HK1210690B - Heat generator - Google Patents
Heat generator Download PDFInfo
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- HK1210690B HK1210690B HK15111572.6A HK15111572A HK1210690B HK 1210690 B HK1210690 B HK 1210690B HK 15111572 A HK15111572 A HK 15111572A HK 1210690 B HK1210690 B HK 1210690B
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- heat
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- generating device
- fragrance
- metal ion
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Description
Technical Field
The present invention relates to a heating appliance. More specifically, the present invention relates to a heat generating device in which generation of unpleasant odor and change in fragrance are suppressed. The present invention also relates to a method for suppressing the generation of unpleasant odor and changes in flavor in a heat-generating appliance.
Background
Conventionally, a disposable warm patch has been frequently used as a body warmer because it is excellent in portability, safety, convenience, and the like, and is inexpensive. In general, a heat-generating composition that generates heat in the presence of air is used for a disposable heating pad, and a heat-retaining effect is exhibited by the heat-generating principle. However, such a disposable warm patch generates a unique odor derived from the heat-generating composition, which becomes a cause of the peculiar unpleasant taste of the disposable warm patch.
In addition, it has been conventionally reported that a heat generating device such as a disposable warm patch is imparted with fragrance, and for example, patent document 1 discloses that a fragrance is contained on the surface of a conventional disposable warm patch and the volatilization and diffusion of the fragrance are promoted by utilizing the heat generation principle of the disposable warm patch. However, when a heat generating device using such a disposable heater patch is made to contain a perfume, there is a problem that a desired fragrance cannot be sufficiently enjoyed due to a change in fragrance of the perfume.
In addition, in the case of a heat-generating appliance subjected to perfuming, since an unpleasant odor derived from the heat-generating composition is generated in addition to a change in the fragrance, it is necessary to suppress the unpleasant odor while maintaining a good fragrance.
Furthermore, since most of heat generating devices are used after being stored for a certain period of time, not only immediately after being manufactured, it is also important to suppress unpleasant odor and flavor change generated during storage.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2001 and 218816
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a more excellent heat generating device in which unpleasant odor is suppressed. Another object of the present invention is to provide a more excellent heat-generating device with suppressed changes in fragrance. Another object of the present invention is to provide a further excellent heat-generating appliance in which unpleasant odor is suppressed and flavor change is suppressed even after storage. Another object of the present invention is to provide a method for suppressing generation of unpleasant odor and/or change in fragrance in a heat-generating appliance.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: by using the metal ion chelating agent for the heat generating device, the heat generating device can suppress unpleasant odor even after storage and can suppress changes in flavor. The present invention has been completed based on the above findings and further repeated studies. That is, the present invention provides the following inventions.
A heat-generating device comprising a heat-generating composition containing a metal ion-containing chelating agent, an oxidizable metal powder, a water-soluble salt and water, wherein at least the heat-generating composition is contained in a gas-permeable containing bag.
Item 2. the heat-generating appliance according to item 1, further comprising an oxidation accelerator and/or a water-retaining agent.
Item 3. the heat-generating appliance according to item 1 or 2, further comprising a fragrance.
The heat generating device according to any one of claims 1 to 3, wherein the metal ion chelating agent is at least 1 selected from the group consisting of an aminocarboxylic acid type metal ion chelating agent, a phosphonic acid type metal ion chelating agent, a condensed phosphoric acid type metal ion chelating agent, a carboxylic acid type metal ion chelating agent, and a substance having a metal ion adsorbing ability.
The heat-generating device according to any one of claims 1 to 4, wherein the metal ion chelating agent is contained in the heat-generating composition in an amount of 0.0001 to 10 wt%.
The heat generating device according to any one of claims 2 to 5, wherein the oxidation accelerator is at least 1 selected from the group consisting of carbon black, black lead, activated carbon, coal, charcoal, bamboo charcoal, graphite, acetylene black, and coffee grounds.
The heat generating device according to any one of claims 2 to 6, wherein the oxidation accelerator has an iodine adsorption performance of 400mg/g or less on average.
The heat generating device according to any one of claims 2 to 7, wherein the oxidation accelerator has conductivity.
The heat generating device according to any one of claims 1 to 8, wherein the metal ion chelating agent is contained in an amount of 0.0002 to 20 parts by weight per 100 parts by weight of the oxidizable metal powder in the heat generating composition.
The heat-generating device according to any one of claims 2 to 9, wherein a blending ratio of the oxidation accelerator in the heat-generating composition is 1 to 30% by weight.
The heat-generating device according to any one of claims 3 to 10, which comprises the heat-generating composition and a perfume in an amount of 0.0001 to 20 parts by weight per 100 parts by weight of the heat-generating composition.
A heat-generating device according to any one of claims 3 to 11, wherein the heat-generating composition contains 0.0003 to 500 parts by weight of a fragrance per 100 parts by weight of the oxidation accelerator.
The heat-generating device according to any one of claims 3 to 12, wherein the perfume is contained in a container
(1) Is accommodated in the accommodating bag with air permeability; or
(2) At least a part of the air-permeable containing bag; or
(3) The sheet, the adhesive component or the other accommodating bag is disposed inside and/or outside the air-permeable accommodating bag.
The heat generating device according to any one of claims 3 to 13, wherein the fragrance is contained in the air-permeable containing bag.
The heat generating device according to any one of claims 3 to 14, wherein the fragrance is supported on a carrier.
The method of suppressing the generation of unpleasant odor and/or flavor change in a heat-generating appliance, comprising the step of storing a heat-generating composition comprising a metal ion chelating agent, an oxidizable metal powder, a water-soluble salt, and water in a storage bag having air permeability.
The suppressing method according to item 16, which comprises a step of storing the heat-generating composition containing the metal ion chelating agent, the oxidizable metal powder, the water-soluble salt, water, and the oxidation accelerator and/or the water retaining agent in a storage bag having air permeability.
The suppressing method according to any one of claims 16 to 17, further comprising a step of including a perfume.
Item 19. a method for suppressing generation of unpleasant odor and/or change in flavor in a heat-generating appliance by using the heat-generating appliance described in any one of items 1 to 15.
Item 20. the heat-generating appliance according to any one of items 1 to 15, for use in a method of suppressing generation of unpleasant odor and/or change in fragrance in a heat-generating appliance.
The heat-generating device according to any one of items 1 to 15, wherein the heat-generating device is used for manufacturing a heat-generating device in which generation of an unpleasant odor and/or a change in fragrance are suppressed.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the heat generating device of the present invention, unpleasant odor derived from the heat generating composition can be effectively suppressed. Further, according to the present invention, even when the heat-generating appliance contains a perfume, it is possible to suppress a change in the fragrance derived from the perfume and maintain a desired fragrance. Further, according to the present invention, even when the heat generating device is used after being stored, unpleasant odor can be effectively suppressed, excellent fragrance can be exhibited, and further, a sufficient heat generating effect can be exhibited as the heat generating device.
Drawings
Fig. 1 is an example of a stick-on heat generating device packaged in an outer bag. The storage bag having air permeability illustrated in fig. 1 is a model diagram of a storage bag having a portion having air permeability on one surface and a portion having no air permeability on the other surface. FIG. 1 shows an example of a mixture containing a perfume and a heat-generating composition.
Fig. 2 is an example of the adhesive heating device packaged in the outer bag. The storage bag having air permeability illustrated in fig. 2 is a model diagram of a storage bag having a portion having air permeability on one surface and a portion having no air permeability on the other surface. Fig. 2 is an illustration of a perfume-containing composition, the perfume being present in the binding composition.
Fig. 3 is an example of the heating device packaged in the outer bag. The storage bag having air permeability illustrated in fig. 3 is a model diagram of a storage bag having a portion having air permeability on one surface and a portion having no air permeability on the other surface. FIG. 3 shows an example of a mixture containing a perfume, the perfume being mixed with a heat-generating composition.
Fig. 4 is an example of the adhesive heating device packaged in the outer bag. The storage bag having air permeability illustrated in fig. 4 is a model diagram of a storage bag having a portion having air permeability on one surface and a portion having no air permeability on the other surface. Figure 4 is an illustration without perfume.
Detailed Description
The heat generating device of the present invention is a heat generating device containing a heat generating composition containing a metal ion chelating agent, an oxidizable metal powder, a water-soluble salt and water, wherein at least the heat generating composition is contained in a gas-permeable containing bag. The heating appliance of the present invention will be described below. In the present specification, the meaning of "including" includes both the meaning of "substantially including" and the meaning of "including".
Exothermic composition
The heating device of the present invention contains a heat-generating composition. The heat-generating composition generates heat in the presence of oxygen and contains a metal ion chelating agent, an oxidizable metal powder, a water-soluble salt and water.
-metal ion chelating agents
The metal ion chelating agent is not limited as long as it has a metal ion chelating ability, and any of a substance having 2 or more coordinating groups and having an ability to bind to a metal ion by a ligand, a substance having an ability to electrically adsorb a metal ion, a substance having an ability to physically adsorb a metal ion to a fine pore, a substance having an ability to chelate a metal ion, a combination thereof, and the like can be used. Examples of these include conventionally known metal ion chelating agents, and more specifically, aminocarboxylic acid-based metal ion chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, 1, 3-propanediaminetetraacetic acid, 1, 3-diamino-2-hydroxypropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycoletherdiaminetetraacetic acid, dicarboxymethylglutamic acid, and salts thereof; phosphonic acid type metal ion chelating agents such as hydroxyethylidene diphosphonic acid, nitrilotrimethylene phosphonic acid, phosphonobutane tricarboxylic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, and salts thereof; condensed phosphoric acid-based metal ion chelating agents such as tripolyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, and salts thereof; carboxylic acid-based metal ion chelating agents such as dihydroxyglycine, dihydroxyethylglycine, citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, ascorbic acid, gluconic acid, and salts thereof; and metal ion chelating agents such as various substances having metal ion adsorption ability, such as zeolite (aluminosilicate), acrylic acid, methacrylic acid, bipyridine, phenanthroline, porphyrin, phthalocyanine, Corrole (core), chlorin, and crown ether. Examples of the salts thereof include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium and calcium; ammonium salts, amine salts and the like.
The metal ion chelating agent is preferably an aminocarboxylic acid type metal ion chelating agent, a condensed phosphoric acid type metal ion chelating agent, or a carboxylic acid type metal ion chelating agent, and more preferably an aminocarboxylic acid type metal ion chelating agent or a carboxylic acid type metal ion chelating agent.
Of these, as a more preferable metal ion chelating agent, ethylenediaminetetraacetic acid, nitrilotriacetic acid, tripolyphosphoric acid, pyrophosphoric acid, citric acid, malic acid, and salts thereof can be exemplified, and ethylenediaminetetraacetic acid, citric acid, and salts thereof can be particularly preferably exemplified.
These may be used alone or in combination of two or more.
The amount of the metal ion chelating agent to be blended is not limited as long as the desired effect can be obtained, and the blending ratio of the metal ion chelating agent in the heat-generating composition is, for example, 0.0001 to 10% by weight, preferably 0.001 to 7% by weight, and more preferably 0.01 to 5% by weight.
The amount of the metal ion chelating agent to be blended is not limited as long as the desired effect can be obtained, and the blending ratio of the metal ion chelating agent in the heat-generating composition is, for example, 0.0002 to 20 parts by weight, preferably 0.002 to 15 parts by weight, and more preferably 0.02 to 10 parts by weight, based on 100 parts by weight of the oxidizable metal powder described later.
The metal ion chelating agent is not limited as long as the effect of the present invention can be obtained, and may be contained as one component for chelating metal ions constituting the heat-generating composition. From the viewpoint of further effectively exhibiting the effects of the present invention, it is preferable to use a metal ion chelating agent dissolved in water in advance and supported by at least one component contained in the heat-generating composition other than the oxidized metal powder by impregnation or the like.
Oxidized metal powder
The oxidizable metal powder contained in the heat-generating composition is not limited as long as it is a metal powder that generates heat by being oxidized, and examples thereof include iron powder, zinc powder, aluminum powder, magnesium powder, and copper powder, and iron powder is preferably used. Examples of the iron powder include reduced iron powder, cast iron powder, atomized iron powder, and electrolytic iron powder. These may be used alone or in combination of two or more.
The oxidizable metal powder may be in any of powder, granule, and fiber forms, and these may be used alone or in combination of two or more.
The average particle size of the oxidizable metal powder is, for example, 0.01 to 1000 μm, preferably 0.1 to 500 μm, and more preferably 0.5 to 300 μm, from the viewpoint of comfort when the heat generating device is worn on the body and used, heat generation efficiency, and the like. The average particle diameter of the oxidizable metal powder can be measured by JIS method using a standard sieve or the like.
The amount of the oxidizable metal powder to be blended is not limited as long as the desired effect can be obtained, and the proportion of the oxidizable metal powder to be blended in the heat-generating composition is, for example, 20 to 80% by weight, preferably 40 to 70% by weight, and more preferably 45 to 60% by weight.
-water soluble salts
The water-soluble salt contained in the heat-generating composition is blended for promoting the oxidation of the oxidizable metal powder, and is not limited as long as a desired effect can be obtained, and as the water-soluble salt, a hydrochloride or a sulfate of an alkali metal such as sodium or potassium is preferable; hydrochloride or sulfate of alkaline earth metal such as calcium or magnesium; and hydrochlorides or sulfates of metals such as iron, copper, aluminum, zinc, nickel, silver and barium. More preferable examples include potassium chloride and sodium chloride. These may be used alone or in combination of two or more.
The amount of the water-soluble salt to be added is not limited as long as the desired effect can be obtained, and the proportion of the water-soluble salt to be added in the heat-generating composition is, for example, 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, still more preferably 0.5 to 7% by weight, and particularly preferably 1 to 5% by weight.
-water
As the water, distilled water, tap water, ion-exchanged water, pure water, ultrapure water, industrial water, or the like can be used.
The amount of water to be added is not limited as long as the desired effect can be obtained, and the proportion of water to be added in the heat-generating composition is, for example, 5 to 60% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight.
By containing the metal ion chelating agent, the oxidizable metal powder, the water-soluble salt, and water in this way, the heat-generating composition can generate heat to an appropriate temperature (for example, about 32 to 85 ℃ (measured according to JIS S4100 (2007)) as a heat-generating device, and can effectively suppress an unpleasant odor derived from the heat-generating composition.
In the heat-generating composition, other components than the above-described components may be blended as necessary, and the components may be blended in the heat-generating composition. Examples of such components include, but are not limited to, an oxidation accelerator, a water retention agent, a surfactant, a hydrogen generation inhibitor, a thickener, and an excipient. Among these components, for example, an oxidation accelerator and a water retention agent are described below.
-oxidation promoters
The oxidation accelerator contained in the heat-generating composition is used for the purpose of further accelerating the supply of oxygen to the heat-generating composition, particularly to the oxidizable metal powder, by sucking air. The oxidation accelerator is not limited as long as oxygen can be supplied in this way, and examples thereof include carbon black, black lead, activated carbon, coal, charcoal, bamboo charcoal, graphite, acetylene black, and coffee grounds, carbon black, activated carbon, bamboo charcoal, and coffee grounds are preferable, and carbon black, activated carbon, and bamboo charcoal are more preferable. These may be used alone or in combination of two or more.
The oxidation accelerator is not limited as long as the desired effect can be obtained, and is preferably in the form of powder, granule, fiber, or the like, and may be present alone or in combination of 2 or more, and the average particle size of the oxidation accelerator is preferably 0.001 to 1000 μm, more preferably 0.005 to 500 μm, and most preferably 0.01 to 200 μm, from the viewpoint of comfort when the heat generating device is worn on the body and used, oxygen supply efficiency, and the like.
In addition, although the oxidation accelerator described above may be used when the heat-generating appliance of the present invention contains a perfume, the iodine adsorption performance of the oxidation accelerator is preferably 400mg/g or less on average from the viewpoint of more effectively maintaining the aromaticity derived from the perfume for a long period of time. In this case, the following are listed: the iodine adsorption performance of the oxidation accelerator is more preferably 300mg/g or less on average, still more preferably 250mg/g or less on average, and particularly preferably 200mg/g or less on average. The lower limit of the iodine adsorption performance is not particularly limited, and theoretically, an average of 0mg/g can be exemplified. In addition, when 2 or more oxidation promoters are used in combination at this time, the average of the iodine adsorption performance of the composition (for example, mixture) preferably satisfies the above-mentioned value. The iodine adsorption performance was measured and calculated by a method specified in JISK1474 method. The oxidation accelerator having an average iodine adsorption performance of 400mg/g or less is not limited, and carbon black, charcoal, bamboo charcoal, coffee grounds charcoal, and the like can be exemplified.
The heat generating device of the present invention may generate heat so as to reach an appropriate temperature when applied to the skin, and the temperature may be about 32 to 85 ℃, and more preferably about 40 to 70 ℃ (measured according to JIS S4100 (2007)). From the viewpoint of further efficiently generating heat to a more preferable temperature, the oxidation accelerator preferably has conductivity. The presence or absence of conductivity is known, and examples of the oxidation accelerator having a certain or more conductivity include, but are not limited to, carbon black, black lead, and activated carbon.
In the present invention, the heat generation temperature of the heat generating device is measured in accordance with JIS S4100 (2007). Specifically, the measurement is carried out by superposing a predetermined primer and a predetermined covering material on a warm part defined in JIS S4100 (2007), raising the temperature to 30 ℃ and holding the mixture at ± 1 ℃, while allowing a heat generating device to stand in the atmosphere at the same temperature as the ambient temperature for 2 hours or more to generate heat by the use method, and then measuring the time from the start of heat generation to the time when the maximum temperature is exceeded and the temperature reaches the predetermined temperature by the predetermined method.
The amount of the oxidation accelerator to be blended is not limited as long as the desired effect can be obtained, and the blending ratio of the oxidation accelerator in the heat-generating composition is, for example, 1 to 30% by weight, preferably 3 to 25% by weight, and more preferably 5 to 23% by weight.
The amount of the oxidation accelerator to be added to the oxidizable metal powder is not limited as long as the desired effect can be obtained, and the oxidation accelerator is 2 to 60 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight, based on 100 parts by weight of the oxidizable metal powder.
Water retention agent
The water retaining agent has a function of retaining water, and is not limited as long as it has the function and can obtain a desired effect, and examples thereof include porous materials, water-absorbent resins, and the like. Examples of the water retaining agent include natural and synthetic inorganic substances such as vermiculite, perlite, calcium silicate, kaolin, talc, montmorillonite, mica, bentonite, calcium carbonate, silica gel, alumina, zeolite, silica, diatomaceous earth, and alumina; examples of the inorganic filler include natural and synthetic organic materials such as pulp, wood flour (sawdust), cotton, polyacrylate resin, polysulfonate resin, anhydrous maleate resin, polyacrylamide resin, polyvinyl alcohol resin, polyethylene oxide resin, polyaspartate resin, polyglutamate resin, polyalphaelate resin, starch, and cellulose, and preferably include vermiculite, perlite, silica gel, diatomaceous earth, alumina, wood flour (sawdust), and polyacrylate resin. These may be used alone or in combination of two or more.
The average particle diameter of the water retaining agent is, for example, 0.1 to 3000 μm, preferably 0.5 to 1000 μm, and more preferably 1 to 500 μm, although not limited thereto as long as the desired effect can be obtained. The average particle diameter of the water retaining agent is also measured in the same manner as in the case of the oxidizable metal powder.
The amount of the water retaining agent to be blended is not limited as long as the desired effect can be obtained, and the water retaining agent to be blended in the heat-generating composition is, for example, 1 to 20% by weight, preferably 3 to 15% by weight, and more preferably 5 to 10% by weight.
Among them, particularly, a substance having a porous structure such as vermiculite functions not only as a water retaining agent but also as a substance for providing an air passage.
The total amount of the metal ion chelating agent, the oxidizable metal powder, the water-soluble salt and the water in the heat-generating composition is not limited as long as the desired effect can be obtained, and may be appropriately set so that the heat-generating temperature of the heat-generating composition becomes a temperature suitable for use as a heat generating device (for example, about 32 to 85 ℃ may be exemplified, and about 40 to 70 ℃ may be more preferably exemplified (value measured according to JIS S4100)). When the heat-generating composition further contains an oxidation accelerator and/or a water-retaining agent, the total amount thereof is not limited as long as the desired effect can be obtained, and the heat-generating temperature of the heat-generating composition can be appropriately set so as to be a temperature suitable for use as a heat-generating device.
In one embodiment of the heat-generating composition used in the heat-generating appliance of the present invention, the metal ion chelating agent is 0.0001 to 10 wt%, the oxidizable metal powder is 20 to 80 wt%, the water-soluble salt is 0.1 to 20 wt%, and water is 5 to 60 wt%, but the present invention is not limited thereto.
In another embodiment of the heat-generating composition used in the heat-generating appliance of the present invention, the compounding ratio of the heat-generating composition includes 0.0001 to 10% by weight of the metal ion chelating agent, 20 to 80% by weight of the oxidizable metal powder, 1 to 30% by weight of the oxidation accelerator, 0.1 to 20% by weight of the water-soluble salt, and 5 to 60% by weight of water.
In another embodiment of the heat-generating composition used in the heat-generating appliance of the present invention, the compounding ratio of the heat-generating composition includes 0.0001 to 10% by weight of the metal ion chelating agent, 20 to 80% by weight of the oxidizable metal powder, 0.1 to 20% by weight of the water-soluble salt, 1 to 20% by weight of the water-retaining agent, and 5 to 60% by weight of water.
In another embodiment of the heat-generating composition used in the heat-generating device of the present invention, the compounding ratio of the heat-generating composition includes 0.0001 to 10% by weight of the metal ion chelating agent, 20 to 80% by weight of the oxidizable metal powder, 1 to 30% by weight of the oxidation accelerator, 0.1 to 20% by weight of the water-soluble salt, 1 to 20% by weight of the water-retaining agent, and 5 to 60% by weight of water.
In addition, as one embodiment of the heat-generating composition used in the heat-generating appliance of the present invention, a composition containing trisodium ethylenediaminetetraacetate, iron powder, sodium chloride, and water can be exemplified.
In addition, as one embodiment of the heat-generating composition used in the heat-generating appliance of the present invention, a composition containing trisodium ethylenediaminetetraacetate, iron powder, carbon black having an average iodine adsorption performance of 400mg/g or less and having conductivity, sodium chloride, and water can be exemplified.
As one embodiment of the heat-generating composition used in the heat-generating appliance of the present invention, a composition containing trisodium ethylenediaminetetraacetate, iron powder, carbon black having an average iodine adsorption capacity of 400mg/g or less and having conductivity, sodium chloride, a water-absorbent polymer, vermiculite and water can be exemplified.
The heat-generating composition is prepared by mixing the metal ion chelating agent, the oxidizable metal powder, the water-soluble salt, and water with the other compounding ingredients described above as necessary. The heat-generating composition may be prepared in the presence of oxygen, or may be prepared under vacuum or in an inert gas atmosphere. They can be prepared according to the production steps of conventionally known heat generating devices.
In the heat generating device of the present invention, as described above, the metal ion chelating agent is used in the heat generating device, and therefore, the heat generating device of the present invention can effectively suppress an unpleasant odor derived from the heat generating composition. Further, according to the present invention, even when a fragrance is contained in the heat-generating appliance, the change or disappearance of the fragrance derived from the fragrance can be suppressed, and a desired fragrance can be maintained. In addition, according to the present invention, even when the heat generating device is used after being stored, unpleasant odor can be effectively suppressed, and excellent aroma can be exhibited. In addition, the heat generating device of the present invention can exhibit a sufficient heat generating effect as a heat generating device.
Breathable containing bag for containing exothermic composition
In the heat generating device of the present invention, the heat generating composition is contained in an air-permeable containing bag (hereinafter, sometimes referred to as "containing bag for heat generating composition") for containing the heat generating composition. The air-permeable storage bag for storing the heat-generating composition is not limited as long as it can store the heat-generating composition and has air permeability, and a conventionally known storage bag can be used. For example, as the heat-generating composition-containing bag, a bag having air permeability used in a conventionally known disposable warm patch or the like can be used in view of prevention of leakage of the heat-generating composition, durability against heat generated from the heat-generating composition, and improvement in the feeling of use of the heat-generating device.
More specifically, the heat-generating composition-containing bag may be a bag having a laminate structure in which a resin film having air permeability is laminated on a woven fabric or a nonwoven fabric having air permeability, but the present invention is not limited thereto. In this case, the resin film having air permeability is disposed inside the accommodating bag for the heat-generating composition, and the woven or nonwoven fabric having air permeability is disposed outside the accommodating bag for the heat-generating composition.
The resin used for the breathable resin film is not particularly limited, and a thermoplastic resin is preferably used. Examples of the thermoplastic resin include polyethylene, polypropylene, polyester, polyamide, polyurethane, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polycarbonate, and an ethylene-vinyl acetate copolymer. In addition, from the viewpoint of wearing the heat generating device on the body for use, preferable examples of the thermoplastic resin include polyethylene, polypropylene, ethylene vinyl acetate copolymer, and the like. These may be used alone or in combination of two or more.
The resin film having air permeability used in the present invention has fine pores for ensuring air permeability in at least a part of the resin film made of the resin. The pores are not limited as long as the pores are of such a size that air can pass through the inside and outside of the heat-generating composition storage bag and the heat-generating composition can be prevented from leaking out of the storage bag. In addition, since the sensible temperature of the heat-generating device during use can also be controlled by the air permeability of the heat-generating composition storage bag, the size, shape, and number of the pores may be appropriately determined in consideration of the sensible temperature of the heat-generating device during use. Means for providing the resin film with fine pores are also conventionally known and can be performed according to conventional procedures.
Examples of the fiber material of the air-permeable woven or nonwoven fabric include synthetic fibers such as nylon, vinylon, polyester, rayon, acrylic resin, polyethylene, polypropylene, acetate, polyvinyl chloride, and polybutylene terephthalate; natural fibers such as cotton, hemp, silk, paper, and the like; and a mixed fiber of a synthetic fiber and a natural fiber. From the viewpoint of the feeling of use, the fiber material may be nylon, polyester, polypropylene, or the like, and more preferably nylon or polyester. These may be used alone or in combination of two or more. The woven or nonwoven fabric is not limited as long as it can allow air to pass through the inside and outside of the bag for containing the heat-generating composition and prevent the heat-generating composition from leaking out of the bag, and the weight per unit area thereof is preferably 25 to 70g/m2。
The laminate of the resin film having air permeability and the woven or nonwoven fabric having air permeability is not limited as long as the resulting laminate has strength as a storage bag for the heat-generating composition and ensures air permeability. As an example, the layers can be laminated by a lamination method, and the following can be exemplified: a method of laminating by thermal bonding as a lamination method; and a method of laminating with an adhesive such as a hot melt adhesive, an acrylic adhesive, or a urethane adhesive. The laminate of these components may be formed on the entire surface of the heat-generating composition storage bag or may be partially laminated as long as the desired effect can be obtained.
Further, a storage bag that is commercially available as a storage bag for a heat-generating composition may be used.
The size and shape of the heat-generating composition storage bag are not limited as long as the desired effect can be obtained, and may be appropriately determined according to the purpose of use.
For example, when the heat-generating appliance of the present invention is used by being attached to clothes, skin, or the like, an adhesive sheet for fixing the heat-generating appliance of the present invention to clothes, skin, or the like with a force capable of peeling the heat-generating appliance of the present invention from the clothes, skin, or the like may be provided outside the heat-generating composition storage bag. As an example of such a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet used in a conventionally known so-called adhesive disposable warm patch or a direct-stick pressure-sensitive adhesive sheet is used.
Perfume
The heating device of the present invention may contain a perfume, which may be appropriately determined depending on the use and interest, but is not limited thereto, and may use a natural perfume such as essential oil alone or in combination, or may use a synthetic simple perfume alone or in combination, and further may use a natural perfume and a synthetic perfume as a blending perfume, the natural perfume (essential oil) may be exemplified by vanilla, lavender, chamomile, rosemary, sage, citronella, ginger, ylang-ylang essence, eucalyptus, mint, rose, lily, lilac, jasmine, cardamom, citronella, orange, lemon, lime, grapefruit, orange flower, cedar, sandalwood, anise, caraway, amber, musk, civet, castoregano, synthetic simple perfumes, as well as phenyl fever, C6 to C16 aldehyde, allyl hexanoate, amyl cinnamaldehyde, amyl salicylate, benzaldehyde, benzyl acetate, benzyl alcohol, borneol, cinnamyl alcohol, citral, citronellol, jasmonic acid, geranyl alcohol, jasmonic acid, geranyl alcohol, linalyl alcohol, geranyl alcohol, dihydrogeranyl alcohol, geranyl alcohol, linalyl alcohol, geranyl alcohol, dihydrogeranyl alcohol, geranyl.
The amount of the perfume to be added to the heat-generating device of the present invention is not limited as long as the desired effect can be obtained, and when the perfume is contained, the amount of the perfume is 0.0001 to 10 parts by weight, preferably 0.001 to 7 parts by weight, and more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the heat-generating composition.
The fragrance is preferably 0.0001 to 20 parts by weight, more preferably 0.001 to 15 parts by weight, and still more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the oxidizable metal powder in the heat-generating composition.
When an oxidation accelerator is contained in the heat-generating composition, the amount of the fragrance is 0.0003 to 500 parts by weight, preferably 0.03 to 100 parts by weight, and more preferably 0.17 to 50 parts by weight, based on 100 parts by weight of the oxidation accelerator in the heat-generating composition.
When the heat generating device of the present invention contains a perfume, the perfume is not limited as long as the perfume can be imparted to the heat generating device, and the perfume may be contained in the air-permeable containing bag or may be present outside the containing bag.
More specifically, when the heat-generating device of the present invention contains a perfume, for example, the perfume may be contained in a storage bag in a state of being mixed with each component to be mixed with the heat-generating composition, the perfume may be contained in at least a part of the storage bag for the heat-generating composition, or the perfume may be contained in a different sheet, an optional adhesive component, or the like in advance, or may be contained in a different storage bag having air permeability, and the sheet, the adhesive component, the storage bag, or the like may be disposed inside and/or outside the storage bag for the heat-generating composition.
When the perfume is mixed with each of the compounding ingredients in the heat-generating composition, for example, the perfume itself may be mixed with each of the compounding ingredients, or a mixture obtained by mixing water or the like with the perfume using a surfactant or the like may be mixed with each of the compounding ingredients, or the perfume and the mixture may be enclosed in a conventionally known microcapsule in advance, and the enclosed microcapsule obtained may be mixed with each of the compounding ingredients, or the perfume and the mixture may be supported on a carrier and then mixed with each of the compounding ingredients. From the viewpoint of preventing as much as possible the adhesion of the fragrance to the respective compounding ingredients in the heat-generating composition, particularly from the viewpoint of preventing as much as possible the adhesion of the fragrance to the oxidation accelerator and the oxidizable metal powder, for example, it is preferable that the fragrance is carried in advance on the carrier and then mixed with the respective compounding ingredients. Such a carrier is not limited as long as the effect of the present invention is not impaired, and examples thereof include silica, vermiculite, perlite, fluorite, zeolite, microsilica, pulp, plastic, rubber, elastomer, and the like. The particle size of the carrier is not limited as long as the effect of the present invention is not impaired, and the average particle size is, for example, about 0.1 to 3000 μm, preferably about 0.5 to 1000 μm, and more preferably about 1 to 500 μm. The amount of the carrier to be added is not limited as long as the effect of the present invention is not impaired.
When the heat-generating composition is loaded, for example, a perfume may be loaded on the components contained in the heat-generating composition. In the case where the heat-generating composition contains an oxidation promoter in addition to the metal ion chelating agent and the oxidizable metal powder in the heat-generating composition, it is preferable to load the fragrance on components other than the metal ion chelating agent, the oxidizable metal powder, and the oxidation promoter from the viewpoint of the influence on heat generation. For example, when the heat-generating composition contains a water-retaining agent, the water-retaining agent contained in the heat-generating composition is preferably loaded with a perfume.
When the heat-generating composition storage bag contains a perfume in at least a part thereof as described above, the perfume may be contained in the storage bag by immersing the perfume in the storage bag in advance, or may be contained by mixing the perfume into at least one of a film, a woven fabric, and a nonwoven fabric constituting the storage bag in advance. The perfume may be encapsulated in microcapsules and contained by being attached to at least one of a film, a woven fabric, and a nonwoven fabric constituting the storage bag.
In addition, when the flavorant is contained in advance in another sheet, an optional adhesive component, or in another permeable storage bag, and the sheet, the adhesive component, the storage bag, or the like is disposed inside and/or outside the heat-generating composition storage bag, as described above, for example, as the sheet, the adhesive component, or the like, an adhesive sheet used in a conventionally known so-called stick-type disposable warm patch, a direct-stick type adhesive sheet, an adhesive component used in these, or the like can be cited, and as the permeable storage bag in which the flavorant is contained in advance, the same storage bag as the heat-generating composition storage bag can be cited.
Since the heat generating device of the present invention uses the metal ion chelating agent, even when the heat generating device contains a perfume, the change or disappearance of the fragrance derived from the perfume can be suppressed while suppressing the taste of the base, and a desired fragrance can be maintained. Further, according to the present invention, even when the heat generating device is used after being stored, since the unpleasant odor can be effectively suppressed as described above, the heat generating device can exhibit excellent aromaticity derived from the perfume. In addition, according to the heat generating device of the present invention, even when the fragrance is contained, a sufficient heat generating effect can be exhibited as the heat generating device.
In addition, the present invention is not limited thereto, and when a fragrance is contained and an oxidation promoter is contained, by using an oxidation promoter having an average iodine adsorption performance of 400mg/g or less, it is possible to more effectively suppress the taste of the base and to exhibit excellent aromaticity derived from the fragrance. In particular, when an oxidation accelerator having an average iodine adsorption property of 400mg/g or less is used, even if the heat-generating device of the present invention is stored in an environment where contact between the heat-generating device and oxygen is inhibited even when the fragrance and the heat-generating composition are present in a state where they are in contact with each other, the disappearance or change of the fragrance during storage can be further effectively suppressed or prevented.
Further, when the perfume is a perfume having a soothing effect such as lavender or chamomile, it can be said that the heat generating device containing such a perfume further has a soothing effect. When the perfume contained in the heater is a perfume having an insect repellent effect, such as eucalyptus, the heater of the present invention can be said to have an insect repellent effect. As described above, the heat generating device of the present invention can be said to have an effect (function) according to the characteristics of the perfume used. The effects (functions) of the individual perfumes have been known.
The heat generating device of the present invention may contain an optional component in addition to the perfume. Examples of such components include insect-repellent components such as pyrethroids and p-menthane; other soothing components such as Capsici fructus extract and vanillylnonanoic acid amide; the cooling component such as l-menthol or camphor may contain any component within a range not interfering with the effect of the present invention. The amount of these additives may be appropriately set within a range not to impair the effects of the present invention.
Heating appliance
The heat generating device of the present invention comprises the heat generating composition, and at least the heat generating composition is contained in a permeable containing bag. The heat-generating device of the present invention is produced by containing the heat-generating composition prepared as described above in the air-permeable containing bag, and further containing a perfume as described above if necessary, and further containing an optional component as appropriate if necessary.
The heat generating device thus manufactured is generally provided and stored in a state of being further packed in an oxygen-impermeable and gas-impermeable outer bag to maintain airtightness. The heat-generating device of the present invention generates heat from the heat-generating composition by contact with oxygen, and therefore it is important that the heat-generating device is stored so as not to generate heat until use, and not to contact oxygen. The heat generating device of the present invention may be used by opening the outer bag to take out the heat generating device from the outer bag and bringing the heat generating composition into contact with oxygen to generate heat. The outer bag used herein is not particularly limited as long as it is an oxygen-impermeable and gas-impermeable bag.
Such a heat generating device can be used for the purpose of heat preservation, blood circulation promotion, fatigue alleviation, relaxation, and the like, and therefore, can be used as a heat preserving device such as a disposable warm patch, a medical device such as a blood circulation promotion device, a fatigue alleviation device, a thermotherapy device, or the like, an aromatic device, an insect repellent device, and the like. When the heat generating device of the present invention contains a perfume, the heat generating device may be referred to as a heat insulating device to which a perfume is added, for example. The heat generating device of the present invention is further valuable in terms of the effects (functions) of the fragrance and the effects (functions) of any component.
As described above, the heat generating device of the present invention contains the metal ion chelating agent, and therefore, can effectively suppress an unpleasant odor derived from the heat generating composition. Further, according to the present invention, even when a fragrance is contained in the heat-generating appliance, the change or disappearance of the fragrance derived from the fragrance can be suppressed, and a desired fragrance can be maintained. In addition, according to the present invention, even when the heat generating device is used after being stored, unpleasant odor can be effectively suppressed, and excellent aroma can be exhibited. In addition, the heat generating device of the present invention can exhibit a sufficient heat generating effect as a heat generating device.
In addition, even when the heat generating device of the present invention contains an oxidation accelerator, the desired effect described above can be obtained, and the heat generating effect can be more effectively exhibited. When the heat generating device of the present invention contains an oxidation promoter and a fragrance, the use of an oxidation promoter having an average iodine adsorption capacity of 400mg/g or less can further effectively suppress the change or disappearance of the fragrance derived from the fragrance and maintain the desired fragrance. In addition, the heat generating device of the present invention can further exhibit the heat generating effect as a heat generating device, particularly a disposable warm patch, with high efficiency by using an oxidation accelerator having a certain or more conductivity. Further, the heat generating device of the present invention can further effectively maintain desired aromaticity and can further efficiently exhibit a heat generating effect as a heat generating device, particularly a disposable warm patch, by using an oxidation accelerator having iodine adsorption performance of 400mg/g or less on average and having conductivity.
Further, since the heat generating device of the present invention contains the metal ion chelating agent, the heat generating device can exhibit excellent aromaticity in use even when the heat generating device is stored for a long period of time in a state where a perfume for perfuming the heat generating device is in contact with the heat generating composition. Thus, in the heat-generating device of the present invention, the fragrance and the heat-generating composition may be present in advance in a state where they are in contact with each other, or may be present in advance in a state where they are not in contact with each other. In the heat generating device of the present invention, the fragrance may be impregnated in the space inside the outer bag by disposing the fragrance outside the heat generating composition containing bag without directly contacting the heat generating composition and packaging and storing the fragrance in the non-air-permeable outer bag. Even in such a case, according to the heat-generating device of the present invention, the deterioration and disappearance of the fragrance in the heat-generating composition can be suppressed and prevented, and therefore, according to the present invention, a heat-generating device having all configurations in which the positional relationship between the fragrance and the heat-generating composition is not limited can be obtained.
In addition, according to the heat-generating device of the present invention, the kind of the perfume is not limited, and thus a desired perfume can be widely used.
The present inventors considered that the cause of the occurrence of a unique unpleasant odor derived from the heat-generating composition and the change in the fragrance in the heat-generating appliance may be: transition metal ions such as iron present in the heat-generating composition, etc. are present alone or together with other components in the heat-generating composition to form compounds or complexes, and act as catalysts, and the catalytic action promotes addition reactions, substitution reactions, coupling reactions, etc. of the various components present in the heat-generating appliance, thereby converting the various components into substances that generate odors. In particular, it is considered possible to: transition metal ions such as iron act on components such as the water-absorbent resin (for example, unsaturated low-molecular substances such as sodium polyacrylate monomers) to convert the components into substances that generate unpleasant odors. In addition, it is considered possible to: when the heat generating device contains a perfume, the transition metal ion or the like acts as a catalyst to promote an addition reaction, a substitution reaction, a coupling reaction, or the like, and also converts the components constituting the perfume into a substance that generates a different odor from the original components. The present invention has been completed based on the findings of the independent findings of the present inventors, and the findings are: the use of a metal ion chelating agent enables suppression of unpleasant base odor of a heat generating appliance, and further suppression of flavor change during storage and use without impairing the heat generating characteristics of the heat generating appliance, and thus the present invention has been completed.
In addition, the present invention can provide a method for suppressing generation of unpleasant odor and/or flavor change in a heat-generating appliance, including a step of storing a heat-generating composition containing a metal ion chelating agent, an oxidizable metal powder, a water-soluble salt, and water in a storage bag having air permeability. The present invention can also provide a method for suppressing the occurrence of unpleasant odor and/or flavor change in a heat-generating appliance, which comprises a step of accommodating a heat-generating composition further containing an oxidation accelerator and/or a water-retaining agent in an air-permeable accommodating bag. The present invention may also provide a method for suppressing generation of unpleasant odor and/or change in fragrance in a heat-generating appliance, which further comprises a step of including a perfume. Further, the present invention may also provide a method for suppressing the generation of unpleasant odor and/or change in fragrance in a heat-generating appliance by using the heat-generating appliance. The present invention can also provide a heat-generating appliance used in a method for suppressing the generation of unpleasant odor and/or change in flavor in the heat-generating appliance. The present invention can also provide a use of the heat generating device for manufacturing a heat generating device in which generation of an unpleasant odor and/or a change in flavor is suppressed. The heat generating device, the components used in these methods, the amounts of the components to be mixed, the production method, the application method, and the like are described in the same manner as described above.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.
Test example 1
(1) Production of Heat generating device (examples 1 to 5)
The heat generating devices having the structures shown in fig. 4 and 1 (examples 1 to 5) were produced in the following manner.
First, the following components were used as the heat-generating composition.
< Heat-generating composition >
Iron powder (DOWA IP CREATION CO., LTD. product name DKP, average particle size 100 μm)
Carbon Black (Mitsubishi chemical, trade name RCF, iodine adsorption 144mg/g, average particle diameter 0.075 μm)
Trisodium ethylenediaminetetraacetate (KISHIDA CHEMICAL Co., Ltd., product name Special grade trisodium ethylenediaminetetraacetate (hydrate))
Water
Vermiculite (average particle size about 500 μm)
Water-absorbent Polymer (crosslinked acrylic acid Polymer partial salt, average particle diameter 250 μm)
Salt
In addition, in the production of a heat generating device containing a perfume, the following perfumes were used.
< fragrance >
Floral (floral) (spice No. BR12942, product of Xiaochuan spice Co., Ltd.)
Rose fragrance (fragrance) (fragrance No. OFR3386, available from Changchuan fragrance Co., Ltd.)
Fruity (fruity) (flavor No. OFR3363, available from Changchuan flavor Co., Ltd.)
Soap (soap) (spice No. BR3906, product of Xiaochuan spice Co., Ltd.)
The respective components of the heat-generating composition are mixed to obtain a mixture. The blending ratios of the iron powder, the carbon black, the trisodium ethylenediamine tetraacetate, the water, the vermiculite, the water-absorbent polymer, and the salt were 50 wt%, 20 wt%, 0.1 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. The resultant mixture was contained in a breathable container bag (130 × 95mm) (e.g., corresponding to 1 in fig. 4) made of a porous film (product name ブレスロン) to which a non-breathable adhesive sheet (product name ニトタック, manufactured by NITTO liftec corporation, for example, corresponding to 5 and 6 in fig. 4) was partially attached, and sealed, thereby obtaining a heat generating device (example 1). Thereafter, the heat generating device of example 1 was quickly accommodated in a non-air-permeable outer bag for disposable warm patch. Thus, a heat generating device containing no perfume was produced.
The heat generating device containing perfume was produced in the following manner. Each component of the heat-generating composition is mixed with each perfume to obtain a mixture. The blending ratios of the iron powder, carbon black, trisodium ethylenediamine tetraacetate, water, vermiculite, water-absorbent polymer, salt, and perfume were 50 wt%, 20 wt%, 0.1 wt%, 20.3 wt%, 5 wt%, 2.5 wt%, 2 wt%, and 0.1 wt%, respectively. The resulting mixture was stored in a breathable storage bag (130 × 95mm) made of a porous film partially equipped with a non-breathable adhesive sheet and sealed (for example, corresponding to 1, 5, and 6 in fig. 1) in the same manner as in example 1, thereby obtaining a heat-generating device. The resulting heat generating device was then quickly contained in a non-breathable outer bag for disposable warm patches.
Among the above-mentioned perfumes, a heat generating device having a floral fragrance was named as example 2, a heat generating device having a rose fragrance was named as example 3, a heat generating device having a fruit fragrance was named as example 4, and a heat generating device having a soap fragrance was named as example 5.
(2) Production of Heat generating device (examples 6 to 10)
A heat-generating device was produced by the same procedure except that trisodium citrate (purified sodium citrate M, trade name, manufactured by Hibiscus chemical Co., Ltd.) was used in place of trisodium ethylenediamine tetraacetic acid (examples 6 to 10). A heat-generating device containing no perfume was used as example 6, a heat-generating device containing a flower fragrance was used as example 7, a heat-generating device containing a rose fragrance was used as example 8, a heat-generating device containing a fruit fragrance was used as example 9, and a heat-generating device containing a soap fragrance was used as example 10.
(3) Production of comparative Heat-generating appliances (comparative examples 1 to 5)
Comparative heat-generating devices (comparative examples 1 to 5) were produced in the same manner as in examples 1 to 5 except that the comparative examples did not contain a metal ion chelating agent. The blending ratios of the iron powder, the carbon black, the water, the vermiculite, the water-absorbent polymer, and the common salt in comparative example 1 were 50 wt%, 20 wt%, 20.5 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. In comparative examples 2 to 5, the blending ratios of the iron powder, carbon black, water, vermiculite, water-absorbent polymer, salt, and flavor were 50 wt%, 20 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, 2 wt%, and 0.1 wt%, respectively. A comparative heat generating device containing no perfume was defined as comparative example 1, a comparative heat generating device containing a floral fragrance was defined as comparative example 2, a comparative heat generating device containing a rose fragrance was defined as comparative example 3, a comparative heat generating device containing a fruit fragrance was defined as comparative example 4, and a comparative heat generating device containing a soap fragrance was defined as comparative example 5.
(4) Evaluation of Heat generating implement
In examples 1 to 10 and comparative examples 1 to 5, the outer bag was opened before and after storage, and each heat generating device was taken out, and the fragrance intensity, the fragrance change, and the heat generating characteristics of each heat generating device were evaluated. Specifically, the non-breathable outer bags of examples 1 to 10 and comparative examples 1 to 5 were opened before storage (24 hours after production), and the flavor intensity and the temperature of the outer bags 1 hour after opening were evaluated. Further, examples 1 to 10 and comparative examples 1 to 5 were stored in a thermostatic bath at 50 ℃ for 14 days in the presence of oxygen, and then the outer bag was opened in the same manner, and the fragrance intensity, the change in fragrance, and the temperature after opening for 1 hour were evaluated. The storage conditions correspond to 9 months at room temperature (25 ℃).
More specifically, 5 subjects smell the fragrance of each heat generating device taken out of the outer bag, and the fragrance intensity and the change in fragrance were evaluated in 5 stages 1 to 5 described below. A higher value of the fragrance intensity indicates a stronger smell. The smaller the value of the change in the fragrance, the smaller the change in the odor before and after storage. In addition, the temperature of each heat generating device was evaluated at the same time. The temperatures are the following values: the value of the outer bag after being opened for 1 hour was measured by superposing a predetermined primer and a predetermined covering material on a warm portion defined in JIS S4100 (2007), raising the temperature to 30 ℃ and holding the same at ± 1 ℃, and placing a heat generating device in the same atmosphere as the ambient temperature to generate heat by the use method.
< fragrance intensity >
1: has no odor
2: weak smell
3: has odor
4: strong smell
5: has strong smell
< aroma Change >
1: is completely unchanged
2: slightly changed
3: small amount of change
4: variations in
5: obvious change of
(5) Results
The evaluation results of the heat generating devices of examples 1 to 10 are shown in Table 1.
[ Table 1]
The evaluation results of the heat generating devices of comparative examples 1 to 5 are shown in Table 2.
[ Table 2]
As is clear from table 1, in the case of containing the metal ion chelating agent, the odor was not substantially perceived before storage (in the "initial stage" in the table) in examples 1 and 6 containing no perfume. In addition, the odor was clearly perceived in examples 2 to 5 and 7 to 10 containing the perfume. The presence or absence of these odors depends on the presence or absence of a perfume, and an unpleasant odor derived from the heat-generating composition is not perceived. The same tendency was observed in examples 1 to 10 after storage, and it was found that: the aroma was not substantially changed by the storage. In particular, the odor in examples 2 to 5 and 7 to 10 was derived from the fragrance contained in each heat-generating device before and after storage, and the fragrance was very good without substantially deteriorating even when stored.
In addition, with respect to the heat generation temperature, it is known that: the temperature 1 hour after unsealing was 55 ℃ both before and after storage, and was sufficiently useful as a heat generating device, particularly a disposable warm patch.
On the other hand, when the metal ion chelating agent was not contained, as is clear from the results of comparative example 1 in table 2, before and after the storage, the odor was clearly perceived even though the fragrance was not contained. The odor is an unpleasant odor derived from the heat-generating composition. In comparative examples 1 to 5, the change in fragrance due to storage was clearly observed in the case where the metal ion chelating agent was not contained. The change in the fragrance is considered to be caused by the fact that the above-mentioned unpleasant odor is not sufficiently suppressed, and that the components contained in the heat generating device such as a perfume are deteriorated.
Thus, it can be seen that: by using the metal ion chelating agent, it is possible to effectively suppress an unpleasant odor derived from the heat-generating composition, and to effectively suppress a change in fragrance regardless of the presence or absence of fragrance. In addition, it can be seen that: by using the metal ion chelating agent, the fragrance derived from the perfume can be effectively sustained even after storage.
Test example 2
(1) Production of Heat-generating appliances (examples 11 to 15)
The heat generating devices (examples 11 to 15) having the structures shown in FIG. 4 and FIG. 1 were produced in the following manner.
First, the following components were used as the heat-generating composition.
< Heat-generating composition >
Iron powder (DOWA IP CREATION CO., LTD. product name DKP, average particle size 100 μm)
Activated carbon (Futamura CHEMICAL CO., LTD., trade name Taige activated carbon, iodine adsorption capacity 1050mg/g, average particle diameter 100 μm)
Trisodium ethylenediaminetetraacetate (KISHIDA CHEMICAL Co., Ltd., product name Special grade trisodium ethylenediaminetetraacetate (hydrate))
Water
Vermiculite (average particle size about 500 μm)
Water-absorbent Polymer (crosslinked acrylic acid Polymer partial salt, average particle diameter 250 μm)
Salt
In addition, in the manufacture of containing perfume heating appliance, perfume using the 4 kinds.
The respective components of the heat-generating composition are mixed to obtain a mixture. The blending ratios of the iron powder, the activated carbon, the trisodium ethylenediamine tetraacetate, the water, the vermiculite, the water-absorbent polymer, the salt, and the flavor were 50 wt%, 20 wt%, 0.1 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. The resulting mixture was stored in a breathable storage bag (130 × 95mm) made of a porous film partially equipped with a non-breathable adhesive sheet and sealed in the same manner as in example 1, to obtain a heat-generating device (example 11). Thereafter, the heat generating device of example 11 was quickly accommodated in a non-air-permeable outer bag for disposable warm patch. Thus, a heat-generating device containing no perfume was produced.
The heat generating device containing perfume was produced in the following manner. Each component of the heat-generating composition is mixed with each perfume to obtain a mixture. Here, the blending ratios of the iron powder, the activated carbon, the trisodium ethylenediamine tetraacetic acid, the water, the vermiculite, the water-absorbent polymer, the salt, and the flavor were 50 wt%, 18 wt%, 0.1 wt%, 18.4 wt%, 4.5 wt%, 2.5 wt%, 2 wt%, and 4.5 wt%, respectively. The resulting mixture was contained in an air-permeable containing bag (130 × 95mm) made of a porous film partially equipped with a non-air-permeable adhesive sheet in the same manner as in example 11, and sealed to obtain a heat-generating device. The resulting heat generating device was then quickly contained in a non-breathable outer bag for disposable warm patches.
Among the above-mentioned perfumes, a heat-generating device having a floral fragrance was used as example 12, a heat-generating device having a rose fragrance was used as example 13, a heat-generating device having a fruit fragrance was used as example 14, and a heat-generating device having a soap fragrance was used as example 15.
(2) Production of Heat-generating devices (examples 16 to 20)
A heat-generating device (examples 16 to 20) was produced in the same manner as in examples 11 to 15, except that trisodium citrate (product name of "refined sodium citrate M", manufactured by Hibiscus chemical Co., Ltd.) was used in place of trisodium ethylenediamine tetraacetate. A heat-generating device containing no perfume was used as example 16, a heat-generating device containing a flower fragrance was used as example 17, a heat-generating device containing a rose fragrance was used as example 18, a heat-generating device containing a fruit fragrance was used as example 19, and a heat-generating device containing a soap fragrance was used as example 20.
(3) Production of comparative Heat-generating appliances (comparative examples 6 to 10)
As comparative examples, comparative heat-generating appliances (comparative examples 6 to 10) were produced in the same manner as in examples 11 to 15 except that the metal ion chelating agent was not contained. The blending ratios of the iron powder, the activated carbon, the water, the vermiculite, the water-absorbent polymer, and the common salt in comparative example 6 were 50 wt%, 20 wt%, 20.5 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. In comparative examples 7 to 10, the blending ratios of the iron powder, the activated carbon, the water, the vermiculite, the water-absorbent polymer, the salt, and the flavor were 50 wt%, 18 wt%, 18.5 wt%, 4.5 wt%, 2.5 wt%, 2 wt%, and 4.5 wt%, respectively. A comparative heat-generating device containing no perfume was set as comparative example 6, a comparative heat-generating device containing a flower fragrance was set as comparative example 7, a comparative heat-generating device containing a rose fragrance was set as comparative example 8, a comparative heat-generating device containing a fruit fragrance was set as comparative example 9, and a comparative heat-generating device containing a soap fragrance was set as comparative example 10.
(4) Evaluation of Heat generating implement
The fragrance intensity before storage, the temperature after opening the outer bag for 1 hour, the fragrance intensity after storage in a thermostatic bath at 50 ℃ for 14 days in the presence of oxygen, the fragrance change, and the temperature after opening the outer bag for 1 hour of examples 11 to 20 and comparative examples 6 to 10 were evaluated in the same manner as in test example 1.
(5) Results
The evaluation results of the heat generating devices of examples 11 to 20 are shown in Table 3.
[ Table 3]
The evaluation results of the heat generating devices of comparative examples 6 to 10 are shown in Table 4.
[ Table 4]
As is clear from Table 3, before preservation, the fragrance was not substantially perceived in examples 11 and 16 which did not contain fragrance. On the other hand, in examples 12 to 15 and 17 to 20 containing a perfume, a very strong odor was observed. The presence or absence of these odors is based on the presence or absence of a perfume, and an unpleasant odor derived from the heat-generating composition is not perceived. In examples 12 to 15 and 17 to 20, the odor sensed was derived from the fragrance contained in each heat generator. Further, in examples 11 to 20, no change in fragrance was observed due to storage, and the fragrance was not substantially deteriorated even when the storage was carried out, and the aroma was very good. In examples 12 to 15 and 17 to 20, the strength of the fragrance after storage was reduced, and this is considered to be because the activated carbon having high iodine adsorption performance adsorbs the fragrance (aroma). The heat generation temperature is known as follows: the temperature 1 hour after unsealing was 55 ℃ both before and after storage, and was sufficiently useful as a heat generating device, particularly a disposable warm patch.
On the other hand, when the metal ion chelating agent is not contained, a change in fragrance tends to be noticeable during storage, and it is considered that the change in fragrance is caused by the deterioration of components contained in a heat generating device such as a perfume.
In addition, the fragrance intensity after storage was reduced in all of examples 12 to 15 and 17 to 20 and comparative examples 7 to 10, and as described above, in examples 12 to 15 and 17 to 20, the change in fragrance was significantly suppressed, so it was found that: according to examples 12 to 15 and 17 to 20, desired aromaticity derived from a perfume can be stably exerted.
Thus, it can be seen that: even in the case of using activated carbon having a high iodine adsorption property, the use of the metal ion chelating agent can significantly suppress the change in the fragrance, and a heat generating device superior to the case of not using the metal ion chelating agent can be obtained.
Test example 3
(1) Production of Heat-generating devices (examples 21 to 25)
The heat generating devices (examples 21 to 25) having the structures shown in FIG. 4 and FIG. 1 were produced in the following manner.
First, the following components were used as the heat-generating composition.
< Heat-generating composition >
Iron powder (DOWA IP CREATION CO., LTD. product name DKP, average particle size 100 μm)
Bamboo charcoal (Kiriya Chemical Co., Ltd., trade name bamboo charcoal パウダー, iodine adsorption capacity 338mg/g, average particle diameter 50 μm)
Trisodium ethylenediaminetetraacetate (KISHIDA CHEMICAL Co., Ltd., product name Special grade trisodium ethylenediaminetetraacetate (hydrate))
Water
Vermiculite (average particle size 500 μm)
Water-absorbent Polymer (crosslinked acrylic acid Polymer partial salt, average particle diameter 250 μm)
Salt
In addition, in the manufacture of containing perfume heating appliance, perfume using the 4 kinds.
The respective components of the heat-generating composition are mixed to obtain a mixture. Here, the blending ratios of the iron powder, bamboo charcoal, trisodium ethylenediamine tetraacetate, water, vermiculite, water-absorbent polymer, and common salt were 50 wt%, 20 wt%, 0.1 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. The resulting mixture was stored in a breathable storage bag (130 × 95mm) made of a porous film partially equipped with a non-breathable adhesive sheet and sealed in the same manner as in example 1, to obtain a heat-generating device (example 21). Thereafter, the heat generating device of example 21 was quickly accommodated in a non-air-permeable outer bag for disposable warm patch. Thus, a heat-generating device containing no perfume was produced.
The heat generating device containing perfume was produced in the following manner. Each component of the heat-generating composition is mixed with each perfume to obtain a mixture. Here, the blending ratios of the iron powder, bamboo charcoal, trisodium ethylenediamine tetraacetate, water, vermiculite, water-absorbent polymer, salt, and perfume were 50 wt%, 20 wt%, 0.1 wt%, 20.3 wt%, 5 wt%, 2.5 wt%, 2 wt%, and 0.1 wt%, respectively. The resulting mixture was contained in an air-permeable containing bag (130 × 95mm) made of a porous film partially equipped with a non-air-permeable adhesive sheet in the same manner as in example 21, and sealed to obtain a heat-generating device. The resulting heat generating device was then quickly contained in a non-breathable outer bag for disposable warm patches.
Among the above-mentioned perfumes, a heat-generating device having a floral fragrance was used as example 22, a heat-generating device having a rose fragrance was used as example 23, a heat-generating device having a fruit fragrance was used as example 24, and a heat-generating device having a soap fragrance was used as example 25.
(2) Production of Heat-generating devices (examples 26 to 30)
A heat-generating device (examples 26 to 30) was produced in the same manner as in examples 21 to 25, except that trisodium citrate (product name of "refined sodium citrate M", manufactured by Hibiscus chemical Co., Ltd.) was used in place of trisodium ethylenediamine tetraacetate. A heat-generating device containing no perfume was used as example 26, a heat-generating device containing a flower fragrance was used as example 27, a heat-generating device containing a rose fragrance was used as example 28, a heat-generating device containing a fruit fragrance was used as example 29, and a heat-generating device containing a soap fragrance was used as example 30.
(3) Production of comparative Heat-generating appliances (comparative examples 11 to 15)
As comparative examples, comparative heat-generating appliances (comparative examples 11 to 15) were produced in the same manner as in examples 21 to 25 except that the metal ion chelating agent was not contained. The blending ratios of the iron powder, bamboo charcoal, water, vermiculite, water-absorbent polymer, and common salt in comparative example 11 were 50 wt%, 20 wt%, 20.5 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. In comparative examples 12 to 15, the blending ratios of the iron powder, bamboo charcoal, water, vermiculite, water-absorbent polymer, salt, and perfume were 50 wt%, 20 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, 2 wt%, and 0.1 wt%, respectively. A comparative heat-generating device containing no perfume was comparative example 11, a comparative heat-generating device containing a floral fragrance was comparative example 12, a comparative heat-generating device containing a rose fragrance was comparative example 13, a comparative heat-generating device containing a fruit fragrance was comparative example 14, and a comparative heat-generating device containing a soap fragrance was comparative example 15.
(4) Evaluation of Heat generating implement
The fragrance intensity before storage, the temperature after opening the outer bag for 1 hour, the fragrance intensity after storage in a thermostatic bath at 50 ℃ for 14 days in the presence of oxygen, the fragrance change, and the temperature after opening the outer bag for 1 hour of examples 21 to 30 and comparative examples 11 to 15 were evaluated in the same manner as in test example 1.
(5) Results
The evaluation results of the heat generating devices of examples 21 to 30 are shown in Table 5.
[ Table 5]
The evaluation results of the heat generating devices of comparative examples 11 to 15 are shown in Table 6.
[ Table 6]
As is clear from Table 5, before preservation, the fragrance was not substantially perceived in examples 21 and 26 which did not contain fragrance. In contrast, before preservation, the fragrance was clearly perceived in examples 22 to 25 and 27 to 30 containing the fragrance. The presence or absence of these odors is based on the presence or absence of fragrance. In addition, the odors sensed in examples 22 to 25 and 27 to 30 were odors derived from the perfumes contained in the respective heat generating devices. In any of examples 21 to 30, no unpleasant odor derived from the heat-generating composition was observed.
In examples 22 to 25 and 27 to 30, it was confirmed that the fragrance intensity after storage tended to decrease, and the change in fragrance was significantly suppressed as compared with the case shown in Table 6 where the metal ion chelating agent was not contained. Thus, it can be seen that: even when the fragrance intensity is lowered, the desired aromaticity can be maintained by containing a metal ion chelating agent.
In comparative example 11 containing no metal ion chelating agent, a noticeable odor was perceived before storage in spite of the absence of a perfume. The odor is an unpleasant odor derived from the heat-generating composition.
The heat generation temperature is known as follows: the temperature 1 hour after unsealing was sufficiently 50 ℃ before and after storage, and the heat generating device was also useful.
Thus, it can be seen that: according to the heat-generating appliance of the present invention using the metal ion chelating agent, an unpleasant odor derived from the heat-generating composition can be effectively suppressed, and a change in fragrance can be effectively suppressed even when the fragrance intensity is reduced by storage.
Test example 4
(1) Production of Heat-generating device (examples 31 to 35)
The heat generating devices (examples 31 to 35) having the structures shown in FIG. 4 and FIG. 1 were produced in the following manner.
First, the following components were used as the heat-generating composition.
< Heat-generating composition >
Iron powder (DOWA IP CREATION CO., LTD. product name DKP, average particle size 100 μm)
Charcoal (trade name: plain Ash manufactured by Dalin industries, Ltd., iodine adsorption of 63mg/g, average particle diameter of 200 μm)
Trisodium ethylenediaminetetraacetate (KISHIDA CHEMICAL Co., Ltd., product name Special grade trisodium ethylenediaminetetraacetate (hydrate))
Water
Vermiculite (average particle size 500 μm)
Water-absorbent Polymer (crosslinked acrylic acid Polymer partial salt, average particle diameter 250 μm)
Salt
In addition, in the manufacture of containing perfume heating appliance, perfume using the 4 kinds.
The respective components of the heat-generating composition are mixed to obtain a mixture. The blending ratios of the iron powder, charcoal, trisodium ethylenediamine tetraacetate, water, vermiculite, water-absorbent polymer, and common salt were 50 wt%, 20 wt%, 0.1 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. The resulting mixture was stored in a breathable storage bag (130 × 95mm) made of a porous film partially equipped with a non-breathable adhesive sheet and sealed in the same manner as in example 1, to obtain a heat-generating device (example 31). Thereafter, the heat-generating device of example 31 was quickly accommodated in a non-air-permeable outer bag for disposable warm patch. Thus, a heat-generating device containing no perfume was produced.
The heat generating device containing perfume was produced in the following manner. Each component of the heat-generating composition is mixed with each perfume to obtain a mixture. The blending ratios of the iron powder, charcoal, trisodium ethylenediamine tetraacetate, water, vermiculite, water-absorbent polymer, salt, and perfume were 50 wt%, 20 wt%, 0.1 wt%, 20.3 wt%, 5 wt%, 2.5 wt%, 2 wt%, and 0.1 wt%, respectively. The resulting mixture was contained in an air-permeable containing bag (130 × 95mm) made of a porous film partially equipped with a non-air-permeable adhesive sheet in the same manner as in example 31, and sealed to obtain a heat-generating device. The resulting heat generating device was then quickly contained in a non-breathable outer bag for disposable warm patches.
Among the above-mentioned perfumes, a heat-generating device having a floral fragrance was used as example 32, a heat-generating device having a rose fragrance was used as example 33, a heat-generating device having a fruit fragrance was used as example 34, and a heat-generating device having a soap fragrance was used as example 35.
(2) Production of Heat generating device (examples 36 to 40)
A heat-generating device (examples 36 to 40) was produced in the same manner as in examples 31 to 35, except that trisodium citrate (product name of "refined sodium citrate M", manufactured by Hibiscus chemical Co., Ltd.) was used instead of trisodium ethylenediamine tetraacetate. A heat-generating device containing no perfume was used as example 36, a heat-generating device containing a flower fragrance was used as example 37, a heat-generating device containing a rose fragrance was used as example 38, a heat-generating device containing a fruit fragrance was used as example 39, and a heat-generating device containing a soap fragrance was used as example 40.
(3) Production of comparative Heat-generating appliances (comparative examples 16 to 20)
As comparative examples, comparative heat-generating appliances (comparative examples 16 to 20) were produced by the same procedure as in examples 31 to 35 except that the metal ion chelating agent was not contained. In comparative example 16, the blending ratios of iron powder, charcoal, water, vermiculite, water-absorbent polymer, and common salt were 50 wt%, 20 wt%, 20.5 wt%, 5 wt%, 2.5 wt%, and 2 wt%, respectively. In comparative examples 17 to 20, the blending ratios of the iron powder, charcoal, water, vermiculite, water-absorbent polymer, salt, and flavor were 50 wt%, 20 wt%, 20.4 wt%, 5 wt%, 2.5 wt%, 2 wt%, and 0.1 wt%, respectively. A comparative heat-generating device containing no perfume was comparative example 16, a comparative heat-generating device containing a flower fragrance was comparative example 17, a comparative heat-generating device containing a rose fragrance was comparative example 18, a comparative heat-generating device containing a fruit fragrance was comparative example 19, and a comparative heat-generating device containing a soap fragrance was comparative example 20.
(4) Evaluation of Heat generating implement
The fragrance intensity before storage, the temperature after opening the outer bag for 1 hour, the fragrance intensity after storage in a thermostatic bath at 50 ℃ for 14 days in the presence of oxygen, the fragrance change, and the temperature after opening the outer bag for 1 hour of examples 31 to 40 and comparative examples 16 to 20 were evaluated in the same manner as in test example 1.
(5) Results
The evaluation results of the heat generating devices of examples 31 to 40 are shown in Table 7.
[ Table 7]
The evaluation results of the heat generating devices of comparative examples 16 to 20 are shown in Table 6.
[ Table 8]
As is clear from Table 7, the odor was not substantially perceived in the fragrance-free examples 31 and 36 before preservation. In contrast, the examples 32 to 35 and 37 to 40 containing the perfume clearly experienced odor. In examples 31 to 40, the fragrance intensity after storage was not reduced, and the change in fragrance due to storage could be greatly suppressed. Before and after storage, the odors of examples 32 to 35 and 37 to 40 were derived from the perfumes contained in the respective heat-generating devices, and were good without substantially being deteriorated by storage. In examples 31 to 40, no unpleasant odor derived from the heat-generating composition was observed.
Further, the temperature 1 hour after the unsealing was 45 ℃ both before and after the storage as the heat generation temperature, and the heat generation device is useful.
In contrast, when the metal ion chelating agent was not contained, as is clear from the results of comparative example 16 in table 8, a distinct odor was perceived even though the fragrance was not contained. This is an unpleasant odor derived from the heat-generating composition. In comparative examples 17 to 20, the change in fragrance was clearly perceived due to storage, and this is considered to be because: the unpleasant odor is not sufficiently suppressed, and components contained in a heat generating device such as a perfume are deteriorated.
Thus, it can be seen that: according to the heat generating device of the present invention using the metal ion chelating agent, unpleasant odor derived from the heat generating composition can be effectively suppressed, and desired aromaticity can be effectively maintained. In addition, it can be seen that: according to the heat generating device of the present invention using the metal ion chelating agent, the change in the fragrance can be effectively suppressed regardless of the presence or absence of the fragrance. In addition, it can be seen that: thus, the excellent effect can be obtained and the sufficient heat retaining effect can be exhibited as a heat generating device.
Test example 5
(1) Production of Heat-generating devices (examples 41 to 45)
The heat generating devices (examples 41 to 45) having the structures shown in FIG. 4 and FIG. 1 were produced in the following manner.
First, the following components were used as the heat-generating composition.
< Heat-generating composition >
Iron powder (DOWA IP CREATION CO., LTD. product name DKP, average particle size 100 μm)
Trisodium ethylenediaminetetraacetate (KISHIDA CHEMICAL Co., Ltd., product name Special grade trisodium ethylenediaminetetraacetate (hydrate))
Water
Salt
In addition, in the manufacture of containing perfume heating appliance, perfume using the 4 kinds.
The respective components of the heat-generating composition are mixed to obtain a mixture. The blending ratios of the iron powder, trisodium ethylenediamine tetraacetate, water and common salt were 70 wt%, 0.1 wt%, 14.9 wt% and 15 wt%, respectively. The resulting mixture was stored in a breathable storage bag (130 × 95mm) made of a porous film partially equipped with a non-breathable adhesive sheet and sealed in the same manner as in example 1, to obtain a heat-generating device (example 41). Thereafter, the heat generating device of example 41 was quickly accommodated in a non-air-permeable outer bag for disposable warm patch. Thus, a heat-generating device containing no perfume was produced.
The heat generating device containing perfume was produced in the following manner. Each component of the heat-generating composition is mixed with each perfume to obtain a mixture. The blending ratios of the iron powder, trisodium ethylenediamine tetraacetate, water, salt, and perfume were 70 wt%, 0.1 wt%, 14.8 wt%, 15 wt%, and 0.1 wt%, respectively. The resulting mixture was contained in a breathable bag (130 × 95mm) made of a porous film partially equipped with a non-breathable adhesive sheet in the same manner as in example 41, and sealed to obtain a heat-generating device. The resulting heat generating device was then quickly contained in a non-breathable outer bag for disposable warm patches.
Among the above-mentioned perfumes, a heat-generating device having a floral fragrance was used as example 42, a heat-generating device having a rose fragrance was used as example 43, a heat-generating device having a fruit fragrance was used as example 44, and a heat-generating device having a soap fragrance was used as example 45.
(2) Production of Heat-generating devices (examples 46 to 50)
A heat-generating device (examples 46 to 50) was produced in the same manner as in examples 41 to 45, except that trisodium citrate (product name of "refined sodium citrate M", manufactured by Hibiscus chemical Co., Ltd.) was used in place of trisodium ethylenediamine tetraacetate. A heat-generating device containing no perfume was used as example 46, a heat-generating device containing a flower fragrance was used as example 47, a heat-generating device containing a rose fragrance was used as example 48, a heat-generating device containing a fruit fragrance was used as example 49, and a heat-generating device containing a soap fragrance was used as example 50.
(3) Production of comparative Heat-generating appliances (comparative examples 21 to 25)
As comparative examples, comparative heat-generating devices (comparative examples 21 to 25) were produced in the same manner as in examples 41 to 45, except that the metal ion chelating agent was not contained. In comparative example 21, the blending ratios of iron powder, water, and common salt were 70 wt%, 15 wt%, and 15 wt%, respectively. In comparative examples 22 to 25, the blending ratios of the iron powder, water, salt and flavor were 70 wt%, 14.9 wt%, 15 wt% and 0.1 wt%, respectively. A comparative heat-generating device containing no perfume was set as comparative example 21, a comparative heat-generating device containing a flower fragrance was set as comparative example 22, a comparative heat-generating device containing a rose fragrance was set as comparative example 23, a comparative heat-generating device containing a fruit fragrance was set as comparative example 24, and a comparative heat-generating device containing a soap fragrance was set as comparative example 25.
(4) Evaluation of Heat generating implement
The fragrance intensity before storage, the temperature after opening the outer bag for 1 hour, the fragrance intensity after storage in a thermostatic bath at 50 ℃ for 14 days in the presence of oxygen, the fragrance change, and the temperature after opening the outer bag for 1 hour of examples 41 to 50 and comparative examples 21 to 25 were evaluated in the same manner as in test example 1.
(5) Results
The evaluation results of the heat generating devices of examples 41 to 50 are shown in Table 9.
[ Table 9]
The evaluation results of the heat generating devices of comparative examples 21 to 25 are shown in Table 10.
[ Table 10]
As is clear from table 9, before preservation, the examples 41 and 46, which did not contain perfume, experienced substantially no odor. In contrast, the odor was clearly perceived in examples 42 to 45 and 47 to 50 containing the perfume. In examples 41 to 50, the flavor intensity after storage was not reduced, and the change in flavor due to storage could be greatly suppressed. Before and after storage, the odors of examples 42 to 45 and 47 to 50 were derived from the perfumes contained in the respective heat-generating devices, and were good without substantially deteriorating due to storage. In examples 41 to 50, no unpleasant odor derived from the heat-generating composition was observed.
Further, the temperature 1 hour after the unsealing was 41 ℃ both before and after the storage as the heat generation temperature, and the heat generation device was useful.
In contrast, when the metal ion chelating agent was not contained, as is clear from the results of comparative example 21 in table 10, the odor was perceived before and after the storage even though the fragrance was not contained. This is an unpleasant odor derived from the heat-generating composition. In comparative examples 22 to 25, the change in fragrance due to storage was further perceived as compared with examples 41 to 50, and this is considered to be because: the unpleasant odor is not sufficiently suppressed, and components contained in a heat generating device such as a perfume are deteriorated.
Thus, it can be seen that: according to the heat-generating device of the present invention using the metal ion chelating agent, the unpleasant odor derived from the heat-generating composition can be effectively suppressed, and the desired aromaticity can be effectively maintained when the fragrance is contained. In addition, it can be seen that: according to the heat-generating device of the present invention using the metal ion chelating agent, the change in the fragrance can be effectively suppressed regardless of the presence or absence of the fragrance, and the effect can be obtained regardless of the presence or absence of the oxidation accelerator, the water retaining agent, or the degree of iodine adsorption ability of the oxidation accelerator or the presence or absence of conductivity. In addition, it can be seen that: according to the heat generating device of the present invention using the metal ion chelating agent, such excellent effects can be obtained and a sufficient heat retaining effect can be exhibited as the heat generating device.
In examples 1 to 50, the heat generating device having the structure shown in fig. 2 or 3 was used in place of the structure shown in fig. 1 or 4, and the excellent effects were exhibited as described above.
Description of the reference numerals
1. Air-permeable storage bag (1a is air-permeable part, 1b is non-air-permeable part)
2. Exothermic composition
3. Perfume
4. Non-air-permeable outer bag
5. Adhesive agent
6. Release paper
Claims (14)
1. A heat generating device comprising a heat generating composition containing a metal ion chelating agent, an oxidizable metal powder, a water-soluble salt, an oxidation accelerator and water, and a perfume, wherein at least the heat generating composition is contained in a gas-permeable containing bag,
the iodine adsorption performance of the oxidation promoter is below 400mg/g on average,
the metal ion chelating agent is at least 1 selected from the group consisting of aminocarboxylic acid type metal ion chelating agents, phosphonic acid type metal ion chelating agents, condensed phosphoric acid type metal ion chelating agents, carboxylic acid type metal ion chelating agents, and substances having metal ion adsorption ability,
the carboxylic acid-based metal ion chelating agent is at least 1 selected from the group consisting of dihydroxyglycine, dihydroxyethylglycine, citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, ascorbic acid, gluconic acid, and salts thereof,
the substance having metal ion adsorption ability is at least 1 selected from the group consisting of zeolite, acrylic acid, methacrylic acid, bipyridine, phenanthroline, porphyrin, phthalocyanine, corrole, chlorin, and crown ether.
2. The heat-generating appliance according to claim 1, further comprising a water-retaining agent.
3. The heat-generating appliance according to claim 1, wherein the oxidation promoter is at least 1 selected from the group consisting of carbon black, black lead, activated carbon, coal, charcoal, bamboo charcoal, and coffee grounds.
4. The heat-generating appliance according to claim 3, wherein the oxidation promoter is acetylene black.
5. The heat-generating appliance according to claim 1, wherein the oxidation promoter has conductivity.
6. The heat-generating appliance according to claim 1 or 2, wherein a blending ratio of the metal ion chelating agent in the heat-generating composition is 0.0001 to 10% by weight.
7. A heat-generating appliance according to claim 1 or 2, wherein the metal ion chelating agent is contained in an amount of 0.0002 to 20 parts by weight per 100 parts by weight of the oxidizable metal powder in the heat-generating composition.
8. The heat-generating device according to claim 1, wherein a blending ratio of the oxidation accelerator in the heat-generating composition is 1 to 30% by weight.
9. The heat-generating device according to claim 1, wherein the heat-generating composition contains 0.0001 to 20 parts by weight of a perfume per 100 parts by weight of the heat-generating composition.
10. A heat-generating device according to claim 1, wherein the heat-generating composition contains 0.0003 to 500 parts by weight of a fragrance per 100 parts by weight of the oxidation accelerator.
11. The heat generating device according to claim 1, wherein the fragrance is contained in the air-permeable containing bag.
12. The heat-generating device according to claim 1, wherein the fragrance is supported on a carrier.
13. A method for suppressing the generation of unpleasant odor and/or change in flavor in a heat-generating appliance, which comprises a step of storing a heat-generating composition containing a metal ion chelating agent, an oxidizable metal powder, a water-soluble salt, an oxidation promoter and water, and a perfume in a storage bag having air permeability, wherein the oxidation promoter has an average iodine adsorption performance of 400mg/g or less.
14. Use of the heat-generating appliance of any one of claims 1 to 12 in a method of inhibiting the generation of unpleasant odors and/or flavor changes in the heat-generating appliance.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012171066A JP6636231B2 (en) | 2012-08-01 | 2012-08-01 | Heating tool |
| JP2012-171066 | 2012-08-01 | ||
| PCT/JP2013/070497 WO2014021269A1 (en) | 2012-08-01 | 2013-07-29 | Heat generator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1210690A1 HK1210690A1 (en) | 2016-05-06 |
| HK1210690B true HK1210690B (en) | 2019-08-23 |
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