amount.
That is, the present invention
A heating element comprising a heating part containing an oxidizable metal, a carbon component and water, and a container for housing the heating part,
Menthol is retained as a cooling agent,
The volatilization amount of the menthol after the heat generation of the heating element is 0.04 mg / 30 min or more and 0.30 mg / 30 min or less,
A heating tool is provided wherein the amount of water vapor generated after the heating element starts to generate heat is 40 mg / 10 min or more and 3,000 mg / 10 min or less.

  ADVANTAGE OF THE INVENTION According to this invention, the heating tool which can provide a cool feeling in a pleasant warm feeling can be provided.

It is a top view of the heating tool which concerns on embodiment. It is a disassembled perspective view of the heating tool which concerns on embodiment. It is a top view which shows an example of the heat generating body which concerns on embodiment. It is AA sectional drawing of FIG. It is sectional drawing of the direction orthogonal to the sheet | seat surface of the container of the heat generating body which concerns on embodiment. It is sectional drawing which showed typically the modification of the heat generating body which concerns on embodiment. It is a schematic diagram which shows the apparatus which measures the surface maximum temperature and water vapor generation amount of the heat generating body which concern on embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

[Heater]
First, an example of the heating tool 50 according to the present embodiment will be described with reference to FIGS. 1 and 2. FIG. 1 is a plan view of the heating tool, and FIG. 2 is an exploded perspective view of the heating tool.
The heating tool 50 according to the present embodiment is of a so-called eye mask type, and a pair of heating elements 100 covers the wearer's eyes and wrinkles, respectively, and applies water vapor heated to a predetermined temperature to the eyes and the periphery thereof. It is used to do. In the present embodiment, the menthol volatilization amount after the heating element 100 starts to generate heat and the water vapor generation amount after the heating element 100 starts to generate heat indicate numerical values of the whole heating device 50.

The heating tool 50 of this embodiment is
A heating element 100 having a heating part 10 containing an oxidizable metal, a carbon component, and water, and a container 20 that houses the heating part 10,
Menthol is retained as a cooling agent,
The volatilization amount of menthol after the heat generation of the heating element 100 is 0.04 mg / 30 min or more and 0.30 mg / 30 min or less,
The amount of water vapor generated after the heating element 100 starts to generate heat is 40 mg / 10 min or more and 3,000 mg / 10 min or less.

As shown in FIG. 1, the heating tool 50 includes a main body 51 and an ear hook 52 in which a hole 54 into which an ear is inserted is formed.
The main body 51 has a horizontally long shape having a longitudinal direction X and a width direction Y orthogonal thereto. The main body 51 has, for example, a substantially oval shape. The ear hooks 52 are used as a pair, and each ear hook 52 is attached to each end of the main body 51 in the longitudinal direction (X direction). The heating tool 50 is mounted so that each ear hook 52 is hung on the wearer's ear and the body 51 covers both eyes of the wearer. Under this wearing condition, steam temperature generated from the heating element 100 described later is applied to the wearer's eyes.

  FIG. 2 shows an exploded perspective view of the heating tool 50 before use. In the figure, the ear hook 52 is arranged at the uppermost part in the heating device 50, and when used, the central part is separated and opened to the left and right, and inverted toward the outside to obtain the state shown in FIG.

The heating tool 50 further includes a bag 53.
The bag body 53 includes a bag body first sheet 55 located on the side close to the skin surface of the wearer and a bag body second sheet 56 located on the side far from the skin surface of the wearer. Here, the bag body first sheet 55 and the bag body second sheet 56 are provided so as to sandwich a heating element 100 described later.

The basis weight of each of the bag body first sheet 55 and the bag body second sheet 56 is 20 g / m ² from the viewpoint of preventing the inside from being seen through and from the viewpoints of heat retention, flexibility, thickness, and the like. The above is preferable, and 40 g / m ² or more is more preferable. From the same viewpoint, each of the basis weight of the bag the first sheet 55 and the bag body second sheet 56 is preferably 200 g / ^{m 2} or less, 110g / ^{m 2} or less is more preferable.
In addition, since the bag body first sheet 55 applies the generated water vapor to the wearer, the bag body second sheet 56 may both have air permeability in order to smoothly supply oxygen to the heating element 100. preferable.
Specifically, the air permeability of these bag sheets (JIS P8117, revised version of 2009, hereinafter the same for “air permeability” in the present specification) is preferably 6,000 seconds / 100 mL or less. 1,000 seconds / 100 mL or less is more preferable, 500 seconds / 100 mL or less is more preferable, and 0 seconds / 100 mL is even more preferable.

  The bag body first sheet 55 and the bag body second sheet 56 have the same shape and are substantially oval. The outer shape of the bag body first sheet 55 and the bag body second sheet 56 is the outer shape of the main body 51. The bag body first sheet 55 and the bag body second sheet 56 are overlapped with each other, and at least part of the peripheral edge portions thereof are joined, and the center portion in the X direction is joined along the Y direction, whereby the bag body 53 is joined. It becomes. In order to join the bag body first sheet 55 and the bag body second sheet 56, for example, a hot melt adhesive can be used. Note that the heating element 100 may be fixed to the bag body 53 by an adhesive, a heat seal, or the like (not shown).

  As the bag body first sheet 55 and the bag body second sheet 56, for example, a fiber sheet including a nonwoven fabric can be used. For example, 1 type, or 2 or more types selected from a needle punch nonwoven fabric, an air through nonwoven fabric, and a spun bond nonwoven fabric can be used.

  The bag 53 is formed with substantially V-shaped notches 53A and 53B 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. . The notches 53A and 53B have different degrees of cut. The notch portion 53A is located between or near the wearer's eyebrows when the heating tool 50 is attached. The notch portion 53B is located on the wearer's nose bridge when the heating tool 50 is worn. Therefore, the notch portion 53B is usually more severed than the notch portion 53A.

  As shown in FIG. 2, the ear hook 52 in the heating device 50 is disposed on the bag first sheet 55 in a state before use. When the heating tool 50 is used, the ear hook 52 is reversed outward to be in an open state. In a state before use, that is, in a state where the left and right ear hooks 52 are positioned on the bag first sheet 55, the contour formed by the left and right ear hooks 52 is the contour of the bag first sheet 55. It is almost the same. The ear hook 52 can be made of the same material as the bag 53.

[Heating element]
Next, the heating element 100 provided in the heating tool 50 will be described. In the present embodiment, a pair of heating elements 100 are disposed on the heating tool 50, and each heating element 100 covers the eyes of the wearer.

  FIG. 3 is a plan view showing an example of the heating element 100 of the present embodiment. 4 is a cross-sectional view taken along the line AA in FIG. The heating element 100 of the present embodiment includes a heating part 10 containing an oxidizable metal, a carbon component, and water, and a container 20 that houses the heating part 10.

Here, the heat generating part 10 constituting the heat generating element 100 will be described.
The heat generating portion 10 is formed from a heat generating composition containing an oxidizable metal, a carbon component, and water.
Specifically, the exothermic part 10 generates heat by an oxidation reaction of an oxidizable metal and imparts a thermal effect, and has a heat generation temperature of 30 ° C. or higher and 70 ° C. or lower in measurement according to JIS S4100. Things can be used. Moreover, the heat generating part 10 brings about the effect | action that water vapor | steam is generated when the contained water is heated.

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

The oxidizable metal preferably has an average particle size of 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more when powdered, from the viewpoint that the oxidation reaction is efficiently performed. . From the same viewpoint, the average particle diameter of the oxidizable metal is preferably 200 μm or less, more preferably 180 μm or less, and further preferably 150 μm or less.
The particle size of the oxidizable metal is the maximum length in the form of powder and can be measured by classification with a sieve, dynamic light scattering method, laser diffraction method, etc. It is preferable to measure.

The content of the oxidizable metal in the heat generating part 10 is preferably 100 g / m ² or more in terms of basis weight from the viewpoint of increasing the surface temperature of the heat generating element 100 to a desired temperature. Preferably it is 200 g / m ² or more, more preferably 300 g / m ² or more. From the same viewpoint, the content of the oxidizable metal in the heating unit 10 is preferably not more than 3,000 g / ^{m 2,} more preferably not more than 2,000 g / ^{m 2,} more preferably 1 , 500 g / m ² or less.
Here, the content of the oxidizable metal in the heat generating part 10 can be obtained by an ash test according to JIS P8128 or a thermogravimetric measuring instrument. In addition, it can be quantified by a vibration sample type magnetization measurement test or the like using the property that magnetization occurs when an external magnetic field is applied. Especially, it is preferable to obtain | require with a thermogravimetry.

  The carbon component has water retention ability, oxygen supply ability, and catalytic ability. For example, one or more materials selected from the group consisting of activated carbon, carbon black, acetylene black, and graphite are used. Can do. Among these, activated carbon is preferably used because it easily adsorbs oxygen when wet. Moreover, 1 type, or 2 or more types of fine powder or small granular materials selected from the group consisting of coconut shell charcoal, wood charcoal, and peat charcoal are more preferably used. From the viewpoint of easily raising the surface temperature of the heating element 100 to a desired temperature, pulverized coal is more preferable.

The carbon component has an average particle size of preferably 10 μm or more, more preferably 12 μm or more, and further preferably 15 μm or more from the viewpoint of being uniformly mixed with the oxidizable metal. From the same viewpoint, the average particle size of the carbon component is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less.
The average particle size of the carbon component refers to the maximum length in the form of powder, and can be measured by a dynamic light scattering method, a laser diffraction method, etc., among which it is preferable to measure by a laser diffraction method. . The carbon component is preferably used in a powder form, but a form other than the powder form can also be used, for example, a fibrous form can be used.

The content of the carbon component in the exothermic part 10 is preferably 1 part by mass or more with respect to 100 parts by mass of the oxidizable metal from the viewpoint of sufficiently obtaining water supply to the exothermic part 10. More preferably, it is 3 mass parts or more, More preferably, it is 6 mass parts or more. Further, the content of the carbon component in the heat generating part 10 is preferably 40 parts by mass or less with respect to 100 parts by mass of the oxidizable metal from the viewpoint of sufficiently obtaining oxygen supply to the heat generating part 10. Yes, more preferably 15 parts by mass or less, still more preferably 12 parts by mass or less.
The content of the carbon component in the exothermic part 10 is expressed as basis weight, and is preferably 10 g / m ² or more, more preferably 20 g / m ² or more, and further preferably 25 g / m. ² or more. Further, the content of the carbon component is preferably 400 g / m ² or less, more preferably 250 g / m ² or less, and further preferably 120 g / m ² or less, expressed as basis weight.

  The content of water in the exothermic part 10 is preferably 20 parts by mass or more with respect to 100 parts by mass of the oxidizable metal from the viewpoint of favorably proceeding the oxidation reaction of the oxidizable metal. Preferably it is 30 mass parts or more, More preferably, it is 40 mass parts or more. The content of water in the heat generating part 10 is preferably 100 parts by mass or less, more preferably 90 parts by mass with respect to 100 parts by mass of the oxidizable metal, from the viewpoint of setting the maximum temperature to be a certain temperature or higher. The amount is not more than part by mass, and more preferably not more than 80 parts by mass. A part of the water in the heat generating portion 10 becomes water vapor due to the temperature rise accompanying heat generation due to the oxidation reaction of the oxidizable metal.

In the exothermic part 10, in order to hold | maintain a water | moisture content and to advance the oxidation reaction of an oxidizable metal efficiently, a water absorbing agent can be included. As the water-absorbing agent, a water-absorbing polymer or a water-absorbing powder can be used.
Examples of the water-absorbing polymer include hydrophilic polymers having a cross-linked structure capable of absorbing and retaining a liquid 20 times or more of their own weight. Examples of the water-absorbing powder include vermiculite, sawdust, silica gel, and One type or two or more types of powders selected from the group consisting of pulp powders may be mentioned. When the water absorbing agent is included, the content is preferably 2 parts by mass or more, preferably 20 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass of water in the heat generating part 10. It is more preferable that

  The exothermic part 10 can further contain a reaction accelerator. By including the reaction accelerator, it is possible to easily maintain 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 materials selected from the group consisting of alkali metals, alkaline earth metal sulfates, and chlorides. Among them, a group consisting of various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride, ferric chloride, and sodium sulfate from the viewpoint of excellent conductivity, chemical stability, and production cost. It is preferable to use 1 type or 2 types or more materials chosen from these.

The content of the reaction accelerator in the exothermic part 10 is preferably 1 part by mass or more with respect to 100 parts by mass of the oxidizable metal, more preferably, from the viewpoint of maintaining a sufficient calorific value for a long time. Is 3 parts by mass or more, more preferably 6 parts by mass or more.
From the same viewpoint, the content of the reaction accelerator in the heat generating part 10 is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, with respect to 100 parts by mass of the oxidizable metal content. More preferably, it is 15 parts by mass or less.

  In this embodiment, although the heat generating part 10 showed the aspect which is a sheet form, this heat generating part 10 may be a powder form and may be a sheet form. However, it is preferably a sheet from the viewpoint of excellent usability. The sheet-like heat generating part 10 is formed by wet papermaking of the heat generating composition, the heat generating composition sandwiched between substrates such as paper, and the heat generating composition applied to a substrate such as paper. And the like. Among them, the heat generating part 10 is formed by wet papermaking the heat generating composition, and is formed by applying the heat generating composition to a substrate such as paper, from the viewpoint of excellent usability and easy manufacture. preferable.

  When the heat generating part 10 is formed by applying a heat generating composition to a substrate such as paper, it is preferable to contain a thickener and a phosphate in the heat generating composition.

When a thickener is contained in the heat generating composition, it is possible to suppress a decrease in heat generation characteristics during storage of the heat generating element 100.
As the thickener contained in the exothermic composition, a substance that absorbs moisture to increase the consistency or imparts thixotropic properties can be used. Polysaccharide thickeners such as bean gum, guar gum, gum arabic, carrageenan, agar, xanthan gum; starch thickeners such as dextrin, pregelatinized starch, starch for processing; carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose Alternatively, one or more selected from cellulose derivative-based thickeners such as hydroxypropylcellulose; metal soap-based thickeners such as stearate; and mineral-based thickeners such as bentonite can be used.
The content of the thickener is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and still more preferably 0.000 parts by mass with respect to 100 parts by mass of the oxidizable metal content. 1 part by mass or more.
The content of the thickener is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass with respect to 100 parts by mass of the oxidizable metal content. Or less.

  When phosphate is contained in the exothermic composition, there is an effect of increasing the fluidity of the exothermic composition, and therefore, when the exothermic part 10 is manufactured by applying it to a base material such as paper, it is easy to manufacture. preferable. As the phosphate, in addition to the primary phosphate potassium salt, the secondary phosphate potassium salt, the tertiary phosphate potassium salt, one or two selected from the primary phosphate sodium salt and the secondary phosphate sodium salt More than seeds can be used. The phosphate content is preferably 0.1 parts by mass or more and more preferably 0.3 parts by mass or more as a phosphate group with respect to 100 parts by mass of the oxidizable metal content. 0.5 parts by mass or more, more preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and further preferably 1.1 parts by mass or less. preferable.

  The heat generating part 10 can be produced, for example, by applying a mixture of the above components to a substrate such as paper. The coating method is not particularly limited, and for example, die coating, roll coating, screen printing, roll gravure, knife coating, curtain coater and the like can be used.

The thickness of the heat generating part 10 is preferably 0.2 mm or more, more preferably 0.4 mm or more, and further preferably 0.5 mm or more. Moreover, the thickness of the heat generating part 10 is preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less.
By making the thickness of the heat generating part 10 in the above range, the heat generating element 100 can be made easy to use while enhancing the heat generating effect.
In addition, the thickness of this heat generating part 10 shows average thickness.

  The exothermic part 10 may contain a surfactant, a drug, a flocculant, a colorant, a paper strength enhancer, a pH control agent, a bulking agent, etc., as necessary, as long as the effects of the present invention are not impaired. .

It continues and the container 20 which comprises the heat generating body 100 is demonstrated.
The container 20 is at least partially permeable and accommodates the heat generating part 10. The container 20 can be configured, for example, by bonding the peripheral portions 203 of two sheets (a container first sheet 201 and a container second sheet 202) as shown in FIG. As the sheet, a gas permeable sheet, a laminated sheet obtained by laminating a nonwoven fabric and a gas permeable sheet, a laminated sheet obtained by laminating a knitted fabric and a gas permeable sheet, and the like can be used as the gas permeable part.
In addition, the container 1st sheet | seat 201 is located in a wearer's skin side rather than the heat generating part 10 here, and the container 2nd sheet | seat 202 is located in the side far from a wearer's skin rather than the heat generating part 10. It is what is done.

  As the air permeable sheet, a resin porous sheet or a resin sheet having a vent hole can be used. For example, one or more of polyethylene, polypropylene, and ethylene vinyl acetate copolymer should be used. Can do. The thickness is preferably 5 μm or more and 200 μm or less. Specifically, the resin-made porous sheet is obtained by forming a melt-kneaded product of a thermoplastic resin and an organic or inorganic filler not compatible with the resin into a film shape and stretching it uniaxially or biaxially. And a fine porous structure, a resin sheet having a vent hole, a non-permeable sheet or a hardly permeable sheet provided with a fine hole with a needle or the like, or the above-mentioned It is preferable that the air-permeable sheet is further provided with fine holes with a needle or the like.

  In the present embodiment, the above-described container first sheet 201 is preferably a sheet having excellent air permeability, while the container second sheet 202 is preferably a sheet having poor air permeability. .

More specifically, the air permeability of the container first sheet 201 is preferably 10,000 seconds / 100 mL or less, more preferably 7,000 seconds / 100 mL, from the viewpoint of providing an appropriate warm feeling to the wearer. Or less, more preferably 5,000 seconds / 100 mL or less, and even more preferably 4,000 seconds / 100 mL or less.
On the other hand, the air permeability of the container first sheet 201 is preferably 100 seconds / 100 mL or more, more preferably 300 seconds / 100 mL or more, from the viewpoint of setting the oxidation reaction in the heat generating portion 10 to an appropriate speed. More preferably, it is 400 seconds / 100 mL or more, and still more preferably 500 seconds / 100 mL or more.

On the other hand, the air permeability of the container second sheet 202 is preferably 10,000 seconds / 100 mL or more, more preferably 20, from the viewpoint of effectively applying water vapor generated in the heat generating part 10 to the wearer. 000 seconds / 100 mL or more.
Further, the upper limit value of the air permeability of the container second sheet 202 is not particularly limited, but is preferably 100,000 seconds / 100 mL or less from the viewpoint of the high availability of the sheet. .
In addition, as the container second sheet 202, one that does not substantially transmit oxygen can be used. For example, polyolefins such as polyethylene and polybutadiene, polyvinyl chloride, polyvinylidene chloride, polyester, polyether, polysulfone, and the like One kind or two or more kinds of polyamides can be used. The thickness is preferably 5 μm or more and 200 μm or less.

Moreover, it is preferable that the water vapor transmission rate of the container 1st sheet | seat 201 is adjusted more than the fixed numerical value from a viewpoint which brings a water vapor | steam to a wearer. On the other hand, from the viewpoint of adjusting the amount released as water vapor and maintaining a high temperature as the heating element 100, it is preferable that the moisture permeability of the container first sheet 201 is adjusted to a certain value or less.
More specifically, the moisture permeability of the container first sheet 201 is preferably 800 g / m ² · 24 hr or more, more preferably 1000 g / m ² · 24 hr or more, from the viewpoint of feeling sufficient warmth due to water vapor. There, more preferably 1300g ^/ m 2 · 24hr or more, from the viewpoint of suppressing reduction in sensation, preferably not more than 8000g ^/ m 2 · 24hr, and more preferably not more than 6000g ^/ m 2 · 24hr, More preferably, it is 5000 g / m ² · 24 hr or less.
The moisture permeability can be measured by the cup method based on JIS Z0208 (established in 1976).

On the other hand, the moisture permeability of the container second sheet 202 is preferably set to a certain value or less from the viewpoint of effectively bringing water vapor to the wearer.
The moisture permeability of the container second sheet 202 is preferably 750 g / m ² · 24 hr or less, more preferably 540 g / m ² · from the viewpoint of effectively applying water vapor generated in the heat generating part 10 to the wearer. 24 hours or less.
In addition, the lower limit value of the moisture permeability of the container second sheet 202 is not particularly limited, and may be 0 g / m ² · 24 hr.

In addition, as shown in FIG. 6, it is good also as a structure which accommodated the container 20 in the 2nd container 40 made from the nonwoven fabric which is a sheet | seat material with a favorable texture in order to improve a usability | use_condition. The second container 40 is preferably composed of a sheet having a basis weight of 5 g / m ² or more, more preferably 10 g / m ² or more. Further, the peripheral edge portion of the sheet is preferably bonded to 200 g / m ² or less, more preferably 120 g / m ² or less.
Among these, a sheet having a basis weight of 20 g / m ² or more and 120 g / m ² or less is preferable from the viewpoint of weight reduction or the like. Examples of such sheets include non-woven fabrics and knitted fabrics.

  Non-woven fabric manufactured by air-through method, spunbond method, needle punch method, melt blown method, card method, thermal fusion method, hydroentanglement method, solvent bonding method using one or more kinds of fibers Can be used. Especially, it is preferable to use the nonwoven fabric which has a stretching property from a viewpoint of a texture or elasticity. The nonwoven fabric having elasticity is preferably a nonwoven fabric containing elastic fibers (for example, polyurethane, polyester) or three-dimensional crimped fibers as constituent fibers, and more preferably, for example, an air-through nonwoven fabric, a spunbond nonwoven fabric, or a needle punch nonwoven fabric.

  Specific non-woven fabric materials include polyesters such as PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene), polyolefins such as ethylene propylene copolymer, polyamide, polyacryl, and the like; cellulose, silk , Natural fibers including cotton, wool and the like; or one or two or more of the composite fibers thereof.

  In addition, since the heat generating body 100 of this embodiment has an oxidizable metal which is oxidized by oxygen, it is normally sealed and stored in an oxygen shielding bag.

The heating tool 50 of this embodiment is characterized in that the heating element 100 in the structure contains a cooling sensation agent. More specifically, menthol is included in the heating element 100 provided in the heating device 50 as a cooling agent.
In the present specification, “menthol” can be specified as a combination of dl-menthol as well as l-menthol. Moreover, in this specification, a cooling sensation agent acts on a wearer's skin, mucous membrane, etc., and gives a cold feeling, ie, a cold feeling, to a wearer.

  As the cooling sensation agent, a cooling sensation agent other than menthol can be further included. As the cooling sensation agent that can be included, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-mentoxy) -1,2-propanediol, Mention may be made of one or more compounds selected from the group consisting of N-ethyl-3-p-menthane carboxamide. As a result, it becomes easier to sustain the cool sensation, and the sensation of cool sensation can be improved by a combination of aromas.

The content of the cooling sensation agent in the heating element 100 is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0% with respect to the total mass of the heating unit 10. 4% by mass or more. Sufficient cooling sensation can be imparted by adjusting the content of the cooling sensation agent to the above lower limit value or more.
On the other hand, the content of the cooling sensation agent in the heating element 100 is preferably 2% by mass or less, more preferably 1.7% by mass or less, and further preferably 1% by mass with respect to the mass of the entire heating unit 10. .5% by mass or less.
From the same viewpoint, the amount of fragrance of the cooling sensation agent in the heating element 100 is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, with respect to the total mass of the heating unit 10. More preferably, it is 0.4% by mass or more, preferably 2% by mass or less, more preferably 1.7% by mass or less, and further preferably 1.5% by mass or less.
The menthol perfume amount is preferably 0.05% by mass or more, more preferably 0.1% by mass with respect to the mass of the entire heating unit 10 from the viewpoint of the balance between the water vapor amount and the menthol volatilization amount. % Or more, more preferably 0.15% by mass or more, preferably 1% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.6% by mass or less. is there.

For example, there are the following forms for carrying the cooling sensation agent.
(1) Form in which the cooling sensation agent is contained in the heat generating part 10 (2) Form in which the sheet to which the cooling sensation agent is attached is disposed inside the container 20 (3) The container body constituting the container 20 Form in which the cooling sensation agent is applied to at least one of the one sheet 201 and the container second sheet 202 (4) Form in which the sheet to which the cooling sensation agent is attached is arranged outside the container 20

  Among these forms of carrying the cooling sensation agent, (4) a form in which a sheet with menthol as a cooling sensation agent is disposed outside the container 20 is preferable. Thereby, while being able to acquire the stable heat_generation | fever characteristic, menthol can be volatilized efficiently and a cool feeling can be provided in a pleasant warm feeling. Moreover, it is preferable also from a viewpoint of simplifying the manufacturing process of the heating tool 50. The outside of the container 20 means the outside of the heating element 100 and any part of the heating tool 50. The outside of the container 20 is preferably a region where heat generated from the heat generator 100 is transmitted, and more preferably a region in contact with the outer surface of the heat generator 100.

In the case where a sheet with a cooling sensation agent is disposed outside the container 20, the cooling sensation agent is preferably supported by 0.15 g / m ² or more with respect to the area of the heat generating part 10 in plan view. Preferably it is carried 0.5 g / m ² or more, more preferably 0.8 g / m ² or more.
In addition, when a sheet with a cooling sensation agent is disposed outside the container 20, the cooling sensation agent is preferably supported by 15 g / m ² or less with respect to the area of the heat generating portion 10 in plan view. Preferably, 10 g / m ² or less is supported, more preferably 8 g / m ² or less.

  In the case where a sheet with a cooling sensation agent is disposed outside the container 20, the side far from the wearer's skin from the viewpoint of efficiently supplying water vapor generated from the heating element 100 to the eyes and the skin around the eyes. It is preferable to arrange on the side of the container second sheet 202 located at the position. Moreover, it is preferable that the sheet | seat is provided in the outer surface of the container 20 from a viewpoint of volatilizing a cooling agent effectively.

FIG. 5 is a cross-sectional view in a direction orthogonal to the sheet surface of the container 20 of the heating element 100. As shown in FIG. 5, in the present embodiment, in the heating element 100 included in the heating tool 50, a sheet 212 with a cooling sensation agent is disposed outside the container 20.
In the present embodiment, the sheet 212 is provided on the outer surface of the container second sheet 202 via an adhesive or the like. In this embodiment, the sheet 212 and the container second sheet 202 have the same size and shape, and cover the entire outer surface of the container second sheet 202. The sheet 212 may be smaller or larger than the container second sheet 202, but preferably has the same shape as the container second sheet 202.
The sheet 212 carries a cooling agent. By supporting the cooling sensation agent on the sheet 212 arranged outside the container 20, the cooling sensation agent can be efficiently supplied to the user.
The sheet 212 may be any sheet as long as it can carry a cooling sensation agent, and may be paper, nonwoven fabric, porous film, or woven fabric.
The cooling sensation agent can be carried on the sheet 212 by means such as dripping, spraying, coating, or impregnation.

In the present embodiment, from the viewpoint of achieving both a pleasant sensation of warmth and cooling, the volatilization amount of menthol per 30 minutes after the start of heat generation of the heating element 100 in the heating device 50 is set to 0.04 mg or more and 0.30 mg or less. (In this specification, these are expressed as “0.04 mg / 30 min” or “0.30 mg / 30 min”.)
Thus, the amount of menthol volatilization in the heating device 50 is set to 0.04 mg / 30 min or more, so that a person who wears the heating device 50 is given an appropriate cooling sensation, and is caused by the heating unit 10. A warm feeling is also brought. On the other hand, when the volatilization amount of menthol in the heating device 50 is set to 0.30 mg / 30 min or less, it is possible to prevent the wearer from being excessively stimulated by menthol.

  The amount of menthol volatilization is preferably 0.05 mg / 30 min or more, more preferably 0.06 mg / 30 min or more, and even more preferably 0.10 mg / 30 min or more, from the viewpoint of imparting an appropriate cooling sensation. More preferably, it is 0.11 mg / 30 min or more, and from the viewpoint of suppressing irritation due to cooling sensation, it is preferably 0.24 mg / 30 min or less, more preferably 0.2 mg / 30 min or less, and even more preferably 0 .16 mg / 30 min or less.

  In addition, in the heating tool 50, since menthol is hold | maintained at each of a pair of heat generating body 100, the amount of menthol volatilization becomes a numerical value which put these together. When the heating tool 50 is an eye mask type, it is preferable that the same amount of menthol is applied to each of the wearer's eyes. Specifically, the amount of menthol volatilization for one eye is preferably 0.02 mg / 30 min or more, and further 0.025 mg / 30 min or more, 0.03 mg / 30 min or more, 0.050 mg / 30 min or more, 0.0. More preferably in the order of 055 mg / 30 min or more, preferably 0.15 mg / 30 min or less, more preferably 0.12 mg / 30 min or less, still more preferably 0.1 mg / 30 min or less, and still more preferably Is 0.08 mg / 30 min or less.

The amount of menthol volatilization can be measured as follows.
First, a 15 cm × 25 cm polyvinyl fluoride resin gas collection bag (Tedlar (registered trademark) bag, manufactured by DuPont) containing a sufficient amount of air to cause the heating element 100 to undergo an oxidation reaction is prepared. One end of the collection bag is connected to an air supply source, and the tip of the tube connected to the outlet or outlet of the other end is immersed in ethanol.
Next, the heating element 100 in which the menthol is held on the sheet 212 is taken out of the oxygen-blocking bag, put in the gas collection bag, and placed on a hot plate set at 35 ° C. for 30 minutes. While being placed on the hot plate, air is allowed to flow from the air supply source into the gas collection bag at a constant speed (100 mL / min), and the other end of the gas collection bag is discharged to the discharge port or discharge port. By discharging air from the tip of the connected tube, the menthol volatilized from the heating element 100 is collected in ethanol. In addition, a weight is placed on the gas collection bag so that the air flowing into the gas collection bag is properly discharged, and the surroundings of the gas collection bag are insulated so that the heating by the hot plate is maintained. Insulate with material.
After mounting for 30 minutes, the heating element 100 is taken out from the gas collection bag, the inside of the gas collection bag is washed with ethanol, and the ethanol used for washing is also collected and totaled in the amount of volatilization of menthol. Analysis of the amount of menthol collected is performed by gas chromatography.
All these operations are performed under atmospheric pressure.

In addition, the amount of water vapor generated in the heating device 50 of the present embodiment is 40 mg / 10 min or more, preferably 100 mg / 10 min or more, more preferably 140 mg / 10 min or more, from the viewpoint of giving the wearer an appropriate vapor feeling. It is.
Further, the amount of water vapor generated in the heating tool 50 of the present embodiment is 3,000 mg / 10 min or less, preferably 1,600 mg / 10 min or less, more preferably, from the viewpoint of suppressing condensation in the heating tool 50. 500 mg / 10 min or less.

  In the present embodiment, the amount of water vapor generated after the heating element 100 starts to generate heat is a numerical value of the whole heating tool 50 including the amount of water vapor generated from each of the pair of heating elements 100. When the heating tool 50 is an eye mask type, it is preferable that the same amount of water vapor is supplied to each eye of the wearer. Specifically, for one eye, the amount of water vapor generated per 10 minutes after the start of heat generation of the heating element 100 is preferably 20 mg / 10 min or more, more preferably 50 mg / 10 min or more, and further preferably It is 70 mg / 10 min or more, preferably 1,500 mg / 10 min or less, more preferably 800 mg / 10 min or less, and further preferably 250 mg / 10 min or less.

In addition, in the heating device 50 of the present embodiment, the menthol volatilization amount after the heating element 100 starts to generate heat is 0.04 mg / 30 min or more and 0.30 mg / 30 min or less, and after the heating element 100 starts to generate heat. When the amount of water vapor generated is 40 mg / 10 min or more and 3,000 mg / 10 min or less, a cool feeling can be imparted in a pleasant warm feeling.
From the viewpoint of imparting a cooling sensation in a higher level and a pleasant warm feeling, the volatilization amount of the menthol is preferably 0.05 mg / 30 min or more, more preferably 0.06 mg / 30 min or more, More preferably, it is 0.10 mg / 30 min or more, further preferably 0.11 mg / 30 min or more, preferably 0.24 mg / 30 min or less, more preferably 0.2 mg / 30 min or less, More preferably, it is 0.16 mg / 30 min or less, and the water vapor generation amount is preferably 100 mg / 10 min or more, more preferably 140 mg / 10 min or more, preferably 1,600 mg / 10 min or less, More preferably, it is 500 mg / 10min or less.

  Here, in order for the heating tool 50 to have the above-described specific amount of water vapor generation amount and menthol volatilization amount, it is important to devise a manufacturing method different from the conventional method. I found. Specifically, the structure of the container 20, the material, the air permeability and moisture permeability of the container 20, the selection of oxidizable metals, carbon components and water contained in the heat generating part 10, the selection of materials, and the menthol application It is important to highly control factors such as fragrance. That is, it is not necessary to simply control the amount of menthol perfume or the amount of oxidizable metal, but a specific amount of water vapor generation and menthol volatilization can be obtained only by appropriately combining various factors. .

The maximum surface temperature of the heating element 100 of the present embodiment can be measured by using an apparatus 30 described later, but the maximum surface temperature of the heating element 100 is a viewpoint that achieves both a warm feeling and a cool feeling comfortable for the wearer. Therefore, it is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 45 ° C. or higher.
The maximum surface temperature of the heating element 100 is preferably 70 ° C. or less, more preferably 65 ° C. or less, and further preferably 60 ° C. or less, from the viewpoint of giving a comfortable warm feeling to the wearer.

  Here, the surface maximum temperature and the amount of water vapor generation of the heating element 100 are numerical values measured as follows using the apparatus 30 shown in FIG. The apparatus 30 shown in FIG. 7 includes an aluminum measurement chamber (volume 4 L) 31, 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 the measurement chamber 31. An outflow path 33 for allowing air to flow out from the upper part, an inlet temperature / humidity meter 34 and an inlet flowmeter 35 provided in the inflow path 32, an outlet temperature / humidity meter 36 and an outlet flowmeter 37 provided in the outflow path 33, and a measurement chamber 31. It consists of a thermometer (thermistor) 38 provided inside. A thermometer having a temperature resolution of about 0.01 ° C. is used.

The measurement of the maximum surface temperature of the heating element 100 is carried out by removing the heating element 100 from the oxygen shielding bag at a measurement environment temperature of 30 ° C. (30 ± 1 ° C.), and for example, water vapor is likely to be released. It is placed in the measurement chamber 31 with the surface facing up, and a thermometer 38 with a metal ball (mass 4.5 g) is placed thereon and measured.
In this state, dehumidified air is allowed to flow from the lower part, and 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 / humidity meter 34 and the outlet temperature / humidity meter 36. The amount of water vapor released from the heating element 100 is calculated from the flow rates measured by the flow meter 35 and the outlet flow meter 37.
The surface temperature in the present specification refers to the highest temperature reached on the surface of the heating element 100 after the heating element 100 is taken out of the oxygen-blocking bag, that is, after the generation of water vapor. It refers to the total amount of water vapor measured up to 10 minutes after the body 100 is taken out of the oxygen barrier bag, that is, when water vapor is generated.

  Further, when attention is paid to the heating element 100 of the present embodiment and one cell, the water vapor generation amount is α [mg / 10 min], the menthol perfume amount per cell is β [mg], and the menthol volatilization amount is γ [ mg / 30 min], the β / α and γ / α values are preferably in the following ranges.

Specifically, the value of the ratio β / α of the menthol flavoring amount β [mg] to the water vapor generation amount α [mg / 10 min] is preferable from the viewpoint of appropriately applying water vapor containing a cooling agent to the wearer. Is 0.01 or more, more preferably 0.015 or more, still more preferably 0.02 or more, and still more preferably 0.025 or more.
From the same viewpoint, the value of β / α is preferably 0.1 or less, more preferably 0.08 or less, further preferably 0.06 or less, and still more preferably 0.05 or less. is there.

Further, the value of the ratio γ / α of the menthol volatilization amount γ [mg / 30 min] to the water vapor generation amount α [mg / 10 min] is preferably from the viewpoint of appropriately applying water vapor containing a cooling agent to the wearer. It is 0.05 × 10 ⁻³ or more, more preferably 0.1 × 10 ⁻³ or more, and further preferably 0.15 × 10 ⁻³ or more.
From the same viewpoint, the value of γ / α is preferably 1.5 × 10 ⁻³ or less, more preferably 1 × 10 ⁻³ or less, and further preferably 0.8 × 10 ⁻³ or less. .

The method for manufacturing the heating tool 50 includes the following steps.
Preparing a heat generating part 10 containing an oxidizable metal, a carbon component and water;
A process of housing the heat generating part 10 by the container 20 and forming the heat generating body 100;
Perfume menthol on the sheet;
And a step of arranging a sheet in which menthol is scented outside the container 20.
When the menthol is flavored to the sheet, the ratio (β / α) of the menthol flavoring amount β [mg] to the water vapor generation amount α [mg / 10 min] is 0.01 or more and 0.1 or less. It is preferable to do. Thereby, the heating tool 50 can provide a cool feeling in a pleasant warm feeling.

The effect of the heating tool 50 of this embodiment is demonstrated.
The heating tool 50 of the present embodiment includes menthol in the heating element 100, and the volatilization amount of menthol after the heating element 100 starts to generate heat is 0.04 mg / 30 min or more and 0.30 mg / 30 min or less. The amount of water vapor generated after heat generation of body 100 is not less than 40 mg / 10 min and not more than 3,000 mg / 10 min. That is, the heating device 50 can impart a cooling sensation in a pleasant sensation of warmth by controlling the parameters of the amount of menthol volatilization and the amount of water vapor generated within a specific time. Here, the pleasant warmth is different from the one that feels warm irritation caused by heat. It is felt for the first time by combining. And the sensation of cooling by menthol is added moderately, and it has the effect of having both a pleasant warmth and a sensation of cooling that are not possible in the past. Moreover, by controlling the parameters of the menthol volatilization amount and the water vapor generation amount within a specific time, it is possible to impart a pleasant warmth and cool feeling to the user effectively.

As mentioned above, although embodiment of this invention was described referring drawings, these are illustrations of this invention and can also employ | adopt various structures other than the above.
For example, in the above-described embodiment, the sheet 212 is disposed outside the container 20, and the cooling sensation agent is carried on the sheet 212. However, the present invention is not limited to this. For example, the heat generating part 10 may contain a cooling agent. Furthermore, a cooling sensation agent may be carried on either one or both of the container first sheet 201 and the container second sheet 202 constituting the container 20, and the cooling sensation agent is placed inside the container 20. A sheet on which is carried may be disposed.
In the above embodiment, the sheet 212 is disposed outside the container second sheet 202, but a sheet carrying a cooling sensation agent may be disposed outside the container first sheet 201. Good.

  In relation to the above-described embodiment, the present invention further discloses the following heating device or application.

<1> A heating element having a heating part containing an oxidizable metal, a carbon component, and water, and a container that houses the heating part,
Menthol is retained as a cooling agent,
The volatilization amount of the menthol after the heat generation of the heating element is 0.04 mg / 30 min or more and 0.30 mg / 30 min or less,
The heating tool, wherein the heat generation amount of the heating element after the start of heat generation is 40 mg / 10 min or more and 3,000 mg / 10 min or less.

<2> The heating tool according to <1>, wherein the menthol is carried on a sheet disposed outside the container.
<3> As the cooling agent, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-mentoxy) -1,2-propanediol, N-ethyl-3-p- The heating device according to <1> or <2>, comprising one or more compounds selected from the group consisting of menthane carboxamides.
<4> The container includes a first sheet positioned closer to the wearer's skin than the heat generating portion and a second sheet positioned closer to the wearer's skin than the heat generating portion. <1> Thru | or the heating tool as described in any one of <3>.
<5> The air permeability measured in accordance with JIS P8117 of the first sheet is preferably 10,000 seconds / 100 mL or less, more preferably 7,000 seconds / 100 mL or less, and further preferably. Is 5,000 seconds / 100 mL or less, more preferably 4,000 seconds / 100 mL or less, preferably 100 seconds / 100 mL or more, more preferably 300 seconds / 100 mL or more, and further preferably Is 400 seconds / 100 mL or more, more preferably 500 seconds / 100 mL or more, according to <4>.
<6> The moisture permeability of the first sheet is preferably 800 g / m ² · 24 hr or more, more preferably 1000 g / m ² · 24 hr or more, and further preferably 1300 g / m ² · 24 hr, , preferably not more than 8000g ^/ m 2 · 24hr, and more preferably not more than 6000g ^/ m 2 · 24hr, and more preferably not more than 5000g ^/ m 2 · 24hr, heat according to <4> or <5> Ingredients.
<7> The air permeability of the second sheet is preferably 10,000 seconds / 100 mL or more, more preferably 20,000 seconds / 100 mL or more, and any one of <4> to <6> Heating tool as described in.
<8> The moisture permeability of the second sheet is preferably 750 g / m ² · 24 hr or less, more preferably 540 g / m ² · 24 hr or less, <4> to <7> The heating device described.
<9> The heating tool according to any one of <4> to <8>, wherein the menthol is supported on a sheet disposed on the second sheet side.
<10> The surface temperature of the heating element in 10 minutes from the start of water vapor generation by the heating element is preferably 35 ° C. or more, more preferably 40 ° C. or more, further preferably 45 ° C. or more, and preferably The heating device according to any one of <1> to <9>, wherein is 70 ° C. or lower, more preferably 65 ° C. or lower, and further preferably 60 ° C. or lower.
<11> The amount of water vapor generated by the heating element is preferably 40 mg / 10 min or more, more preferably 100 mg / 10 min or more, still more preferably 140 mg / 10 min or more, and preferably 3,000 mg / 10 min. <1> thru / or <10> which is below, More preferably, it is 1,600 mg / 10min or less, More preferably, it is 500 mg / 10min or less.
<12> The heating device according to any one of <1> to <11>, wherein the heating unit further includes a reaction accelerator.
<13> The thickness of the heat generating part is preferably 0.2 mm or more, more preferably 0.4 mm or more, still more preferably 0.5 mm or more, and the thickness of the heat generating part is preferably The heating device according to any one of <1> to <12>, which is 5 mm or less, more preferably 3 mm or less, and further preferably 2 mm or less.
<14> The content of the cooling agent in the heating element is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the mass of the entire heating unit, Preferably it is 0.4 mass% or more, Preferably it is 2 mass% or less, More preferably, it is 1.7 mass% or less, More preferably, it is 1.5 mass% or less. The heating tool according to any one of <1> to <13>.
<15> The cooling agent volatilization amount of the heating element is preferably 0.05 mg / 30 min or more, more preferably 0.06 mg / 30 min or more, and further preferably 0.010 mg / 30 min or more. More preferably, it is 0.011 mg / 30 min or more, preferably 0.24 mg / 30 min or less, more preferably 0.2 mg / 30 min or less, and further preferably 0.16 mg / 30 min or less. <1> thru / or <14> a heating tool given in any 1 paragraph.
<16> preparing a heat generating part containing an oxidizable metal, a carbon component, and water;
A step of accommodating the heat generating part by a container and forming the heat generator;
Perfume menthol on the sheet;
Placing the menthol-scented sheet outside the container, and in the step of scenting the sheet with menthol, the menthol perfume amount β [mg], the water vapor generation amount α [mg / 10 min] is a method for manufacturing a heating tool, wherein the ratio (β / α) is 0.01 or more and 0.1 or less.
<17> The heating element further includes 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (1-menthoxy) -1,2-propanediol, N-ethyl- as a cooling agent. The method for producing a heating tool according to <16>, comprising one or more compounds selected from the group consisting of 3-p-menthane carboxamide.
<18> The heating tool according to <16> or <17>, wherein the container includes a first sheet located on a skin side of the wearer and a second sheet located on a side far from the skin of the wearer. Manufacturing method.
<19> The air permeability measured according to JIS P8117 of the first sheet is preferably 10,000 seconds / 100 mL or less, more preferably 7,000 seconds / 100 mL or less, and still more preferably. Is 5,000 seconds / 100 mL or less, more preferably 4,000 seconds / 100 mL or less, preferably 100 seconds / 100 mL or more, more preferably 300 seconds / 100 mL or more, and further preferably Is 400 seconds / 100 mL or more, more preferably 500 seconds / 100 mL or more, The method for producing a heating tool according to <18>.
<20> The moisture permeability of the first sheet is preferably 800 g / m ² · 24 hr or more, more preferably 1000 g / m ² · 24 hr or more, and further preferably 1300 g / m ² · 24 hr, , preferably not more than 8000g ^/ m 2 · 24hr, and more preferably not more than 6000g ^/ m 2 · 24hr, and more preferably not more than 5000g ^/ m 2 · 24hr, heat according to <18> or <19> Manufacturing method of the tool.
<21> The air permeability of the second sheet is preferably 10,000 seconds / 100 mL or more, more preferably 20,000 seconds / 100 mL or more, and any one of <18> to <20> The manufacturing method of the heating tool as described in any one of.
<22> The cooling sensation agent is preferably supported at 0.15 g / m ² or more, more preferably 0.5 g / m ² or more, and even more preferably 0.8 g / m ² or more with respect to the area of the heat generating portion. Any one of <16> to <21>, preferably 15 g / m ² or less, more preferably 10 g / m ² or less, and still more preferably 8 g / m ² or less. The manufacturing method of the heating tool as described in one.
<23> The volatilization amount of the cooling agent in the heating element is preferably 0.06 mg / 30 min or more, more preferably 0.07 mg / 30 min or more, and further preferably 0.074 mg / 30 min or more. Moreover, it is preferably 0.24 mg / 30 min or less, more preferably 0.2 mg / 30 min or less, and further preferably 0.16 mg / 30 min or less, any one of <16> to <22> The manufacturing method of the heating tool as described in any one of.
<24> Use in which the heating tool according to any one of <1> to <15> is worn as an eye mask.

  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.

Examples 1 to 4 and Comparative Examples 1 and 2
According to the following procedure, the heating tool of the structure shown in Table 3 or Table 4 was produced.

<Preparation of the heat generating part 10>
・ Heat generation part A
Paper made of wood pulp (20 g / m ² , manufactured by Ino Paper Co., Ltd.) and a water-absorbing polymer (sodium polyacrylate, spherical, average particle size 300 μm, 50 g / m ² , Aquaric CA, manufactured by Nippon Shokubai Co., Ltd.) A polymer sheet formed by laminating wood pulp paper (30 g / m ² , manufactured by Ino Paper Co., Ltd.) is used as a base material, and one side of the base material mixed with the components shown in Table 1 below is die coated. By this method, coating was carried out so that the amount of iron was 372 g / m ² to prepare a sheet-like coated product.
The sheet-like coated product was cut into a size of 50 mm × 50 mm, and 0.084 g of sodium chloride (Phospital Sodium Chloride (manufactured by Otsuka Pharmaceutical Co., Ltd.)) was uniformly sprayed on the coated surface. A 6 mm exothermic part A was obtained.

・ Heat generation part B
By using a laminated paper obtained by laminating polyethylene on wood pulp paper (30 g / m ² ) and mixing one of the components shown in Table 2 other than the water-absorbing polymer on one side with a die coating method. Then, coating was performed so that the iron powder was 372 g / m ² , and a water-absorbing polymer was further sprayed onto the coated surface to prepare a sheet-like coated product. The sheet-like coated product is cut into a size of 50 mm × 50 mm, and 0.084 g of sodium chloride (Phospital Sodium Chloride (manufactured by Otsuka Pharmaceutical Co., Ltd.)) is uniformly sprayed on the coated surface to obtain a 50 mm × 50 mm A paper made of wood pulp having a size (20 g / m ² ) was placed thereon to obtain a heating part B having a thickness of 0.5 mm.

・ Heat generation part C
Pulp fiber 9.6 parts by mass, activated carbon 10.8 parts by mass, polyamide epichlorohydrin resin (manufactured by Seiko PMC Co., Ltd., trade name “WS4020”) 0.8 parts by mass with respect to 100 parts by mass of iron powder, carboxy 0.22 parts by mass of sodium methylcellulose was mixed, and water was further added to a solid part concentration of 12% to make a slurry. This slurry was diluted with water to 0.3% immediately before being sent to the papermaking head of the papermaking machine, and a papermaking sheet was prepared with the papermaking machine. The paper sheet was cut into 50 mm × 50 mm, three sheets were stacked, 45 parts of 5% saline was injected into 100 parts of these paper sheets, and menthol solution (1-menthol: 20% by mass, polyethylene glycol 400). : 80 mass%) was injected to obtain a heating part C. In addition, the density | concentration of the inject | poured menthol is 0.9 mass% in the total mass of the heat generating part C, and the menthol amount in one heat generating part C is 15.3 mg.

<Preparation of heating element 100>
A heating element 100 having the form shown in FIG. 5 was produced according to the following procedure.
The heat generating part A is a porous stretched polyethylene moisture permeable film containing calcium carbonate (air permeability 3,500 sec / 100 mL, moisture permeability 1,500 g / m ² · 24 hr) as the container first sheet 201. The heat generating part B is a porous stretched polyethylene moisture permeable film containing calcium carbonate (air permeability is 500 seconds / 100 mL and moisture permeability is 4,700 g / m ² · 24 hr as the container first sheet 201. ), And the heat generating part C is a porous first polyethylene moisture permeable film containing calcium carbonate (air permeability 15000 sec / 100 mL, moisture permeability 650 g / m ² · 24 hr) as the container first sheet 201. Using. Moreover, as for the heat generating part A, B, and C, as the container 2nd sheet | seat 202, all are the non-air-permeable films made from polyethylene (the air permeability is 100,000 second / 100 mL or more, and the water vapor permeability is 0 g / m ^2. 24 hr) was used. A water absorbent paper (basis weight 35 g / m ² ) to be the sheet 212 was laminated with an adhesive in advance on the outer surface of the container second sheet 202 of the heat generating parts A and B.
Each heating part A or B is sandwiched between the container first sheet 201 and the container second sheet 202, and the water absorbent paper laminated on the container second sheet 202 is stacked so that the water absorbent paper faces outward. In 203, the two sheets (the container first sheet 201 and the container second sheet 202) were joined together to obtain the heat generating body 100 including the heat generating portion A or B. The heat generating part C is sandwiched between the container first sheet 201 and the container second sheet 202, and the two sheets (the container first sheet 201 and the container second sheet 202) are arranged at the peripheral part 203. The heat generating body 100 provided with the heat generating part C was obtained by bonding.
The heating element 100 was stored in an oxygen-blocking bag until evaluation described below was performed.

<Retention of cooling agent>
In the heating elements 100 of Examples 1 to 4 and Comparative Example 1, the cooling sensation agent was held as follows.
A cooling sensitizer solution was prepared by dissolving l-menthol and eucalyptus oil in a mass ratio of 8:21 (l-menthol: 10.3 mass%, eucalyptus oil: 26.9 mass%) using ethanol as a solvent. did. In Example 1 and Example 4, 39 mg of the cooling sensation agent solution was applied to the sheet 212 laminated on the outside of the container second sheet 202 of the obtained heating element 100, whereby the heating element 100 was cooled. The agent was retained. Ethanol was volatilized, and 4 mg of menthol and 10.5 mg of eucalyptus oil were supported on the sheet 212 per 100 heating elements. In addition, 70 mass% of eucalyptus oil was 1,8-cineole, a total of 11.36 mg was carry | supported as a cooling sensation agent, and the menthol flavoring amount was 4 mg.
That is, for example, 0.61% by mass (the total amount of l-menthol and eucalyptus oil was 0.78% by mass) of the cooling sensation agent was applied to the total mass of the heat generating unit 10 of Example 1.

In Example 2, 19.5 mg of the above-mentioned cooling sensitizer solution was applied to the sheet 212, in Example 3, 78 mg of the above-mentioned cooling sensitizer solution was applied to the sheet 212, and in Comparative Example 1, the above-mentioned cooling agent solution was applied to the sheet 212. 9.75 mg of the sensitizer solution was applied, and each ethanol was volatilized. The amount of menthol perfume per one heating element 100 was 2 mg in Example 2, 8 mg in Example 3, and 1 mg in Comparative Example 1.
In addition, the menthol perfume amount of the heating tool 50 described below (using two heating elements 100) is as shown in Table 3.

<Preparation of heating tool 50>
Using the two heating elements 100 obtained as described above so as to have the configuration shown in Table 3 or Table 4, the eye mask-shaped heating tool 50 shown in FIG. 1 was produced. A polypropylene nonwoven fabric (needle punch method) with a basis weight of 80 g / m ² was used as the bag first sheet 55, and a polyethylene terephthalate nonwoven fabric (air through method) with a basis weight of 30 g / m ² was used as the bag second sheet 56.

  About each heating tool of the structure shown in Table 3 or Table 4, the measurement and evaluation shown below were performed. The results are shown in Table 3 or Table 4.

・ Measurement <Menthol Volatilization>
First, a 15 cm × 25 cm polyvinyl fluoride resin gas collection bag (Tedlar (registered trademark) bag, manufactured by DuPont) containing a sufficient amount of air to cause the heating element 100 to undergo an oxidation reaction is prepared. One end of the collection bag was connected to an air supply source, and the tip of the tube connected to the outlet or outlet of the other end was immersed in ethanol.
Next, the heating element 100 in which the menthol was held on the sheet 212 was taken out of the oxygen-blocking bag, placed in the gas collection bag, and placed on a hot plate set at 35 ° C. for 30 minutes. While being placed on the hot plate, air is allowed to flow from the air supply source into the gas collection bag at a constant speed (100 mL / min), and the other end of the gas collection bag is discharged to the discharge port or discharge port. Menthol that had volatilized from the heating element 100 was collected in ethanol by discharging air from the tip of the connected tube. In addition, a weight is placed on the gas collection bag so that the air flowing into the gas collection bag is properly discharged, and the surroundings of the gas collection bag are insulated so that the heating by the hot plate is maintained. Insulated with material.
After mounting for 30 minutes, the heating element 100 is taken out from the gas collection bag, the inside of the gas collection bag is washed with ethanol, and the ethanol used for washing is also collected and totaled in the amount of volatilization of menthol. The amount of menthol collected was analyzed by gas chromatography (Agilent 6890N, manufactured by Agilent Technologies).
All these operations were performed under atmospheric pressure.
In addition, since the heating tool 50 uses two heating elements 100, the amount of menthol volatilization of the heating tool 50 was set to double the amount measured per heating element 100.

<Water vapor generation amount>
It measured using the apparatus 30 shown in FIG. Remove the heating element 100 from the oxygen shielding bag, place it on the skin side of the heating element 100 (container first sheet 201) and place it on the measurement chamber 31, and attach a metal ball (mass 4.5 g). The measured thermometer 38 was placed on the thermometer 38 and measured. In this state, dehumidified air is flowed from the bottom, and the difference between the 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 / humidity meter 34 and the outlet temperature / humidity meter 36. The amount of water vapor released by the water vapor generating warming tool 100 was calculated from the flow rate measured by the flow meter 35 and the outlet flow meter 37. The amount of water vapor generated was the total amount measured up to 10 minutes after the time when the heating device 50 was taken out of the oxygen shielding bag.
In addition, since the heating tool 50 uses two heating elements 100, the amount of water vapor generated was twice the amount measured per heating element 100.

<Maximum surface temperature>
The maximum surface temperature of the heating element 100 was measured using an apparatus 30 shown in FIG. That is, the heating element 100 is taken out of the oxygen shielding bag at a measurement environment temperature of 30 ° C. (30 ± 1 ° C.), and the surface (container first sheet 201) located on the skin side of the heating element 100 is placed in the measurement chamber 31. A thermometer 38 mounted and mounted with a metal ball (mass 4.5 g) was measured on it, and the measured value was the maximum temperature reached on the surface of the heating element 100 after the heating element 100 was taken out of the oxygen shielding bag. It was.

・ Evaluation Three skilled panelists wore each heating tool for 30 minutes, and discussed and decided which position of the following evaluation criteria corresponded.
[Cool feeling]
5: Feeling a stimulus 4: Feeling a slight stimulus 3: A feeling of moderate cooling 2: A feeling of a slight cooling 1: A slight feeling of cooling 0: No feeling of cooling [warm feeling]
5: Hot 4: Slightly hot 3: Feeling a pleasant warmth 2: Feeling a little warm 1: Feeling a little warm 0: Not warm

  In Examples 1 to 4, a sufficient amount of menthol volatilization was obtained as compared with Comparative Example 1, and it was possible to obtain a cool feeling while feeling a pleasant warm feeling as compared with Comparative Example 1. In Example 3 and Example 4, although the surface temperature of the heating element is lower than in Examples 1 and 2, a comfortable warm feeling due to warm water vapor is obtained, and the cooling feeling after wearing the heating tool is Comparative Example 1. And it was better than Examples 1 and 2.

  Since the comparative example 2 was too irritation | stimulated by menthol and it was difficult to continue wearing a heating tool, it was not able to evaluate.

DESCRIPTION OF SYMBOLS 10 Heat generating part 20 Container 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 40 Second container 50 Heating tool 51 Main body 52 Ear hook part 53 Bag body 53A, 53B Notch part 54 Hole 55 Bag body first sheet 56 Bag body second sheet 100 Heat generating body 201 Container body first sheet 202 Container body second sheet 203 Peripheral part 212 Sheet

Claims (8)

A heating element comprising a heating part containing an oxidizable metal, a carbon component and water, and a container for housing the heating part,
Menthol is retained as a cooling agent,
The volatilization amount of the menthol after the heat generation of the heating element is 0.04 mg / 30 min or more and 0.30 mg / 30 min or less,
The heating tool, wherein the heat generation amount of the heating element after the start of heat generation is 40 mg / 10 min or more and 3,000 mg / 10 min or less.   The heating tool according to claim 1, wherein the menthol is carried on a sheet disposed outside the container.   As the cooling agent, 1,8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (1-menthoxy) -1,2-propanediol, N-ethyl-3-p-menthane carboxamide The heating tool according to claim 1 or 2, comprising one or more compounds selected from the group consisting of:   The said container is provided with the 1st sheet | seat located in a wearer's skin side rather than the said heat generating part, and the 2nd sheet | seat located in the side far from the said wearer's skin rather than the said heat generating part. The heating tool as described in any one of Claims.   The heating tool according to claim 4, wherein the air permeability of the first sheet measured in accordance with JIS P8117 is 100 seconds / 100 mL or more and 10,000 seconds / 100 mL or less. The heating tool according to claim 4 or 5, wherein the moisture permeability of the first sheet measured in accordance with JIS Z0208 is 800 g / m ² · 24 hr or more and 8,000 g / m ² · 24 hr or less.   The heating tool according to any one of claims 4 to 6, wherein the menthol is carried on a sheet disposed on the second sheet side.   The heating tool according to any one of claims 1 to 7, wherein a maximum surface temperature of the heating element in 10 minutes from the start of water vapor generation by the heating element is 35 ° C or more and 70 ° C or less.

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