CN111031973A - Warming appliance - Google Patents

Abstract

The warmer (1) is provided with a first sheet (11) having air permeability, a second sheet (12), a heat-generating layer (13) disposed between the first sheet (11) and the second sheet (12), and a drug layer (16) disposed between the heat-generating layer (13) and the second sheet (12), and is configured in such a manner that the air permeability from the heat-generating layer (13) to the first sheet (11) is higher than the air permeability from the heat-generating layer (13) to the second sheet (12), the drug layer (16) is composed of a drug composition containing a cold-sensitive agent and a solvent having a molecular weight of 1,000 or less, and the amount of the cold-sensitive agent that has volatilized after the heat generation of the heat-generating layer (13) has started is 1mg/2 hours or more and 5mg/2 hours or less.

Description

Warming appliance

Technical Field

The present invention relates to a warmer.

Background

Conventionally, steam heating appliances have been configured using an oxidizable metal such as iron powder, an electrolyte such as sodium chloride, and water, and using oxidation heat generated by an oxidation reaction of the oxidizable metal. In addition, in the case where such a steam heating device can supply a medicine component to a wearer, a technique of providing a function other than warming is being developed.

For example, patent document 1 discloses a steam heating appliance for alleviating a sensation of inflammation, because a sensation of inflammation specific to the steam heating appliance may be felt in summer or the like. That is, a heat generating device in which a cooling agent such as menthol is contained in a heat generating portion from the viewpoint of alleviating a sensation of inflammation by simultaneously providing a sensation of warmth and a sensation of coolness is disclosed.

On the other hand, patent document 2 discloses a technique of forming an uncoated region of a liquid medicine in a warmer containing a liquid medicine such as menthol, and utilizing surface tension between the uncoated region and a heat generating layer, thereby suppressing interlayer peeling, from the viewpoint of suppressing interlayer peeling between a layer coated with the liquid medicine and a layer coated with the heat generating element.

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2010-158507

Patent document 2: japanese patent laid-open publication No. 2016 and No. 73415

Disclosure of Invention

The present invention provides a warmer, comprising:

a first sheet having breathability;

a second sheet material;

a heat generating layer disposed between the first sheet and the second sheet; and

a chemical agent layer disposed between the heat generating layer and the second sheet

The air permeability from the heat generating layer to the first sheet is higher than the air permeability from the heat generating layer to the second sheet,

the drug layer is composed of a drug composition containing a psychrotonic agent and a solvent having a molecular weight of 1,000 or less.

Drawings

The above objects, and other objects, features and advantages will become more apparent from the following description of preferred embodiments and the accompanying drawings attached to the embodiments.

Fig. 1 is a sectional view showing a warmer according to an embodiment of the present invention.

FIG. 2 is a sectional view showing a heat generating element according to an embodiment of the present invention.

FIG. 3 is a perspective view showing a heat generating element.

Fig. 4 is a sectional view showing a part of a heat generating portion.

Fig. 5 is a view showing an example of a state in which the user wears the heating device.

Detailed Description

In recent years, users have increasingly demanded higher standards for feeling and feeling of effect when using a steam heating appliance, and for example, demand for feeling stiffness, fatigue, and pain at a part to which the steam heating appliance is applied, and for feeling such a reduction effect immediately after application has been strong.

However, when only a warm stimulus and a cool feeling are simultaneously given as in the technique described in patent document 1, such a demand of the user cannot be sufficiently satisfied.

Further, the technique disclosed in patent document 2 focuses on interlayer peeling, does not focus on such a user's demand, and cannot sufficiently respond to the demand.

The present inventors have made diligent studies to meet the high demands of users, and as a result, have found that by optimizing the initial volatilization behavior of the cooling sensation agent with respect to the initial heating behavior of the warmer, the feeling of effect on stiffness, fatigue, pain, and the like, and the quick-acting feeling thereof are improved. Further, as a result of further studies for achieving the above object, it has been found that by combining a solvent having a specific molecular weight with a cooling agent and controlling the arrangement of the cooling agent in a heating appliance, after the use of the heating appliance is started, the comfortable stimulus by the cooling agent can be increased early, the rise of the heat generation temperature can be further improved, and as a result, an unexpected effect that the feeling of effectiveness and the quick-acting feeling are extremely high has been found, and the present invention has been completed.

The present invention provides a heating appliance having a high feeling of effect on stiffness, fatigue, pain, and the like, and having an excellent quick-acting feeling of these.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and detailed description thereof will be omitted as appropriate without being repeated.

In the present embodiment, the air permeability is a value measured in accordance with JIS P8117, and 100ml of air is passed through 6.45cm under a constant pressure²Is defined as the time of the area of (a). The air permeability can be measured by a measuring machine using a joker's air permeability meter or the like.

That is, the air permeability is large, which means that it takes time for air to pass through, that is, the air permeability is low. Conversely, less air permeability means higher air permeability. Thus, the magnitude of air permeability is inversely related to the level of air permeability.

In the present embodiment, the basis weight refers to the mass of the area of the heat generating layer in a plan view.

Fig. 1 is a sectional view showing a warmer according to an embodiment of the present invention. FIG. 2 is a sectional view showing a heat generating element according to an embodiment of the present invention.

As shown in fig. 1, the heating appliance 1 includes: a first sheet 11 having air permeability, a second sheet 12, and 2 heating elements 18 arranged in parallel and disposed between the first sheet 11 and the second sheet 12. That is, the warmer 1 has an outer bag formed of the first sheet 11 and the second sheet 12.

As shown in fig. 2, the heat-generating element 18 includes, in order from the second sheet 12 side: a heat generating part 20 in which a base material layer 10, a drug layer 16, a heat generating layer 13, and a water retaining layer 19 are sequentially laminated, and an inner bag 17 which accommodates the heat generating part 20 therein. The inner bag 17 is formed by joining the sheet 171 and the peripheral edge of the sheet 172.

Thus, the heating appliance 1 includes: the sheet includes a first sheet 11 having air permeability, a second sheet 12, a heat generating layer 13 disposed between the first sheet 11 and the second sheet 12, and a chemical layer 16 disposed between the heat generating layer 13 and the second sheet 12.

The heating appliance 1 is configured such that the air permeability of the heat generating layer 13 to the first sheet 11 is higher than the air permeability of the heat generating layer 13 to the second sheet 12. This makes it difficult for the warm steam generated in the heat generating layer 13 to be released from the second sheet 12 side to the outside and also makes it easy to be preferentially released from the first sheet 11 side. This enables the warm steam and the cooling agent to be effectively supplied to the skin of the user.

Further, a first adhesive layer 14 and a second adhesive layer 15 are formed on the outer surface of the first sheet 11, and a release paper 21 is provided thereon. Thus, the release paper 21 can be peeled off when the heating appliance 1 is used, and the heating appliance 1 can be fixed to the skin of the user by the first adhesive layer 14 and the second adhesive layer 15, so that the heating appliance 1 can be prevented from being detached from the user even if the user moves, and the warm steam can be stably supplied to the user.

Hereinafter, each configuration will be described in detail.

[ heating part 20]

The heat generating member 20 has a structure in which a base material layer 10, a drug layer 16, a heat generating layer 13, and a water retaining layer 19 are laminated in this order.

The heat-generating layer 13 generates steam when generating heat, and is composed of a heat-generating composition containing at least an oxidizable metal and water, for example, an oxidizable metal, a carbon component, water, and the like.

The oxidizable metal is a metal that emits heat of oxidation reaction, and examples thereof include powders and fibers of iron, aluminum, zinc, manganese, magnesium, calcium, and a mixed metal obtained by mixing 2 or more of these metals.

From the viewpoint of efficiently carrying out the oxidation reaction, the average particle diameter of the oxidizable metal when it is in the form of a powder is preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more. From the same viewpoint, the average particle diameter of the oxidizable metal is preferably 200 μm or less, more preferably 180 μm or less, and still more preferably 150 μm or less.

The particle size of the oxidizable metal is the maximum length in the form of powder, and can be measured by classification with a sieve, a dynamic light scattering method, a laser diffraction method, or the like, and among them, it is preferable to measure by a laser diffraction method.

The content of the oxidizable metal in the heat-generating layer 13 is preferably 100g/m in terms of basis weight, from the viewpoint of enabling the heat-generating layer 13 to be raised to a desired temperature in the heating device 1 including the chemical layer 16²Above, more preferably 200g/m²Above, more preferably 300g/m²Above, it is more preferably 500g/m²The above. From the same viewpoint, the content of the oxidizable metal in the heat-generating layer 13 is preferably 3,000g/m²Hereinafter, more preferably 2,000g/m²Hereinafter, more preferably 1,500g/m²The following.

Here, the content of the oxidizable metal in the heat-generating layer 13 can be determined by an ash test or a thermogravimetric analyzer in accordance with JIS P8128. Further, it is possible to utilize the property of magnetization occurring when an external magnetic field is applied and to perform quantification by a vibration sample type magnetization measurement test or the like. Among them, it is preferable to obtain the weight by a thermogravimetry measuring instrument.

The carbon component has water retention capacity, oxygen gas supply capacity, and catalytic capacity, and 1 or 2 or more kinds of materials selected from activated carbon, carbon black, acetylene black, and graphite can be used, for example. Among them, activated carbon is preferably used because oxygen is easily adsorbed when wet. Further, 1 or 2 or more kinds of fine powder or granule selected from coconut shell carbon, wood flour carbon, and peat can be more preferably used. Wood powder carbon is more preferable because the surface temperature of the heating element 18 can be easily raised to a desired temperature.

From the viewpoint of uniform mixing with the oxidizable metal, the average particle diameter of the carbon component is preferably 10 μm or more, more preferably 12 μm or more, and still more preferably 15 μm or more. From the same viewpoint, the average particle diameter of the carbon component is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less.

The average particle diameter of the carbon component means the maximum length in the form of powder, and can be measured by a dynamic light scattering method, a laser diffraction method, or the like, and among them, it is preferably measured by a laser diffraction method. The carbon component is preferably in the form of powder, but a form other than powder may be used, and for example, a carbon component in the form of fiber may be used.

From the viewpoint of sufficiently obtaining the supply of water to the heat-generating layer 13, the content of the carbon component in the heat-generating layer 13 is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 6 parts by mass or more, relative to 100 parts by mass of the content of the oxidizable metal. In addition, from the viewpoint of sufficiently obtaining the oxygen gas supply to the heat generating layer 13, the content of the carbon component in the heat generating layer 13 is preferably 40 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less with respect to 100 parts by mass of the content of the oxidizable metal.

The content of the carbon component in the heat-generating layer 13 is preferably 10g/m in basis weight²Above, more preferably 20g/m²Above, it is more preferably 25g/m²The above. The content of the carbon component is preferably 400g/m in basis weight²Hereinafter, it is more preferably 250g/m²Hereinafter, it is more preferably 120g/m²The following.

From the viewpoint of allowing the oxidation reaction of the oxidizable metal to proceed satisfactorily, the content of water in the heat generating layer 13 is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more, per 100 parts by mass of the oxidizable metal. From the viewpoint of setting the maximum reaching temperature to be equal to or higher than a certain temperature, the content of water in the heat generating layer 13 is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less with respect to 100 parts by mass of the oxidizable metal. The water in the heat generating layer 13 is partly converted into water vapor due to a temperature increase caused by heat generation by an oxidation reaction of the oxidizable metal.

The heat-generating layer 13 may contain a water absorbing agent in order to retain moisture and efficiently perform an oxidation reaction of the oxidizable metal. As the water absorbing agent, a polymer having water absorption property or a powder having water absorption property can be used.

The water-absorbing polymer includes a hydrophilic polymer having a crosslinked structure capable of absorbing and holding a liquid 20 times or more its own weight, and the water-absorbing powder includes 1 or 2 or more kinds of powder selected from vermiculite, sawdust, silica gel, and pulp powder. The content of the water absorbing agent is preferably 2 parts by mass or more, and preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of water in the heat generating layer 13.

The heat generating layer 13 may further contain a reaction accelerator. The oxidation reaction of the oxidizable metal can be easily continued by containing the reaction promoter. Further, by using the reaction accelerator, an oxide film formed on the oxidizable metal by the oxidation reaction is broken, and the oxidation reaction is accelerated. Examples of the reaction accelerator include 1 or 2 or more kinds of materials selected from sulfates or chlorides of alkali metals and alkaline earth metals. Among them, from the viewpoint of excellent conductivity, chemical stability, and production cost, it is preferable to use 1 or 2 or more kinds of materials selected from various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ferrous chloride, and ferric chloride, and sodium sulfate.

When the thickener is contained in the heat-generating composition, the deterioration of the heat-generating characteristics during the storage of the heat-generating element 18 can be suppressed.

As the thickener contained in the heat-generating composition, one or more than 1 kind selected from the group consisting of alginate such as sodium alginate, gum arabic, tragacanth gum, locust bean gum, guar gum, arabic gum, carrageenan, agar, xanthan gum, and other polysaccharide thickeners, dextrin, α -modified starch, and starch for processing, cellulose derivative thickeners such as carboxymethyl cellulose, ethyl acetate cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, and hydroxypropyl cellulose, metal soap thickeners such as stearate, and mineral thickeners such as bentonite, can be mainly used to increase the consistency or impart thixotropy by absorbing water.

When the phosphate is contained in the heat-generating composition, the fluidity of the heat-generating composition is improved, and therefore, it is preferable from the viewpoint of ease of production when the heat-generating layer 13 is produced by applying the phosphate to a base material such as paper. As the phosphate, 1 or 2 or more selected from potassium dihydrogen phosphate salt, dipotassium hydrogen phosphate salt, tripotassium phosphate salt, sodium dihydrogen phosphate salt, and disodium hydrogen phosphate salt can be used.

The heat generating layer 13 may be a powder or a molded product of a powder, or may be a sheet, and in the present embodiment, is a sheet having a rectangular shape (square, rectangular) in a plan view.

In the present embodiment, the heat generating layer 13 is shown as a sheet, but the heat generating layer 13 may be in the form of powder or a sheet. However, the sheet-like shape is preferable because of its excellent feeling in use.

Examples of the method for producing the heat-generating layer 13 include a heat-generating layer obtained by wet-papermaking a heat-generating composition, a heat-generating layer obtained by pressing a heat-generating composition, a heat-generating layer obtained by sandwiching a heat-generating composition between the following base material layers 10, and a heat-generating layer obtained by dispersing a heat-generating composition in water to prepare a heat-generating powder water dispersion and coating the heat-generating powder water dispersion on the base material layers 10. Among them, from the viewpoint of excellent feeling in use and easy production, a method of dispersing the heat-generating composition in water to prepare a heat-generating powder water dispersion and applying the heat-generating powder water dispersion to the base layer 10 is preferable.

The substrate layer 10 preferably has one surface capable of absorbing and retaining moisture and the other surface impermeable to moisture. The basis weight of the base material layer 10 is preferably 10g/m²Above and 200g/m²Hereinafter, more preferably 35g/m²Above and 150g/m²The following.

As shown in fig. 2, as the base material layer 10, a sheet obtained by laminating and laminating a hydrophilic layer 10a and a liquid impermeable layer 10b is used.

The hydrophilic layer 10a is a layer containing hydrophilic fibers.

The ratio of the hydrophilic fibers contained in the entire base layer 10 is preferably 20 mass% or more and 99.9 mass% or less, and more preferably 50 mass% or more and 99.5 mass% or less.

As the hydrophilic fiber, for example, cellulose fiber is preferably used. As the cellulose fiber, chemical fiber (synthetic fiber) and natural fiber can be used. As the chemical fiber of cellulose, rayon and cellulose acetate can be used, for example. On the other hand, examples of natural cellulose fibers include various plant fibers such as wood pulp, non-wood pulp, cotton, hemp, wheat straw, hemp, jute, kapok, coconut, rush, and the like. Among these cellulose fibers, wood pulp is preferably used from the viewpoint that a relatively coarse fiber can be easily obtained.

Examples of the resin constituting the liquid impermeable layer 10b include resins such as polyolefins, e.g., polyethylene and polypropylene, polyesters, polyamides, polyurethanes, polystyrene, nylon, polyvinylidene chloride, and polyethylene-vinyl acetate copolymers.

The method of laminating the hydrophilic layer 10a and the liquid-impermeable layer 10b may use a known lamination process.

The base material layer 10 is preferably located on the side farther from the skin than the heat generating layer 13, and the hydrophilic layer 10a is preferably located on the side closer to the heat generating layer 13.

The drug layer 16 is composed of a drug composition containing a cold feeling agent and a solvent having a molecular weight of 1,000 or less. That is, unlike the prior art in which the drug composition is caused to permeate into the heat generating portion. In addition, the medicine layer 16 supplies warm steam to the user together with the cooling agent when the warmer 1 is used. The heater 1 can improve the volatility of the cooling agent by including the chemical agent layer 16.

The drug layer 16 is formed by any method, and when the heat generating portion 20 has the base material layer 10 as shown in fig. 2, the drug layer 16 is preferably formed by coating a drug composition containing a cold-sensitive agent and a solvent having a molecular weight of 1,000 or less on the base material layer 10. Thereby, the surface of the base layer 10 is covered with the chemical agent layer 16. The coverage is not limited to the case of being continuous, and may be partially discontinuous.

Further, a part of the cooling agent may penetrate into the base layer 10 or the heat generating layer 13 adjacent to the chemical layer 16. In this case, for example, the concentration of the cooling agent is highest on the surface of the heat generating layer 13 in contact with the drug layer 16.

The chemical layer 16 can be confirmed by measuring the distribution of the cooling agent in the heat generating layer 13 before the reaction by a known machine analysis method. For example, the heat generating portion 20 including the drug layer 16 may be analyzed in the cross-sectional direction using a three-dimensional measurement X-ray Computed Tomography (CT) apparatus, and confirmed by elemental analysis. It can be confirmed by infrared absorption spectroscopy that the medicine layer 16 is present on the surface side where the amount of the refrigerant is large, on both surfaces of the heat generating portion 20.

Examples of the psychrotoctant include 1 or 2 or more compounds selected from the group consisting of menthol, 1, 8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1, 2-propanediol, and N-ethyl-3-p-menthanecarboxamide. This makes it easy to maintain the cool feeling, to improve the cool feeling by the combination of the fragrances, and the like. From the viewpoint of improving the comfortable stimulation by the psychrotosensitive agent and improving the handling property, menthol is preferable.

The cold feeling agent is dissolved in a solvent having a molecular weight of 1,000 or less.

In the present specification, "menthol" refers to a substance containing dl-menthol in addition to l-menthol, and the amount thereof and the like are specified. In the present specification, a cooling agent is a substance that acts on the skin, mucous membrane, or the like of a user to give the user a cool sensation, that is, a cool sensation.

The solvent having a molecular weight of 1,000 or less is preferably a polyhydric alcohol, and more preferably 1 or 2 or more selected from polyethylene glycol (PEG), glycerin, and propylene glycol. Among these, polyethylene glycol is preferable from the viewpoint of maintaining good volatility of the cold feeling agent and obtaining good heat generating property, and from the viewpoint of improving the feeling of effect on the application site and obtaining a high quick-acting feeling.

The molecular weight of the solvent is 1,000 or less, but is preferably 600 or less, more preferably 450 or less, from the viewpoint of effectively obtaining a comfortable stimulus by the cold feeling agent and obtaining a good heat-generating property, from the viewpoint of reducing the content of the cold feeling agent as much as possible, and from the viewpoint of maintaining a good volatility of the cold feeling agent. The lower limit is not particularly limited, but is preferably 50 or more, and more preferably 100 or more.

The molecular weight as used herein refers to a weight average molecular weight when a molecular weight distribution such as polyethylene glycol is generated. When the heating element 18 contains PEG, the weight average molecular weight is specified by extracting the solvent in the heating element 18 by a solvent extraction method performed when the content of the solvent in the heating element 18 described below is determined, and analyzing the extract by GPC.

The content of the solvent having a molecular weight of 1,000 or less is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the cold-sensitive agent and the solvent in the pharmaceutical composition, from the viewpoint of imparting a good warm feeling immediately after the start of use and effectively obtaining a comfortable stimulus by the cold-sensitive agent.

On the other hand, the content of the solvent having a molecular weight of 1,000 or less is preferably 85% by mass or less, more preferably 70% by mass or less, based on the total amount of the psychrophilic agent and the solvent in the pharmaceutical composition, from the viewpoint of ensuring safety and imparting a pleasant stimulus to the psychrophilic agent.

In the heat-generating member 20, the content of the solvent having a molecular weight of 1,000 or less per unit area of the heat-generating layer 13 in a plan view is preferably 2.0mg/cm from the viewpoint of imparting a good temperature feeling immediately after the start of use and effectively obtaining a comfortable stimulus by the cooling agent²Above, more preferably 4.0mg/cm²The above.

On the other hand, in the heat-generating layer 20, the content of the solvent having a molecular weight of 1,000 or less is preferably 20mg/cm per unit area of the heat-generating layer 13 in a plan view from the viewpoint of ensuring safety and providing comfortable stimulation by the cooling agent²Hereinafter, more preferably 15mg/cm²The following.

The content of the solvent having a molecular weight of 1,000 or less is determined as a value obtained by dividing the mass of the solvent having a molecular weight of 1,000 or less contained in the heat generating portion 20 by the area of the heat generating layer 13 in a plan view.

The content of the solvent having a molecular weight of 1,000 or less contained in the heating element 18 is determined by analyzing and quantifying an extract obtained by a solvent extraction method by gas chromatography. Specifically, the heating element 18 is taken out from the warmer 1, the heating element 18 is immersed in a solvent (preferably ethanol), and the resultant is left at room temperature for 9 hours in a sealed state to obtain an extract liquid. Thereafter, the obtained extract was analyzed by gas chromatography.

The content of the cool feeling agent with respect to the area of the heat-generating layer 13 in plan view is preferably 1.0mg/cm from the viewpoint of effectively obtaining comfortable stimulation by the cool feeling agent²Above, more preferably 1.5mg/cm²Above, more preferably 1.7mg/cm²The above.

On the other hand, from the viewpoint of ensuring safety and imparting comfortable stimulation to the cooling agent, and from the viewpoint of maintaining good heat generation characteristics, the content of the cooling agent with respect to the area of the heat generation layer 13 when viewed from the top is preferably 6.0mg/cm²Hereinafter, more preferably 4.5mg/cm²Hereinafter, more preferably 3.2mg/cm²The following.

The content of the cooling agent is determined by dividing the amount of the cooling agent contained in the heat generating portion 20 by the area of the heat generating layer 13 when viewed from above.

The amount of the cooling agent contained in the heating element 18 is determined by analyzing an extract obtained by a solvent extraction method by gas chromatography. Specifically, the heating element 18 is taken out from the warmer 1, the heating element 18 is immersed in a solvent (preferably ethanol), sealed, and then left at room temperature for 9 hours. The thus-obtained extract was analyzed by gas chromatography.

The weight ratio of the oxidizable metal to the cooling agent contained in the heating appliance 1 (oxidizable metal/cooling agent) is preferably 5 or more and 55 or less, more preferably 10 or more and 50 or less, and still more preferably 10 or more and 40 or less.

Among these, the weight ratio of the oxidizable metal to menthol is preferably 5 or more and 55 or less, more preferably 10 or more and 50 or less, and further preferably 10 or more and 40 or less, from the viewpoint of more effectively obtaining an effect feeling and a quick-acting feeling.

The volatile amount of the cold feeling agent is, for example, 1mg/2 hours or more and 5mg/2 hours or less. From the viewpoint of obtaining an effect feeling on pain and quick-acting property by a cold feeling agent, it is preferably 1.3mg/2 hours or more, and from the viewpoint of obtaining a stimulus feeling, it is more preferably 1.7mg/2 hours or more, and still more preferably 1.9mg/2 hours or more. On the other hand, the volatile amount of the cooling agent is preferably 3.5mg/2 hours or less, more preferably 3.0mg/2 hours or less, and even more preferably 2.8mg/2 hours, from the viewpoint of ensuring safety and providing comfortable irritation by the cooling agent, and from the viewpoint of maintaining good heat-generating characteristics and improving the feeling of effect and quick-acting feeling.

The volatile amount of the cold-feeling agent can be measured as follows.

First, a gas collection bag (Tedlar (registered trademark) bag, manufactured by DuPont inc.) of a polyvinyl fluoride resin of 15cm × 25cm containing air in an amount sufficient for the heating element 18 or the heater 1 containing a refrigerant to perform an oxidation reaction is prepared, one end of the gas collection bag is connected to an air supply source, and the outlet port at the other end or the tip of a tube connected to the outlet port is immersed in ethanol.

Subsequently, the heating element 18 or the warmer 1 containing the cooling agent was taken out from the oxygen-barrier bag, put into the gas collecting bag, and placed on a hot plate set at 35 ℃ for 2 hours. While the bag is placed on the hot plate, air is introduced into the gas collection bag from the air supply source at a constant speed (100mL/min), and the air is discharged from the outlet port at the other end of the gas collection bag or the tip of the pipe connected to the outlet port, whereby the volatile refrigerant is trapped in ethanol. Further, a weight is placed on the gas collecting bag so that the air flowing into the gas collecting bag is appropriately discharged, and the periphery of the gas collecting bag is insulated with a heat insulating material so as to maintain the heating by the heating plate.

After being placed for 2 hours, the heating element 18 or the warmer 1 was taken out from the gas collection bag, and the gas collection bag was washed with ethanol, and the ethanol used for washing was also captured and added to the amount of the menthol dispersed. Analysis of the amount of captured menthol was performed by gas chromatography.

These operations are all carried out at atmospheric pressure.

The pharmaceutical composition may contain other components in addition to the cooling agent and the solvent as described above within a range not impairing the effects of the present invention. In addition, from the viewpoint of further increasing the volatilization rate of the cold feeling agent, it is preferable that the pharmaceutical composition contains substantially no surfactant. When the pharmaceutical composition contains a fragrance component other than the psychrophilic agent, the amount of the fragrance component is preferably small relative to the psychrophilic agent, and the fragrance component is more preferably not substantially contained in the pharmaceutical composition.

Here, the substantial absence of the compound to be administered in the drug composition means that the content of the compound to be administered in the drug layer is preferably less than 0.1%, more preferably less than 0.01%, and even more preferably is not contained in the drug layer, based on the total amount of the psychrotosensitive agent and the solvent having a molecular weight of 1,000 or less.

The water retaining layer 19 contains water, and thus can supply warm steam or maintain good heat generation characteristics.

The water content in the water retaining layer 19 is preferably 10 to 45 mass%, more preferably 12 to 40 mass%, of the maximum water absorption capacity of the water retaining layer 19, and still more preferably 13 to 30 mass% in order to prevent abnormal heat generation and stably obtain good heat generation characteristics even when the heat generating composition is filled in a large amount in 1 heat generating portion 20 for some reason or is unevenly present in a specific portion in the production of the heat generating portion 20.

From the same viewpoint, the content of water contained in the water-retaining layer 19 is preferably 12 mass% or more, and more preferably 13 mass% or more of the maximum water absorption capacity of the water-retaining layer 19.

The water content in the water-retaining layer 19 is preferably 40% by mass or less, and more preferably 30% by mass or less.

Further, the maximum water absorption can be measured as follows.

Maximum water absorption (W) of the Water-retaining layer_max) As described below, mayThe measurement method described in JIS L1906 was used. Specifically, the mass (W) of the water-retaining layer 19 is measured₀) The water-retaining layer 19 was immersed in a 5 mass% aqueous solution of sodium chloride for 5 minutes, taken out with a pair of tweezers, left suspended in the air for 1 minute to allow unabsorbed water to drip off, and the mass (W) was measured₁) And the maximum water absorption (W) is calculated by the following formula_max)。

W_max＝W₁－W₀

The water-retaining layer 19 preferably has water absorbency to absorb and retain 10 to 45 mass% of water having the maximum water absorption capacity, and preferably has air permeability regardless of the presence or absence of air permeability.

The water-retaining layer 19 having an air permeability when it has absorbed water in an amount of 10 to 45 mass% of the maximum water absorption capacity is preferably 500 seconds/100 ml or less, and more preferably 1 to 300 seconds/100 ml. By setting the air permeability as described above, the air permeability of the heat generating member 20 can be sufficiently ensured, so that the oxygen gas can be sufficiently supplied to obtain high heat generating efficiency, the oxidation reaction of the oxidizable metal becomes favorable, and a large amount of water vapor can be generated. Further, it is more preferably 300 seconds/100 ml or less, and still more preferably 1 second/100 ml or more from the viewpoint of preventing excessive temperature rise.

Fig. 4 shows an example in which the heat generating layer 13 and the water retaining layer 19 are laminated, and a substance containing the fiber material of the component (a) and the water-absorbent polymer of the component (b) is used as the water retaining layer 19. Further, the water-retaining layer 19 is formed of a water-absorbent sheet 102. In fig. 4, the oxidizable metal (M) and the carbon component (C) are shown for the heat generating layer 13.

The water-retaining layer 19 may be formed of a sheet containing the component (a), for example, a single fiber sheet, or two or more layers may be stacked. Specific examples of the fibrous sheet include paper, nonwoven fabric, and a laminate formed by laminating paper and nonwoven fabric, which are made of the following fibrous materials. The sheet containing the component (a) may be, specifically, a sheet such as paper or nonwoven fabric obtained by laminating or laminating a fibrous material on a non-water-absorbing material such as polyethylene fiber, polypropylene fiber, polyethylene sheet or polypropylene sheet, or a sheet such as paper or nonwoven fabric obtained by further laminating or mixing a fibrous material such as pulp fiber or rayon fiber with another fibrous material. It is preferable to use a sheet containing the component (a) in the water-retaining layer 19, because the water content in the water-retaining layer 19 can be easily adjusted to make the water content in the heat-generating layer appropriate, and good heating and temperature feeling can be maintained well.

The water-retaining layer 19 may further contain the component (b). When the component (b) is contained in the water-retaining layer 19, the form of the water-retaining layer 19 can be exemplified by: (i) preparing 1 sheet in a state that the component (a) and the component (b) are uniformly mixed; (ii) a form in which the component (b) is disposed between the same or different sheets containing the component (a); (iii) the component (b) is dispersed to form a sheet. Among these, since the water content of the heat generating layer 13 can be easily controlled, the water content in the water retaining layer 19 and the water content in the water retaining layer 19 can be easily adjusted, and the form of (ii) is preferable. The water-retaining layer 19 in the form of (ii) may be formed by, for example, uniformly dispersing the component (b) on a sheet containing the component (a) and spraying 200g/m of the component (b) from above²After the amount of water, the same or different sheets containing the component (a) were further laminated thereon at 100. + -. 0.5 ℃ at 5kg/cm²And dried until the water content becomes 5 mass% or less.

As the component (a), either hydrophilic fiber or hydrophobic fiber is used, preferably hydrophilic fiber, and among them, cellulose fiber is more preferably used from the viewpoint of promoting the movement of water in the water-retaining layer 19, easily adjusting the water content contained in the water-retaining layer 19, and making the water content in the heat-generating layer appropriate, thereby making it possible to maintain a good heat generation and temperature rise and a good temperature feeling. As the cellulose fiber, chemical fiber (synthetic fiber) or natural fiber can be used.

As the chemical fiber in the cellulose fiber, rayon or cellulose acetate, for example, can be used. On the other hand, as the natural fibers in the cellulose fibers, for example, 1 or 2 or more kinds selected from various plant fibers, wood pulp fibers, non-wood pulp fibers, cotton fibers, hemp fibers, wheat straw fibers, hemp fibers, jute fibers, kapok fibers, coconut fibers, and rush fibers can be used. Among these cellulose fibers, wood pulp fibers are preferably used from the viewpoint of easily adjusting the water content contained in the water holding layer 19, adjusting the water content in the heat generating layer to an appropriate level, and maintaining the heat generation and temperature rise and the temperature feeling well.

The fiber length of each fiber material is preferably 0.5-6 mm, and more preferably 0.8-4 mm. The fiber length of the fiber material is preferably 0.5mm or more, and more preferably 0.8mm or more. The fiber length of the fiber material is preferably 6mm or less, and more preferably 4mm or less.

The water-retaining layer 19 may contain, in addition to the hydrophilic fibers, hydrophobic fibers, particularly, heat-fusible fibers, as necessary. The content of the hot-melt fibers is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on the total amount of the fibers in the water-retaining layer 19.

The content of the hot-melt fibers is preferably 0.1 mass% or more, and more preferably 0.5 mass% or more, based on the total amount of the fibers in the water-retaining layer 19. The content of the hot-melt fibers is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total amount of the fibers in the water-retaining layer 19.

It is preferable to use a hydrophilic polymer having a crosslinked structure capable of absorbing and holding a liquid 20 times or more its own weight as the component (b) as in the case of the component (a) because the content of water contained in the water-retaining layer 19 can be appropriately adjusted.

The shape of the component (b) may be 1 or 2 or more selected from the group consisting of a sphere, a block, a grape string and a fiber. The average particle diameter of the component (b) is preferably 1 to 1000 μm, more preferably 10 to 500 μm. The average particle diameter of the component (b) is preferably 1 μm or more, more preferably 10 μm or more. The average particle diameter of the component (b) is preferably 1000 μm or less, and more preferably 500 μm or less.

The average particle diameter of the component (b) is measured by a dynamic light scattering method, a laser diffraction method, or the like.

Specific examples of the component (b) include 1 or 2 or more selected from the group consisting of starch, crosslinked carboxymethylated cellulose, polyacrylic acid such as a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid, a salt thereof, and a polyacrylate graft polymer. Among them, from the viewpoint of easily adjusting the water content contained in the water holding layer 19 to make the water content in the heat generating layer appropriate and thereby to maintain a good heat generation temperature and a good temperature feeling, polyacrylic acid, a salt thereof, and a polyacrylate graft polymer such as a polymer or a copolymer of acrylic acid or an acrylic acid alkali metal salt are preferably used.

The ratio of the component (b) in the water-retaining layer 19 is preferably 10 to 70% by mass in a dry state, and more preferably 20 to 65% by mass in order to promote rapid movement of water in the water-retaining layer 19, facilitate adjustment of the water content in the water-retaining layer 19, and make the water content in the heat-generating layer appropriate, thereby maintaining a good heat-generating temperature rise and a good temperature sensation.

From the same viewpoint, the content of the component (b) in the water-retaining layer 19 is preferably 10% by mass or more, more preferably 20% by mass or more, and on the other hand, is preferably 70% by mass or less, more preferably 65% by mass or less in a dry state.

The basis weight of the water retaining layer 19 in a dry state is preferably 20 to 200g/m in terms of easy adjustment of the water content in the water retaining layer 19 to make the water content in the heat generating layer appropriate, thereby making it possible to increase the temperature of heat generation and maintain the temperature feeling well²More preferably 35 to 150g/m²More preferably 50 to 140g/m²。

The basis weight of the component (b) contained in the water retaining layer 19 is preferably 5 to 150g/m in a dry state from the viewpoint of easily adjusting the content of water contained in the water retaining layer 19 to make the water content in the heat generating layer appropriate, thereby making it possible to maintain a good heat generation and temperature rise and a good temperature feeling²More preferably 10 to 100g/m²More preferably 30 to 90g/m²。

The water-retaining layer 19 preferably has a basis weight of 20g/m in a dry state²Above, more preferably 35g/m²Above, more preferably 50g/m²The above. The water-retaining layer 19 preferably has a basis weight in a dry stateIs 200g/m²Hereinafter, it is more preferably 150g/m²Hereinafter, it is more preferably 140g/m²The following.

The basis weight of the component (b) contained in the water-retaining layer 19 is preferably 5g/m in a dry state²Above, more preferably 10g/m²Above, more preferably 30g/m²The above. Further, the water-retaining layer 19 preferably has a basis weight of 150g/m in a dry state²Hereinafter, more preferably 100g/m²Hereinafter, more preferably 90g/m²The following.

The water retaining layer 19 may have the heat generating layer 13 formed on one surface of the water retaining layer 19 as shown in fig. 4, or may have the heat generating layer 13 formed on both surfaces of the water retaining layer 19.

Next, a method for producing the heat generating member 20 will be described.

First, a base material layer 10 is prepared, and a drug composition containing a cold-sensitive agent and a solvent having a molecular weight of 1,000 or less is applied on the base material layer 10 to form a drug layer 16.

The method of coating the chemical composition is not particularly limited, and die coating, roll coating, screen printing, roll gravure printing, knife coating, curtain coater, and the like can be used.

The viscosity of the drug composition at a temperature near the temperature when the drug composition is applied is preferably 5 to 100 mPas, and more preferably 10 to 50 mPas from the viewpoints of ease of application and spreadability of the drug solution. For example, when menthol is used as a cold feeling agent, the pharmaceutical composition preferably has a viscosity in the above range under the conditions of 50 ℃ and 50 RH. The measurement of the viscosity was performed using a spindle 4 of a B-type viscometer with a spindle rotation speed of 60 rpm.

Next, the heat-generating layer 13 is formed by applying a heat-generating powder water dispersion in which the heat-generating composition is dispersed in water onto the chemical layer 16. That is, the heat generating layer 13 is a coating layer of the heat generating composition. The method of coating the heat-generating powder water dispersion is not particularly limited, and examples thereof include die coating.

The heat-generating powder water dispersion can be obtained by further uniformly dispersing the oxidizable metal, the carbon component, the water-insoluble component, and the like by stirring with a stirrer. The heat-generating powder water dispersion may be prepared by mixing all the above components at once, or may be prepared by dissolving the reaction accelerator in a solution prepared by dissolving the thickener in water in advance to prepare an aqueous solution, and then mixing the aqueous solution with a mixture prepared by premixing the oxidizable metal and the carbon component.

Thereafter, the water retaining layer 19 is formed on the heat generating layer 13, thereby manufacturing the heat generating member 20. The method for forming the water-retaining layer 19 is not particularly limited, and for example, a layer containing particles of a water-absorbent polymer may be disposed.

This makes it possible to manufacture the heat generating portion 20 in which the medicine layer 16 is formed between the base layer 10 and the heat generating layer 13.

[ heating element 18]

The heating element 18 includes a heating portion 20 and an inner bag 17 accommodating the heating portion 20 therein.

The inner bag 17 is formed by joining the sheet 171 to the peripheral edge of the sheet 172. The regions other than the peripheral edge portions of the sheets 171 and 172 are non-bonded regions, and the heat generating layer 13 is disposed in the non-bonded regions.

The sheet 171 is disposed on the skin side of the heat generating layer 13 when the user attaches the warming device 1 to the skin.

The sheet 171 is an air-permeable sheet, and the air permeability thereof is preferably 40,000 seconds/100 ml or less, and more preferably 25,000 seconds/100 ml or less.

By setting the air permeability of the sheet 171 to 40,000 seconds/100 ml or less, the air permeability of the sheet 171 can be ensured, and the steam from the heat generating layer 13 can be easily released to the outside of the sheet 171.

On the other hand, the air permeability of the sheet 171 is preferably 10 seconds/100 ml or more, and more preferably 100 seconds/100 ml or more. By setting the air permeability of the sheet 171 to 10 seconds/100 ml or more, the heat generation temperature can be controlled to prevent abnormal heat generation.

As the sheet 171 having such air permeability, for example, a porous sheet made of a synthetic resin having moisture permeability but not water permeability is preferably used. Specifically, a film in which polyethylene contains calcium carbonate or the like and is stretched can be used.

The sheet 172 is located on the side farther from the skin than the heat generating layer 13 when the user applies the warming device 1 to the skin.

The air permeability of the sheet 172 is preferably higher than that of the sheet 171 from the viewpoint of facilitating the release of steam to the outside of the sheet 171.

The air permeability of the sheet 172 is preferably 150,000 seconds/100 ml or less, more preferably 100,000 seconds/100 ml or less, and even more preferably 85,000 seconds/100 ml or less, from the viewpoint of keeping good heat generation characteristics while absorbing a small amount of oxygen. On the other hand, from the viewpoint of efficiently supplying steam to the user without causing steam leakage to the outside, it is preferably 50,000 seconds/100 ml or more, and more preferably 60,000 seconds/100 ml or more.

As the sheet 172 having such air permeability, for example, a porous sheet made of a synthetic resin having moisture permeability but not water permeability is preferably used. Specifically, a film in which polyethylene contains calcium carbonate or the like and is stretched can be used.

Here, by providing the sheet 172 having air permeability to the heating appliance 1, the air permeability of the entire sheet layer composed of the second sheet 12 and the sheet 172 is lower than the air permeability of the entire sheet layer composed of the first sheet 11, the sheet 171, and the base layer 10. In other words, the second sheet 12 is the outermost layer, and the air permeability of the entire sheet layer from the second sheet 12 to the heat generating layer 13 is higher than the air permeability of the entire sheet layer from the first sheet 11 to the heat generating layer 13 with the first sheet 11 being the outermost layer. Specifically, the air permeability of the entire sheet layer from the second sheet 12 to the heat generating layer 13 is preferably 80,000 seconds/100 ml or more.

The planar shape of the heating element 18 is preferably a rectangular shape, and more preferably a square shape.

The heating element 18 is housed inside an outer bag formed of the first sheet 11 and the second sheet 12. Further, a part of the sheet 172 of the heating element 18 may be fixed to the second sheet 12 with an adhesive such as a hot-melt adhesive. This can suppress the movement of the heating element 20 inside the outer bag.

The maximum temperature of the surface of the heating element 18 in the present embodiment is preferably 36 ℃ or higher, more preferably 38 ℃ or higher, and even more preferably 41 ℃ or higher, from the viewpoint of making the user feel both warm and cool.

The maximum temperature of the surface of the heating element 18 is preferably 60 ℃ or lower, more preferably 55 ℃ or lower, and still more preferably 50 ℃ or lower, from the viewpoint of providing a comfortable temperature feeling to the user.

The maximum surface temperature can be measured using a measuring instrument in accordance with JIS S4100.

[ outer bag ]

Next, the outer bag, that is, the first sheet 11 and the second sheet 12 constituting the outer shell of the warmer 1 will be described.

In the present embodiment, the first sheet 11 and the second sheet 12 are both the same size and have the same planar shape. In the present embodiment, the heater 1 has a long shape having a longitudinal direction X and a width direction Y orthogonal thereto in a plan view from the first sheet 11 side.

In this way, by making the heating unit 1 a long flat shape in a plan view from the first sheet 11 side, the heating unit 1 can be attached so as to extend in the left-right direction of the user.

As described above, the bag body may be configured by forming the first sheet 11 and the second sheet 12 as separate sheets and bonding the outer peripheral edges thereof to each other, or the bag body may be configured by forming the first sheet 11 and the second sheet 12 as continuous sheets and folding the continuous sheets in two and bonding the opposite outer peripheral edges thereof to each other.

The first sheet 11 is located on the skin side of the user when the user wears the warming appliance 1. The first sheet 11 is an air-permeable sheet and has an air permeability of 8000 sec/100 ml or less. Among these, the air permeability of the first sheet 11 is 6,000 seconds/100 ml or less, and more preferably 1,000 seconds/100 ml or less, from the viewpoint of reliably ensuring the air permeability of the steam generated by the heat-generating layer 13. The lower limit of the air permeability of the first sheet 11 is not particularly limited. However, if the basis weight or the like of the inner bag 17 positioned on the inner side, particularly the inner side, for preventing the inside of the first sheet 11 from being seen through is taken into consideration, it is preferably 1 second/100 ml or more.

As the first sheet 11, a fibrous sheet typified by a nonwoven fabric can be used.

In the present embodiment, the second sheet 12 is made of a sheet having the same air permeability as the first sheet 11. However, from the viewpoint of appearance, it is preferable that the first sheet 11 is made of a nonwoven fabric.

Here, the warmer 1 may be configured to be expandable and contractible at least in the X-axis direction. For example, the first sheet 11 and the second sheet 12 may be made of stretchable sheets having the above-described air permeability and being stretchable in the X-axis direction. Examples of the stretchable sheet include synthetic fibers selected from polyesters such as polyethylene terephthalate (PET), polyolefins such as Polyethylene (PE) and polypropylene (PP), polyamides, polyacrylic acids, and the like; natural fibers selected from cellulose, silk, cotton, wool, and the like; or a sheet comprising a composite of these fibers. Alternatively, as the stretchable sheet, a nonwoven fabric produced by a method selected from the group consisting of a hot air method, a spunbond method, a needle-punch method, a melt-blown method, a carding method, a hot melt method, a spunlace method, and a solvent bonding method using 2 or more kinds of fibers may be used. In addition, woven fabrics and the like may be used in addition to the nonwoven fabrics. From the viewpoint of hand and elasticity, it is preferable to use a nonwoven fabric having elasticity as the elastic sheet. The nonwoven fabric having elasticity is preferably a through-air nonwoven fabric or a spunbond nonwoven fabric containing elastic fibers (e.g., polyurethane or polyester) as constituent fibers, and a nonwoven fabric obtained by surface-treating a nonwoven fabric with silicone or a surfactant may be used from the viewpoint of hand feeling. The first sheet 11 and the second sheet 12 may be made of the same material, or may be made of different materials.

Next, the first adhesive layer 14 and the second adhesive layer 15 will be described.

The first adhesive layer 14 and the second adhesive layer 15 are provided on the outer surface of the first sheet 11. The first adhesive layer 14 and the second adhesive layer 15 are used to attach the warmer 1 to the skin of a user.

The first adhesive layers 14 are formed of a pair of first adhesive layers 14, and the pair of first adhesive layers 14 are arranged in parallel on the outer surface of the first sheet 11, extending in one direction and spaced apart from each other, and are preferably arranged at the ends of the first sheet 11 in the X-axis direction. The pair of first adhesive layers 14 preferably do not overlap with the heat generating layer 13 in a plan view from the outer surface side of the first sheet 11 in view of heat generating characteristics.

On the other hand, the second adhesive layer 15 is disposed in a region between the pair of first adhesive layers 14 when viewed from the first sheet 11 side in plan view, and extends in the same direction as the first adhesive layers 14. In the present embodiment, the second adhesive layer 15 has a rectangular shape when viewed from the first sheet side.

The first adhesive layer 14 and the second adhesive layer 15 are formed by applying an adhesive containing at least 1 or more selected from acrylic resins, vinyl acetate resins, and olefin resins to the outer surface of the first sheet 11.

The warmer 1 as described above is preferably enclosed in an oxygen-barrier bag.

When the heating device 1 is used, the oxygen barrier pouch is opened, and the heating device 1 is taken out. Thereafter, the release paper 21 is removed, and the warmer 1 is attached to the back of the neck of the user via the first adhesive layer 14 and the second adhesive layer 15. Thereby, the warmer 1 is fixed to the user.

When the oxidizable metal in the heat generating layer 13 comes into contact with air, the oxidizable metal is oxidized, and the heat generating layer 13 generates heat. The heat generation layer 13 generates heat, and the moisture in the heat generation layer 13 evaporates to generate steam. The vapor is released to the outside of the warmer 1 through the base material layer 10, the sheet 171, and the first sheet 11.

When the base material layer 10 is not provided in the heat generating element, the steam is released to the outside through the sheet 171 and the first sheet 11.

On the other hand, since the sheet 172 of the inner bag 17 is a non-air-permeable layer, the steam generated in the heat generating layer 13 is blocked by the sheet 172 and hardly released from the second sheet 12 side to the outside. This allows steam to be preferentially discharged from the sheet 171, and thus, the steam can be reliably supplied to the skin of the user.

Next, the reason why the volatilization behavior of the cooling agent is appropriate for the heat generation behavior and the effect thereof, which are the idea of the present inventors, can be realized by the warmer 1, and the effects thereof will be described.

As described above, the heater 1 of the present invention includes the medicine layer 16 separated from the heat generating layer 13, and does not allow the refrigerant to be uniformly distributed throughout the entire heat generating portion by a solvent or a surfactant as in the heat generating device described in patent document 1. This can effectively suppress the influence of the cooling agent on the heat generation characteristics, and can provide a good temperature immediately after the use of the heating appliance 1 is started, and the cooling effect can be easily obtained. Further, by disposing the chemical layer 16 between the heat generating layer 13 and the second sheet 12, it is possible to suppress the failure to obtain sufficient heat generation due to the reduction in air permeability of the first sheet 11 by the cooling agent, and to stably obtain a good temperature rise at the time of heat generation. Further, by including a solvent having a molecular weight of 1,000 or less in the drug layer 16 whose arrangement is controlled, the volatilization rate of the cooling agent increases, the cooling agent smoothly volatilizes with a rapid rise in heat generation temperature after the start of use, and a sufficient amount of the cooling agent can be volatilized. These functions in combination, and as a result, it is considered that the heating temperature of the warmer 1 is increased as described above, and the rapidity of the increase in the heating temperature and the rapidity of the initial volatilization speed of the cold feeling agent are appropriately combined. In the present invention, in addition to this, an effect of further improving the volatilization amount of the cold feeling agent can be obtained, and it is estimated that by combining all of these, an effect of improving the feeling of effect on stiffness, fatigue, or pain at the application site, and an effect of improving the quick-acting feeling, which are not achieved at present, can be obtained. Further, a cooling sensation by the cooling sensation agent can be obtained, and the satisfaction of the user can be improved.

Although the mechanism by which the volatilization behavior of the cooling agent can be controlled by using a solvent having a molecular weight of 1,000 or less is not clear in detail, it is considered that the higher the molecular weight of the solvent, the more likely the solvent acts on the oxidizable metal or carbon component in the heat-generating layer 13 to inhibit the oxidation reaction, and as a result, the temperature rise at the start of heat generation of the heating appliance 1 is lowered, whereas the decrease in the temperature rise, and the decrease in the volatilization amount and speed of the cooling agent can be suppressed by reducing the molecular weight of the solvent to 1,000 or less.

Further, in the warming apparatus 1, the chemical layer 16 is disposed between the heat-generating layer 13 and the second sheet 12, and the cooling agent is adsorbed to the water retaining layer 19 located between the heat-generating layer 13 and the first sheet, whereby the water retaining property of the water retaining layer 19 can be suppressed from being lowered. As a result, good heat generation can be stably obtained.

Further, by disposing the chemical layer 16 between the heat generating layer 13 and the second sheet 12, the adhesiveness of the first adhesive layer 14 and the second adhesive layer 15 disposed on the first sheet 11 can be maintained well. In other words, the cold sensitive agent oozing out of the chemical layer 16 can be inhibited from acting on the first adhesive layer 14 and the second adhesive layer 15 to reduce the adhesiveness thereof.

The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range in which the object of the present invention can be achieved are included in the present invention.

For example, although the sheet 172 is an air-impermeable layer in the above embodiment, for example, either the second sheet 12 or the sheet 172 may be an air-impermeable layer, or both may be air-impermeable layers.

Further, a non-air-permeable sheet may be disposed inside the inner bag 17. In this case, a non-air-permeable sheet is disposed on the sheet 172 side of the heat generating layer 13. The non-air-permeable sheet preferably covers the entire heat generating layer 13 when viewed from the second sheet 12 side. In this case, the second sheet 12 or the sheet 172 may be a non-air-permeable layer or an air-permeable layer.

Further, in the above embodiment, both the end portions of the first adhesive layer 14 and the second adhesive layer 15 reach the outer peripheral edge of the first sheet 11 when viewed from the first sheet side in a plan view, but the present invention is not limited to this.

In the above embodiment, the example in which the first adhesive layer 14 and the second adhesive layer 15 are formed on the outer surface of the first sheet 11 has been described, but the first adhesive layer 14 and the second adhesive layer 15 may not be formed. In this case, the heating device 1 may have other fixing portions by providing stretchable ear portions or the like at both end portions of the heating device 1.

In the above embodiment, the heat generating layer 13 is accommodated in the inner bag 17, but the inner bag 17 may be omitted. In this case, the air-permeable layer including the first sheet 11 and configured to supply air to the heat generating layer 13 may be formed of one first sheet 11. This can simplify the structure of the heating appliance.

In the above embodiment, the warmer 1 is attached to the back side of the neck, but the warmer is not limited to this, and may be attached to the skin surface of another part of the user.

In the above embodiment, the present invention further discloses the following heating appliance.

< 1 > a warmer, comprising:

a first sheet having breathability;

a second sheet material;

a heat generating layer disposed between the first sheet and the second sheet; and

a chemical agent layer disposed between the heat generating layer and the second sheet

The air permeability from the heat generating layer to the first sheet is higher than the air permeability from the heat generating layer to the second sheet,

the drug layer is composed of a drug composition containing a psychrotonic agent and a solvent having a molecular weight of 1,000 or less.

< 2 > such as < 1 > wherein a water-retaining layer is preferably provided between the heat-generating layer and the first sheet.

< 3 > the warming device as described in < 1 > or < 2 >, wherein the cooling agent preferably comprises 1 or 2 or more compounds selected from the group consisting of menthol, 1, 8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1, 2-propanediol, and N-ethyl-3-p-menthanecarboxamide.

The warming device of any one of < 4 > such as < 1 > to < 3 >, wherein the content of the solvent is preferably 30% by mass or more and 85% by mass or less with respect to the total amount of the cold sensitizer and the solvent in the pharmaceutical composition.

The warming device of any one of < 5 > such as < 1 > to < 4 > wherein the solvent preferably comprises a polyol.

The warming device of any one of < 6 > such as < 1 > to < 5 >, wherein the solvent is preferably 1 or 2 or more selected from polyethylene glycol, glycerin, and propylene glycol.

The warmer of < 7 > such as < 1 > to < 6 > wherein the solvent preferably has a molecular weight of 600 or less.

The warming instrument of any one of < 8 > such as < 1 > to < 7 >, wherein the content of the cooling agent with respect to the area of the heat-generating layer when viewed from the top is preferably 1.0mg/cm²The above.

The warming instrument of any one of < 9 > such as < 1 > to < 8 >, wherein the content of the cooling agent with respect to the area of the heat-generating layer when viewed from the top is preferably 6.0mg/cm²The following.

The warming instrument of any one of < 10 > such as < 1 > to < 9 >, wherein the content of the solvent is preferably 2.0mg/cm per unit area of the heat-generating layer when viewed from above²The above.

The warming instrument of any one of < 11 > such as < 1 > to < 10 >, wherein the content of the solvent is preferably 20.0mg/cm per unit area of the heat-generating layer as viewed from above²The following.

A warming device according to any of < 12 > such as < 1 > to < 11 > wherein the medicament composition preferably comprises substantially no surfactant.

The heater of < 13 > such as < 1 > to < 12 > wherein the heat generating layer preferably comprises an oxidizable metal, a water absorbing agent and water.

The warming appliance of any one of < 14 > such as < 1 > to < 13 >, wherein the heat-generating layer preferably comprises a tackifier.

Warming appliance as described in < 15 > such as < 13 > or < 14 >, whichWherein the oxidizable metal is preferably 100g/m in basis weight²Above and 3,000g/m²The following.

The warming appliance of any one of < 16 > such as < 1 > to < 15 >, wherein the heat-generating layer is preferably a coating layer of a heat-generating composition.

The warming appliance of any one of < 17 > such as < 1 > to < 16 >, wherein the air permeability of the heat generating layer to the second sheet is preferably 80,000 seconds/100 ml or more.

The heating device of any of < 18 > and < 1 > to < 17 >, wherein the heat generating portion preferably has an inner bag, and a sheet disposed on a skin side farther than the heat generating layer among the sheets constituting the inner bag has a higher air permeability than a sheet disposed on a skin side farther than the heat generating layer.

< 19 > the warmer of < 18 > wherein the sheet material constituting the inner bag disposed on the skin side of the heat-generating layer preferably has an air permeability of 40,000 seconds/100 ml or less and 10 seconds/100 ml or more.

The sheet material constituting the inner bag preferably has an air permeability of 50,000 seconds/100 ml or more and 150,000 seconds/100 ml or less, the sheet material being disposed on the skin side of the heat-generating layer.

The heater of any of < 21 > such as < 1 > to < 20 >, wherein a base material layer, the drug layer, and the heat-generating layer are laminated in this order on the heat-generating body, and the base material layer is disposed so as to be located farther from the skin than the heat-generating layer.

< 22 > if < 2 > to < 21 > any item the warming device, wherein, the heat-generating body has stacked on the layer according to the preface the substrate layer the medicament layer generate heat the layer of protecting water, just the substrate layer is in order to be located the mode configuration of the position that is farther away from the skin side than the layer that generates heat, the layer of protecting water is in order to be located the mode configuration that leans on the skin side more than the layer that generates heat.

The warming instrument of any one of < 23 > and < 1 > to < 22 >, wherein a volatilization amount of the cooling agent after the heat generation layer starts to generate heat is preferably 1mg/2 hours or more and 5mg/2 hours or less.

The heating device of any of < 24 > to < 23 >, wherein the maximum temperature of the surface of the heating element is preferably 38 ℃ or more and 55 ℃ or less.

The warmer of < 25 > such as < 1 > to < 24 > wherein the first sheet preferably has an adhesive layer on the side opposite to the heat-generating layer.

< 26 > a warmer, comprising:

a first sheet having breathability;

a second sheet material;

a heat generating layer disposed between the first sheet and the second sheet; and

a chemical layer disposed between the heat-generating layer and the second sheet,

the heating body is sequentially laminated with a base material layer, the medicament layer and the heating layer,

the base material layer is disposed so as to be located farther from the skin side than the heat generating layer, and

the air permeability from the heat generating layer to the first sheet is higher than the air permeability from the heat generating layer to the second sheet,

the medicinal layer contains Mentholum as cold feeling agent, and is composed of medicinal composition containing Mentholum and solvent with molecular weight of 1,000 or less,

the solvent is 30 to 85 mass% based on the total amount of the cold-feeling agent and the solvent,

the weight ratio of the cold-sensitive agent to the oxidizable metal contained in the heat-generating layer is 5 to 55.

< 27 > a method of using a warming device, which is the method of using a warming device of any one of < 1 > to < 25 >, wherein the first sheet is preferably applied to the skin of a user.

< 28 > as < 27 > wherein the warming vapor is applied to the skin of the user.

Use of a warming device of any of < 29 > to < 26 > for simultaneously providing a cooling agent and warming steam to the skin of a user.

Examples

The present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to this embodiment. Unless otherwise specified, "%" and "part" mean "% by mass" and "part by mass", respectively.

A warmer of the structure shown in fig. 1 was produced as follows.

< example 1 >

[ preparation of Heat-generating powder Water Dispersion ]

100 parts by mass of an oxidizable metal, 8 parts by mass of a carbon component, 62 parts by mass of water, 11 parts by mass of a reaction accelerator, and 0.2 part by mass of a thickener were prepared according to the following procedure. The thickener was dissolved in water, and then the reaction accelerator was dissolved to prepare an aqueous solution, while a powder in which an oxidizable metal and a carbon component were premixed was prepared, and the premixed powder was added to the aqueous solution and stirred with a disk turbine type stirring blade at 150rpm for 10 minutes to obtain a slurry-like heat-generating powder water dispersion.

Further, the types, product names and manufacturers of the oxidizable metal, the carbon component, water, the reaction accelerator, and the thickener are as follows.

< raw Material composition >

Oxidizable metal: iron powder (iron powder RKH, average particle size 45 μm, DOWA IP Creation Co., Ltd.)

Carbon component: activated carbon (CARBORAFFIN, average particle diameter 40 μm, manufactured by Japan Enviro Chemicals Ltd.)

Water: tap water

Reaction accelerator (b): sodium chloride (Japanese pharmacopoeia sodium chloride, available from Otsuka chemical Co., Ltd.)

Tackifier: xanthan Gum (Echo Gum BT, DSP GOKYO FOOD & CHEMICAL Co., Ltd.; manufactured by Ltd.)

[ production of Heat-generating part ]

As the water-retaining layer, paper A (20 g/m) made of wood pulp was used²Ipomoea paper Co., Ltd.), and a water-absorbent polymer (sodium polyacrylate, spherical, having an average particle diameter of 300 μm or 50g/m²Aqualic CA, manufactured by Nippon catalyst Co., Ltd.) and a wood pulp-made paper B (30 g/m)²And illite paper corporation) are laminated and integrated in this order. Further, a polyethylene laminated paper (manufactured by showa paper industry co., ltd.) was prepared as the base material layer.

At 25cm²A polyethylene laminate (5 cm. times.5 cm) was coated with a cold-sensitive agent-dissolved solvent (coating weight 60 g/m) having the composition shown in Table 1²) On the coated side, at 25cm²(5 cm. times.5 cm) at a ratio of 600g/m²The amount of the heat-generating powder dispersed in water is applied. Then, the polymer sheet is disposed on the formed heat generating layer, thereby producing a heat generating portion as a laminated structure.

[ production of heating element ]

The heat-generating member was placed in an inner bag having an air permeability of 16,000 seconds/100 ml in a first sheet (air-permeable sheet disposed on the skin side) and an air permeability of 80,000 seconds/100 ml or more in a second sheet (air-impermeable sheet), and the peripheral edge portion was hermetically sealed. In this case, the heat generating layer is disposed so that the base material layer side is positioned on the second sheet side. Thereby obtaining a heat-generating body.

[ production of warming device ]

A needle-punched nonwoven fabric (air permeability of 1 second/100 ml, basis weight of 80 g/m) was used²) As the first sheet, a spunbonded nonwoven fabric (air permeability of 1 second/100 ml, basis weight of 38 g/m) was used²) As a second sheet. Then, 2 heating elements were disposed inside the first sheet and the second sheet at a distance. Thereafter, the first sheet and the second sheet are stacked, and the peripheral edge portion is hermetically sealed.

Further, an adhesive layer was disposed on the first sheet side, thereby obtaining a heater.

< examples 2 to 8 >

A heater was obtained in the same manner as in example 1 except that the cooling agent and the solvent having the compositions shown in table 1 were prepared.

< comparative examples 1 and 2 >

0.7 parts of polyamide epichlorohydrin resin (trade name "WS 4020" manufactured by Astro PMC Co., Ltd.) as a cationic flocculant and 0.18 parts of sodium carboxymethylcellulose (trade name "HE 1500F" manufactured by first Industrial pharmaceutical Co., Ltd.) as an anionic flocculant were added to 100 parts of the solid content (total of oxidizable metal, fibrous material and activated carbon) of the raw material composition. Further, water (industrial water) was added to obtain a slurry so that the solid content concentration became 12%.

The raw material composition is as follows.

< compounding of raw Material composition >

Oxidizable metal: iron powder, manufactured by DOWA IP Creation co., ltd., under the trade name "RKH": 83 percent

Fibrous material: pulp fiber (manufactured by Fletcher Challenge Canada Inc., trade name NBKP "Mackenzi (adjusted to CSF200 ml)"): 8 percent of

Reaction promoters: activated carbon (product name "CARBORAFFIN" manufactured by Japan Enviro Chemicals Ltd., average particle diameter 45 μm) 9%

The slurry was diluted to 0.3% with water just before the paper making head, and paper was made by an inclined short wire paper machine at a line speed of 15 m/min to prepare a wet formed sheet.

The sheet was pressed and dewatered by holding it between felts, and dried directly between heating rolls at 140 ℃ until the water content became 5% or less. Basis weight after drying 450g/m²The thickness is 0.45 mm. The composition of the formed sheet thus obtained was measured using a thermogravimetric apparatus (manufactured by seiko instruments inc., TG/DTA6200), and the results were 83% of iron, 9% of activated carbon, and 8% of pulp.

The obtained molded sheet was cut into pieces of 49mm × 49mm, 3 pieces were stacked, and an electrolyte solution was injected so that the amount of the electrolyte solution (5% saline) was 45 parts per 100 parts of the molded sheet.

Thereafter, a solvent having a composition shown in table 1 and a refrigerant dissolved therein was injected into the molded sheet, and the solvent was allowed to permeate the entire molded sheet by capillary action, thereby obtaining a heat-generating part.

Using the obtained heat-generating member, a heat-generating body was produced in the same manner as in example 1, thereby obtaining a heating device.

< comparative example 3 >

A heating appliance was obtained in the same manner as in example 1 except that the cooling agent and the solvent having the compositions shown in table 1 were prepared and the cooling agent was placed at the positions shown in table 1.

Specifically, at 25cm²(5 cm. times.5 cm) polyethylene on 25cm²(5 cm. times.5 cm) at a ratio of 600g/m²After coating the heat-generating powder water dispersion in the amount of (2), a solvent having a composition shown in Table 1 and a cold-sensitive agent dissolved therein was applied (coating amount: 60 g/m)²) The polymer sheet is disposed on the coated surface to produce a heat-generating part as a laminated structure.

< comparative example 4 >

A heating appliance was obtained in the same manner as in example 1 except that the cooling agent and the solvent having the compositions shown in table 1 were prepared and the cooling agent was placed at the positions shown in table 1.

Specifically, at 25cm²(5 cm. times.5 cm) polyethylene on 25cm²(5 cm. times.5 cm) at a ratio of 600g/m²The above-mentioned heat-generating powder water dispersion was coated in the above-mentioned amount, and then the above-mentioned polymer sheet was disposed on the coated surface and coated thereon (coating amount: 60 g/m)²) A heat generating portion was produced by preparing a laminated structure by dissolving a solvent containing a refrigerant in the composition shown in table 1.

< comparative example 5 >

A heater was obtained in the same manner as in example 1 except that the cooling agent and the solvent having the compositions shown in table 1 were prepared.

The following evaluations were carried out using the heating devices obtained in the above examples and comparative examples. The results are shown in Table 1. Further, the warmer was sealed in an oxygen barrier bag immediately before evaluation.

(evaluation)

Exothermic property (temperature rise by initial heat application)

Using a measuring instrument in accordance with JIS S4100, the temperature sensor of the measuring instrument was attached to the center of the surface of the outer surface of the first sheet of the heating device on which the heat generating portion was present, the heat generating portion was started to generate heat at room temperature of 20 ℃, absolute humidity of 50%, and in the presence of oxygen, and the time (minutes) required until the temperature reached 42 ℃ at which a comfortable temperature sensation was felt was measured.

Volatile amount of menthol

First, a gas collection bag (Tedlar (registered trademark) bag, manufactured by DuPont inc.) of a polyvinyl fluoride resin of 15cm × 25cm containing air in an amount sufficient for the heating element to perform an oxidation reaction was prepared, one end of the gas collection bag was connected to an air supply source, and the outlet port of the other end or the tip of a tube connected to the outlet port was immersed in ethanol.

Subsequently, the heating element holding menthol was taken out from the oxygen barrier bag, put into the gas collecting bag, and placed on a hot plate set at 35 ℃ for 2 hours. While being placed on the hot plate, air is flowed into the gas collection bag from the air supply source at a constant speed (100mL/min), and the air is discharged from the outlet port at the other end of the gas collection bag or the tip of the tube connected to the outlet port, whereby menthol volatilized from the heating body is captured in ethanol. Further, a weight is placed on the gas collecting bag so that the air flowing into the gas collecting bag is appropriately discharged, and the periphery of the gas collecting bag is insulated with a heat insulating material so as to maintain the heating by the heating plate.

After the mounting for 2 hours, the heating element was taken out from the gas collection bag, the gas collection bag was washed with ethanol, and the ethanol used for washing was also captured and added to the amount of the volatile menthol.

Analysis of the captured amount of menthol was performed by a gas chromatograph (Agilent 6890N, manufactured by Agilent technologies ltd.).

These operations are all carried out at atmospheric pressure.

Since 2 heating elements were used in the heating device, the amount of menthol volatilized by the heating device was 2 times the amount measured for each heating element.

Sensory evaluation

[ Effect feeling on shoulder and waist pain ]

After 8 hours of application of each warming device to 5 subjects who felt pain in the shoulder or waist, the degree of improvement in stiffness or pain was evaluated on the following 5-level basis, and the average value was taken.

5: the pain is alleviated, and a feeling of effect as particularly reduced is felt

4: the pain is alleviated and the feeling of effectiveness is felt

3: when worn, the wearer feels a sensation such as pain being alleviated, but the feeling of effectiveness is not good

2: feeling of effect on pain is not so great

1: the effect on pain was not felt at all

[ quick-acting feeling ]

Whether or not the patient feels stiffness or pain was evaluated on the following 5-scale criteria at the time point of 10 to 30 minutes after the application of each warming device to 5 subjects who felt shoulder or waist pain, and the average value was taken.

5: a significant perception of pain relief

4: pain relief is felt

3: pain relief was slightly felt

2: feeling is not obvious

1: no pain relief was felt.

[ evaluation of menthol feeling ]

After 6 hours of application of each warming device to 5 subjects, the intensity of the sensation of stimulation of menthol was evaluated on the following 5-scale basis, and the average value was taken.

5: very excellent (the irritating sensation of menthol is just right, the sensation of menthol is also felt in the early stage, and the sensation is sustained.)

4: excellent (menthol feels just stiff, but menthol is perceived as slightly time consuming or slightly shorter in duration.)

3: no problem (feeling of menthol, but the intensity of menthol or the duration of menthol sensation was slightly insufficient.)

2: the feeling of menthol is obviously weaker

1: completely without menthol feeling

[ Table 1]

TABLE 1

In addition, the method is as follows: kalcol 200GD (manufactured by Kawang corporation) molecular weight 298.55

In addition, 2: EMANON CH60 (manufactured by Huawang company)

When example 3 is compared with example 8, it is considered that since PEG400 is used in example 3, the temperature rise time at 42 ℃ and the amount of menthol volatilized are further increased as compared with example 8 using PEG1000, and as a result, the feeling of pain effect, quick-acting feeling, and menthol feeling are more excellent. That is, it is presumed that the effect of the present invention can be easily obtained by lowering the molecular weight of the solvent.

In comparative example 3, the quick-acting feeling was not obtained and the feeling of menthol was weak because the temperature rise time at 42 ℃ was long. In comparative example 4, the temperature did not rise to 42 ℃, and therefore, the sensation of effect on pain, quick-acting sensation, and menthol sensation were not all sufficient.

In the case of using polyethylene glycol having a molecular weight of 2000 in the warmer of example 1, the volatilization amount of menthol was not more than 1mg/2 hours, and the sensation of effect, quick-acting sensation, and irritation were poor.

Claims (10)

1. A warming appliance, wherein,

the disclosed device is provided with:

a first sheet having breathability;

a second sheet material;

a heat generating layer disposed between the first sheet and the second sheet; and

a chemical agent layer disposed between the heat generating layer and the second sheet

The air permeability from the heat generating layer to the first sheet is higher than the air permeability from the heat generating layer to the second sheet,

the drug layer is composed of a drug composition containing a psychrotonic agent and a solvent having a molecular weight of 1,000 or less.

2. The warming appliance according to claim 1,

the heating layer and the water retaining layer are arranged between the first sheet materials.

3. The warming appliance according to claim 1 or 2,

the cold feeling agent comprises 1 or more than 2 compounds selected from menthol, 1, 8-cineole, menthyl lactate, menthyl acetate, monomenthyl succinate, 3- (l-menthoxy) -1, 2-propanediol, and N-ethyl-3-p-menthane carboxamide.

4. A warmer according to any one of claims 1 to 3, wherein,

the content of the solvent is 30 to 85 mass% based on the total amount of the pharmaceutical composition.

5. A warmer according to any one of claims 1 to 4, wherein,

the solvent is 1 or more than 2 selected from polyethylene glycol, glycerol and propylene glycol.

6. A warmer according to any one of claims 1 to 5, wherein,

the air permeability from the heat generating layer to the second sheet is 80,000 seconds/100 ml or more.

7. A warmer according to any one of claims 1 to 6, wherein,

an adhesive layer is provided on the surface of the first sheet opposite to the heat generating layer.

8. A warmer according to any one of claims 1 to 7, wherein,

the heat-generating layer contains an oxidizable metal, and the weight ratio of the oxidizable metal to the cooling agent contained in the warmer is 5 or more and 55 or less.

9. A method of using the warmer according to any one of claims 1 to 8,

applying the first sheet to the skin of a user.

10. Use of a warming device according to any one of claims 1 to 8 for simultaneously providing a cooling agent and warming steam to the skin of a user.

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